CN118434793A

CN118434793A - Main chain polymer, optical film, method for producing same, and multilayer film

Info

Publication number: CN118434793A
Application number: CN202280083897.1A
Authority: CN
Inventors: 一条洋树; 坂下竜一; 村上范武; 七田优辉; 稻叶礼人; 北川贵裕; 横井大洋; 伊部公太; 小林修
Original assignee: Sagami Chemical Research Institute; Tosoh Corp
Current assignee: Sagami Chemical Research Institute; Tosoh Corp
Priority date: 2021-12-22
Filing date: 2022-12-22
Publication date: 2024-08-02

Abstract

The main chain polymer of the present embodiment is a main chain polymer as follows: a photoreactive inverse wavelength dispersion unit having two functions of photoreactivity and birefringence inverse wavelength dispersion in a polymer main chain, wherein the photoreactive inverse wavelength dispersion unit has a structure represented by the following chemical formula (1). In the chemical formula (1), L ¹、L², which may be the same or different, represents a carbonyl group, an ester bond, an amide bond, an ether bond, or a single bond; * Represents bonding positions to other structures in the main chain polymer. Ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, or the condensed ring aromatic ring may have a substituent. R ⁰、R¹、R²、R³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms. [ chemical formula 1]

Description

Main chain polymer, optical film, method for producing same, and multilayer film

Technical Field

The invention relates to a main chain type polymer, a composition, an optical film and a manufacturing method.

Background

An organic EL display or a liquid crystal display is widely used as an important display device in a multimedia society for various intelligent devices, computer displays, televisions, and the like. In addition, in these displays, many optical films are used to improve display characteristics, and they have a great effect on contrast improvement, color tone compensation, and the like when viewed from the front or the inclined plane.

As a representative film of an optical film related to an organic EL display or a liquid crystal display, a retardation film can be cited. By combining with a polarizing plate, the retardation film can be used as an antireflection layer for various displays. In this application, a retardation film having a larger retardation in the longer wavelength region, that is, a film having inverse wavelength dispersibility (hereinafter, also referred to as an inverse wavelength dispersion film) is particularly required. For example, when an inverse wavelength dispersion film is used for the use of a circularly polarizing plate for organic EL, the retardation is preferably about 1/4 of the measurement wavelength λ. In detail, the ratio Re (450)/Re (550) of the in-plane retardation at 450nm to the in-plane retardation at 550nm is preferably 0.80 to 0.89.

Various polymerizable liquid crystal compounds having inverse wavelength dispersibility have been developed as a raw material for producing inverse wavelength dispersion films, but when producing inverse wavelength dispersion films, these polymerizable liquid crystal compounds are applied to alignment films produced in advance by rubbing treatment or photo-alignment treatment (for example, refer to patent documents 1 to 3), produced by photo-alignment treatment, and then cured by light or heat to form films. That is, the process of forming the alignment film is indispensable (for example, patent document 4). Further, a polymerizable liquid crystal compound having inverse wavelength dispersibility is produced by multistage synthesis (for example, patent document 5). In addition, it has been proposed to form a retardation film using a side chain type acrylate resin without an alignment film (for example, refer to patent documents 6 and 7). However, the side chain type liquid crystal acrylate resin containing a photoreactive group has problems in that it requires multiple stages in monomer synthesis, and is expensive and low in heat resistance temperature. The linear liquid crystal polyester resin containing a photoreactive group can form an optical film and a retardation film by irradiation of polarized ultraviolet rays and heat treatment without an alignment film, and it is expected that an optical film and a retardation film excellent in heat resistance can be produced from inexpensive monomers. However, linear liquid crystal polyester resins have a problem that they have excellent heat resistance but require a relatively high processing temperature of 200 degrees or more (for example, patent documents 8 to 10). Therefore, when a linear liquid crystal polyester resin is used as an optical film or a retardation film, there is a problem that an inexpensive general-purpose resin film support base material such as polyethylene terephthalate (heat-resistant temperature about 160 ℃), polyethylene naphthalate (heat-resistant temperature about 200 ℃), cycloolefin polymer (heat-resistant temperature about 160 ℃) or the like cannot be used.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. Hei 8-160430

Patent document 2: japanese patent laid-open No. 2003-505561

Patent document 3: international publication No. 2010-150748

Patent document 4: japanese patent 6172556

Patent document 5: japanese patent 6754845

Patent document 6: japanese patent laid-open No. 2002-226858

Patent document 7: international publication No. 2014/017497 booklet

Patent document 8: japanese patent laid-open No. 2018-188529

Patent document 9: japanese patent laid-open No. 2021-028375

Patent document 10: japanese patent laid-open No. 2021-028384

Disclosure of Invention

Problems to be solved by the invention

As described in the background art, when a polymerizable liquid crystal compound having inverse wavelength dispersibility is used as a raw material for producing an inverse wavelength dispersion film, a step of forming a liquid crystal alignment film is indispensable, and it is difficult to say that the method is advantageous in a process for producing an inverse wavelength dispersion film.

In addition, a polymerizable liquid crystal compound having inverse wavelength dispersibility, which is used as a raw material for producing an inverse wavelength dispersion film, often needs to be synthesized in multiple stages, and is poor in economical efficiency.

Accordingly, in the present invention, studies have been made to provide a reverse wavelength dispersion film which does not require an alignment film forming step and can be formed by applying a polymer.

Solution for solving the problem

The present inventors have made intensive studies to solve the above problems, and as a result, have found that a phase difference film having inverse wavelength dispersibility can be formed without requiring an alignment film by using a resin composition containing a polymer having a specific photoreactive structure, which exhibits inverse wavelength dispersibility of birefringence, and a photoreactive inverse wavelength dispersing unit (hereinafter, also referred to as photoreactive inverse wavelength dispersing unit a or unit a) having two functions of exhibiting such photoreactivity and inverse wavelength dispersibility of birefringence, and a polymer having a specific photoreactive group and a specific additive.

The present invention has been made based on such an insight, and specifically has the following configuration.

A main chain polymer having a photoreactive inverse wavelength dispersion unit having two functions of photoreactivity and birefringence inverse wavelength dispersion in the polymer main chain, wherein the photoreactive inverse wavelength dispersion unit has a structure represented by the following chemical formula (1).

[ Chemical formula 1]

[ In the above chemical formula (1), L ¹、L² may be the same or different and represents a carbonyl group, an ester bond, an amide bond, an ether bond or a single bond.

* Represents a bonding position to other structures in the main chain polymer.

Ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, or the condensed ring aromatic ring may have a substituent.

R ⁰、R¹、R²、R³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a group represented by the following chemical formula (Z1). ]

[ Chemical formula 2]

[ In the above chemical formula (Z1), rz ³ and Rz ⁴ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms.

Arz represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, or the condensed ring aromatic ring may have a substituent.

The wavy line means a bonding position to a portion other than R ⁰、R¹、R²、R³ or R ⁴ in the formula (1). ]

A dihydroxy compound represented by the following formula (1').

[ Chemical formula 3]

[ In the above chemical formula (1'), R ⁰、R¹、R²、R³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a group represented by the following chemical formula (Z1). Ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, or the condensed ring aromatic ring may have a substituent. ]

[ Chemical formula 4]

A process for producing a dihydroxy compound, wherein a dihydroxy compound represented by the following formula (1 ') is obtained by reacting a dihydroxy compound represented by the following formula (3) with a ketone represented by the following formula (4').

[ Chemical formula 5]

[ In the above chemical formula (3), R ⁰、R¹ and R ⁷ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms.

R ^2f represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a formyl group. ]

[ Chemical formula 6]

[ In the above formula (4'), R ⁸ represents an alkyl group having 1 to 8 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms.

Ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, and the condensed ring aromatic ring may have a substituent. ]

[ Chemical formula 7]

[ In the above chemical formula (1'), R ⁰、R¹、R²、R³、R⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a group represented by the following chemical formula (Z1). Ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, or the condensed ring aromatic ring may have a substituent. ]

[ Chemical formula 8]

Arz represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, or the condensed ring aromatic ring may have a substituent. The wavy line means a bonding position to a portion other than R ⁰、R¹、R²、R³ or R ⁴ in the formula (1). ]

Effects of the invention

According to the present invention, a reverse wavelength dispersion film that can be formed by coating a polymer without requiring an alignment film forming step can be provided.

Detailed Description

The present invention will be described in detail below. The following description will be given with reference to the typical embodiments or specific examples, but the present invention is not limited to these embodiments. In the present specification, the numerical range indicated by "to" refers to a range in which numerical values described before and after "to" are included as a lower limit value and an upper limit value.

In the present specification, the structure of the range enclosed by brackets in the polymer structure represents a repeating unit in the polymer structure.

In the present specification, the numbers described in the right lower part of brackets in the polymer structure indicate the content ratio of the repeating units in the polymer structure.

In the present specification, the bonding direction of the exemplified divalent group or chemical structure (for example, an ester bond or a repeating unit in a polymer structure) is not particularly limited within a chemically allowable range.

One embodiment of the present invention is a main chain polymer having a photoreactive inverse wavelength dispersion unit a (hereinafter, may be referred to as a polymer of the present invention) having a polymer main chain that has two functions of photoreactivity and birefringent inverse wavelength dispersion.

The photoreactive inverse wavelength dispersion unit a may be a structure represented by the following chemical formula (1).

[ Chemical formula 9]

In the formula (1), L ¹、L² may be the same or different and represents a carbonyl group, an ester bond, an amide bond, an ether bond or a single bond.

* Represents a bonding position to other structures in the main chain polymer.

Ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, and the condensed ring aromatic ring may have a substituent.

[ Chemical formula 10]

In the formula (1), R ⁰、R¹、R²、R³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a group represented by the formula (Z1); examples of the halogen atom include: chlorine atom, bromine atom, iodine atom, fluorine atom; examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl.

In the formula (Z1), rz ³ and Rz ⁴ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms; examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom; examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl.

In the formula (Z1), as Rz ³ and Rz ⁴, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a hydrogen atom, a methyl group, and an ethyl group are preferable from the viewpoint that the polymer of the present invention exhibits good optical characteristics.

Arz represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, and the condensed ring aromatic ring may have a substituent.

As the monocyclic aromatic ring which may have a substituent(s) with an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a ring constituting atom in Arz, for example, there may be mentioned: benzene, pyridine, pyrazine, pyrimidine, pyridazine, furan, pyrrole, imidazole, thiophene, pyrazole, oxazole, isoxazole, thiazole, triazole.

Examples of the Arz polycyclic aromatic ring which may have a substituent with an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a ring constituting atom include: biphenyl, terphenyl, bipyridine, bithiophene, and bifuran.

Examples of the condensed ring type aromatic ring which may have a substituent with an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom as a ring constituting atom in Arz include: naphthalene, anthracene, phenanthrene, quinoline, benzofuran, benzimidazole, benzothiophene, indole, indazole, benzoxazole, benzothiazole, benzotriazole.

From the viewpoint of easy availability, arz is preferably a monocyclic aromatic ring which has a ring-constituting atom which is an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, and which may have a substituent. The aromatic ring is more preferably a benzene ring, a furan ring, a thiophene ring, a thiazole ring or an oxazole ring in view of the polymer of the present invention exhibiting good optical characteristics, and the aromatic ring is more preferably a benzene ring or a thiophene ring in view of the polymer of the present invention exhibiting good optical characteristics.

From the viewpoint that the polymer of the present invention exhibits good optical properties, R ⁰、R¹、R²、R³ and R ⁴ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a group represented by the following chemical formulas (Z1-1) to (Z1-4), and particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

[ Chemical formula 11]

In the formula (1), L ¹ and L ² may be the same or different and each represents a carbonyl group, an ester bond, an amide bond, an ether bond or a single bond.

As L ¹ and L ², carbonyl, ester bond or ether bond is preferable.

In the formula (1), ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, and the condensed ring aromatic ring may have a substituent.

The substituents in the monocyclic aromatic ring, polycyclic aromatic ring, and condensed ring type aromatic ring include: alkyl group having 1 to 8 carbon atoms, halogen atom, alkoxy group having 1 to 4 carbon atoms, acyl group having 2 to 4 carbon atoms.

Examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl.

Examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom, iodine atom.

Examples of the alkoxy group having 1 to 4 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy.

Examples of the acyl group having 2 to 4 carbon atoms include: acetyl, propionyl, butyryl.

Examples of the monocyclic aromatic ring in Ar which may have a substituent by using an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a ring constituting atom include: benzene, pyridine, pyrazine, pyrimidine, pyridazine, furan, pyrrole, imidazole, thiophene, pyrazole, oxazole, isoxazole, thiazole, triazole.

Examples of the polycyclic aromatic ring in Ar which may have a substituent by using an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom as a ring constituting atom include: biphenyl, terphenyl, bipyridine, bithiophene, and bifuran.

Examples of the condensed ring type aromatic ring in Ar which may have a substituent by using an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom as a ring constituting atom include: naphthalene, anthracene, phenanthrene, quinoline, benzofuran, benzimidazole, benzothiophene, indole, indazole, benzoxazole, benzothiazole, benzotriazole.

Ar is preferably a monocyclic aromatic ring which may have a substituent by using an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom as a ring constituting atom, in view of easy availability. The aromatic ring is more preferably a benzene ring, a furan ring, a thiophene ring, a thiazole ring or an oxazole ring in view of the polymer of the present invention exhibiting good optical characteristics, and the aromatic ring is more preferably a benzene ring or a thiophene ring in view of the polymer of the present invention exhibiting good optical characteristics.

Preferable examples of Ar include structures represented by the following chemical formulas (Ar-1) to (Ar-7).

[ Chemical formula 12]

[ In the above chemical formulas (Ar-1) to (Ar-7), X ¹、X²、X³、X⁴、X⁵、X⁶、X⁷ and X ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group, an alkylthio group having 1 to 6 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms.

R ^e represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

* Represents a bonding position to a portion other than Ar in the above chemical formula (1). ]

In the formulae (Ar-1) to (Ar-7), X ¹、X²、X³、X⁴、X⁵、X⁶、X⁷ and X ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group, an alkylthio group having 1 to 6 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms; examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl; examples of the alkoxy group having 1 to 6 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy; examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom, iodine atom; examples of the alkylthio group having 1 to 6 carbon atoms include: methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, hexylthio; examples of the dialkylamino group having 2 to 8 carbon atoms include: dimethylamino, diethylamino, dipropylamino, dibutylamino.

In view of the excellent optical properties of the polymer of the present invention, X ¹、X²、X³、X⁴、X⁵、X⁶、X⁷ and X ⁸ are preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom, and in view of easy introduction, a hydrogen atom, a methyl group, a methoxy group, or a halogen atom is particularly preferred.

In (Ar-1) to (Ar-7), R ^e represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and examples of the alkyl group having 1 to 10 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl.

R ^e is preferably a hydrogen atom, a methyl group or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group, from the viewpoint of excellent optical properties of the polymer of the present invention.

Specific examples of the photoreactive inverse wavelength dispersion unit a represented by the general formula (1) include photoreactive inverse wavelength dispersion units a represented by the following chemical formulas (1-1-1) to (1-7-4).

[ Chemical formula 13]

[ Chemical formula 14]

[ Chemical formula 15]

[ Chemical formula 16]

[ Chemical formula 17]

[ Chemical formula 18]

[ Chemical formula 19]

[ In the formulae (1-1-1) to (1-7-4), L ¹ and L ² may be the same or different and each represents a carbonyl group, an ester bond, an amide bond, an ether bond or a single bond.

* Represents a bonding position to other structures in the main chain polymer. ]

Of these (1-1) to (1-7-4), preferred are (1-1) to (1-2-11), (1-6-1) to (1-6-4), and (1-7-1) to (1-7-4), and particularly preferred are (1-2-1) to (1-2-8), and (1-7-1) to (1-7-3).

Preferably, the polymer of the present invention further has at least one repeating unit selected from the group consisting of the following chemical formulas (2A), (2B), (2C), and (2D).

[ Chemical formula 20]

In the chemical formula (2A), the ring C, the ring D, and the ring E each independently represent a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, a condensed aromatic ring, and an aliphatic hydrocarbon ring, and an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom may have a substituent as a ring constituent atom.

R ⁵ and R ⁶ may be the same or different and each represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, and an optionally substituted aromatic group having 3 to 12 carbon atoms.

N is 0 or 1.

L ³ and L ⁴, which may be the same or different, represent a carbonyl group, an ester bond, an amide bond, an ether bond, or a single bond.

* Represents bonding positions to other structures in the above-described main chain polymer. ]

In the formula (2A), the ring C, the ring D, and the ring E each independently represent a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, a condensed aromatic ring, and an aliphatic hydrocarbon ring, and an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom may have a substituent as a ring constituent atom.

Specific examples of the monocyclic aromatic ring which may have a substituent by using an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom as a ring constituting atom in the ring C include: benzene, pyridine, pyrazine, pyrimidine, pyridazine, furan, pyrrole, imidazole, thiophene, pyrazole, oxazole, isoxazole, thiazole, triazole.

Examples of the polycyclic aromatic ring in which the ring C has a ring-constituting atom which is an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom and may have a substituent include: biphenyl, terphenyl, bipyridine, bithiophene, and bifuran.

Examples of the condensed ring type aromatic ring which may have a substituent with an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom as a ring constituting atom in the ring C include: naphthalene, anthracene, phenanthrene, quinoline, benzofuran, benzimidazole, benzothiophene, indole, indazole, benzoxazole, benzothiazole, benzotriazole.

Specific examples of the aliphatic hydrocarbon ring which may have a substituent(s) and in which an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom is used as a ring constituting atom in the ring C include, for example: cyclopentane, cyclohexane, tricyclo [5.2.1.0 (2, 6) ] decane.

The ring C is preferably a monocyclic aromatic ring having a substituent by using an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom as a ring constituting atom, from the viewpoint of easy availability of a raw material carboxylic acid, and particularly preferably a benzene ring from the viewpoint of easy introduction.

In the formula (2A), the ring D and the ring E each independently represent a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, a condensed aromatic ring, and an aliphatic hydrocarbon ring, and an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom may have a substituent as a ring constituting atom.

The ring D and the ring E may be the same ring as the ring C, but a monocyclic aromatic ring having an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a ring constituent atom is preferable, and a benzene ring is particularly preferable in view of easy introduction.

Examples of the substituent in the monocyclic aromatic ring, polycyclic aromatic ring, condensed aromatic ring and aliphatic hydrocarbon ring include an alkyl group having 1 to 8 carbon atoms, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, and an acyl group having 2 to 4 carbon atoms; examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl; examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom, iodine atom; examples of the alkoxy group having 1 to 4 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy; examples of the acyl group having 2 to 4 carbon atoms include: acetyl, propionyl, and butyryl.

In the formula (2A), R ⁵ and R ⁶ may be the same or different and each represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, and an optionally substituted aromatic group having 3 to 12 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include: among them, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and eicosyl are preferred, and methyl and ethyl are particularly preferred from the viewpoint of easy introduction.

Examples of the cycloalkyl group having 3 to 8 carbon atoms include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl.

Examples of the aromatic group having 3 to 12 carbon atoms include: phenyl, naphthyl, biphenyl, pyridyl.

[ Chemical formula 21]

[ In the above chemical formula (2B), L ⁹ and L ¹⁰ may be the same or different and each represents a carbonyl group, an ester bond, an amide bond, an ether bond or a single bond.

[ Chemical formula 22]

[ In the above chemical formula (2C), X ⁹ represents an alkylene chain having 1 to 10 carbon atoms or a single bond.

X ¹⁰ represents-O-, -N (R ^c) -.

X ¹¹ represents-O-, -N (R ^d) -.

R ^c、R^d may be the same or different and represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

L ¹¹ and L ¹², which may be the same or different, represent a carbonyl group, an ester bond, an amide bond, an ether bond, or a single bond.

[ Chemical formula 23]

In the chemical formula (2D), the ring G represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, a condensed ring aromatic ring, a spiro ring, and an aliphatic hydrocarbon ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is used as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, the condensed ring aromatic ring, the spiro ring, and the aliphatic hydrocarbon ring may have a substituent.

L ¹³ and L ¹⁴ may be the same or different and each represents a single bond or an alkylene chain having 1 to 6 carbon atoms.

L ¹⁵ and L ¹⁶, which may be the same or different, represent a carbonyl group, an ester bond, an amide bond, an ether bond, or a single bond.

In the formula (2D), the ring G independently represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, a condensed ring aromatic ring, a spiro ring, and an aliphatic hydrocarbon ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is used as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, the condensed ring aromatic ring, the spiro ring, and the aliphatic hydrocarbon ring may have a substituent.

Specific examples of the monocyclic aromatic ring in which the ring G has a ring-constituting atom which is an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom and which may have a substituent include: benzene, pyridine, pyrazine, pyrimidine, pyridazine, furan, pyrrole, imidazole, thiophene, pyrazole, oxazole, isoxazole, thiazole, triazole.

Examples of the polycyclic aromatic ring in ring G which may have a substituent with an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom as a ring constituting atom include: biphenyl, terphenyl, bipyridine, bithiophene, and bifuran.

Examples of the condensed ring aromatic ring in which the ring G has a ring-constituting atom which is an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom and which may have a substituent include: naphthalene, anthracene, phenanthrene, quinoline, benzofuran, benzimidazole, benzothiophene, indole, indazole, benzoxazole, benzothiazole, benzotriazole.

Examples of the spiro ring in the ring G which may have a substituent with an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom as a ring constituting atom include structures represented by the following chemical formula (sp 1-1).

[ Chemical formula 24]

Examples of the aliphatic hydrocarbon ring which may have a substituent(s) in ring G using an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom as a ring constituting atom include: cyclopropane, cyclopentane, cyclohexane, tricyclo [5.2.1.0 (2, 6) ] decane.

The ring G is preferably a monocyclic aromatic ring or an aliphatic hydrocarbon ring having an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom as a ring constituting atom, and particularly preferably a benzene ring, cyclohexane or tricyclo [5.2.1.0 (2, 6) ] decane, from the viewpoint of good optical properties.

As a preferred example of the repeating unit represented by the general formula (2A), a repeating unit represented by the following chemical formula (2' A) can be given.

[ Chemical formula 25]

In formula (2' A), the rings C, R ⁵、R⁶、L³、L⁴ and n have the same meanings as those of the rings C, R ⁵、R⁶、L³、L⁴ and n in formula (2A), respectively.

Specific examples of the repeating unit represented by the general formula (2A) include structures represented by the following chemical formulas (2A-1-1) to (2A-2-20).

[ Chemical formula 26]

[ Chemical formula 27]

[ Chemical formula 28]

[ Chemical formula 29]

[ Chemical formula 30]

[ Chemical formula 31]

[ In the formulae (2A-1-1) to (2A-2-20), L ³、L⁴ may be the same or different and represents a carbonyl group, an ester bond, an amide bond, an ether bond or a single bond. ]

Among these (2A-1-1) to (2A-2-20), from the viewpoint of easiness of synthesis of monomers as a raw material of the polymer of the present invention, (2A-1-1) to (2A-1-10), (2A-1-36) to (2A-1-40), (2A-1-51) to (2A-1-55), (2A-1-91) to (2A-1-105) and (2A-2-1) to (2A-2-4) are preferable, and from the viewpoint of excellent optical characteristics of the polymer of the present invention, (2A-1-1) to (2A-1-10), (2A-1-36) to (2A-1-40), (2A-1-91) to (2A-1-105) and (2A-1-51) to (2A-1-55) and (2A-1-104) are particularly preferable.

Specific examples of the repeating unit represented by the general formula (2B) include structures represented by the following chemical formulas (2B-1) to (2B-3).

[ Chemical formula 32]

Among these (2B-1) to (2B-3), from the viewpoint of excellent optical properties of the polymer of the present invention, (2B-1) is preferable.

Specific examples of the repeating unit represented by the general formula (2C) include structures represented by the following chemical formulas (2C-1-1) to (2C-2-23).

[ Chemical formula 33]

[ Chemical formula 34]

[ Chemical formula 35]

Among these (2C-1-1) to (2C-2-23), from the viewpoint of excellent optical properties of the polymer of the present invention, (2C-1-1) to (2C-1-8), (2C-2-2) to (2C-2-6), and (2C-2-13) to (2C-2-19) are preferable.

Specific examples of the repeating unit represented by the general formula (2D) include structures represented by the following chemical formulas (2D-1-1) to (2D-14-1).

[ Chemical formula 36]

[ Chemical formula 37]

[ Chemical formula 38]

[ Chemical formula 39]

[ Chemical formula 40]

Among these (2D-1-1) to (2D-14-1), from the viewpoint of excellent optical properties of the polymer of the present invention, (2D-1-1), (2D-2-1), (2D-3-1), (2D-7-3), (2D-7-4), (2D-7-6), (2D-8-1) to (2D-13-1) and (2D-14-1) are preferable.

Further, for the purpose of adjusting the physical properties of expression, the polymer of the present invention preferably contains at least one of the repeating units represented by the following chemical formulas (5-1) to (5-13).

[ Chemical formula 41]

[ In the formulae (5-1) to (5-13), L ⁵ and L ⁶ may be the same or different and each represents a carbonyl group, an ester bond, an amide bond, an ether bond or a single bond.

N represents an integer of 4 to 500.

The polymer of the present invention may have a structure represented by the following chemical formulas (6-1) to (6-12) for the purpose of adjusting the physical properties of expression.

[ Chemical formula 42]

[ In the formulae (6-1) to (6-12), L ⁷、L⁸ may be the same or different and represents a carbonyl group, an ester bond, an amide bond, an ether bond or a single bond.

Specific examples of the polymer of the present invention include structures represented by the following chemical formulas (P1-1-1-1) to (P7-12-1).

[ Chemical formula 43]

[ Chemical formula 44]

[ Chemical formula 45]

[ Chemical formula 46]

[ Chemical formula 47]

[ Chemical formula 48]

[ Chemical formula 49]

[ Chemical formula 50]

[ Chemical formula 51]

[ Chemical formula 52]

[ Chemical formula 53]

[ Chemical formula 54]

[ Chemical formula 55]

[ Chemical formula 56]

[ Chemical formula 57]

[ Chemical formula 58]

[ Chemical formula 59]

[ Chemical formula 60]

[ Chemical formula 61]

[ Chemical formula 62]

[ Chemical formula 63]

Among these (P1-1-1-1) to (P7-12-1), from the viewpoint of good optical properties of the polymer of the present invention, (P1-2-1-1) to (P1-2-5-1-4), (P2-2-1) to (P2-2-3), (P3-2-1) to (P3-2-2), (P4-1-1) to (P4-2-9), and (P5-1) to (P5-1-19) are preferable.

In the polymer of the present invention, the content of the photoreactive inverse wavelength dispersion unit a in the polymer is 1mol% to 50mol%, preferably 5mol% to 45mol%, and more preferably 20mol% to 45mol%.

In the polymer of the present invention, when the repeating units represented by (2A), (2B), (2C) and (2D) are contained, the content of the repeating units represented by (2A), (2B), (2C) and (2D) in the polymer is 1mol% to 99mol%, preferably 10mol% to 70mol%, more preferably 15mol% to 60mol%.

The weight average molecular weight of the polymer of the present invention is preferably 1,000 to 100,000, particularly preferably 1,100 to 50,000.

In the polymer of the present invention, it is preferable that at least one of the terminals is a monocarboxylic acid ester, in view of shifting the absorption band to a short wavelength and providing a film having a low Yellowness Index (YI) when the film is formed.

The monocarboxylic acid ester may have a structure represented by the following chemical formula (2').

[ Chemical formula 64]

In the chemical formula (2'), R ¹⁰ represents a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms which may be substituted, a cycloalkyl group having 3 to 8 carbon atoms which may be substituted, and an aromatic group having 3 to 12 carbon atoms which may be substituted.

* Represents bonding positions to other structures in the main chain polymer. ]

In the formula (2'), examples of the alkyl group having 1 to 20 carbon atoms in R ¹⁰ include: among them, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and eicosyl are preferred, and methyl and ethyl are particularly preferred from the viewpoint of easy introduction.

Examples of monocarboxylic acid esters include: the structures shown in the following chemical formulas (2 '-1) to (2' -37).

[ Chemical formula 65]

And [ (x) represents a bonding position with other structures in the above-mentioned main chain type polymer. ]

Among these (2 '-1) to (2' -37), from the viewpoint of easy introduction, (2 '-1) to (2' -13) and (2 '-20) to (2' -37) are preferable, and (2 '-1) to (2' -6) and (2 '-13) and (2' -20) to (2 '-23) and (2' -29) and (2 '-31) to (2' -36) are particularly preferable.

Specific examples of the polymer of the present invention having at least one terminal of the polymer is a monocarboxylic acid ester include structures represented by the following chemical formulas (PA 1-1-1-1) to (PA 7-12-1).

[ Chemical formula 66]

[ Chemical formula 67]

[ Chemical formula 68]

[ Chemical formula 69]

[ Chemical formula 70]

[ Chemical formula 71]

[ Chemical formula 72]

[ Chemical formula 73]

[ Chemical formula 74]

[ Chemical formula 75]

[ Chemical formula 76]

[ Chemical formula 77]

[ Chemical formula 78]

[ Chemical formula 79]

[ Chemical formula 80]

[ Chemical formula 81]

[ Chemical formula 82]

[ Chemical formula 83]

[ Chemical formula 84]

[ Chemical formula 85]

[ Chemical formula 86]

[ Chemical formula 87]

[ Chemical formula 88]

[ Chemical formula 89]

(In the above-mentioned chemical formulas (PA 1-1-1-1) to (PA 7-12-1), R ¹⁰ has the same meaning as R ¹⁰ in the above-mentioned chemical formula (2')

Among these formulae (PA 1-1-1-1-1) to (PA 7-12-1), the formulae are preferable in view of good optical characteristics (PA1-2-1-1-1)～(PA1-2-5-1-4)、(PA2-2-1)～(PA2-2-3)、(PA3-2-1)～(PA3-2-2)、(PA4-1-1)～(PA5-1-19)、(PA7-1-1)～(PA7-12-1).

The method for producing a polymer of the present invention can be produced by polymerizing a raw material composition containing a dihydroxy compound represented by the following chemical formula (1'), and in particular, it is preferable to polymerize a raw material composition containing one or more selected from the group consisting of dicarboxylic acid dichlorides and dicarboxylic acids. The method of producing the polymer of the present invention is also included in one embodiment of the present invention.

[ Chemical formula 90]

[ Chemical formula 91]

In the formula (1'), R ⁰、R¹、R²、R³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a group represented by the formula (Z1); examples of the halogen atom include: chlorine atom, bromine atom, iodine atom, fluorine atom; examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl.

In the formula (Z1), rz ³ and Rz ⁴ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms; examples of the halogen atom include: chlorine atom, bromine atom, iodine atom, fluorine atom; examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl.

As Arz, a monocyclic aromatic ring which may have a substituent by using an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a ring constituting atom, for example, may be mentioned: benzene, pyridine, pyrazine, pyrimidine, pyridazine, furan, pyrrole, imidazole, thiophene, pyrazole, oxazole, isoxazole, thiazole, triazole.

R ⁰、R¹、R²、R³ and R ⁴ are preferably a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, or a group represented by the following chemical formulas (Z1-1) to (Z1-4) in view of their excellent optical properties after the introduction of the polymer of the present invention, and particularly preferably a hydrogen atom, methyl group or ethyl group in view of their ease of introduction.

[ Chemical formula 92]

In the chemical formula (1'), ar is the same as in the chemical formula (1), and preferable examples thereof include structures represented by the following chemical formulas (Ar-1) to (Ar-7).

[ Chemical formula 93]

R ^e represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

In (Ar-1) to (Ar-7), X ¹、X²、X³、X⁴、X⁵、X⁶、X⁷ and X ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group, an alkylthio group having 1 to 6 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms; examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl; examples of the alkoxy group having 1 to 6 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy; examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom, iodine atom; examples of the alkylthio group having 1 to 6 carbon atoms include: methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, hexylthio; examples of the dialkylamino group having 2 to 8 carbon atoms include: dimethylamino, diethylamino, dipropylamino, dibutylamino.

In view of excellent optical properties after the introduction of the polymer of the present invention, X ¹、X²、X³、X⁴、X⁵、X⁶、X⁷ and X ⁸ are preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom, and in view of easy introduction, a hydrogen atom, a methyl group, a methoxy group, or a halogen atom is particularly preferred.

The dihydroxy compound represented by the above chemical formula (1 ') is preferably a dihydroxy compound represented by the following chemical formulas (1 ' -1-1) to (1 ' -7-4).

[ Chemical formula 94]

[ Chemical formula 95]

[ Chemical formula 96]

[ Chemical formula 97]

[ Chemical formula 98]

[ Chemical formula 99]

[ Chemical formula 100]

Of these (1 ' -1-1) to (1 ' -7-4), preferred are (1 ' -2-1) to (1 ' -2-11), (1 ' -6-1) to (1 ' -6-4) and (1 ' -7-1) to (1 ' -7-4), and particularly preferred are (1 ' -2-1) to (1 ' -2-6) and (1 ' -2-1) to (1 ' -2-11) and (1 ' -6-2) to (1 ' -6-3) and (1 ' -7-2).

Examples of the dicarboxylic acid include: aliphatic polycarboxylic acids (specifically, saturated polycarboxylic acids having 2 to 20 carbon atoms such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and sebacic acid, unsaturated polycarboxylic acids such as maleic acid, fumaric acid, and itaconic acid), alicyclic polycarboxylic acids (cyclobutanedicarboxylic acid, trans-1, 4-cyclohexanedicarboxylic acid, and cis-1, 4-cyclohexanedicarboxylic acid), and aromatic polycarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, 4 '-biphthalic acid, 4' -oxybis (benzoic acid), and 2, 5-furandicarboxylic acid).

Examples of dicarboxylic acid dichlorides include: unsaturated polycarboxylic acid dichlorides having 2 to 20 carbon atoms such as oxalic acid dichlorides, malonic acid dichlorides, succinic acid dichlorides, glutaric acid dichlorides, adipic acid dichlorides, sebacic acid dichlorides, saturated polycarboxylic acid dichlorides such as fumaric acid dichlorides and itaconic acid dichlorides, and aromatic polycarboxylic acid dichlorides such as cyclobutane dicarboxylic acid dichlorides, cyclopentane dicarboxylic acid dichlorides, trans-1, 4-cyclohexane dicarboxylic acid dichlorides, cis-1, 4-cyclohexane dicarboxylic acid dichlorides, terephthalic acid dichlorides, isophthalic acid dichlorides, phthalic acid dichlorides, 4 '-biphenyl dicarboxylic acid dichlorides, 4' -oxybis (benzoic acid dichlorides), 2, 5-furan dicarboxylic acid dichlorides.

In the method for producing a polymer of the present invention, it is preferable to polymerize a compound represented by the following chemical formulas (2 "a), (2"B), (2"C) and (2"D) by further containing the compound in the raw material composition.

[ Chemical formula 101]

[ In the above chemical formula (2 "A"), the ring C, the ring D and the ring E each independently represent a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, a condensed ring aromatic ring and an aliphatic hydrocarbon ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom is used as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, the condensed ring aromatic ring and the aliphatic hydrocarbon ring may have a substituent.

Qn ¹、Qn², which may be the same or different, represents hydroxy, amino, carboxy or-C (=o) Cl.

N is 0 or 1.]

In the formula (2 "a), the ring C, the ring D, and the ring E each independently represent a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, a condensed aromatic ring, and an aliphatic hydrocarbon ring, and an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom may have a substituent as a ring constituting atom.

Examples of the monocyclic aromatic ring which may have a substituent(s) by using an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a ring constituting atom in the specific ring C include: benzene, pyridine, pyrazine, pyrimidine, pyridazine, furan, pyrrole, imidazole, thiophene, pyrazole, oxazole, isoxazole, thiazole, triazole.

The ring C is preferably a monocyclic aromatic ring having a ring member atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, from the viewpoint of easy availability, and particularly preferably a benzene ring from the viewpoint of easy introduction.

In the formula (2 "a), the ring D and the ring E each independently represent a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, a condensed ring aromatic ring, and an aliphatic hydrocarbon ring, and an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is used as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, the condensed ring aromatic ring, and the aliphatic carbonized water may have a substituent.

The rings D and E are preferably each independently the same ring as the ring C, from the viewpoint of easy introduction, and are preferably monocyclic aromatic rings having an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a ring constituting atom, and from the viewpoint of easy introduction, benzene rings are particularly preferred.

Examples of the substituent in the monocyclic aromatic ring, polycyclic aromatic ring, condensed aromatic ring, and aliphatic hydrocarbon ring include: alkyl group having 1 to 8 carbon atoms, halogen atom, alkoxy group having 1 to 4 carbon atoms, and acyl group having 2 to 4 carbon atoms; examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl; examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom, iodine atom; examples of the alkoxy group having 1 to 4 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy; examples of the acyl group having 2 to 4 carbon atoms include: acetyl, propionyl, and butyryl.

In the formula (2 "A), R ⁵ and R ⁶ may be the same or different and each represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, and an optionally substituted aromatic group having 3 to 12 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include: among them, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and eicosyl are preferred from the viewpoint of excellent optical properties after the polymer of the present invention is introduced, and methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl are particularly preferred from the viewpoint of easy introduction.

In the formula (2 "a), qn ¹ and Qn ² may be the same or different and represent a hydroxyl group, an amino group, a carboxyl group or-C (=o) Cl.

[ Chemical formula 102]

[ In the above chemical formula (2"B), qn ³ and Qn ⁴ may be the same or different and represent a hydroxyl group, an amino group, a carboxyl group or-C (=O) Cl. ]

[ Chemical formula 103]

[ In the above chemical formula (2"C), X ⁹ represents an alkylene chain having 1 to 10 carbon atoms or a single bond.

X ¹⁰ represents-O-or-N (R ^c) -.

X ¹¹ represents-O-or-N (R ^d) -.

R ^c and R ^d may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

Qn ⁵ and Qn ⁶ may be the same or different and represent a hydroxyl group, an amino group, a carboxyl group or-C (=o) Cl. ]

[ Chemical formula 104]

[ In the above chemical formula (2"D), the ring G represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, a condensed ring aromatic ring, a spiro ring and an aliphatic hydrocarbon ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom is used as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, the condensed ring aromatic ring, the spiro ring and the aliphatic hydrocarbon ring may have a substituent.

Qn ⁷ and Qn ⁸ may be the same or different and represent a hydroxyl group, an amino group, a carboxyl group or-C (=o) Cl. ]

In the formula (2"D), the ring G independently represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, a condensed ring aromatic ring, a spiro ring and an aliphatic hydrocarbon ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom is used as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, the condensed ring aromatic ring, the spiro ring and the aliphatic hydrocarbon ring may have a substituent.

[ Chemical formula 105]

Examples of the aliphatic hydrocarbon ring which may have a substituent(s) in ring G using an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom as a ring constituting atom include: cyclopentane, cyclohexane, tricyclo [5.2.1.0 (2, 6) ] decane.

The ring G is preferably a monocyclic aromatic ring or an aliphatic hydrocarbon ring in which an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is used as a ring constituting atom, and benzene, cyclohexane, and tricyclo [5.2.1.0 (2, 6) ] decane are particularly preferred from the viewpoint of good optical properties of the polymer.

Specific examples of the compound represented by the formula (2 "A) include structures represented by the following chemical formulas (2" A-1-1) to (2 "A-2-20).

[ Chemical formula 106]

[ Chemical formula 107]

[ Chemical formula 108]

[ Chemical formula 109]

[ Chemical formula 110]

[ Chemical formula 111]

[ In the formulae (2 "A-1-1) to (2" A-2-20), qn ¹、Qn² may be the same or different and represents a hydroxyl group, an amino group, a carboxyl group or-C (=O) Cl. ]

Among these (2 "A-1-1) to (2" A-2-20), from the viewpoint of easy synthesis of the polymer of the present invention, (2 "A-1-1) to (2" A-1-10), (2 "A-1-36) to (2" A-1-40), (2 "A-1-51) to (2" A-1-55), (2 "A-2-1) to (2" A-2-4) are preferred, and from the viewpoint of excellent optical properties of the polymer of the present invention, (2 "A-1-1) to (2" A-1-10), (2 "A-1-36) to (2" A-1-40) and (2 "A-1-51) to (2" A-1-55) are particularly preferred.

Specific examples of the compound represented by the formula (2"B) include structures represented by the following chemical formulas (2"B-1) to (2"B-2).

[ Chemical formula 112]

Of these (2"B-1) to (2"B-2), (2"B-1) is preferable in view of excellent optical properties of the polymer of the present invention.

Specific examples of the compound represented by the formula (2"C) include structures represented by the following chemical formulas (2"C-1-1) to (2"C-2-23).

[ Chemical formula 113]

[ Chemical formula 114]

[ Chemical formula 115]

Of these (2"C-1-1) to (2"C-2-23), from the viewpoint of excellent optical properties of the polymer of the present invention, (2"C-1-4) to (2"C-1-8) and (2"C-2-1) to (2"C-2-23) are preferable.

Specific examples of the compound represented by the formula (2"D) include structures represented by the following chemical formulas (2"D-1-1) to (2"D-14-1).

[ Chemical formula 116]

[ Chemistry 117]

[ Chemical formula 118]

[ Chemical formula 119]

Of these (2"D-1-1) to (2"D-14-1), the polymer of the present invention is preferable in view of excellent optical properties (2"D-1-1)、(2"D-2-1)、(2"D-3-1)、(2"D-3-1)(2"D-4-3)、(2"D-7-3)、(2"D-7-4)、(2"D-7-4)～(2"D-13-1)、(2"D-14-1).

The method for producing a polymer of the present invention may use a polyhydric hydroxyl compound as a raw material for the purpose of adjusting the physical properties of the polymer produced.

Examples of the polyhydric hydroxyl compound include: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 2-butanediol, 2, 3-butanediol, 2, 4-dimethyl-2, 4-pentanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-heptanediol, cyclopentanediol, cyclohexanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-dodecanediol, hydroquinone, tetramethylhydroquinone, 4,4' -dihydroxybiphenyl, vanillyl alcohol, furandimethanol, 2-bis (4-hydroxyphenyl) propane, 4' - (1, 3-dimethylbutylidene) diphenol, 6' -dihydroxy-4, 4',7,7' -hexamethyl-2, 2' -spirochroman (spirobicromane), tricyclodecanedimethanol, 2' -dihydroxydiphenyl ether, 4' -methylenebis (2, 6-dimethylphenol), 3', 5' -tetramethylbiphenyl-4, 4' -diol, 1-bis (4-hydroxyphenyl) cyclohexane, 2-butene-1, 4-diol, 2, 2-diisobutyl-1, 3-propanediol, bis [4- (2-hydroxyethoxy) phenyl ] sulfone, 2, 4-tetramethyl-1, 3-cyclobutanediol, 1, 4-bis (3-hydroxyphenoxy) benzene, 4 '-cyclohexanol, bis (4-hydroxy-3-methylphenyl) sulfide, 2-diisoamyl-1, 3-propanediol 4,4' -dihydroxydiphenylmethane, dihydroxynaphthalene, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, 1, 4-benzenedimethanol, 3, 9-bis (1, 1-dimethyl-2-hydroxyethyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane, 4,4' -biphenyldimethanol, 1, 3-bis (hexafluoro-alpha-hydroxyisopropyl) benzene, 3, 6-dihydroxybenzonorbornane, 2-benzyloxy-1, 3-propanediol, 4' -dihydroxybenzophenone, 4' -dihydroxydiphenyl ether, 9-bis (4-hydroxyphenyl) fluorene, 1, 8-bis (hydroxymethyl) anthracene, 1, 4-bis [2- (4-hydroxyphenyl) -2-propyl ] benzene, alpha, alpha ' -bis (4-hydroxy-3, 5-dimethylphenyl) -1, 4-diisopropylbenzene, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2' -methylenebis (4-methylphenol), 1, 3-bis (4-hydroxyphenoxy) benzene, 2-bis (4-hydroxyphenyl) butane, 1-bis (4-hydroxy-3-methylphenyl) cyclohexane 2, 2-bis (4-hydroxy-3-methylphenyl) propane, 2' -dihydroxybenzophenone, 2' -bis (hydroxymethyl) diphenyl ether, 7' -dihydroxy-4, 4',4' -tetramethyl-2, 2' -spirochroman, 1, 4-bis (hydroxymethyl) -2,3,5, 6-tetramethylbenzene, 4' -ethylenebisphenol, cyclohexanedimethanol, polyethylene glycol, 1, 3-adamantanediol, 1-hydroxy-3- (hydroxymethyl) adamantane, Examples of the other polyhydric hydroxyl compounds include 2, 7-dihydroxy-9H-fluoren-9-one, a hydroxyl compound having a valence of 2 of polyethylene glycol having various molecular weights, glycerin, trimethylolpropane, triethanolamine, 2,3, 4' -tetrahydroxybenzophenone, 1,2, 3-butanetriol, a hydroxyl compound having a valence of 3 of 2, 6-bis (hydroxymethyl) -4-methylphenol, and a hydroxyl compound having a valence of 4 of pentaerythritol.

The polymerization method is not particularly limited, and examples thereof include a polymerization method known in the art, for example, an interfacial polymerization method.

As the interfacial polymerization method, for example, a method of performing interfacial polymerization in a two-layer system of an aqueous-organic solvent can be cited.

In the case of interfacial polymerization in a two-layer system of an aqueous-organic solvent, a phase transfer catalyst and a base are preferably used for the purpose of promoting the reaction.

Examples of the phase transfer catalyst include: benzyl triethyl ammonium chloride, benzyl triethyl ammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrapentyl ammonium chloride, tetrapentyl ammonium bromide, tetraheptyl ammonium chloride, tetraheptyl ammonium bromide, dimethyl dipalmityl ammonium chloride, and dimethyl dipalmityl ammonium bromide; phosphonium salts of tetraethylphosphonium chloride, tetraethylphosphonium bromide, tributylhexyl phosphonium chloride, tributylhexyl phosphonium bromide, tetra-n-octyl phosphonium chloride, tetra-n-octyl phosphonium bromide, tributyl-n-octyl phosphonium chloride, tributyl-n-octyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium bromide, tetraphenyl phosphonium chloride.

As the base, there can be exemplified: alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrides such as sodium hydride; alkali metal alkoxides such as sodium methoxide and sodium ethoxide, and tetrabutylammonium hydroxide.

The reaction temperature of the interfacial polymerization is preferably from-30℃to 50℃and particularly preferably from 0℃to 40℃and the reaction time is preferably from 30 minutes to 24 hours.

The organic solvent used in the interfacial polymerization may be any organic solvent that is harmless to the reaction, and examples thereof include: ether solvents such as dioxane, tetrahydrofuran (hereinafter abbreviated as THF), diethyl ether, diisopropyl ether, cyclopentyl methyl ether, and dimethoxyethane; aromatic solvents such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and pyridine; halogen solvents such as methylene chloride, chloroform, and carbon tetrachloride; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone. These solvents may be used singly or in any ratio by mixing two or more kinds.

The solution polymerization method may be a method using a condensing agent in an organic solvent.

As the organic solvent used in the solution polymerization method, any organic solvent that is harmless to the reaction may be used, and examples thereof include: ether solvents such as dioxane, THF, diethyl ether, diisopropyl ether, cyclopentyl methyl ether, and dimethoxyethane; aromatic solvents such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and pyridine; halogen solvents such as methylene chloride, chloroform, and carbon tetrachloride; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide and NMP; ester solvents such as ethyl acetate and butyl acetate. These solvents may be used singly or in any ratio by mixing two or more kinds.

Examples of the condensing agent used in the solution polymerization method include: 1- [3- (dimethylamino) propyl ] -3-ethylcarbodiimide, 1- [3- (dimethylamino) propyl ] -3-ethylcarbodiimide hydrochloride, N ' -diisopropylcarbodiimide, N ' -dicyclohexylcarbodiimide, bis (2, 6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide-p-toluenesulfonate, N ' -di-tert-butylcarbodiimide, 1- [3- (dimethylamino) propyl ] -3-ethylcarbodiimide methyliodide, of which 1- [3- (dimethylamino) propyl ] -3-ethylcarbodiimide, 1- [3- (dimethylamino) propyl ] -3-ethylcarbodiimide hydrochloride, N ' -diisopropylcarbodiimide, N ' -dicyclohexylcarbodiimide are preferred. Two or more of these ester bond-forming condensing agents may be used.

The reaction temperature in the solution polymerization method is preferably from-30℃to 90℃and particularly preferably from 0℃to 60℃and the reaction time is preferably from 30 minutes to 24 hours.

In the solution polymerization method, it is preferable to add a base for the purpose of facilitating the reaction.

Examples of the base to be used include: organic bases, inorganic bases, organometallic compounds, metal alkoxides, metal amides.

As the organic base, there may be mentioned: triethylamine, tributylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, piperidine, piperazine, pyrrolidine, morpholine, N-methylmorpholine, imidazole, N-methylimidazole.

Examples of the inorganic base include: lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydride, and potassium hydride.

Examples of the organometallic compound include: n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium.

Examples of the metal alkoxide include: sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide.

As the metal amide, there may be mentioned: lithium amide, sodium amide, lithium diisopropylamide, lithium hexamethyldisilazane, sodium hexamethyldisilazane, potassium hexamethyldisilazane.

Among these bases, organic bases are preferable from the viewpoint of satisfactory reaction and low cost, and triethylamine, tributylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, piperidine, piperazine, and pyrrolidine are more preferable.

The amount of the base used is not particularly limited, and the amount of the solvent may be used.

For the base, a liquid, granular or powdery solid may be used as it is, depending on the properties thereof. In addition, a solution of these bases may be used, and the concentration thereof is not particularly limited.

Another embodiment of the present invention relates to a dihydroxy compound represented by formula (1') below (hereinafter, sometimes referred to as a dihydroxy compound of the present invention). The dihydroxy compound of the present invention serves as a starting material for the polymer of the present invention.

[ Chemical formula 120]

[ Chemical formula 121]

[ In the formula (Z1), rz ³ and Rz ⁴ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms.

As Arz, a monocyclic aromatic ring which may have a substituent by using an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a ring constituting atom is preferable from the viewpoint of easy availability. The aromatic ring is more preferably a benzene ring, a furan ring, a thiophene ring, a thiazole ring or an oxazole ring in view of the polymer of the present invention exhibiting good optical characteristics, and the benzene ring or the thiophene ring is more preferably in view of the polymer of the present invention exhibiting good optical characteristics.

[ Chemical formula 122]

In the formula (1'), ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is used as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, and the condensed ring aromatic ring may have a substituent.

In view of easy availability, ar is preferably a monocyclic aromatic ring which may have a substituent by using an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a ring constituting atom. The aromatic ring is more preferably a benzene ring, a furan ring, a thiophene ring, a thiazole ring or an oxazole ring in view of the polymer of the present invention exhibiting good optical characteristics, and the benzene ring or the thiophene ring is more preferably in view of the polymer of the present invention exhibiting good optical characteristics.

[ Chemical formula 123]

R ^e represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

* Represents a bonding position to a portion other than Ar in the above chemical formula (1'). ]

Each of X ¹、X²、X³、X⁴、X⁵、X⁶、X⁷ and X ⁸ is independently preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom, and particularly preferably a hydrogen atom, a methyl group, a methoxy group, or a halogen atom.

Preferable examples of the dihydroxy compound of the present invention include dihydroxy compounds represented by the following chemical formulas (1' -2).

[ Chemical formula 124]

[ In the above chemical formula (1' -2), R ⁰、R¹、R²、R³、R⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

X ⁶、X⁷ and X ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group, an alkylthio group having 1 to 6 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms. ]

In the formula (1' -2), R ⁰、R¹、R²、R³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl.

R ⁰、R¹、R²、R³ and R ⁴ are preferably a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group or tert-butyl group, from the viewpoint of easy introduction, and particularly preferably a hydrogen atom, methyl group or ethyl group, from the viewpoint of easy introduction.

In the formula (1' -2), X ⁶、X⁷ and X ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group, an alkylthio group having 1 to 6 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms; examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl; examples of the alkoxy group having 1 to 6 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy; examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom, iodine atom; examples of the alkylthio group having 1 to 6 carbon atoms include: methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, hexylthio; examples of the dialkylamino group having 2 to 8 carbon atoms include: dimethylamino, diethylamino, dipropylamino, dibutylamino.

The dihydroxy compound of the present invention is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom, and particularly preferably a hydrogen atom, a methyl group, a methoxy group, a chlorine atom, a bromine atom, or a fluorine atom, because of its excellent optical properties after being introduced into the polymer of the present invention, and because of its ease of introduction, X ⁶、X⁷ and X ⁸ are preferred.

More preferable examples of the dihydroxy compound represented by general formula (1 ') include dihydroxy compounds represented by the following chemical formulas (1 ' -2-1) to (1 ' -7-4).

[ Chemical formula 125]

[ Chemical formula 126]

[ Chemical formula 127]

[ Chemical formula 128]

[ Chemical formula 129]

[ Chemistry 130]

Of these (1 ' -2-1) to (1 ' -7-4), preferred are (1 ' -2-2) to (1 ' -2-11), (1 ' -6-1) to (1 ' -6-4) and (1 ' -7-1) to (1 ' -7-4), and particularly preferred are (1 ' -2-1) to (1 ' -2-6) and (1 ' -2-1) to (1 ' -2-11) and (1 ' -6-2) to (1 ' -6-3) and (1 ' -7-1).

The method for producing a dihydroxy compound represented by formula (1 ') of the present invention is a method in which a dihydroxy compound represented by formula (3) below is reacted with a ketone represented by formula (4') below.

[ Chemical formula 131]

In the chemical formula (3), R ⁰、R¹ and R ⁷ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms.

R ^2f represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a formyl group.

In the above chemical formula (4'), ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring type aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is used as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, and the condensed ring type aromatic ring may have a substituent. R ⁸ represents an alkyl group having 1 to 8 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms.

In the above chemical formula (1'), ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is used as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, and the condensed ring aromatic ring may have a substituent. R ⁰、R¹、R²、R³、R⁴ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a group represented by the following chemical formula (Z1).

[ Chemical formula 132]

[ In the above formula (Z1), rz ³ and Rz ⁴ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms.

In the formula (3), R ⁰、R¹、R⁷ independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl.

R ^2f represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a formyl group, and examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl.

R ⁰、R¹、R^2f、R⁷ is preferably a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group or tert-butyl group, from the viewpoint of excellent optical properties after the introduction of the dihydroxy compound of the present invention into the polymer of the present invention, and particularly preferably a hydrogen atom, methyl group or ethyl group, from the viewpoint of easy introduction.

Specific examples of the dihydroxy compound represented by formula (3) include structures represented by the following chemical formulas (3-1) to (3-11).

[ Chemical formula 133]

[ Chemical formula 134]

Of these (3-1) to (3-11), preferred are (3-1) to (3-4) and (3-10) to (3-11), and particularly preferred are (3-1) and (3-3) and (3-10) to (3-11).

The dihydroxy compound represented by formula (3) can be easily produced by a known method or a method described in the literature. In addition, commercially available products may be used.

In the formula (4'), R ⁸ represents an alkyl group having 1 to 8 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms, and examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl; examples of the haloalkyl group having 1 to 6 carbon atoms include: chloromethyl, 2-trifluoroethyl, and the like.

R ⁸ is preferably methyl, ethyl, propyl or butyl in view of excellent optical properties after the introduction of the dihydroxy compound of the present invention into the polymer of the present invention, and is particularly preferably methyl or ethyl in view of easy introduction.

In the formula (4'), ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is used as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, and the condensed ring aromatic ring may have a substituent.

Examples of the acyl group having 2 to 4 carbon atoms include: acetyl, propionyl, and butyryl.

Ar is preferably a monocyclic aromatic ring having a ring-constituting atom which is an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, and an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, which may have a substituent, as a ring-constituting atom, from the viewpoint of easy availability, and particularly preferably a benzene ring, a furan ring, a thiophene ring, a thiazole ring or an oxazole ring, from the viewpoint of excellent optical properties after the dihydroxy compound of the present invention is introduced into the polymer of the present invention, and further preferably a benzene ring or a thiophene ring.

[ Chemical formula 135]

R ^e represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

In the formulae (Ar-1) to (Ar-7), X ¹、X²、X³、X⁴、X⁵、X⁶、X⁷ and X ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group, an alkylthio group having 1 to 6 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms, and examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl; examples of the alkoxy group having 1 to 6 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy; examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom, iodine atom; examples of the alkylthio group having 1 to 6 carbon atoms include: methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, hexylthio; examples of the dialkylamino group having 2 to 8 carbon atoms include: dimethylamino, diethylamino, dipropylamino, dibutylamino.

In view of the excellent optical properties of the dihydroxy compounds of the present invention after being introduced into the polymers of the present invention, X ¹、X²、X³、X⁴、X⁵、X⁶、X⁷ and X ⁸ are preferably hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, or halogen atoms, and in view of easy introduction, hydrogen atoms, methyl groups, methoxy groups, or halogen atoms are particularly preferred.

Among the ketones represented by the formula (4'), the ketones represented by the following formula (4) are preferable.

[ Chemical formula 136]

[ In the above chemical formula (4), R ⁸ represents an alkyl group having 1 to 8 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms.

In the formula (4), R ⁸ represents an alkyl group having 1 to 8 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms, and examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl; examples of the haloalkyl group having 1 to 6 carbon atoms include: chloromethyl, 2-trifluoroethyl, and the like.

In the formula (4), X ⁶、X⁷ and X ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group, an alkylthio group having 1 to 6 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms; examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl; examples of the alkoxy group having 1 to 6 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy; examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom, iodine atom; examples of the alkylthio group having 1 to 6 carbon atoms include: methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, hexylthio; examples of the dialkylamino group having 2 to 8 carbon atoms include: dimethylamino, diethylamino, dipropylamino, dibutylamino.

In view of the excellent optical properties of the dihydroxy compound of the present invention after being introduced into the polymer of the present invention, X ⁶、X⁷ and X ⁸ are preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom, and in view of easy introduction, a hydrogen atom, a methyl group, a methoxy group, a chlorine atom, a bromine atom, or a fluorine atom is particularly preferred.

Specific examples of the ketone represented by the formula (4) include structures represented by the following chemical formulas (4-1-1) to (4-2-13).

[ Chemical formula 137]

Of these (4-1-1) to (4-2-13), from the viewpoint of excellent optical properties after the introduction of the dihydroxy compound of the present invention into the polymer of the present invention, (4-1-1) to (4-1-13) are preferred, and (4-1-1) to (4-1-6) and (4-1-13) are particularly preferred.

The ketone represented by the formula (4) can be easily produced by a known method or a method described in the literature. In addition, commercially available products may be used.

The dihydroxy compound represented by formula (1 ') of the present invention can be synthesized by reacting the dihydroxy compound represented by formula (3) with the ketone represented by formula (4').

[ Chemical formula 138]

As the ratio of the dihydroxy compound represented by formula (3) to the ketone represented by formula (4 ') in the method for producing the dihydroxy compound represented by formula (1'), the dihydroxy compound represented by formula (3) is preferable in terms of molar ratio: ketone represented by formula (4') =1:0.8 to 1:2.2.

In the method for producing the dihydroxy compound represented by formula (1'), it is preferable to add a base in order to allow the reaction to proceed smoothly.

Examples of the organometallic compound include: n-butyllithium, sec-butyllithium, tert-butyl, phenyllithium.

Among these bases, inorganic bases are preferable, and sodium hydroxide and potassium hydroxide are more preferable, because they can perform a reaction well and are inexpensive.

The amount of the base to be used is preferably 3 to 10 molar equivalents, more preferably 5 to 7 molar equivalents, relative to 1 molar equivalent of the formula (3).

In the method for producing the dihydroxy compound represented by formula (1'), the method can be performed in the absence of a solvent or in a solvent. The solvent is not particularly limited as long as it is a solvent harmless to the reaction, and examples thereof include: halogen solvents such as methylene chloride and chloroform; ether solvents such as dioxane, tetrahydrofuran (hereinafter abbreviated as THF), diisopropyl ether, and cyclopentyl methyl ether; aromatic solvents such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, etc.; amide solvents such as N, N-dimethylformamide (hereinafter abbreviated as DMF), N-dimethylacetamide, and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP); alcohol solvents such as methanol, ethanol, propanol, isopropanol, and tert-butanol; and water. These solvents may be used alone or in combination of two or more. Among them, the alcohol-based solvent is preferable, and ethanol and methanol are more preferable, in terms of good yield of the reaction.

The reaction temperature in the process for producing a dihydroxy compound represented by formula (1') is preferably a reaction temperature appropriately selected from the range of-20 ℃ to 100 ℃ inclusive, and particularly preferably a reaction temperature appropriately selected from the range of 0 ℃ to 70 ℃ inclusive. The reaction time is appropriately determined according to the progress of the reaction, and is preferably appropriately selected from the range of 1 hour to 24 hours.

In the method for producing a dihydroxy compound represented by formula (1'), it is preferable to neutralize the reaction system with an acid after completion of the reaction.

The acids used include: hydrochloric acid, sulfuric acid, acetic acid, chloroacetic acid, and citric acid. Among them, acetic acid is preferable.

The amount of the acid to be used is not particularly limited as long as it is an amount capable of neutralizing the base to be used.

The dihydroxy compound obtained by the production method of formula (1') can be purified to an appropriate purity. As the purification method, there can be mentioned: washing, column chromatography, reprecipitation, grinding (trituration), adsorption treatment and recrystallization. The purification is preferably performed by washing, reprecipitation, recrystallization or milling in view of the small amount of the organic solvent to be used, and is more preferably performed by milling in view of the convenience of operation.

In the milling, an organic solvent may be used.

The organic solvent used for polishing is not particularly limited as long as it is a solvent capable of removing by-products, and examples thereof include: alcohol solvents such as methanol, ethanol, and isopropanol; nitrile solvents such as acetonitrile; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; hydrocarbon solvents such as pentane, hexane, heptane, and octane; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Methanol, ethanol, ethyl acetate or acetonitrile is preferable in terms of low cost and efficient removal of by-products, and these solvents may be used in a mixture of two or more.

The method for producing a polymer having a monocarboxylic acid ester at the end of at least one of the polymers of the present invention includes the following production methods: when polymerizing a raw material composition containing a dihydroxy compound represented by the above chemical formula (1'), a monocarboxylic acid derivative compound represented by any one of the following chemical formulas (2-1) or (2-2) is added.

[ Chemical formula 139]

[ In the above chemical formula (2-1) or (2-2), R ^5a、R^6a、R⁷ independently represents a group selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, and an optionally substituted aromatic group having 3 to 12 carbon atoms.

X ⁰ represents a release group. ]

In the chemical formula (2-1) or (2-2), examples of the alkyl group having 1 to 20 carbon atoms in R ^5a、R^6a、R⁷ include: among them, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and eicosyl are preferred, and methyl and ethyl are particularly preferred from the viewpoint of easy introduction.

Examples of the cycloalkyl group having 3 to 8 carbon atoms include: cyclohexyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl.

In the chemical formula (2-2), as the release group represented by X ⁰, a halogen atom is exemplified, and as the halogen atom, for example, there is exemplified: fluorine atom, chlorine atom, bromine atom, iodine atom.

The monocarboxylic acid derivative compound may be represented by, for example, the chemical formula (2-1) or (2-2). Specific chemical formula (2-1) includes: acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, difluoroacetic anhydride, valeric anhydride, isovaleric anhydride, pivalic anhydride, trifluoroacetic anhydride, caproic anhydride, benzoic anhydride, 3-pyridinecarboxylic anhydride, cyclohexanecarboxylic anhydride, heptanoic anhydride, chloroacetic anhydride, chlorodifluoroacetic anhydride, 2-methylbenzoic anhydride, n-octanoic anhydride, 4-methoxybenzoic anhydride, nonanoic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, pentafluoropropionic anhydride, decanoic anhydride, 2-methyl-6-nitrobenzoic anhydride, lauric anhydride, 3,4, 5-trimethoxybenzoic anhydride, heptafluorobutyric anhydride, and the like, preferably acetic anhydride, propionic anhydride, maleic anhydride, benzoic anhydride, Butyric anhydride, isobutyric anhydride, valeric anhydride, isovaleric anhydride, pivalic anhydride, trifluoroacetic anhydride, caproic anhydride, benzoic anhydride, cyclohexanecarboxylic anhydride, heptanoic anhydride, chloroacetic anhydride, 2-methylbenzoic anhydride, particularly preferably acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, isovaleric anhydride, pivalic anhydride, caproic anhydride, benzoic anhydride, cyclohexanecarboxylic anhydride, heptanoic anhydride, 2-methylbenzoic anhydride; Specific chemical formula (2-2) includes: benzoyl fluoride, undecanoyl fluoride, acetyl fluoride, chloropropane, cyclopropanecarbonyl chloride, butyryl chloride, isobutyryl chloride, chloroacetyl chloride, pentanoyl chloride, isopentanoyl chloride, pivaloyl chloride, 2-chloropropionyl chloride, 3-chloropropionyl chloride, 2-furoyl chloride, cyclopentanecarbonyl chloride, hexanoyl chloride, 2-dimethylbutyryl chloride, 4-methylpentanoyl chloride, 3-dimethylbutyryl chloride, benzoyl chloride, 4-chlorobutyryl chloride, 2-thiophenecanoyl chloride, cyclohexanecarbonyl chloride, dichloroacetyl fluoride, tetrahydro-2H-pyran-4-carbonyl chloride, heptanoyl chloride, p-methylbenzoyl chloride, o-methylbenzoyl chloride, M-methylbenzoyl chloride, 3-chloropivaloyl chloride, 5-chlorovaleryl chloride, bromoacetyl fluoride, 3-fluorobenzoyl chloride, 2-fluorobenzoyl chloride, 4-fluorobenzoyl chloride, 3-methyl-2-thiophenecanoyl chloride, n-octanoyl chloride, 2-propylpentanoyl chloride, 2-ethylhexanoyl chloride, 4-cyanobenzoyl chloride, 3, 5-dimethylbenzoyl chloride, 4-methoxybenzoyl chloride, 3-methoxybenzoyl chloride, 2-bromopropionyl chloride, 3-bromopropionyl chloride, 6-chloronicotinyl chloride, 5-chlorothiophene-2-carbonyl chloride, trichloroacetyl fluoride, dodecanoyl chloride, 4- (trifluoromethyl) benzoyl chloride, acetyl bromide, propionyl bromide, dodecanoyl chloride, Isobutyryl bromide, pentanoyl bromide, benzoyl bromide, bromoacetyl bromide, 2-bromopropionyl bromide, 2-bromoisobutyryl bromide, 2-bromobutyryl bromide, acetyl iodide, and the like; Preferably acetyl fluoride, chloropropane, cyclopropanecarbonyl chloride, butyryl chloride, isobutyryl chloride, chloroacetyl fluoride, valeryl chloride, isovaleryl chloride, pivaloyl chloride, 2-chloropropionyl chloride, 3-chloropropionyl chloride, 2-furoyl chloride, cyclopentanecarbonyl chloride, hexanoyl chloride, 2-dimethylbutyryl chloride, 4-methylpentanoyl chloride, 3-dimethylbutyryl chloride, benzoyl chloride, 4-chlorobutyryl chloride, cyclohexanecarbonyl chloride, dichloroacetyl fluoride, heptanoyl chloride, p-methylbenzoyl chloride, o-methylbenzoyl chloride, m-methylbenzoyl chloride, 3-chloropivaloyl chloride, 5-chlorovaleryl chloride, bromoacetyl fluoride, 3-fluorobenzoyl chloride, 2-fluorobenzoyl chloride, 4-fluorobenzoyl chloride, N-octanoyl chloride, 2-propylpentanoyl chloride, 2-ethylhexanoyl chloride, 4-cyanobenzoyl chloride, 3, 5-dimethylbenzoyl chloride, 4-methoxybenzoyl chloride, 3-methoxybenzoyl chloride, 2-bromopropionyl chloride, 3-bromopropionyl chloride, trichloroacetyl fluoride, dodecanoyl chloride, 4- (trifluoromethyl) benzoyl chloride; particularly preferred are acetyl fluoride, chloro propane, cyclopropanecarbonyl chloride, butanoyl chloride, isobutyryl chloride, pentanoyl chloride, isopentanoyl chloride, pivaloyl chloride, cyclopentanecarbonyl chloride, hexanoyl chloride, 2-dimethylbutyryl chloride, 4-methylpentanoyl chloride, 3-dimethylbutyryl chloride, benzoyl chloride, cyclohexanecarbonyl chloride, heptanoyl chloride, p-methylbenzoyl chloride, o-methylbenzoyl chloride, m-methylbenzoyl chloride, n-octanoyl chloride, 2-propylpentanoyl chloride, 2-ethylhexanoyl chloride, 3, 5-dimethylbenzoyl chloride, dodecanoyl chloride.

The polymer of the present invention may be prepared into a resin composition (hereinafter, may be referred to as a resin composition of the present invention) containing 70 to 99.99% by weight of the polymer of the present invention and 0.01 to 30% by weight of the thermal reorientation promoter. The resin composition is also included in one embodiment of the present invention.

The resin composition of the present invention contains a thermal reorientation promoter. Since the optical film obtained by using the resin composition of the present invention has improved molecular mobility due to the thermal reorientation promoter, thermal reorientation treatment of the polymer can be performed even on a general-purpose resin support substrate having a low heat-resistant temperature.

The molecular weight of the thermal reorientation promoter contained in the resin composition of the invention is preferably 100 to 20000, particularly preferably 300 to 20000, from the viewpoint of suppressing precipitation and bleeding of the thermal reorientation promoter in a high-temperature environment or suppressing volatilization of the thermal reorientation promoter in a high-temperature environment.

The blending ratio of the polymer of the present invention and the thermal reorientation promoter in the resin composition of the present invention is: the polymer of the present invention is 70 wt% to 99.99 wt% and the thermal reorientation promoter is 0.01 wt% to 30 wt%. Further preferably, from the viewpoint of suppressing precipitation and bleeding of the thermal reorientation promoter in a high-temperature environment: 85 to 99.9 weight percent of polymer and 0.1 to 15 weight percent of thermal reorientation promoter; from the viewpoint of promoting the efficiency of thermal reorientation, it is particularly preferable that: 85 to 99.0 weight percent of polymer and 1.0 to 15 weight percent of thermal reorientation promoter. In the present invention, when the proportion of the thermal reorientation promoter is less than 0.01% by weight, it is difficult to promote thermal reorientation; when the amount is more than 30% by weight, precipitation or bleeding of the thermal reorientation promoter tends to occur.

Examples of the thermal reorientation promoter contained in the resin composition of the present invention include plasticizers, antioxidants, light stabilizers, and the like.

Examples of the plasticizer include: carboxylic acid esters, phosphoric acid esters, polymer plasticizers, and the like.

Specific examples of the carboxylic acid ester include: phthalate esters, trimellitate esters, pyromellitate esters, citrate esters, oleate esters, ricinoleate esters, sebacate esters, stearate esters, adipate esters, epoxidized esters, and the like. Among them, phthalate and adipate are preferable from the viewpoint of easy availability.

Examples of the phthalate include phthalate having a molecular weight of 100 to 20000, which includes a structure represented by the following formula (7).

[ Chemical formula 140]

( In the formula (7), R ^a and R ^b each independently represent one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic group, a heterocyclic group, a polycyclic aromatic group and a condensed cyclic aromatic group, and these groups may have a bond such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group. R ^a and R ^b are each independently preferably an alkyl group having 2 to 20 carbon atoms, from the viewpoint of the effect of improving the molecular orientation of a polymer which is expected to be less likely to precipitate and exude. )

Specific phthalates include, for example: dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, di-n-decyl phthalate, diisodecyl phthalate, di (undecyl) phthalate, ditridecyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, di-2-ethylhexyl phthalate, benzyl butyl phthalate, di-2-ethylhexyl isophthalate, and the like.

Examples of the trimellitate include trimellitates having a molecular weight of 100 to 20000, which include structures represented by the following formula (8).

[ Chemical formula 141]

(In the formula (8), R ¹¹、R¹² and R ¹³ each independently represent one selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic group, a heterocyclic group, a polycyclic aromatic group and a condensed cyclic aromatic group, these groups may have bonds such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group.)

Specific examples of trimellitates include: trimethyl trimellitate, triethyl trimellitate, tributyl trimellitate, tri (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, trinonyl trimellitate, triisodecyl trimellitate, tri-undecyl trimellitate, tri-dodecyl trimellitate, tri-tridecyl trimellitate, tri-tetradecyl trimellitate, and the like.

Examples of the pyromellitic ester include pyromellitic esters having a molecular weight of 100 to 20000, which include a structure represented by the following formula (9).

[ Chemical formula 142]

(In the formula (9), R ¹⁴、R¹⁵、R¹⁶ and R ¹⁷ each independently represent one selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic group, a heterocyclic group, a polycyclic aromatic group and a condensed cyclic aromatic group, these groups may have bonds such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group.)

Specific examples of the pyromellitic acid ester include: tetramethyl pyromellitate, tetraethyl pyromellitate, tetrapropyl pyromellitate, tetrabutyl pyromellitate, 2-ethylhexyl pyromellitate, tetra (2-ethylhexyl) pyromellitate, tetra-n-octyl pyromellitate, tetraisooctyl pyromellitate, tetranonyl pyromellitate, tetraisononyl pyromellitate, tetra-n-decyl pyromellitate, tetraisodecyl pyromellitate, tetra (undecyl) pyromellitate, tetra (dodecyl) pyromellitate, tetra (tridecyl) pyromellitate, tetra (tetradecyl) pyromellitate, and the like.

Examples of the citrate esters include: comprises a citrate ester having a molecular weight of 100 to 20000 and having a structure represented by the following formula (10).

[ Chemical formula 143]

( In the formula (10), R ¹⁸、R¹⁹ and R ²⁰ each independently represent one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring, a heterocyclic group, a polycyclic aromatic group, and a condensed cyclic aromatic group, and these groups may have a bond such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group. Rh represents one selected from the group consisting of a hydrogen atom, an acyl group having 1 to 20 carbon atoms which may be substituted, an alkyl group having 1 to 20 carbon atoms, an aromatic group, a heterocyclic group, a polycyclic aromatic group, and a condensed ring aromatic group, these groups may have bonds such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group. )

Specific examples of the citrate esters include: trimethyl citrate, triethyl citrate, tripropyl citrate, tributyl citrate, tripentyl citrate, trihexyl citrate, acetyl trimethyl citrate, acetyl triethyl citrate, acetyl tripropyl citrate, acetyl tributyl citrate, acetyl tripentyl citrate, acetyl trihexyl citrate, trihexyl butyl citrate (trihexyl O-butyryl citrate), and the like.

Examples of the oleic acid ester include: comprises oleic acid ester having a molecular weight of 100 to 20000 and having a structure represented by the following formula (11).

[ Chemical formula 144]

(In the formula (11), R ²¹ represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring which may be substituted, and these groups may have a bond such as-O-group, - (C=O) O-group, -O (C=O) -O-group, -C (=O) -NH-group, -NH- (C=O) -group, -CH=CH-group, or-C≡C-group.)

Specific examples of the oleic acid ester include: methyl oleate, ethyl oleate, propyl oleate, butyl oleate, hexyl oleate, heptyl oleate, n-octyl oleate, nonyl oleate, n-decyl oleate, and the like.

Examples of ricinoleic acid esters include: comprises ricinoleic acid ester having a molecular weight of 100 to 20000 and having a structure represented by the following formula (12).

[ Chemical formula 145]

( In the formula (12), R ²² represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring which may be substituted, and these groups may have a bond such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group. R ²³ represents one selected from the group consisting of a hydrogen atom, an acetyl group having 1 to 20 carbon atoms which may be substituted, an alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or an condensed ring type aromatic ring, and these groups may have a bond such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group. )

Specific examples of ricinoleic acid esters include: methyl ricinoleate, ethyl ricinoleate, propyl ricinoleate, butyl ricinoleate, pentyl ricinoleate, hexyl ricinoleate, methyl acetylricinoleate, ethyl acetylricinoleate, propyl acetylricinoleate, and the like.

Examples of the sebacate include: comprising sebacate esters having a molecular weight of 100 to 20000 and having a structure represented by the following formula (13).

[ Chemical formula 146]

(In the formula (13), R ²⁴ and R ²⁵ each independently represent one selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, and a condensed ring type aromatic ring, these groups may have bonds such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group.)

Specific examples of the sebacate include: dimethyl sebacate, diethyl sebacate, dipropyl sebacate, dibutyl sebacate, di (2-ethylhexyl) sebacate, di-n-octyl sebacate, diisooctyl sebacate, dinonyl sebacate, diisodecyl sebacate, di-undecyl sebacate, didodecyl sebacate, ditridecyl sebacate, ditetradecyl sebacate, and the like.

Examples of the stearate include: comprises a stearic acid ester having a molecular weight of 100 to 20000 and having a structure represented by the following formula (14).

[ Chemical formula 147]

(In the formula (14), R ²⁶ represents one selected from the group consisting of an alkyl group having 1 to 40 carbon atoms, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring which may be substituted, and these groups may have a bond such as-O-group, - (C=O) O-group, -O (C=O) -O-group, -C (=O) -NH-group, -NH- (C=O) -group, -CH=CH-group, or-C≡C-group.)

Specific examples of the stearate include: methyl stearate, ethyl stearate, propyl stearate, butyl stearate, pentyl stearate, hexyl stearate, heptyl stearate, n-octyl stearate, nonyl stearate, decyl stearate, dodecyl stearate, phenyl stearate, glycidyl stearate, methyl dichlorostearate, glyceryl monostearate, glyceryl tristearate and the like.

Examples of the adipic acid ester include: comprises adipic acid ester with molecular weight of 100-20000 represented by the following formula (15).

[ Chemical formula 148]

( In the formula (15), R ²⁷ and R ²⁸ each independently represent one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, and a condensed ring type aromatic ring, and these groups may have a bond such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group. R ²⁷ and R ²⁸ are each independently preferably an alkyl group having 2 to 20 carbon atoms, from the viewpoint of the effect of improving the molecular orientation of a polymer which is expected to be less likely to precipitate and exude. )

Specific examples of the adipate ester include: dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisobutyl adipate, bis [2- (2-butoxyethoxy) ethyl ] adipate, di (2-ethylhexyl) adipate, di-n-octyl adipate, diisooctyl adipate, dinonyl adipate, diisononyl adipate, di-n-decyl adipate, diisodecyl adipate, di-undecyl adipate, di-dodecyl adipate, ditridecyl adipate, ditetradecyl adipate, and the like.

The epoxidized ester is not particularly limited as long as it has a molecular weight of 100 or more and has 1 or more epoxy group and ester bond, and examples thereof include: di-2-ethylhexyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate, di-9, 10-epoxystearyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate, epoxidized soybean oil, epoxidized linseed oil, epoxidized isobutyl fatty acid, epoxidized 2-ethylhexyl fatty acid, and the like.

The carboxylic acid ester is not limited to the carboxylic acid esters represented by the formulas (7) to (15) as long as the molecular weight is 100 to 20000, and examples thereof include: dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, bis (2-ethylhexyl) isophthalate, di-n-decyl isophthalate, diisodecyl isophthalate, di-undecyl isophthalate, di-dodecyl isophthalate, ditridecyl isophthalate, ditetradecyl isophthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, and, dibutyl terephthalate, bis (2-ethylhexyl) terephthalate, di-n-decyl terephthalate, diisodecyl terephthalate, di-undecyl terephthalate, di-dodecyl terephthalate, ditridecyl terephthalate, ditetradecyl terephthalate, diisodecyl 4-cyclohexene-1, 2-dicarboxylate, bis (2-ethylhexyl) 4-cyclohexene-1, 2-dicarboxylate, dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, bis (2-ethylhexyl) succinate, di-n-decyl succinate, diisodecyl succinate, Di-undecyl succinate, di-dodecyl succinate, di-tridecyl succinate, di-tetradecyl succinate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, bis (2-ethylhexyl) maleate, di-n-decyl maleate, diisodecyl maleate, di-undecyl maleate, di-dodecyl maleate, di-tridecyl maleate, di-tetradecyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, bis (2-ethylhexyl) fumarate, di-n-decyl fumarate, Diisodecyl fumarate, di-undecyl fumarate, di-dodecyl fumarate, ditridecyl fumarate, ditetradecyl fumarate, dimethyl suberate, diethyl suberate, dipropyl suberate, dibutyl suberate, bis (2-ethylhexyl) suberate, di-n-decyl suberate, diisodecyl suberate, di-undecyl suberate, didodecyl suberate, ditridecyl suberate, ditetradecyl suberate, dimethyl azelate, diethyl azelate, dipropyl azelate, dibutyl azelate, bis (2-ethylhexyl) azelate, di-n-decyl azelate, diisodecyl azelate, di-undecyl azelate, di-dodecyl azelate, ditridecyl azelate, ditetradecyl azelate, dimethyl laurate, diethyl laurate, dipropyl laurate, dibutyl laurate, bis (2-ethylhexyl) laurate, di-n-decyl laurate, diisodecyl laurate, di-undecyl laurate, di-dodecyl laurate, ditridecyl laurate, ditetradecyl laurate, dimethyl myristate, diethyl myristate, dipropyl myristate, dibutyl myristate, bis (2-ethylhexyl) myristate, di-n-decyl myristate, diisodecyl myristate, di-undecyl myristate, didodecyl myristate, ditridecyl myristate, ditetradecyl myristate, dimethyl palmitate, diethyl palmitate, dipropyl palmitate, dibutyl palmitate, bis (2-ethylhexyl) palmitate, di-n-decyl palmitate, diisodecyl palmitate, di-undecyl palmitate, didodecyl palmitate, ditridecyl palmitate, dimethyl stearyl acid, diethyl stearyl acid, dipropyl stearyl acid, dibutyl stearyl acid, bis (2-ethylhexyl) stearyl acid, di-n-decyl stearyl acid, diisodecyl stearyl acid, di-undecyl stearyl acid, didodecyl stearyl acid, ditridecyl stearyl acid, ditetradecyl stearyl acid, dimethyl eicosanoate, diethyl eicosanoate, dipropyl eicosanoate, dibutyl eicosanoate, bis (2-ethylhexyl) eicosanoate, di-n-decyl eicosanoate, diisodecyl eicosanoate, di-undecyl eicosanoate, didodecyl eicosanoate, ditridecyl eicosanoate, and the like.

The phosphate may be a compound represented by the following formula (16).

[ Chemical formula 149]

( In the formula (16), R ²⁹、R³⁰ and R ³¹ each independently represent one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, and a condensed ring type aromatic ring, and these groups may have a bond such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group. R ²⁹～R³¹ is preferably an alkyl group having 3 to 20 carbon atoms, respectively, from the viewpoint of the effect of improving the molecular orientation of the polymer in which precipitation and bleeding are less expected. )

Specific examples of the phosphate esters include: trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, tri-n-octyl phosphate, trisonyl phosphate, tri-n-decyl phosphate, tri (2-ethylhexyl) phosphate, tri (2-butoxyethyl) phosphate, tri (2-chloroethyl) phosphate, tri (1, 3-dichloro-2-propyl) phosphate, 2-ethylhexyl diphenyl phosphate, triphenyl phosphate, tri (xylene) phosphate, toluene diphenyl phosphate, tri (2-ethylhexyl) phosphate, tricresyl phosphate, and the like.

Specific examples of the polymer plasticizer include: polyester plasticizers, ether plasticizers, and the like.

Examples of the polyester plasticizer include a polymer containing a constituent unit represented by the following formula (17) and a polyester plasticizer having a molecular weight of 100 to 20000.

[ Chemical formula 150]

(In the formula (17), R ³² and R ³³ each independently represent one selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, and a condensed ring type aromatic ring, these groups may have bonds such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group.)

Specific examples of the polyester plasticizer include ：ADK CIZER PN-160、PN-9302、PN-150、PN-170、PN-7230、PN-1010、PN-1020、P-200、PN-650、PN-7650、PN-1030、PN-1430、HPN-3130、PN-400、P-5040、PN-7250、PN-250、PN-7220、PN-7550、PN-446、PN-310、P-300、PN-280、PN-5090( or more, trade names, manufactured by ADEKA of the company, D620, D623, D643, D645, D633, D620N, D623N, D643D, D640A, D671N (trade names, manufactured by mitsubishi chemical corporation), POLYCIZER W-230-H, W-1430-EL, W-2050, W-2310 (trade names, manufactured by DIC corporation), and the like.

The ether plasticizer includes an ether plasticizer having a molecular weight of 100 to 20000, which contains a constituent unit represented by the following formula (18).

[ Chemical formula 151]

(In the formula (18), R ³⁴ represents one selected from the group consisting of an alkylene chain having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, and a condensed ring type aromatic ring which may be substituted, these groups may have bonds such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group.)

Specific examples of the ether plasticizer include: ADK CIZER RS-107, RS-700, RS-735, RS-966, RS-1000, (trade name, manufactured by ADEKA of Kyowa Co., ltd.), MONOCIZER W-260, W-262 (trade name, manufactured by DIC Co., ltd.), diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, decadiethylene glycol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 300, polyethylene glycol 600, polyethylene glycol 1000, polyethylene glycol 2000, polyethylene glycol 4000, polyethylene glycol 6000, polyethylene glycol 11000, polyethylene glycol 20000, and the like.

Examples of the antioxidant include: phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants, hydroxylamine antioxidants, vitamin E antioxidants, and the like.

The phenolic antioxidants include those having a molecular weight of 100 to 20000, which contain a structure represented by the following formula (19).

[ Chemical formula 152]

(In the formula (19), at least one of R ³⁵、R³⁹ represents one selected from the group consisting of a secondary alkyl group having 3 to 20 carbon atoms, a tertiary alkyl group having 4 to 20 carbon atoms, a thioether group having 6 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring which may have a bond such as-O-group, - (C=O) O-group, -O (C=O) -O-group, -C (=O) -NH-group, -NH- (C=O) -group, -CH=CH-group, or-C≡C-group, the other represents one selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioether group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a polycyclic aromatic ring, and a condensed ring type aromatic ring, these groups may have bonds such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group, the structures thereof are not particularly limited, but from the viewpoint of easy availability, t-butyl R ³⁶～R³⁸ each independently represents a group selected from the group consisting of a hydrogen atom, and a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a condensed ring type aromatic ring which may be substituted may have a bond such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group. )

Specific examples of the phenolic antioxidants include, for example: irganox 245 (bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoic acid ] [ ethylenebis (ethylene oxide) ]), irganox 1010 (pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoate ]), irganox 1035 (2, 2' -thiodiethyl bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoate ]), irganox 1076 (octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoate), irganox 1098 (N, N ' - (hexane-1, 6-diyl) bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide ]), irganox 1135 (octyl 3, 5-di-tert-butyl-4-hydroxy-hydrocinnamate), irganox 1330 (2, 4, 6-tris (3 ',5' -di-tert-butyl-4 ' -hydroxybenzyl) mesitylene), irganox 1520 (2, 4-bis (octylthiomethyl) -6-methylphenol), irganox 259 (1, 6-hexanediol bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]), irganox 3114 (1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione), irganox 565 (4- [ [4, 6-bis (octylthio) -1,3, 5-triazin-2-yl ] amino ] -2, 6-di-t-butylphenol) (trade name, BASF JAPAN Co., ltd., all of which are incorporated herein by reference), tetrakis [3- (3 ',5' -di-t-butyl-4 ' -hydroxyphenyl) propionate ], bis [3- [3- (t-butyl) -4-hydroxy-5-tolyl ] propionate ]2,4,8, 10-tetraoxaspiro [5,5] undecane-3, 9-diylbis (2-methylpropan-2, 1-diyl) ester, and the like.

The phenolic antioxidant is not limited to the phenolic antioxidant represented by the formula (15) as long as the molecular weight is 100 to 20000, and examples thereof include: and (3) a caliwanyloxy radical, 3', 5' -tetra-tert-butyl-4, 4' -stilbenequinone, 4- (hexyloxy) -2,3, 6-trimethylphenol, and the like.

Examples of the amine-based antioxidant include amine-based antioxidants having a molecular weight of 100 to 20000, which include a structure represented by the following formula (20).

[ Chemical formula 153]

( In the formula (20), R ⁴⁰ represents a ring selected from the group consisting of an aromatic ring, a polycyclic aromatic ring, and a condensed ring type aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and these aromatic ring, polycyclic aromatic ring, and condensed ring type aromatic ring may have a substituent. R ⁴¹ represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a condensed ring type aromatic ring, and these groups may have a bond such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group. R ⁴¹ preferably has 9 to 20 carbon atoms, from the viewpoint of the effect of improving the molecular orientation of the polymer which is expected to be less likely to precipitate and exude. )

Specific examples of the amine antioxidant represented by the formula (20) include: 6-ethoxy-2, 4-trimethyl-1, 2-dihydroquinoline, N-phenyl-1-naphthylamine, N, N '-di-sec-butyl-1, 4-phenylenediamine, 4-isopropylaminodiphenylamine, N, N' -diphenyl-1, 4-phenylenediamine, N- (1, 3-dimethylbutyl) -N '-phenyl-N, N' -phenylenediamine, N, N '-di-2-naphthyl-1, 4-phenylenediamine, 4' -bis (. Alpha.,. Alpha. -dimethylbenzyl) diphenylamine, and the like.

The amine antioxidant is not limited to the one represented by the formula (20) as long as the molecular weight is 100 to 20000, and examples thereof include: 6-ethoxy-2, 4-trimethyl-1, 2-dihydroquinoline, poly (2, 4-trimethyl-1, 2-dihydroquinoline), and the like.

Examples of the phosphorus antioxidant include phosphorus antioxidants having a molecular weight of 100 to 20000, which include structures represented by the following formula (21).

[ Chemical formula 154]

(In the formula (21), R ⁴² and R ⁴³ each independently represents one selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, and a condensed ring type aromatic ring, R ⁴⁴ represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, and a condensed aromatic ring which may be substituted, these groups may have bonds such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group, R ⁴²、R⁴³ and R ⁴⁴ are each independently preferably 3 to 20 carbon atoms from the viewpoint of the effect of improving the molecular orientation of a polymer which is expected to be less likely to precipitate and exude.

Specific examples of the phosphorus antioxidant include: trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, triphenyl phosphite, trihexyl phosphite, triorth toluene phosphite, tricresyl phosphite, tri-p-toluene phosphite, tri (2-ethylhexyl) phosphite, trioctyl phosphite, triisodecyl phosphite, tri (1, 3-hexafluoro-2-propyl) phosphite, 3, 9-bis (2, 4-di-t-butylphenoxy) -2,4,8, 10-tetraoxa 3, 9-diphosphro [5.5] undecane, tri (2, 4-di-t-butylphenyl) phosphite, trio-oil phosphite, and the like.

Examples of the sulfur-based antioxidant include sulfur-based antioxidants having a molecular weight of 100 to 20000, which include a structure represented by the following formula (22).

[ Chemical formula 155]

R⁴⁵-S-R⁴⁶ (22)

( In the formula (22), R ⁴⁵ represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a heterocycle, an aromatic ring, a polycyclic aromatic ring, and a condensed ring type aromatic ring which may be substituted, and these groups may have a bond such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group. R ⁴⁶ represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring, a heterocycle, a polycyclic aromatic ring, and a condensed ring aromatic ring, and these groups may have a bond such as-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group. R ⁴⁵ and R ⁴⁶ are each independently preferably 6 to 20 carbon atoms, from the viewpoint of the effect of improving the molecular orientation of a polymer which is expected to be less likely to precipitate and exude. )

Specific examples of the sulfur-based antioxidant include: di (dodecyl) 3,3 '-thiodipropionate, di (octadecyl) 3,3' -thiodipropionate, pentaerythritol tetrakis [3- (dodecylthio) propionate ], and the like.

Examples of the light stabilizer include hindered amine light stabilizers.

Examples of the hindered amine light stabilizer include hindered amine light stabilizers having a molecular weight of 100 to 20000, which are constituent units represented by the following formula (23).

[ Chemical formula 156]

Wherein R ⁴⁷ represents one of the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted, R ⁴⁸、R⁴⁹、R⁵⁰ and R ⁵¹ each independently represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms which may be substituted, a heterocycle, an aromatic ring, a polycyclic aromatic ring, and a condensed ring type aromatic ring, these groups may have-O-groups, - (C=O) O-groups, -O (C=O) -O-groups-C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group, wherein, from the viewpoint of availability, it is particularly preferable that the methyl group R ⁵² represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted, an alkoxy group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a condensed ring type aromatic ring, and these groups may have an-O-group, - (c=o) O-group, -O (c=o) -O-group, -C (=o) -NH-group, -NH- (c=o) -group, -ch=ch-group, or-c≡c-group, and the like. )

Specific examples of the hindered amine light stabilizer include: 2, 6-tetramethyl-4-piperidinyl methacrylate, 1,2, 6-pentamethyl-4-piperidinyl methacrylate, N, N '-bis (2, 6-tetramethylpiperidin-4-yl) hexane-1, 6-diamine, N, N' -bis (2, 6-tetramethyl-4-piperidinyl) isophthalamide, bis (2, 6-tetramethyl-4-piperidinyl) sebacate bis (2, 6-tetramethyl-4-piperidinyl-1-oxy) sebacate bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, bis (1, 2, 6-pentamethyl-4-piperidinyl) butyl (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate, and the like.

Among these thermal reorientation promoters, plasticizers are preferred in view of their availability, good compatibility with the polymer, and particularly excellent thermal reorientation promoters after being contained in the polymer.

In order to reduce the film thickness unevenness of the obtained film, the resin composition of the present invention may contain at least one or more surfactants. Examples of the surfactant that can be contained include: alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoroalkyl ethylene oxide derivatives, polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts, and the like, with fluorosurfactants being particularly preferred.

The resin composition of the present invention may contain other polymers, polyelectrolytes, conductive complexes, pigments, dyes, antistatic agents, antiblocking agents, lubricants, and the like within a range not exceeding the gist of the present invention.

The resin composition of the present invention can be obtained by mixing a polymer having a photoreactive inverse wavelength dispersion unit that exhibits both photoreactivity and birefringent inverse wavelength dispersion with a thermal reorientation promoter (hereinafter referred to as a polymer or the like).

As the method of mixing, a method such as a melt mixing method or a solution mixing method can be used. The melt-mixing method is a method of producing a polymer or the like by melting and kneading the polymer or the like by heating. The solution mixing method is a method of dissolving a polymer or the like in a solvent and mixing the solution. As the solvent used for the solution mixing method, for example, there may be used: halogen solvents such as 1, 3-hexafluoroisopropanol, methylene chloride and chloroform; aromatic solvents such as toluene and xylene; ketone solvents such as cyclopentanone, acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, and propanol; ether solvents such as dioxane and tetrahydrofuran; dimethylformamide, N-methylpyrrolidone, etc. The polymer and the like may be dissolved in a solvent and then mixed, or the powder, particle and the like of each polymer may be kneaded and then dissolved in a solvent. The resulting mixed polymer solution may be poured into a lean solvent to precipitate the resin composition, or the mixed polymer solution may be directly used for producing an optical film.

The polymer of the present invention and the resin composition of the present invention are useful as an optical film. An optical film comprising the polymer of the present invention or the resin composition of the present invention (hereinafter, sometimes referred to as "the optical film of the present invention") is also included in one embodiment of the present invention.

The optical film of the present invention can satisfy the following formula (I).

Re(450)≤Re(550)…(I)

(In the formula (I), re (450) represents the in-plane phase difference value measured at a wavelength of 450nm, and Re (550) represents the in-plane phase difference value measured at a wavelength of 550 nm.)

The meaning satisfying the above formula (I) is the same as that satisfying the following formula (II).

Re(450)/Re(550)≤1…(II)

(In the formula (II), re (450) represents the in-plane phase difference value measured at a wavelength of 450nm, and Re (550) represents the in-plane phase difference value measured at a wavelength of 550 nm.)

The optical film of the present invention can be used with its film thickness adjusted according to the purpose, and is preferably 1 μm to 20 μm, more preferably 10 μm or less.

In the optical film of the present invention, the Yellowness Index (YI) at a film thickness of 5 μm is preferably 5% or less, more preferably 3% or less, in the optical film composed of the polymer of the present invention having a monocarboxylic acid ester at least one end.

The Yellowness Index (YI) is the degree to which the hue of a polymer deviates from colorless or white to yellow, expressed as a positive value, and is preferably low in application as an optical film.

By using the resin composition of the present invention as an optical film, the retardation Re of the following formula (X) measured by a light irradiation treatment and a heat baking treatment at 190℃at a high temperature using a light source of 589nm becomes high, and the retardation Re is preferably 5 to 400, more preferably 5 to 300, particularly preferably 5 to 150.

Re＝(ny-nx)×d (X)

(In the formula (X), nx represents a refractive index in a fast axis direction (a direction in which a refractive index is smallest) in a plane, ny represents a refractive index in a slow axis direction (a direction in which a refractive index is largest) in a plane, and d represents a film thickness (nm))

By using the resin composition of the present invention as an optical film, the retardation Re of the following formula (X) measured by a light irradiation treatment and a heat baking treatment at 150℃at a high temperature using a light source of 589nm becomes high, and the retardation Re is preferably 35 to 400, more preferably 35 to 300, particularly preferably 35 to 150.

Re＝(ny-nx)×d (X)

More specifically, the phase difference Re being increased at a high temperature means that the phase difference Re is increased by 1.3 times or more as compared with that before the thermal reorientation promoting material is contained. This is believed to be because the use of a thermal reorientation promoter enhances the molecular mobility of the polymer.

The method for producing the optical film of the present invention is not particularly limited, and examples thereof include: a method of a melt film-forming method or a solution casting method.

The melt film-forming method is not particularly limited, and examples thereof include a melt extrusion method using a T-die, a calender molding method, a hot press method, a coextrusion method, a co-melt method, a multilayer extrusion and a blow molding method.

The solution casting method is a method in which a solution of a polymer (hereinafter, also referred to as a polymer) dissolved in a solvent (hereinafter, referred to as a "casting dope") is cast on a support substrate, and then the solvent is removed by heating to obtain a film. In this case, as a method of casting the casting dope on the support substrate, spin coating, T-die, doctor blade, bar coating, roll coating, lip coating may be used. In particular, the most common method in industry is a T-die method in which a casting dope is continuously extruded from a die onto a support substrate in a belt shape or a drum shape. Examples of the support substrate used include: glass substrates of quartz glass substrates, metal substrates of stainless steel or iron type, films of polyethylene terephthalate.

In order to reduce film thickness unevenness, the optical film of the present invention may contain at least one or more surfactants. Examples of the surfactant include: fluorine-containing surfactants of alkyl carboxylate, alkyl phosphate, alkyl sulfonate, fluoroalkyl carboxylate, fluoroalkyl phosphate, fluoroalkyl sulfonate, polyoxyethylene derivative, fluoroalkyl ethylene oxide derivative, polyethylene glycol derivative, alkyl ammonium salt, fluoroalkyl ammonium salt, and fluoroalkyl carboxylate, fluoroalkyl phosphate, fluoroalkyl sulfonate, fluoroalkyl ethylene oxide derivative, and fluoroalkyl ammonium salt are particularly preferable.

In the optical film of the present invention, in particular, since the retardation of the inverse wavelength dispersion is expressed, the film can be suitably used as an inverse wavelength dispersion film.

In the optical film of the present invention, after the film is formed by the method of the melt film forming method or the solution casting method, it is preferable to irradiate either polarized ultraviolet rays or oblique incident ultraviolet rays so as to express a retardation of the reverse wavelength dispersibility.

In the case of using ultraviolet rays, the wavelength of ultraviolet rays may be appropriately selected from the range of 200nm to 400 nm. The irradiation energy is preferably 10mJ/cm ² to 10000mJ/cm ², particularly preferably 10mJ/cm ² to 1000mJ/cm ².

The optical film of the present invention is preferably subjected to a heat treatment after the irradiation with ultraviolet rays so that the retardation of the inverse wavelength dispersion is further expressed. The heat treatment temperature may be exemplified by 50℃or more and 400℃or less.

The optical film of the present invention can be used as a retardation film by performing polarized ultraviolet irradiation or oblique incident ultraviolet irradiation and further performing heat treatment to express three-dimensional refractive index anisotropy.

When the optical film of the present invention is used as a retardation film, the film may be used as a single film or as a multilayer film obtained by laminating other films. A multilayer film provided with the optical film is also included in one embodiment of the present invention.

Examples of the laminated film include: a linear polarizing film, a PET film, a PEN film, a PVA film, a cellulose ester film such as a TAC film, and a film composed of a cycloolefin polymer.

The multilayer film can be used as a retardation film, a polarizing plate, a circularly polarizing film, a liquid crystal alignment film.

[ Summary ]

[1] A main chain polymer having a photoreactive inverse wavelength dispersion unit having two functions of photoreactivity and birefringence inverse wavelength dispersion in the polymer main chain, wherein the photoreactive inverse wavelength dispersion unit has a structure represented by the following chemical formula (1).

[ Chemical formula 157]

* Represents a bonding position to other structures in the main chain polymer.

[ Chemical formula 158]

[2] The main chain polymer according to the above [1], wherein Ar in the above formula (1) is any one of the following formulas (Ar-1) to (Ar-7).

[ Chemical formula 159]

R ^e represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[3] The main chain polymer according to the above [1], wherein the polymer further has at least one structure selected from the group consisting of the following chemical formulas (2A), (2B), (2C) and (2D).

[ Chemical formula 160]

N is 0 or 1.

[ Chemical formula 161]

[ Chemical formula 162]

X ¹⁰ represents-O-, -N (R ^c) -.

X ¹¹ represents-O-, -N (R ^d) -.

* Represents bonding positions to other structures in the backbone polymer. ]

[ Chemical formula 163]

[4] The main chain polymer according to any one of the above [1] to [3], wherein at least one terminal of the main chain polymer is a monocarboxylic acid ester represented by the following chemical formula (2').

[ Chemical formula 164]

[ In the above chemical formula (2'), R ¹⁰ represents a group selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, and an optionally substituted aromatic group having 3 to 12 carbon atoms.

* Represents bonding positions to other structures in the main chain polymer. ]

[5] A resin composition comprising 70 to 99.99% by weight of the main chain polymer of any one of the above [1] to [3], and 0.01 to 30% by weight of a thermal reorientation promoter.

[6] A resin composition comprising 70 to 99.99% by weight of the main chain polymer according to [4] and 0.01 to 30% by weight of a thermal reorientation promoter.

[7] A method for producing the main chain polymer according to any one of the above [1] to [3], wherein a raw material composition comprising a dihydroxy compound represented by the following chemical formula (1') is polymerized.

[ Chemical formula 165]

[ Chemical formula 166]

[8] A method for producing a main chain polymer according to the above [4], wherein a monocarboxylic acid derivative compound represented by any one of the following chemical formulas (2-1) and (2-2) is further added when polymerizing a raw material composition containing a dihydroxy compound represented by the chemical formula (1').

[ Chemical formula 167]

[ In the above chemical formula (2-1) or (2-2), R ^5a、R^6a and R ⁷ each independently represent a group selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, and an optionally substituted aromatic group having 3 to 12 carbon atoms. ]

[9] An optical film comprising the main chain polymer of any one of [1] to [3] or the resin composition of [5 ].

[10] An optical film comprising the main chain polymer according to [4] above or the resin composition according to [6] above.

[11] The optical film according to the above [9] or [10], wherein the phase difference (Re) satisfies the following formula (I).

Re(450)≤Re(550)…(I)

[12] The optical film according to [10], wherein the Yellowness Index (YI) of the film thickness of 5 μm is 5% or less.

[13] The method for producing an optical film according to any one of [9] to [12], wherein any one of polarized ultraviolet rays and oblique incident ultraviolet rays is irradiated.

[14] The method according to item [13] above, further comprising a heat treatment step.

[15] A multilayer film comprising the optical film of any one of [9] to [12 ].

[16] A dihydroxy compound represented by the following formula (1').

[ Chemical formula 168]

[ Chemical formula 169]

[17] A process for producing a dihydroxy compound, wherein a dihydroxy compound represented by the following formula (1 ') is obtained by reacting a dihydroxy compound represented by the following formula (3) with a ketone represented by the following formula (4').

[ Chemical formula 170]

[ Chemical formula 171]

[ Chemical formula 172]

[ Chemical formula 173]

Examples (example)

Hereinafter, the present invention will be described in further detail by way of examples, but the present invention should not be construed as being limited to these examples.

The compounds (2' -2-1-DC) in the examples were synthesized according to the method described in Macromolecules,2018, volume 51 (23), pages 9430-9441.

The compound (6' -1-DH) of the example was synthesized according to the method described in patent No. 5325733.

< Determination of Nuclear magnetic resonance Spectrometry >

The ¹ H-NMR spectrum was measured by using a nuclear magnetic resonance apparatus (trade name: ECZ 400S, japan electronic Co., ltd.).

< Determination of film thickness of film >

The film thickness of the film in the examples was measured using a spectroscopic ellipsometer (manufactured by J.A. Woollam Co., ltd.; trade name: RC 2-U).

< Evaluation of Yellowness Index (YI) >)

For the Yellowness (YI) in the examples, a light beam was set in a spectral haze meter (trade name: SH7000, light source D65, manufactured by the Japanese electric color Co., ltd.)The attachment was determined by measurement according to ASTM E313-05.

The appearance of the film in the examples was confirmed by visual inspection, and the acceptable film appearance in which coloring was not recognized was evaluated as "a", the film appearance in which coloring was recognized but extremely slight and acceptable was evaluated as "B", and the film appearance in which coloring was recognized significantly and unacceptable was evaluated as "C".

< Polarized ultraviolet irradiation >)

For polarized ultraviolet irradiation in the examples, an ultra-high pressure mercury lamp light source (trade name: REX-250, manufactured by Korea spectroscopy) equipped with a band-pass filter (248 nm, 313nm or 365 nm) was used, and only P-polarized light was extracted from a polarizing beam splitter of a corresponding wavelength and irradiated.

< Heating treatment >)

The heat treatment of the film in the examples was performed using an inert oven (ESPEC, trade name: IPHH-202) having a constant temperature in an oxidizing atmosphere.

< Determination of phase Difference Property (Re) >)

For the measurement of the retardation property (Re) in examples, a sample tilt-type automatic birefringence meter (trade name: axoScan, manufactured by AXOMETRICS Co., ltd.) was used, and the measurement was performed using light having a wavelength of 589 nm.

Re＝(ny-nx)×d…(III)

(In the formula (III), nx represents a refractive index in a fast axis direction (a direction in which a refractive index is smallest) in a film plane, ny represents a refractive index in a slow axis direction (a direction in which a refractive index is largest) in a film plane, and d (nm) represents a thickness of the film.)

< Determination of wavelength Dispersion Property (Re (450)/Re (550)) >)

For the wavelength dispersion characteristics (Re (450)/Re (550)) in the examples, the ratio of the in-plane retardation Re (450) measured by using a sample tilt-type automatic birefringence meter (trade name: axoScan, manufactured by AXOMETRIS Co., ltd.) to the in-plane retardation Re (550) measured by using light having a wavelength of 450nm was calculated.

[ Dihydroxy Compound example 1]

[ Chemical formula 174]

After 2, 5-dihydroxybenzaldehyde (5.00 g,36.2 mmol) and 2-acetylthiophene (4.57 g,36.2 mmol) were dissolved in ethanol (36 mL), an aqueous solution (7.4 mL) of potassium hydroxide (11.0 g,195 mmol) was added dropwise with ice water cooling. After the reaction system was stirred at room temperature for 3 hours, acetic acid (13.0 mL,228 mmol) was added under ice-water cooling. After the resulting reaction mixture was added to water (100 mL), methylene chloride (30 mL) was added and stirred vigorously. The resulting solid was taken out by filtration and washed with dichloromethane (50 mL) and distilled water (50 mL). The resulting solid was dried under vacuum at 60℃for 5 hours to give 5.01g of compound (1' -2-1) as a yellow solid (yield ：56％).¹H-NMR(400MHz,DMSO-d₆)δ10.0-8.42(br,2H),8.17(m,1H),7.99(m,1H),7.94(d,J＝15.6Hz,1H),7.62(d,J＝15.6Hz,1H),7.25(m,1H),7.17(s,1H),6.63-6.76(m,2H).

[ Dihydroxy Compound example 2]

[ Chemical formula 175]

2, 5-Dihydroxybenzaldehyde (58.1 g, 426 mmol) and 2-acetyl-5-chlorothiophene (67.5 g, 426 mmol) were dissolved in methanol (216 mL), and then 48% aqueous sodium hydroxide solution (126 mL,2.25 mol) was added dropwise under ice water cooling. After the reaction system was stirred at 50℃for 3 hours, acetic acid (168 mL,2.93 mol) was added under ice-water cooling. To the resulting reaction mixture were added water (270 mL), toluene (95 mL) and isopropyl alcohol (13.5 mL), and then further added water (54 mL). The resulting solid was removed by filtration and washed with water (50 mL), toluene (270 mL). After suspending the obtained solid in acetonitrile (235 mL) -methanol (59 mL) mixed solvent, the system was warmed with an oil bath at 70 ℃ and stirred for 1.5 hours. The system was cooled again with an ice-water bath and the solids produced in the system were filtered off with a buchner funnel. Next, the solid was washed with acetonitrile (270 mL) from the top of the Buchner funnel, and then dried under vacuum to obtain 81.4g of compound (1' -2-2) as yellow microcrystals (yield ：69％).¹H-NMR(400MHz,DMSO-d₆)δ9.88-8.62(br,2H),8.12(d,J＝4.1Hz,1H),7.95(d,J＝15.8Hz,1H),7.60(d,J＝15.8Hz,1H),7.31(d,J＝4.1Hz,1H),7.19(s,1H),6.75-6.68(m,2H).

[ Dihydroxy Compound example 3]

[ Chemical formula 176]

After 2, 5-dihydroxybenzaldehyde (10.0 g,72.4 mmol) and 2-acetyl-5-bromothiophene (14.8 g,72.4 mmol) were dissolved in ethanol (72 mL), a solution of potassium hydroxide (21.9 g, 399mmol) in water (14.8 mL) was added dropwise with ice water cooling. After the reaction system was stirred at room temperature for 3 hours, acetic acid (26.1 mL, 458 mmol) was added with ice water cooling. After the resulting reaction mixture was added to water (200 mL), methylene chloride (60 mL) was added and stirred vigorously. The resulting solid was taken out by filtration and washed with dichloromethane (100 mL) and distilled water (100 mL). By vacuum drying the obtained solid at 60℃for 5 hours, 6.08g of compound (1' -2-3) was obtained as a yellow solid (yield ：26％).¹H-NMR(400MHz,DMSO-d₆)δ9.45(br,1H),8.83(br,1H),7.99(d,J＝4.6Hz,1H),7.85(d,J＝15.8Hz,1H),7.55(d,J＝15.8Hz,1H),7.15(m,1H),6.69(m,2H),6.49(d,J＝4.6Hz,1H).

[ Dihydroxy Compound example 4]

[ Chemical formula 177]

After 2, 5-dihydroxybenzaldehyde (2.00 g,14.5 mmol) and 2-acetyl-5-methoxythiophene (2.26 g,14.5 mmol) were dissolved in ethanol (14.4 mL), a solution of potassium hydroxide (4.39 g,78.2 mmol) in water (2.8 mL) was added dropwise with cooling in ice water. After the reaction system was stirred at room temperature for 3 hours, acetic acid (5.22 mL,91.2 mmol) was added with ice water cooling. After the resulting reaction mixture was added to water (50 mL), it was vigorously stirred. The resulting solid was taken out by filtration and washed with dichloromethane (50 mL) and distilled water (100 mL). The resulting solid was dried under vacuum at 60℃for 5 hours to give 1.05g of compound (1' -2-5) as a yellow solid (yield ：26％).¹H-NMR(400MHz,DMSO-d₆)δ9.46(br,1H),8.85(br,1H),7.99(d,J＝4.6Hz,1H),7.85(d,J＝15.8Hz,1H),7.55(d,J＝15.8Hz,1H),7.15(m,1H),6.70-6.68(m,2H),6.49(d,J＝4.6Hz,1H),3.94(s,3H).

[ Dihydroxy Compound example 5]

[ Chemical formula 178]

After 2, 5-dihydroxybenzaldehyde (2.00 g,14.5 mmol) and 2-acetyl-5-methylthiophene (2.03 g,14.5 mmol) were dissolved in ethanol (14.4 mL), a solution of potassium hydroxide (4.39 g,78.2 mmol) in water (2.8 mL) was added dropwise with cooling in ice water. After the reaction system was stirred at room temperature for 3 hours, acetic acid (5.22 mL,91.2 mmol) was added with ice water cooling. After the resulting reaction mixture was added to water (50 mL), it was vigorously stirred. The resulting solid was taken out by filtration and washed with dichloromethane (50 mL) and distilled water (100 mL). By drying the obtained solid at 60℃under vacuum for 5 hours, 1.66g of the compound (1' -2-6) was obtained as a yellow solid (yield ：44％).¹H-NMR(400MHz,DMSO-d₆)δ9.92-8.58(br,2H),7.99(d,J＝3.9Hz,1H),7.89(d,J＝15.8Hz,1H),7.56(d,J＝15.8Hz,1H),7.14(m,1H),6.96(d,J＝3.9Hz,1H),6.73-6.67(m,2H),2.49(s,3H).

[ Dihydroxy Compound example 6]

[ Chemical formula 179]

After 2, 5-dihydroxybenzaldehyde (1.00 g,7.24 mmol) and 2-acetyl-5-methylfuran (899 mg,7.24 mmol) were dissolved in ethanol (7.2 mL), a solution of potassium hydroxide (2.19 g,39.1 mmol) in water (1.4 mL) was added dropwise with cooling in ice water. After the reaction system was stirred at room temperature for 3 hours, acetic acid (2.61 mL,45.6 mmol) was added with ice water cooling. After the resulting reaction mixture was added to water (50 mL), it was vigorously stirred. The resulting solid was taken out by filtration and washed with dichloromethane (50 mL) and distilled water (100 mL). By drying the obtained solid at 60℃under vacuum for 5 hours, 1.07g of the compound (1' -2-6-Furan) was obtained as a yellow solid (yield ：61％).¹H-NMR(400MHz,DMSO-d₆)δ9.53(br,1H),8.87(br,1H),7.89(d,J＝16.0Hz,1H),7.57(d,J＝3.5Hz,1H),7.42(d,J＝16.0Hz,1H),7.10(m,1H),6.72-6.66(m,2H),6.37(d,J＝3.5Hz,1H),2.36(s,3H).

[ Dihydroxy Compound example 7]

[ Chemical formula 180]

2, 5-Dihydroxybenzaldehyde (4.49 g,32.3 mmol) and 2-acetyl-4-methyl-5-chlorothiophene (5.65 g,32.3 mmol) were dissolved in methanol (16 mL), and 48% aqueous sodium hydroxide solution (10 mL,180 mmol) was added dropwise under ice water cooling. After the reaction system was stirred at room temperature for 4 hours, acetic acid (17 mL, 294 mmol) was added under ice-water cooling. To the resulting reaction mixture was added water (30 mL) and stirred vigorously. The resulting solid was removed by filtration and washed with hexane (100 mL) and distilled water (100 mL). By drying the obtained solid in vacuo at 50℃for 5 hours, 7.51g of compound (1' -2-7) was obtained as an orange solid (yield ：79％).1H-NMR(400MHz,DMSO-d₆)δ9.60(br,1H),9.02(br,1H),8.16(s,1H),7.98(d,J＝15.6Hz,1H),7.62(d,J＝15.6Hz,1H),7.23(m,1H),6.79-6.74(m,2H),2.23(s,3H).

[ Dihydroxy Compound example 8]

[ Chemical formula 181]

2, 5-Dihydroxy-4-methylbenzaldehyde (1.84 g,12.1 mmol) and 2-acetyl-5-chlorothiophene (2.50 g,15.5 mmol) were dissolved in methanol (16 mL), and then 48% aqueous sodium hydroxide solution (3.7 mL,66.1 mmol) was added dropwise under ice water cooling. After the reaction system was stirred at room temperature for 6.5 hours, acetic acid (4.8 mL,83.7 mmol) was added with ice water cooling. To the resulting reaction mixture were added dichloromethane (10 mL) and water (34 mL), followed by vigorous stirring. The resulting solid was taken out by filtration, and purified water (50 mL), dichloromethane: the mixture of methanol (10 mL, volume ratio: dichloromethane/methanol=5/1) was washed. The resulting solid was dried under vacuum at 50℃for 3 hours to give 1.67g of compound (1' -2-10) as a yellow solid (yield ：47％).¹H-NMR(400MHz,DMSO-d₆)δ9.62(br,1H),8.78(br,1H),8.05(d,J＝4.2Hz,1H),7.96(d,J＝15.6Hz,1H),7.51(d,J＝15.6Hz,1H),7.34(d,J＝4.2Hz,1H),7.12(s,1H),6.66(s,1H),2.10(s,3H).

[ Dihydroxy Compound example 9]

[ Chemical formula 182]

After 4-chloro-2, 5-dihydroxybenzaldehyde (2.59 g,15.0 mmol) and 2-acetyl-5-chlorothiophene (2.14 g,15.0 mmol) were dissolved in methanol (15 mL), 48% aqueous sodium hydroxide solution (4.5 mL,80.4 mmol) was added dropwise with ice water cooling. After the reaction system was stirred at room temperature for 4 hours, acetic acid (6.0 mL,105 mmol) was added with ice water cooling. To the resulting reaction mixture were added water (15 mL) and toluene (3.4 mL), followed by vigorous stirring. The resulting solid was taken out by filtration, and purified water (50 mL), dichloromethane: the mixture of methanol (10 mL, volume ratio: dichloromethane/methanol=50/1) was washed. The resulting solid was dried under vacuum at 50℃for 3 hours to give 1.85g of compound (1' -2-11) as a yellow solid (yield ：39％).¹H-NMR(400MHz,DMSO-d₆)δ9.95(br,1H),9.61(br,1H),8.11(d,J＝4.2Hz,1H),7.91(d,J＝15.7Hz,1H),7.63(d,J＝15.7Hz,1H),7.37(s,1H),7.36(d,J＝4.2Hz,1H),6.90(s,1H).

[ Dihydroxy Compound example 10]

[ Chemical formula 183]

2, 5-Dihydroxy terephthalaldehyde (1.29 g,7.74 mmol) and 2-acetyl-5-chlorothiophene (2.49 g,15.5 mmol) were dissolved in methanol (12 mL), and 48% aqueous sodium hydroxide solution (1.8 mL,32.1 mmol) was added dropwise with ice water cooling. After the reaction system was stirred at room temperature for 2.5 hours, acetic acid (3.1 mL,54.1 mmol) was added under ice-water cooling. To the resulting reaction mixture were added dichloromethane (6.5 mL) and water (22 mL), followed by vigorous stirring. The resulting solid was removed by filtration and washed with distilled water (50 mL) and methanol (6.0 mL). The resulting solid was dried under vacuum at 50℃for 3 hours to give 2.0g of compound (1' -7-2) as a red solid (yield ：57％).¹H-NMR(400MHz,DMSO-d₆)δ9.87(br,2H),8.11(d,J＝4.2Hz,2H),7.96(d,J＝15.6Hz,2H),7.66(d,J＝15.6Hz,2H),7.37(d,J＝4.2Hz,2H),7.30(s,2H).

[ Dihydroxy Compound example 11]

[ Chemical formula 184]

2, 5-Bis (methoxymethoxy) benzaldehyde (4.53 g,20.0 mmol) and 2-acetyl-1-methylpyrrole (2.35 mL,20.0 mmol) were dissolved in methanol (10 mL), and then 48% aqueous sodium hydroxide solution (6.1 mL,110 mmol) was added dropwise under ice water cooling. After stirring the reaction system at room temperature for 2 hours, the temperature was raised to 50℃and stirred for 2 hours. After completion of the reaction, methanol (90 mL) and 10% aqueous hydrochloric acid (50 mL) were added thereto under ice-water cooling, and the mixture was stirred at 50℃for 1 hour. The reaction solution was concentrated under reduced pressure, extracted with ethyl acetate (100 ml×3), and then the combined organic layers were washed with saturated brine (50 ml×3) and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the crude product obtained was washed with ethyl acetate (2.0 mL) and cold methanol (1.0 mL). The obtained solid was dried under vacuum at 50℃for 3 hours to give compound (1' -6-2) as a yellow solid (yield: 2.11g, yield ：43％).1H-NMR(400MHz,DMSO-d6)δ9.43(brs,1H),8.86(brs,1H),7.85(d,J＝15.8Hz,1H),7.50(d,J＝15.8Hz,1H),7.31(dd,J＝4.1,1.8Hz,1H),7.18(t,J＝1.8Hz,1H),7.13(d,J＝2.7Hz,1H),6.73(d,J＝8.7Hz,1H),6.69(dd,J＝8.7,2.7Hz,1H),6.18(dd,J＝4.1,2.5Hz,1H),3.94(s,3H).

[ Dihydroxy Compound example 12]

[ Chemical formula 185]

2, 5-Bis (methoxymethoxy) benzaldehyde (4.53 g,20.0 mmol) and 2-acetyl-1-ethylpyrrole (2.72 mL,20.0 mmol) were dissolved in methanol (10 mL), and then 48% aqueous sodium hydroxide solution (6.1 mL,110 mmol) was added dropwise under ice water cooling. After stirring the reaction system at room temperature for 2 hours, the temperature was raised to 50℃and stirred for 2 hours. After completion of the reaction, methanol (90 mL) and 10% aqueous hydrochloric acid (50 mL) were added thereto under ice-water cooling, and the mixture was stirred at 50℃for 1 hour. The reaction solution was concentrated under reduced pressure, extracted with ethyl acetate (100 ml×3), and then the combined organic layers were washed with saturated brine (50 ml×2) and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the crude product obtained was purified by distillation with hexane: the mixture of ethyl acetate (2.0 mL, capacity ratio: hexane/ethyl acetate=1/1) and cold methanol (1.0 mL) were washed. The obtained solid was dried under vacuum at 50℃for 3 hours to give Compound (1' -6-3) as a yellow solid (yield: 2.02g, yield ：39％).1H-NMR(400MHz,DMSO-d6)δ9.43(brs,1H),8.86(brs,1H),7.85(d,J＝15.7Hz,1H),7.51(d,J＝15.7Hz,1H),7.33(dd,J＝4.1,1.7Hz,1H),7.25(dd,J＝2.4,1.7Hz,1H),7.13(d,J＝2.8Hz,1H),6.73(d,J＝8.6Hz,1H),6.69(dd,J＝8.6,2.8Hz,1H),6.19(dd,J＝4.1,2.4Hz,1H),4.40(q,J＝7.1Hz,2H),1.29(t,J＝7.1Hz,3H).

Synthesis example 1

[ Chemical formula 186]

Thionyl chloride (15.5 mL) and DMF (250. Mu.L) were added to a solution of 2-chloro-4-methoxybenzoic acid (5.00 g,26.8 mmol) in toluene (25 mL) under argon, stirred at 100℃for 1 hour, and then excess thionyl chloride was distilled off under reduced pressure, and THF (45 mL) was added to the resulting residue. The solution was used in its entirety for the next reaction.

A solution of 4- (methylamino) phenol sulfate (4.61 g,13.4 mmol) in THF (45 mL) -water (45 mL) was cooled to 0deg.C, sodium bicarbonate (5.63 g,67.0 mmol) was added with stirring, and then a solution of the previously prepared acid chloride in THF was added dropwise over 5 minutes. The mixture was warmed to room temperature, stirred vigorously for 1.5 hours, then concentrated hydrochloric acid (10 mL) was added, and concentrated under reduced pressure. After removing the solid produced in the system by filtration, a crude solid was obtained by washing with water (200 mL). Purification by further reprecipitation (hexane: 50mL, ethyl acetate: 5mL, ethanol: 3 mL) gave 2-chloro-4' -hydroxy-4-methoxy-N-methylbenzamide as a white solid (yield: 6.42g, yield) ：82％).¹H-NMR(400MHz,DMSO-d₆):δ9.50(brs,1H),7.16(d,J＝8.6Hz,1H),6.99(d,J＝8.7Hz,2H),6.85(d,J＝2.4Hz,1H),6.73(dd,J＝8.6,2.4Hz,1H),6.56(d,J＝8.7Hz,2H),3.69(s,3H),3.28(s,3H).

A suspension of 2-chloro-4' -hydroxy-4-methoxy-N-methylbenzanilide (5.00 g,17.1 mmol) in methylene chloride (170 mL) was cooled to 0deg.C under argon, and then a 1M solution of boron tribromide in methylene chloride (68.4 mL,68.4 mmol) was added dropwise over 15 minutes. After the reaction system was warmed to room temperature, it was stirred for 13 hours and cooled again to 0 ℃. After ice (400 g) was added, stirring was performed at room temperature until the ice was dissolved. After methylene chloride was removed by distillation, the mixture was concentrated under reduced pressure and extracted with ethyl acetate (200 mL. Times.3). The resulting organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography (hexane: ethyl acetate=5:95), and dried under reduced pressure (120 ℃ C., vacuum pump) to give compound (2 "A-1-36-DH) as a white solid (yield: 3.67g, yield ：77％).¹H-NMR(400MHz,DMSO-d₆):δ10.4-9.15(br,2H),7.02(m,1H),6.95(d,J＝8.5Hz,2H),6.61(m,1H),6.56(d,J＝8.5Hz,2H),6.53(m,1H),3.27(s,3H).

Synthesis example 2

[ Chemical formula 187]

A mixture of 4-hydroxybenzoic acid (40.1 g,290 mmol), thionyl chloride (276 g,2.32 mol) and N, N-dimethylformamide (21.2 mg, 290. Mu. Mol) was stirred under reflux for 1 hour, and then excess thionyl chloride was removed by distillation to give 4-hydroxybenzoyl chloride. The obtained 4-hydroxybenzoyl chloride was prepared as a solution in THF (350 mL), and all was used in the next reaction.

Sodium bicarbonate (122 g,1.45 mol) was added over 5 minutes while stirring a mixture of p-methylaminophenol sulfate (50.0 g,290 mmol), water (350 mL), THF (350 mL) under a nitrogen atmosphere with ice-water cooling. Next, the THF solution of 4-hydroxybenzoyl chloride prepared above was added dropwise over 5 minutes. After the dropwise addition, the mixture was stirred for 15 hours while gradually warmed to room temperature, and then THF was distilled off under reduced pressure. The resulting solid was taken out by filtration, washed with water (1L), and then washed with 2M hydrochloric acid (600 mL) and acetonitrile (200 mL) to give Compound (2' A-1-1-DH) as a white solid (yield: 44.3g, yield: 62.7%) .¹H-NMR(400MHz,DMSO-d₆):δ9.97-9.22(br,2H),7.03(d,J＝8.7Hz,2H),6.86(d,J＝8.7Hz,2H),6.58(d,J＝8.7Hz,2H),6.50(d,J＝8.7Hz,2H),3.20(s,3H).

Synthesis example 3

[ Chemical formula 188]

A mixture of vanillic acid (5.0 g,29.7 mmol), thionyl chloride (28.3 g,238 mol) and N, N-dimethylformamide (2.17 mg, 29.7. Mu. Mol) was stirred under reflux for 1 hour, and then thionyl chloride was removed by distillation to give vanillyl chloride. The obtained vanillyl chloride was prepared as a solution in THF (35 mL), and all were used in the next reaction.

Sodium bicarbonate (12.5 g,149 mol) was added over 5 minutes while a mixture of p-methylaminophenol sulfate (5.12 g,29.7 mmol), water (35 mL), THF (35 mL) was stirred under ice-water cooling under nitrogen. Next, the above prepared solution of vanillyl chloride in THF was added dropwise over 5 minutes. After the dropwise addition, the mixture was stirred for 15 hours while gradually warmed to room temperature, and then THF was distilled off under reduced pressure. The resulting mixture was extracted with ethyl acetate (50 mL. Times.3), and the organic layer was washed with 2M hydrochloric acid (200 mL) and water (200 mL) and dried over anhydrous sodium sulfate. The obtained organic layer was concentrated under reduced pressure to obtain Compound (2 "A-1-6-DH) as a white solid (yield: 4.90g, yield ：60％).¹H-NMR(400MHz,DMSO-d₆):δ9.60-9.09(br,2H),6.90-6.84(m,2H),6.70-6.62(m,2H),6.60-6.54(m,2H),6.52(m,1H),3.51(s,3H),3.22(s,3H).

Synthesis example 4

[ Chemical formula 189]

After cooling 4' -hydroxyacetanilide (3.85 g,25.5 mmol) in ice-water under nitrogen, a 1mol/L solution of borane-THF complex in THF (100 mL,100 mmol) was slowly added. After the reaction system was warmed to room temperature, it was stirred at 60℃for 24 hours. After the reaction was completed, it was cooled in an ice bath, and methanol (21 mL) was added over 5 minutes. After water (100 mL) was added to the obtained reaction mixture, THF was distilled off by an evaporator, and extracted with methylene chloride (100 mL. Times.3). The resulting organic layer was dried over sodium sulfate and concentrated under reduced pressure. The obtained composition was purified by silica gel column chromatography (ethyl acetate/hexane=61/39 Vol%) to give 4-ethylaminophenol as a brown solid (yield: 2.07g, yield ：59％).¹H-NMR(400MHz,CDCl₃):δ6.69(d,J＝8.9Hz,2H),6.53(d,J＝8.9Hz,2H),4.60-3.20(br,2H),3.09(q,J＝7.2Hz,2H),1.22(t,J＝7.2Hz,3H).

A mixture of 4-hydroxybenzoic acid (2.01 g,29.7 mmol), thionyl chloride (13.9 g,117 mmol) and N, N-dimethylformamide (1.07 mg, 14.6. Mu. Mol) was stirred under reflux for 1 hour, and then thionyl chloride was removed by distillation to give 4-hydroxybenzoyl chloride. The obtained 4-hydroxybenzoyl chloride was prepared as a solution in THF (13 mL), and all of the solution was used in the next reaction.

Sodium bicarbonate (6.12 g,72.9 mmol) was added over 5 minutes while a mixture of 4-ethylaminophenol (2.00 g,14.6 mmol), water (13 mL), THF (13 mL) was stirred under ice-water cooling under nitrogen. Next, the THF solution of 4-hydroxybenzoyl chloride prepared above was added dropwise over 5 minutes. After the dropwise addition, the mixture was stirred for 15 hours while gradually warmed to room temperature, and then THF was distilled off under reduced pressure. The resulting mixture was extracted with ethyl acetate (50 mL. Times.3), and the organic layer was washed with 2N hydrochloric acid (100 mL. Times.2) and water (100 mL) and then dried over anhydrous sodium sulfate. The obtained organic layer was concentrated under reduced pressure to give Compound (2 "A-1-2-DH) as a white solid (yield: 1.99g, yield ：53％).¹H-NMR(400MHz,DMSO-d₆):δ8.85-10.12(2H),7.02(d,J＝8.7Hz,2H),6.83(d,J＝8.7Hz,2H),6.59(d,J＝8.7Hz,2H),6.49(d,J＝8.7Hz,2H),3.70(q,J＝7.2Hz,2H),1.01(t,J＝7.2Hz,3H).

Synthesis example 5

[ Chemical formula 190]

To a solution of piperidine pentamethylene dithiocarbamate (18.5 g,75 mmol) in NMP (40.5 mL) at 15℃was added slowly a solution of 1, 4-benzoquinone (16.2 g,150 mmol) in NMP (32.4 mL) -acetic acid (40.5 mL) with stirring. The reaction system was warmed to 50℃and stirred for 2 hours. After confirming that a solid was formed in the reaction system, the reaction system was cooled to room temperature, and acetone (100 mL) was added. The solid in the system was taken out by filtration, washed with a mixed solvent of acetone (50 mL) -acetic acid (50 mL), and dried under reduced pressure to obtain 10.2g of compound (6C) as a yellow solid (yield ：20.7％).¹H-NMR(400MHz,CD₃OD):δ6.83(s,2H),3.99-3.97(m,4H),1.98-1.92(m,7H),1.84-1.82(m,2H).

Synthesis example 6

[ Chemical formula 191]

Dimethyl malonate (1.5 g,11.3 mol) was added to a solution of the compound (6C) (3.7 g,11.3 mmol) obtained in Synthesis example 5 in DMF (15 mL) under nitrogen atmosphere at room temperature. The reaction system was warmed to 100 ℃ with stirring and stirring was continued for 6 hours. Then, after cooling the reaction system to room temperature, water (100 mL) was added. The mixture was extracted with ethyl acetate (100 mL. Times.2), and the combined organic layers were washed with 1N hydrochloric acid (100 mL) and saturated brine (50 mL). After drying the organic layer over sodium sulfate, a crude purified product was obtained by drying under reduced pressure. The crude product was purified by silica gel column chromatography (methanol: dichloromethane=3:97 to 4:96) to give 950mg of compound (6' -2-DH) as a pale brown solid (yield: 4%). ¹ H-NMR (400 MHz, DMSO-d 6): delta 10.09 (s, 2H), 6.70 (s, 2H), 3.77 (s, 6H).

Synthesis example 7

[ Chemical formula 192]

Diethyl malonate (1.2 g,7.40 mmol) was added to a solution of the compound (6C) (2.4 g,7.40 mmol) obtained in synthesis example 5 in DMF (24 mL) under nitrogen atmosphere at room temperature. The reaction system was warmed to 100 ℃ with stirring and stirring was continued for 6 hours. Then, after cooling the reaction system to room temperature, water (100 mL) was added. The mixture was extracted with ethyl acetate (100 mL. Times.2), and the combined organic layers were washed with 1N hydrochloric acid (100 mL) and saturated brine (50 mL). The organic layer was dried over sodium sulfate, and then dried under reduced pressure to obtain a crude purified product. The crude product was purified by silica gel column chromatography (methanol: dichloromethane=3:97 to 4:96) to give 470mg of compound (6' -3-DH) as a pale brown solid (yield: 18%). 1H-NMR (400 MHz, CDCl ₃): δ10.08 (s, 2H), 6.69 (s, 2H), 4.22 (q, J=7.2 Hz, 4H), 1.27 (t, J=7.2 Hz, 6H).

Synthesis example 8

[ Chemical formula 193]

To a solution of the compound (6C) (4.33 g,13.2 mmol) obtained in Synthesis example 5 in DMF (30 mL) was added ethyl cyanoacetate (1.5 g,13.2 mmol) at room temperature under nitrogen atmosphere. The reaction system was warmed to 100 ℃ with stirring and stirring was continued for 6 hours. Then, after cooling the reaction system to room temperature, water (100 mL) was added. The mixture was extracted with ethyl acetate (100 mL. Times.2), and the combined organic layers were washed with 1N hydrochloric acid (100 mL) and saturated brine (50 mL). After drying the organic layer over sodium sulfate, a crude purified product was obtained by drying under reduced pressure. The crude product was purified by silica gel column chromatography (methanol: dichloromethane=3:97 to 4:96) to give 950mg of compound (6' -5-DH) as pale brown solid (yield) ：24％).1H-NMR(400MHz,DMSO-d6):δ10.39(s,1H),10.34(s,1H),6.78(s,2H),4.25(q,J＝7.2Hz,2H),1.28(t,J＝7.2Hz,3H).

Synthesis example 9

[ Chemical formula 194]

To a solution of the compound (6C) (4.22 g,12.9 mmol) obtained in Synthesis example 5 in DMF (15 mL) was added methyl acetoacetate (1.5 g,12.9 mmol) at room temperature under nitrogen atmosphere. The reaction system was warmed to 100 ℃ with stirring and stirring was continued for 6 hours. Then, after cooling the reaction system to room temperature, water (100 mL) was added. The mixture was extracted with ethyl acetate (100 mL. Times.2), and the combined organic layers were washed with 1N hydrochloric acid (100 mL) and saturated brine (50 mL). After drying the organic layer over sodium sulfate, a crude purified product was obtained by drying under reduced pressure. The crude product was purified by silica gel column chromatography (methanol: dichloromethane=3:97 to 4:96) to give 940mg of compound (6' -7-DH) as pale brown solid (yield: 25%). 1H-NMR (400 MHz, DMSO-d 6): delta 10.14 (s, 1H), 10.12 (s, 1H), 6.74 (s, 2H), 3.85 (s, 3H), 2.50 (s, 3H).

Synthesis example 10

[ Chemical formula 195]

To a solution of the compound (6C) (4.89 g,14.9 mmol) obtained in Synthesis example 5 in DMF (30 mL) was added acetylacetone (1.5 g,14.9 mmol) at room temperature under nitrogen atmosphere. The reaction system was warmed to 100 ℃ with stirring and stirring was continued for 8 hours. Then, after cooling the reaction system to room temperature, water (100 mL) was added. The mixture was extracted with ethyl acetate (100 mL. Times.2), and the combined organic layers were washed with 1N hydrochloric acid (100 mL) and saturated brine (50 mL). After drying the organic layer over sodium sulfate, a crude purified product was obtained by drying under reduced pressure. The crude product was purified by silica gel column chromatography (methanol: dichloromethane=3:97 to 4:96) to give 940mg of compound (6' -6-DH) as a pale brown solid (yield: 22%). 1H-NMR (400 MHz, DMSO-d 6): delta 10.11 (s, 2H), 6.74 (s, 2H), 2.61 (s, 6H).

Synthesis example 11

[ Chemical formula 196]

A mixture of 4-acetoxybenzoic acid (7.56 g,42.0 mmol), thionyl chloride (24.0 mL,331 mmol) and N, N-dimethylformamide (catalyst amount) was boiled under reflux for 3 hours under argon. The volatile components were distilled off, and 4-acetoxybenzoyl chloride was obtained by azeotropy with toluene (3X 20 mL). The obtained 4-acetoxybenzoyl chloride was prepared into a tetrahydrofuran (50 mL) solution, and all was used in the next reaction.

Methyl hydrazine (1.05 mL,19.8 mmol) and triethylamine (8.40 mL,60.3 mmol) were dissolved in tetrahydrofuran (40 mL) under argon. Under ice water cooling, a tetrahydrofuran solution of 4-acetoxybenzoyl chloride prepared in advance was slowly added, warmed to room temperature and stirred overnight. The solvent was distilled off under reduced pressure, 1M hydrochloric acid (100 mL) was added, and the mixture was extracted with ethyl acetate (2X 100 mL). The combined organic layers were washed with saturated aqueous sodium hydrogencarbonate (100 mL) and saturated brine (100 mL) in this order, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was suspended in methanol (75 mL), and a solution of sodium hydroxide (4.13 g,103 mmol) in water (25 mL) was added thereto, followed by stirring at room temperature for 1 hour. The solvent was distilled off under reduced pressure, 2M hydrochloric acid (75 mL) was added, and extracted with ethyl acetate (2X 100 mL). The combined organic layers were washed successively with water (100 mL), saturated aqueous sodium bicarbonate (2X 100 mL) and saturated brine (100 mL), and then dried over anhydrous sodium sulfate. The precipitated solid was separated by filtration, and washed with ethyl acetate and water to give compound (2"C-2-2) as a white solid. The organic layer was separated from the filtrate, concentrated under reduced pressure, and the residue was purified by silica gel column chromatography, and the obtained solid was washed by slurry in diethyl ether (50 mL) to give compound (2"C-2-2) as a white solid. The total yield was 3.02g, and the yield was 53％.¹H-NMR(400MHz,DMSO-d₆):δ10.76(brs,1H),10.12(brs,1H),9.81(brs,1H),7.66-7.46(brm,2H),7.46-7.36(m,2H),6.82-6.73(m,2H),6.73-6.60(brm,2H),3.15(s,3H).

Synthesis example 12

[ Chemical formula 197]

A mixture of 4-hydroxybenzoic acid (2.49 g,18.0 mmol), toluene (18 mL), thionyl chloride (10.5 mL,145 mmol) and N, N-dimethylformamide (catalyst amount) was boiled under reflux for 1 hour under argon. The volatile components were distilled off, and 4-hydroxybenzoyl chloride was obtained by azeotropy with toluene (3X 15 mL). The obtained 4-hydroxybenzoyl chloride was prepared as a tetrahydrofuran (18 mL) solution, and all of the solution was used in the next reaction.

4- (Dodecylamino) phenol (4.16 g,15.0 mmol) and sodium bicarbonate (2.52 g,30.0 mmol) were suspended in a mixed solvent of tetrahydrofuran (17 mL)/water (17 mL) under argon. After slowly adding the tetrahydrofuran solution of the 4-hydroxybenzoyl chloride prepared in advance under ice water cooling, the temperature was raised to room temperature and stirred for 4 hours. The solvent was distilled off under reduced pressure, water (50 mL) was added to the residue, and the mixture was extracted with ethyl acetate (3X 50 mL). The combined organic layers were washed with saturated aqueous sodium hydrogencarbonate (80 mL), 2M hydrochloric acid (80 mL) and saturated brine (80 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was dissolved in methanol (50 mL), a solution of sodium hydroxide (1.21 g,30.3 mmol) in water (10 mL) was added, and after stirring at room temperature for 1 hour, it was concentrated under reduced pressure. To the residue was added water (35 mL), the pH was adjusted to 1 with concentrated hydrochloric acid, and the mixture was extracted with ethyl acetate (3X 50 mL). The combined organic layers were washed with saturated aqueous sodium bicarbonate (100 mL) and saturated brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. After purifying the residue by silica gel column chromatography, the obtained solid was slurry-washed in a mixed solvent of toluene (15 mL)/hexane (15 mL) to obtain compound (1-1-104-DH) as an off-white solid (yield: 4.74g, yield) ：80％).1H-NMR(400MHz,DMSO-d₆):δ9.69(brs,1H),9.47(brs,1H),7.10-7.00(m,2H),6.92-6.80(m,2H),6.68-6.58(m,2H),6.58-6.48(m,2H),3.69(t,J＝7.5Hz,2H),1.53-1.36(m,2H),1.34-1.12(m,18H),0.85(t,J＝6.8Hz,3H).

Synthesis example 13

[ Chemical formula 198]

A mixture of monomethyl terephthalate (9.19 g,50.0 mmol), thionyl chloride (59.53 g,0.50 mol) and toluene (50 mL) was stirred under reflux for 1 hour, and then thionyl chloride was distilled off to give methyl 4- (chloroformyl) benzoate. The obtained methyl 4- (chloroformyl) benzoate was prepared into a THF (50 mL) solution, and all of the solution was used in the next reaction.

A mixed solution of p-methylaminophenol sulfate (8.44 g,24.5 mmol), sodium bicarbonate (12.60 g,0.15 mol), THF (50 mL), and water (50 mL) was cooled to 0deg.C, and a THF (50 mL) solution of methyl 4- (chloroformyl) benzoate prepared in advance was added dropwise over 15 minutes, and then the mixture was warmed to room temperature and stirred vigorously for 12 hours. After completion of the reaction, the solvent was concentrated under reduced pressure, and the solid produced in the system was taken out by filtration, and then washed with a saturated aqueous sodium carbonate solution (50 mL) and water (50 mL) to obtain a white crude solid (crude yield: 13.53g, crude yield: 97%).

To the crude solid obtained was added methanol (50 mL), 48% aqueous sodium hydroxide solution (6.0 mL,0.11 mol) and stirred at room temperature for 4 hours. After completion of the reaction, water (50 mL) was added, and the insoluble matter was separated by filtration. After adding concentrated hydrochloric acid to the filtrate to ph=2, the resulting solid was removed by filtration and reprecipitated from ethyl acetate/hexane to give compound (2 "a-1-1-CH) as a white solid (yield: 11.67g, overall yield) ：83％).¹H-NMR(400MHz,(DMSO-d₆:δ13.01(brs,1H),9.53(s,1H),7.74(d,J＝7.3Hz,2H),7.32(d,J＝7.3Hz,2H),6.96(d,J＝7.8Hz,2H),6.60(d,J＝7.8Hz,2H),3.31(s,3H).

Synthesis example 14

[ Chemical formula 199]

A mixed solution of 4- (ethylamino) phenol (4.84 g,25.0 mmol), sodium bicarbonate (4.21 g,50.1 mmol), THF (30 mL) and water (60 mL) was cooled to 0deg.C, and a solution of methyl 4- (chloroformyl) benzoate (5.24 g,25.1 mmol) in THF (30 mL) was added dropwise over 15 minutes, and then the mixture was warmed to room temperature and stirred vigorously for 12 hours. After completion of the reaction, the solvent was concentrated under reduced pressure, and the solid produced in the system was taken out by filtration, and then washed with a saturated aqueous sodium carbonate solution (50 mL) and water (50 mL) to obtain a brown crude solid (crude yield 7.93g, crude yield 89%).

Methanol (80 mL) and water (80 mL) were added to the crude solid, and after cooling to 0deg.C, 48% aqueous sodium hydroxide (4.0 mL,72.3 mmol) was added, and the reaction system was warmed to room temperature and heated to reflux for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, and then concentrated under reduced pressure. After adding concentrated hydrochloric acid to the residue to ph=2, the resulting solid was taken out by filtration and dried under reduced pressure to give compound (2 "a-1-2-CH) as a brown solid (yield: 6.93g, overall yield) 97％).1H-NMR(400MHz,DMSO-d₆):δ12.99(brs,1H),9.52(s,1H),7.73(d,J＝7.8Hz,2H),7.31(d,J＝7.8Hz,2H),6.92(d,J＝8.2Hz,2H),6.60(d,J＝8.2Hz,2H),3.80(q,J＝7.0Hz,2H),1.09(t,J＝7.0Hz,3H).

Synthesis example 15

[ Chemical formula 200]

A mixed solution of 3-methyl-4- (methylamino) phenol (2.06 g,15.0 mmol), sodium bicarbonate (2.52 g,30.0 mol), THF (30 mL) and water (15 mL) was cooled to 0℃and a solution of methyl 4- (chloroformyl) benzoate in THF (15 mL) was added dropwise over 15 minutes, then the temperature was raised to room temperature and stirred vigorously for 12 hours. After the reaction was completed, the solvent was concentrated under reduced pressure, and extracted with ethyl acetate (50 ml×3). The combined organic phases were washed with saturated aqueous sodium carbonate (50 mL) and saturated brine (50 mL), dehydrated over magnesium sulfate, and concentrated under reduced pressure to give a white crude solid (crude yield: 3.76g, crude yield: 84%).

To the crude solid obtained were added methanol (40 mL) and water (40 mL), and 48% aqueous sodium hydroxide solution (3.2 mL,57.9 mmol) was added, and the mixture was stirred at room temperature for 12 hours and at a heating reflux for 1 hour. After the reaction was completed, it was concentrated under reduced pressure. After adding concentrated hydrochloric acid to the residue to ph=2, the resulting solid was removed by filtration and reprecipitated from ethyl acetate/hexane to give compound (2 "a-1-46-CH) as a white solid (yield: 3.49g, overall yield) ：82％).¹H-NMR(400MHz,DMSO-d₆):δ13.05(brs,1H),9.45(s,1H),7.73(d,J＝8.5Hz,2H),7.31(d,J＝8.5Hz,2H),6.99(d,J＝8.4Hz,1H),6.49(d,J＝2.8Hz,1H),6.46(dd,J＝8.4,2.8Hz,1H),3.21(s,3H),2.05(s,3H).

Synthesis example 16

[ Chemical formula 201]

A mixed solution of 4- (ethylamino) -3-methylphenol (3.02 g,20.0 mmol), sodium bicarbonate (3.36 g,40.0 mol), THF (40 mL) and water (20 mL) was cooled to 0deg.C, and a solution of methyl 4- (chloroformyl) benzoate in THF (20 mL) was added dropwise over 15 minutes, then the mixture was warmed to room temperature and stirred vigorously for 12 hours. After the reaction was completed, the solvent was concentrated under reduced pressure, and extracted with ethyl acetate (50 ml×3). The combined organic phases were washed with saturated aqueous sodium carbonate (50 mL) and saturated brine (50 mL), dehydrated over magnesium sulfate and concentrated under reduced pressure to give a brown crude solid (crude yield: 23.5 g).

To the crude solid obtained was added methanol (50 mL), 48% aqueous sodium hydroxide solution (2.5 mL,45.2 mmol) and stirred at room temperature for 12 hours. After completion of the reaction, water (50 mL) was added, and concentrated under reduced pressure. After adding concentrated hydrochloric acid to the residue to ph=2, the resulting solid was removed by filtration to give compound (2 "a-1-47-CH) as a white solid (yield: 3.65g, overall yield) ：61％).¹H-NMR(400MHz,DMSO-d₆):δ13.04(brs,1H),9.45(s,1H),7.72(d,J＝8.5Hz,2H),7.30(d,J＝8.5Hz,2H),6.95(d,J＝8.4Hz,1H),6.49(d,J＝7.8Hz,1H),6.48(dd,J＝7.8,2.7Hz,1H),3.99(dq,J＝14.0,7.0Hz,1H),3.42(dq,J＝14.0,7.0Hz,1H),2.03(s,3H).

Synthesis example 17

[ Chemical formula 202]

A mixture of 4-hydroxybenzoic acid (3.63 g,26.3 mmol), thionyl chloride (24.60 g,0.207 mol) and N, N-dimethylformamide (3.0 mg) was stirred under reflux for 1 hour, and then thionyl chloride was removed by distillation to give 4-hydroxybenzoyl chloride. The obtained 4-hydroxybenzoyl chloride was prepared as a solution in THF (50 mL), and all was used in the next reaction.

Sodium bicarbonate (4.20 g,50.0 mmol) was added to a mixture of ethyl 4- (methylamino) benzoate (4.13 g,25.0 mmol), water (50 mL), and THF (50 mL) under nitrogen with stirring under ice-water cooling. Next, a THF solution of 4-hydroxybenzoyl chloride prepared in advance was added dropwise over 5 minutes. After the dropwise addition, the mixture was stirred for 12 hours while gradually warming to room temperature, and then THF was distilled off under reduced pressure. The resulting solid was taken out by filtration, washed with saturated aqueous sodium hydrogencarbonate (50 mL) and water (50 mL), and dried under reduced pressure to give a white crude solid (crude yield: 7.12 g).

To the crude solid obtained was added methanol (85 mL), 48% aqueous sodium hydroxide solution (2.8 mL,50.0 mmol) and stirred at room temperature for 12 hours. After completion of the reaction, water (50 mL) was added, and the insoluble matter was separated by filtration. After adding concentrated hydrochloric acid to the obtained filtrate to ph=2, the resulting solid was removed by filtration to give compound (2 "a-1-1-HC) as a white solid (yield: 5.40g, overall yield) ：80％).¹H-NMR(400MHz,DMSO-d₆):δ12.94(brs,1H),9.86(s,1H),7.81(d,J＝8.6Hz,2H),7.21(d,J＝8.6Hz,2H),7.11(d,J＝8.7Hz,2H),6.58(d,J＝8.7Hz,2H),3.38(s,3H).

Synthesis example 18

[ Chemical formula 203]

A mixed solution of ethyl 4- (ethylamino) benzoate (13.6 g,70.4 mmol), sodium bicarbonate (11.8 g,0.14 mol), THF (85 mL) and water (170 mL) was cooled to 0deg.C, and a solution of 4-methoxybenzoyl chloride (12.0 g,70.3 mmol) in THF (85 mL) was added dropwise over 30 minutes, and then the mixture was warmed to room temperature and stirred vigorously for 12 hours. After the reaction was completed, the solvent was concentrated under reduced pressure, and extracted with ethyl acetate (50 ml×3). The combined organic phases were washed with saturated aqueous sodium carbonate (50 mL) and saturated brine (50 mL), dehydrated over magnesium sulfate and concentrated under reduced pressure to give a brown crude solid (crude yield: 23.5 g).

After cooling the resulting solution of crude solid in dichloromethane (30 mL) to 0deg.C, a solution of boron tribromide (19.6 mL,0.21 mmol) in dichloromethane (40 mL) was added dropwise over 30 minutes. After the reaction system was warmed to room temperature, it was stirred for 12 hours and cooled again to 0 ℃. After 2M hydrochloric acid (100 mL) was slowly added, the solvent was distilled off by concentration under reduced pressure, and the resultant solid was taken out by filtration and washed with acetonitrile (50 mL). The resulting solid was dried under reduced pressure. On the other hand, the filtrate was extracted with ethyl acetate (100 mL. Times.3). The combined organic layers were dried over anhydrous magnesium sulfate and concentrated under reduced pressure.

The resulting residue was washed with cold acetonitrile (50 mL), and dried under reduced pressure to give Compound (2' A-1-2-HC) as a white solid (yield: 9.86g, yield) 49％).1H-NMR(400MHz,DMSO-d₆):δ12.96(brs,1H),9.84(s,1H),7.81(d,J＝8.7Hz,2H),7.18(d,J＝8.7Hz,2H),7.10(d,J＝8.7Hz,2H),6.56(d,J＝8.7Hz,2H),3.89(q,J＝7.0Hz,2H),1.09(t,J＝7.0Hz,3H).

Synthesis example 19

[ Chemical formula 204]

A mixed solution of methyl 3-methyl-4- (methylamino) benzoate (2.15 g,12.0 mmol), triethylamine (3.03 mL,23.9 mmol) and methylene chloride (40 mL) was cooled to 0℃and a solution of 4-methoxybenzoyl chloride (2.17 g,12.6 mmol) in methylene chloride (15 mL) was added dropwise over 15 minutes, and the mixture was warmed to room temperature and stirred for 8 hours. After completion of the reaction, water (20 mL) was added thereto, and the mixture was extracted with chloroform (50 mL. Times.3). The combined organic layers were dehydrated with magnesium sulfate and concentrated under reduced pressure to give a white crude solid (crude yield: 3.02 g).

After cooling the resulting solution of crude solid in dichloromethane (30 mL) to 0deg.C, a solution of boron tribromide in dichloromethane (3.50 mL,6.4 mmol) was added dropwise over 15 minutes. After the reaction system was warmed to room temperature, it was stirred for 12 hours and cooled again to 0 ℃. After 2M hydrochloric acid (10 mL) was slowly added, the solvent was distilled off by concentration under reduced pressure, and the resultant solid was taken out by filtration and washed with acetonitrile (50 mL). The obtained solid was dried under reduced pressure to give Compound (2 "A-1-46-HC) as a white solid (yield: 2.34g, overall yield ：69％).1H-NMR(400MHz,DMSO-d₆):δ12.98(brs,1H),9.81(s,1H),7.77(s,1H),7.69(d,J＝7.1Hz,1H),7.26(d,J＝7.1Hz,1H),7.67(d,J＝7.3Hz,2H),6.54(d,J＝7.3Hz,2H),3.22(s,3H),2.17(s,3H).

Example 1

[ Chemical formula 205]

A reaction vessel was charged with a solution of the compound (2 "A-1-36-DH) (333 mg,1.20 mmol) obtained in Synthesis example 1 and the compound (1' -2-1) (197mg, 0.800 mmol) obtained in dihydroxyl compound example 1 as diol monomers, and then a solution of sodium hydroxide (160 mg,4.00 mmol) in water (19.2 mL) and a 2wt% aqueous solution of tetrabutylammonium bromide (0.8 mL) under nitrogen flow, followed by stirring. Further, trans-1, 4-cyclohexanedicarboxylic acid dichloride (418 mg,2.00 mmol) as a dicarboxylic acid dichloride monomer was dissolved in chloroform (20 mL), and the solution was added to the reaction system. After the reaction system was stirred for 3 hours, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (100 mL) and water (100 mL), and dried in vacuo to give 583mg of polymer 1 (yield: 73%).

Examples 1 to 1

6.0 Mass% of polymer 1 was dissolved in 94.0 mass% of 1, 3-hexafluoroisopropanol. After casting it on a quartz glass substrate, it was spin-coated and dried in an oven at 60 ℃ for 30 minutes to obtain a thin film. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Example 2

[ Chemical formula 206]

407Mg of polymer 2 (yield: 52%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-36-DH) (222 mg,0.800 mmol) obtained in Synthesis example 1 and the compound (1' -2-1) (298 mg,1.20 mmol) obtained in dihydroxy compound example 1 were used as diol monomers.

Examples 2 to 1

A film was obtained in the same manner as in example 1-1, except that polymer 2 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 2 to 2

A film was obtained in the same manner as in example 1-1, except that polymer 2 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 2 to 3

A film was obtained in the same manner as in example 1-1, except that polymer 2 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 100mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 2 to 4

A film was obtained in the same manner as in example 1-1, except that polymer 2 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Example 3

[ Chemical formula 207]

527Mg of polymer 3 (yield: 68%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-36-DH) (111 mg,0.400 mmol) obtained in Synthesis example 1 and the compound (1' -2-1) (390 mg,1.60 mmol) obtained in dihydroxyl compound example 1 were used as diol monomers.

Examples 3 to 1

A film was obtained in the same manner as in example 1-1, except that polymer 3 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 3 to 2

A film was obtained in the same manner as in example 1-1, except that polymer 3 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Example 4

[ Chemical formula 208]

191Mg of Polymer 4 (yield: 24%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-36-DH) (333 mg,1.20 mmol) obtained in Synthesis example 1, the compound (1 '-2-1) (98.4 mg,0.400 mmol) obtained in dihydroxyl compound example 1 and the compound (6' -1-DH) (99.2 mg,0.400 mmol) were used as diol monomers.

Examples 4 to 1

A film was obtained in the same manner as in example 1-1, except that polymer 4 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 4 to 2

A film was obtained in the same manner as in example 1-1, except that polymer 4 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 4 to 3

A film was obtained in the same manner as in example 1-1, except that polymer 4 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 4 to 4

A film was obtained in the same manner as in example 1-1, except that polymer 4 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Example 5

[ Chemical formula 209]

191Mg of Polymer 5 (yield: 42%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-1-DH) (292 mg,1.20 mmol) obtained in Synthesis example 2, the compound (1 '-2-1) (98.4 mg,0.400 mmol) obtained in dihydroxyl compound example 1 and the compound (6' -1-DH) (99.2 mg,0.400 mmol) were used as diol monomers.

Examples 5 to 1

A film was obtained in the same manner as in example 1-1, except that polymer 5 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 5 to 2

A film was obtained in the same manner as in example 1-1, except that polymer 5 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 5 to 3

A film was obtained in the same manner as in example 1-1, except that polymer 5 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 5 to 4

A film was obtained in the same manner as in example 1-1, except that polymer 5 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Example 6

[ Chemical formula 210]

562Mg of polymer 6 (yield: 71%) was obtained in the same manner as in example 1, except that the compound (2 "A-1-1-DH) (292 mg,1.20 mmol) obtained in Synthesis example 2, the compound (1 '-2-1) (98.4 mg,0.400 mmol) obtained in dihydroxyl compound example 1 and the compound (6' -2-DH) (126 mg,0.400 mmol) obtained in Synthesis example 6 were used as diol monomers.

Examples 6 to 1

A film was obtained in the same manner as in example 1-1, except that polymer 6 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 6 to 2

A film was obtained in the same manner as in example 1-1, except that polymer 6 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 6 to 3

A film was obtained in the same manner as in example 1-1, except that polymer 6 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 6 to 4

A film was obtained in the same manner as in example 1-1, except that polymer 6 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Example 7

[ Chemical formula 211]

Polymer 7 (yield: 57%) was obtained in 457mg in the same manner as in example 1 except that the compound (2 "A-1-1-DH) (292 mg,1.20 mmol) obtained in Synthesis example 2, the compound (1 '-2-1) (98.4 mg,0.400 mmol) obtained in dihydroxyl compound example 1 and the compound (6' -3-DH) (137 mg,0.400 mmol) obtained in Synthesis example 7 were used as diol monomers.

Examples 7 to 1

A film was obtained in the same manner as in example 1-1, except that polymer 7 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 7 to 2

A film was obtained in the same manner as in example 1-1, except that polymer 7 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 7 to 3

A film was obtained in the same manner as in example 1-1, except that polymer 7 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 7 to 4

A film was obtained in the same manner as in example 1-1, except that polymer 7 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Example 8

[ Chemical formula 212]

340Mg of polymer 8 (yield: 44%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-1-DH) (292 mg,1.20 mmol) obtained in Synthesis example 2, the compound (1 '-2-1) (98.4 mg,0.400 mmol) obtained in dihydroxyl compound example 1 and the compound (6' -5-DH) (118 mg,0.400 mmol) obtained in Synthesis example 8 were used as diol monomers.

Examples 8 to 1

A film was obtained in the same manner as in example 1-1, except that polymer 8 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 8 to 2

A film was obtained in the same manner as in example 1-1, except that polymer 8 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 8 to 3

A film was obtained in the same manner as in example 1-1, except that polymer 8 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 8 to 4

A film was obtained in the same manner as in example 1-1, except that polymer 8 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Example 9

[ Chemical formula 213]

531Mg of polymer 9 (yield: 68%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-1-DH) (292 mg,1.20 mmol) obtained in Synthesis example 2, the dihydroxy compound (1 '-2-1) (98.4 mg,0.400 mmol) obtained in example 1 and the compound (6' -7-DH) (119 mg,0.400 mmol) obtained in Synthesis example 9 were used as diol monomers.

Examples 9 to 1

A film was obtained in the same manner as in example 1-1, except that polymer 9 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 9 to 2

A film was obtained in the same manner as in example 1-1, except that polymer 9 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 9 to 3

A film was obtained in the same manner as in example 1-1, except that polymer 9 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 9 to 4

A film was obtained in the same manner as in example 1-1, except that polymer 9 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Example 10

[ Chemical formula 214]

658Mg of a polymer 10 (yield: 85%) was obtained in the same manner as in example 1, except that the compound (2 "A-1-1-DH) (292 mg,1.20 mmol) obtained in Synthesis example 2, the compound (1 '-2-1) (98.4 mg,0.400 mmol) obtained in dihydroxyl compound example 1 and the compound (6' -6-DH) (113 mg,0.400 mmol) obtained in Synthesis example 10 were used as diol monomers.

Example 10-1

A film was obtained in the same manner as in example 1-1, except that polymer 10 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Example 10-2

A film was obtained in the same manner as in example 1-1, except that polymer 10 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 10 to 3

A film was obtained in the same manner as in example 1-1, except that polymer 10 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Example 11

[ Chemical formula 215]

354Mg of polymer 11 (yield: 43%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-36-DH) (444 mg,1.60 mmol) obtained in Synthesis example 1 and the compound (1' -2-2) (112 mg,0.400 mmol) obtained in dihydroxyl compound example 2 were used as diol monomers.

Example 11-1

A film was obtained in the same manner as in example 1-1, except that polymer 11 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 100mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 11 to 2

A film was obtained in the same manner as in example 1-1, except that polymer 11 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Example 12

[ Chemical formula 216]

565Mg of Polymer 12 (yield: 68%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-36-DH) (333 mg,1.60 mmol) obtained in Synthesis example 1 and the compound (1' -2-2) (224 mg,0.800 mmol) obtained in dihydroxy compound example 2 were used as diol monomers.

Example 12-1

A film was obtained in the same manner as in example 1-1, except that the polymer 12 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 12 to 2

A film was obtained in the same manner as in example 1-1, except that the polymer 12 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 12 to 3

A film was obtained in the same manner as in example 1-1, except that the polymer 12 was used in place of the polymer 1. The resulting film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 313nm at 170mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 12 to 4

A film was obtained in the same manner as in example 1-1, except that the polymer 12 was used in place of the polymer 1. The resulting film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 313nm at 170mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 12 to 5

A film was obtained in the same manner as in example 1-1, except that the polymer 12 was used in place of the polymer 1. The resulting film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 313nm at 340mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 12 to 6

A film was obtained in the same manner as in example 1-1, except that the polymer 12 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 365nm at 700mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 12 to 7

A film was obtained in the same manner as in example 1-1, except that the polymer 12 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light 1400mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Example 13

[ Chemical formula 217]

463Mg of polymer 13 (yield: 56%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-36-DH) (222 mg,0.800 mmol) obtained in Synthesis example 1 and the compound (1' -2-2) (337 mg,1.20 mmol) obtained in dihydroxyl compound example 2 were used as diol monomers.

Example 13-1

A film was obtained in the same manner as in example 1-1, except that polymer 13 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 50mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 13 to 2

A film was obtained in the same manner as in example 1-1, except that polymer 13 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 50mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 13 to 3

A film was obtained in the same manner as in example 1-1, except that polymer 13 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 13 to 4

A film was obtained in the same manner as in example 1-1, except that polymer 13 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 13 to 5

A film was obtained in the same manner as in example 1-1, except that polymer 13 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 13 to 6

A film was obtained in the same manner as in example 1-1, except that polymer 13 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 13 to 7

A film was obtained in the same manner as in example 1-1, except that polymer 13 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 13 to 8

A film was obtained in the same manner as in example 1-1, except that polymer 13 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 13 to 9

A film was obtained in the same manner as in example 1-1, except that polymer 13 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Examples 13 to 10

A film was obtained in the same manner as in example 1-1, except that polymer 13 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 1.

Example 14

[ Chemical formula 218]

595Mg of Polymer 14 (yield: 72%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-36-DH) (111 mg,0.400 mmol) obtained in Synthesis example 1 and the compound (1' -2-2) (449 mg,1.60 mmol) obtained in dihydroxyl compound example 2 were used as diol monomers.

Example 14-1

A film was obtained in the same manner as in example 1-1, except that polymer 14 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 14-2

A film was obtained in the same manner as in example 1-1, except that polymer 14 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 14 to 3

A film was obtained in the same manner as in example 1-1, except that polymer 14 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 14 to 4

A film was obtained in the same manner as in example 1-1, except that polymer 14 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 15

[ Chemical formula 219]

343Mg of Polymer 15 (yield: 41%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-6-DH) (219 mg,0.800 mmol) obtained in Synthesis example 3 and the compound (1' -2-2) (337 mg,1.20 mmol) obtained in dihydroxy compound example 2 were used as diol monomers.

Example 15-1

A film was obtained in the same manner as in example 1-1, except that the polymer 15 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 15 to 2

A film was obtained in the same manner as in example 1-1, except that the polymer 15 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 15 to 3

A film was obtained in the same manner as in example 1-1, except that the polymer 15 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 15 to 4

A film was obtained in the same manner as in example 1-1, except that the polymer 15 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 16

[ Chemical formula 220]

To a reaction vessel, 2 "A-1-1-DH" (212 mg,0.871 mmol) as diol monomer, 1' -2-2 (571 mg,2.03 mmol) as dihydroxy compound example 2, and trans-1, 4-cyclohexanedicarboxylic acid (400 mg,2.32 mmol) as dicarboxylic acid monomer, and 2"-2-1-DC (251 mg,0.581 mmol) were added, and after that, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (1.23 g,6.39 mmol) as condensing agent, NMP (11.2 mL) as solvent, and 4-dimethylaminopyridine (78.1 mg,0.639 mmol) as catalyst were added, stirring was started. After the reaction system was stirred for 3 hours, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (100 mL) and water (100 mL), and dried in vacuo to give 455mg of polymer 16 (yield: 34%).

Example 16-1

A film was obtained in the same manner as in example 1-1, except that the polymer 16 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 16-2

A film was obtained in the same manner as in example 1-1, except that the polymer 16 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 16 to 3

A film was obtained in the same manner as in example 1-1, except that the polymer 16 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 16 to 4

A film was obtained in the same manner as in example 1-1, except that the polymer 16 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 17

[ Chemical formula 221]

In the same manner as in example 16 except for using the compound (2 "A-1-2-DH) (299 mg,1.16 mmol) obtained in Synthesis example 4 as a diol monomer, the compound (1' -2-2) (489 mg,1.74 mmol) obtained in dihydroxy compound example 2 and trans-1, 4-cyclohexanedicarboxylic acid (500 mg,2.90 mmol) as a dicarboxylic acid monomer, 511mg of polymer 17 (yield: 43%) was obtained.

Example 17-1

A film was obtained in the same manner as in example 1-1, except that polymer 17 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 17-2

A film was obtained in the same manner as in example 1-1, except that polymer 17 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 17 to 3

A film was obtained in the same manner as in example 1-1, except that polymer 17 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 17 to 4

A film was obtained in the same manner as in example 1-1, except that polymer 17 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 18

[ Chemical formula 222]

987Mg of polymer 18 (yield: 83%) was obtained in the same manner as in example 16 except that the compound (2 "A-1-2-DH) (149 mg,0.581 mmol) obtained in Synthesis example 4, the compound (1' -2-2) (652 mg,2.32 mmol) obtained in dihydroxy compound example 2, trans-1, 4-cyclohexanedicarboxylic acid (500 mg,2.90 mmol) as a dicarboxylic acid monomer and NMP (5.2 mL) as a solvent were used as diol monomers.

Example 18-1

A film was obtained in the same manner as in example 1-1, except that the polymer 18 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 18-2

A film was obtained in the same manner as in example 1-1, except that the polymer 18 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 500mJ/cm ² at 365nm and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 19

[ Chemical formula 223]

414Mg of polymer 19 (yield: 35%) was obtained in the same manner as in example 16 except that the compound (2 "A-1-1-DH) (141 mg,581 mmol) obtained in Synthesis example 2, the compound (1' -2-2) (652 mg,2.32 mmol) obtained in dihydroxyl compound example 2, trans-1, 4-cyclohexanedicarboxylic acid (500 mg,2.90 mmol) as a dicarboxylic acid monomer and NMP (29 mL) as a solvent were used as diol monomers.

Example 19-1

A film was obtained in the same manner as in example 1-1, except that polymer 19 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light (50 mJ/cm ²) and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 19-2

A film was obtained in the same manner as in example 1-1, except that polymer 19 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 19 to 3

A film was obtained in the same manner as in example 1-1, except that polymer 19 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light (50 mJ/cm ²) and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 19 to 4

A film was obtained in the same manner as in example 1-1, except that polymer 19 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 20

[ Chemical formula 224]

510Mg of a polymer 20 (yield: 65%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-1-DH) (195 mg,0.800 mmol) obtained in Synthesis example 2, the compound (1 '-2-1) (197mg, 0.800 mmol) obtained in dihydroxyl compound example 1 and the compound (6' -5-DH) (118 mg,0.400 mmol) obtained in Synthesis example 8 were used as diol monomers.

Example 20-1

A film was obtained in the same manner as in example 1-1, except that the polymer 20 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 20 to 2

A film was obtained in the same manner as in example 1-1, except that the polymer 20 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 21

[ Chemical formula 225]

588Mg of polymer 21 (yield: 68%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-36-DH) (333 mg,1.20 mmol) obtained in Synthesis example 1 and the compound (1' -2-3) (260 mg,0.800 mmol) obtained in dihydroxy compound example 3 were used as diol monomers.

Example 21-1

A film was obtained in the same manner as in example 1-1, except that polymer 21 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 22

[ Chemical formula 226]

621Mg of polymer 22 (yield: 70%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-36-DH) (222 mg,0.800 mmol) obtained in Synthesis example 1 and the compound (1' -2-3) (390 mg,1.20 mmol) obtained in dihydroxy compound example 3 were used as diol monomers.

Example 22-1

A film was obtained in the same manner as in example 1-1, except that the polymer 22 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 22-2

A film was obtained in the same manner as in example 1-1, except that the polymer 22 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 22 to 3

A film was obtained in the same manner as in example 1-1, except that the polymer 22 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 22 to 4

A film was obtained in the same manner as in example 1-1, except that the polymer 22 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 22 to 5

A film was obtained in the same manner as in example 1-1, except that the polymer 22 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 22 to 6

A film was obtained in the same manner as in example 1-1, except that the polymer 22 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 23

[ Chemical formula 227]

In the same manner as in example 1 except that the compound (2 "A-1-36-DH) (222 mg,0.800 mmol) obtained in Synthesis example 1 and the compound (1' -2-5) (331 mg,1.20 mmol) obtained in dihydroxy compound example 4 were used as diol monomers, 523mg of polymer 23 (yield: 63%) was obtained.

Example 23-1

A film was obtained in the same manner as in example 1-1, except that polymer 23 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 23-2

A film was obtained in the same manner as in example 1-1, except that polymer 23 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 23 to 3

A film was obtained in the same manner as in example 1-1, except that polymer 23 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 23 to 4

A film was obtained in the same manner as in example 1-1, except that polymer 23 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 24

[ Chemical formula 228]

690Mg of Polymer 24 (yield: 84%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-36-DH) (333 mg,1.20 mmol) obtained in Synthesis example 1 and the compound (1' -2-5) (221 mg,0.800 mmol) obtained in dihydroxy compound example 4 were used as diol monomers.

Example 24-1

A film was obtained in the same manner as in example 1-1, except that the polymer 24 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 24-2

A film was obtained in the same manner as in example 1-1, except that the polymer 24 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 24 to 3

A film was obtained in the same manner as in example 1-1, except that the polymer 24 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 24 to 4

A film was obtained in the same manner as in example 1-1, except that the polymer 24 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 25

[ Chemical formula 229]

512Mg of polymer 25 (yield: 65%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-1-DH) (292 mg,1.20 mmol) obtained in Synthesis example 2 and the compound (1' -2-5) (221 mg,0.800 mmol) obtained in dihydroxyl compound example 4 were used as diol monomers.

Example 25-1

A film was obtained in the same manner as in example 1-1, except that the polymer 25 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 25 to 2

A film was obtained in the same manner as in example 1-1, except that the polymer 25 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 25 to 3

A film was obtained in the same manner as in example 1-1, except that the polymer 25 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Examples 25 to 4

A film was obtained in the same manner as in example 1-1, except that the polymer 25 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 26

[ Chemical formula 230]

In the same manner as in example 1 except that the compound (2 "A-1-36-DH) (222 mg,0.800 mmol) obtained in Synthesis example 1 and the compound (1' -2-6) (312 mg,1.20 mmol) obtained in dihydroxy compound example 5 were used as diol monomers, 523mg of polymer 26 (yield: 65%) was obtained.

Example 26-1

A film was obtained in the same manner as in example 1-1, except that the polymer 26 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 26-2

A film was obtained in the same manner as in example 1-1, except that the polymer 26 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 27

[ Chemical formula 231]

445Mg of polymer 27 (yield: 56%) was obtained in the same manner as in example 1 except that the compound (2 "A-1-36-DH) (333 mg,1.20 mmol) obtained in Synthesis example 1 and the compound (1' -2-6-Furan) (195 mg,0.800 mmol) obtained in dihydroxy compound example 6 were used as diol monomers.

Example 27-1

A film was obtained in the same manner as in example 1-1, except that polymer 27 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 27-2

A film was obtained in the same manner as in example 1-1, except that polymer 27 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with polarized ultraviolet light of 248nm at 1000mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 2.

Example 28

[ Chemical formula 232]

To the reaction vessel, compound (2"D-1) (281mg, 2.03 mmol) as a diol monomer, compound (1' -2-2) (1.06 g,3.78 mmol) obtained in example 2 as a dihydroxy compound, and trans-1, 4-cyclohexanedicarboxylic acid (400 mg,2.32 mmol) as a dicarboxylic acid monomer were added under nitrogen flow, pyridine (7.9 mL) as a solvent was added, and stirring was started at 30 ℃. Further, diisopropylcarbodiimide (1.61 g,12.8 mmol) was added as a condensing agent. After the reaction system was stirred for 3 hours, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL) and water (300 mL), and dried under vacuum to obtain 1.56g of polymer 28 (yield: 73%).

Example 28-1

A film was obtained in the same manner as in example 1-1, except that the polymer 28 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 3.

Example 28-2

A film was obtained in the same manner as in example 1-1, except that the polymer 28 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 3.

Example 29

[ Chemical formula 233]

In the same manner as in example 28 except that compound (2"B-1) (230 mg,1.16 mmol) as a diol monomer, compound (1' -2-2) (4819 mg,1.74 mmol) obtained in example 2 of a dihydroxy compound, trans-1, 4-cyclohexanedicarboxylic acid (500 mg,2.90 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (806 mg,6.39 mmol) as a condensing agent and pyridine (4.2 mL) as a solvent were used, 606mg of polymer 29 (yield: 54%) was obtained.

Example 29-1

A film was obtained in the same manner as in example 1-1, except that polymer 29 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 3.

Example 29-2

A film was obtained in the same manner as in example 1-1, except that polymer 29 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 3.

Example 30

[ Chemical formula 234]

837Mg of a polymer 30 (yield: 73%) was obtained in the same manner as in example 28 except that (2"B-1) (57.6 mg,0.290 mmol) as a diol monomer, the compound (1' -2-2) (4819 mg,1.74 mmol) obtained in example 2, the compound (2" A-1-1-DH) (212 mg,0.871 mmol) obtained in example 2, trans-1, 4-cyclohexanedicarboxylic acid (500 mg,2.90 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (806 mg,6.39 mmol) as a condensing agent, and pyridine (4.3 mL) as a solvent were used.

Example 30-1

A film was obtained in the same manner as in example 1-1, except that the polymer 30 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 3.

Examples 30-2

A film was obtained in the same manner as in example 1-1, except that the polymer 30 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 3.

Example 31

[ Chemical formula 235]

4.53G of Polymer 31 (yield: 58%) was obtained in the same manner as in example 28 except that the compound (2 "-1-1-DH) (1.44 g,5.92 mmol) obtained in Synthesis example 2, the compound (1' -2-2) (3.22 g,11.5 mmol) obtained in dihydroxyl compound example 2, PEG20000 (801 mg), trans-1, 4-cyclohexanedicarboxylic acid (3.00 g,17.4 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (4.84 g,38.3 mmol) as a condensing agent and pyridine (29.6 mL) as a solvent were used as diol monomers.

Example 31-1

A film was obtained in the same manner as in example 1-1, except that the polymer 31 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 3.

Examples 31 to 2

A film was obtained in the same manner as in example 1-1, except that the polymer 31 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 3.

Example 32

[ Chemical formula 236]

1.36G of Polymer 32 (yield: 65%) was obtained in the same manner as in example 28 except that compound (2"B-1) (230 mg,1.16 mmol) as a diol monomer, compound (2"D-1-1) (225 mg,1.63 mmol), dihydroxy compound (1' -2-2) (848 mg,3.02 mmol) obtained in example 2, trans-1, 4-cyclohexanedicarboxylic acid (1.00 g,5.81 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (1.61 g,12.8 mmol) as a condensing agent, and pyridine (16.2 mL) as a solvent were used.

Example 32-1

A film was obtained in the same manner as in example 1-1, except that the polymer 32 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 3.

Example 32-2

A film was obtained in the same manner as in example 1-1, except that the polymer 32 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 3.

Example 33

[ Chemical formula 237]

2.02G of Polymer 33 (yield: 78%) was obtained in the same manner as in example 28 except that compound (2"C-1-6) (833 mg,2.32 mmol) as a diol monomer, compound (1' -2-2) (978 mg,3.49 mmol) obtained in example 2 as a dihydroxy compound, trans-1, 4-cyclohexanedicarboxylic acid (1.00 mg,5.81 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (1.61 g,12.8 mmol) as a condensing agent, and pyridine (9.8 mL) as a solvent were used.

Example 33-1

A film was obtained in the same manner as in example 1-1, except that polymer 33 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 3.

Example 34

[ Chemical formula 238]

1.77G of Polymer 34 (yield: 85%) was obtained in the same manner as in example 28 except that the compound (1' -2-2) (1.40 g,5.00 mmol) obtained in example 2, as a diol monomer, trans-1, 4-cyclohexanedicarboxylic acid (861 mg,5.00 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (1.39 g,11.0 mmol) as a condensing agent, pyridine (2.0 mL) as a solvent and NMP (1.9 mL) were used as dihydroxy compounds.

Example 34-1

A film was obtained in the same manner as in example 1-1, except that the polymer 34 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 3.

Example 35

[ Chemical formula 239]

884Mg of a polymer 35 (yield: 76%) was obtained in the same manner as in example 28 except that the compound (2 "A-1-1-DH) (212 mg,0.871 mmol) obtained in Synthesis example 2, the compound (1' -2-2) (489 mg,1.74 mmol) obtained in dihydroxyl compound example 2, methyl hydroquinone (2"D-5-1) (36.0 mg,0.290 mmol), trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (500 mg,2.90 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (806 mg,6.39 mmol) as a condensing agent and pyridine (4.2 mL) as a solvent were used as diol monomers.

Example 35-1

A film was obtained in the same manner as in example 1-1, except that the polymer 35 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 36

[ Chemical formula 240]

889Mg of a polymer 36 (yield: 78%) was obtained in the same manner as in example 28 except that the compound (2 "A-1-1-DH) (212 mg,0.871 mmol) obtained in Synthesis example 2, dihydroxy compound (1' -2-2) (489 mg,1.74 mmol), chlorohydroquinone (2"D-6-1) (42.0 mg,0.290 mmol), trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (500 mg,2.90 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (806 mg,6.39 mmol) as a condensing agent and pyridine (4.2 mL) as a solvent were used as diol monomers.

Example 36-1

A film was obtained in the same manner as in example 1-1, except that polymer 36 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 37

[ Chemical formula 241]

872Mg of a polymer 37 (yield: 76%) was obtained in the same manner as in example 28 except that the compound (2 "A-1-1-DH) (212 mg,0.871 mmol) obtained in Synthesis example 2, the compound (1' -2-2) (489 mg,1.74 mmol) obtained in dihydroxyl compound example 2, tert-butylhydroquinone (2"D-8-1) (48.3 mg,0.290 mmol), trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (500 mg,2.90 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (806 mg,6.39 mmol) as a condensing agent and pyridine (4.3 mL) as a solvent were used as diol monomers.

Example 37-1

A film was obtained in the same manner as in example 1-1, except that polymer 37 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 38

[ Chemical formula 242]

876Mg of a polymer 38 (yield: 76%) was obtained in the same manner as in example 28 except that the compound (2 "A-1-1-DH) (212 mg,0.871 mmol) obtained in Synthesis example 2 as a diol monomer, the compound (1' -2-2) (489 mg,1.74 mmol) obtained in dihydroxyl compound example 2, 5-di-tert-butylhydroquinone (2"D-11-1) (64.6 mg,0.290 mmol), trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (500 mg,2.90 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (806 mg,6.39 mmol) as a condensing agent, and pyridine (4.3 mL) as a solvent were used.

Example 38-1

A film was obtained in the same manner as in example 1-1, except that polymer 38 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 39

[ Chemical formula 243]

841Mg of Polymer 39 (yield: 64%) was obtained in the same manner as in example 28 except that the compound (2 "A-1-1-DH) (212 mg,0.871 mmol) obtained in Synthesis example 2 as a diol monomer, the compound (1 ' -2-2) (489 mg,1.74 mmol) obtained in dihydroxyl compound example 2, 6' -dihydroxy-4, 4', 7' -hexamethyl-2, 2' -spirodihydropyran (2"D-14-1) (107 mg,0.290 mmol), trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (500 mg,2.90 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (806 mg,6.39 mmol) as a condensing agent, and pyridine (4.5 mL) as a solvent were used.

Example 39-1

A film was obtained in the same manner as in example 1-1, except that polymer 39 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 40

[ Chemical formula 244]

1.33G of Polymer 40 (yield: 59%) was obtained in the same manner as in example 28 except that the dihydroxyl compound (1' -2-2) (847 mg,3.02 mmol) obtained in example 2, the compound (2"D-1-1) (192 mg,1.39 mmol), 2- (1, 3-tetramethylbutyl) hydroquinone (2"D-10-1) (310 mg,1.39 mmol), PEG20000 (116 mg, 5.81. Mu. Mol), trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (1.00 g,5.81 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (1.61 g,12.8 mmol) as a condensing agent and pyridine (8.4 mL) as a solvent were used as diol monomers.

Example 40-1

A film was obtained in the same manner as in example 1-1, except that the polymer 40 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 41

[ Chemical formula 245]

1.71G of Polymer 41 (yield: 78%) was obtained in the same manner as in example 28 except that the dihydroxyl compound (1' -2-2) (1.04 g,3.72 mmol) obtained in example 2, the compound (2"D-1-1) (225 mg,1.63 mmol) obtained in Synthesis example 11, the compound (2"C-2-2) (133 mg, 465. Mu. Mol) obtained in Synthesis example 11, the trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (1.00 g,5.81 mmol) obtained in dicarboxylic acid monomer, diisopropylcarbodiimide (1.61 g,12.8 mmol) obtained in condensing agent and pyridine (8.1 mL) obtained in solvent were used.

Example 41-1

A film was obtained in the same manner as in example 1-1, except that polymer 41 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 42

[ Chemical formula 246]

1.80G of Polymer 42 (yield: 63%) was obtained in the same manner as in example 28 except that the dihydroxyl compound (1' -2-2) (1.24 g,4.43 mmol) obtained in example 2, the compound (2 "A-1-104-DH) (541 mg,1.36 mmol) obtained in Synthesis example 12, PEG20000 (263 mg, 13.1. Mu. Mol), trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (1.00 g,5.81 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (1.61 g,12.8 mmol) as a condensing agent and pyridine (10.8 mL) as a solvent were used as diol monomers.

Example 42-1

A film was obtained in the same manner as in example 1-1, except that the polymer 42 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 43

[ Chemical formula 247]

1.47G of Polymer 43 (yield: 61%) was obtained in the same manner as in example 28 except that the compound (1' -2-2) (1.06 g,3.78 mmol) obtained in example 2, the compound (2 "A-1-1-CH) (879 mg,3.24 mmol) obtained in Synthesis example 13, the dihydroxy compound (as a diol monomer), the trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (651 mg,3.78 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (1.50 g,11.9 mmol) as a condensing agent and pyridine (9.1 mL) as a solvent were used.

Example 43-1

A film was obtained in the same manner as in example 1-1, except that the polymer 43 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 44

[ Chemical formula 248]

1.42G of Polymer 44 (yield: 58%) was obtained in the same manner as in example 28 except that the compound (1' -2-2) (1.06 mg,3.78 mmol) obtained in example 2, the compound (2 "A-1-2-CH) (925 mg,3.24 mmol) obtained in Synthesis example 14, the dihydroxy compound (1.06 mg,3.78 mmol) obtained as a diol monomer, the trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) obtained as a dicarboxylic acid monomer, the diisopropylcarbodiimide (1.50 g,11.9 mmol) obtained as a condensing agent and the pyridine (9.2 mL) obtained as a solvent were used.

Example 44-1

A film was obtained in the same manner as in example 1-1, except that the polymer 44 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 45

[ Chemical formula 249]

1.02G of Polymer 45 (yield: 62%) was obtained in the same manner as in example 28 except that the compound (1' -2-2) (708 mg,2.52 mmol) obtained in example 2, the compound (2 "A-1-46-CH) (611 mg,2.16 mmol) obtained in Synthesis example 15, the trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (434 mg,2.52 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (1.00 g,7.92 mmol) as a condensing agent and pyridine (6.1 mL) as a solvent were used as dihydroxy compounds of the diol monomer.

Example 45-1

A film was obtained in the same manner as in example 1-1, except that polymer 45 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 46

[ Chemical formula 250]

1.28G of Polymer 46 (yield: 77%) was obtained in the same manner as in example 28 except that the compound (1' -2-2) (708 mg,2.52 mmol) obtained in example 2, the compound (2 "A-1-47-CH) (647 mg,2.16 mmol) obtained in Synthesis example 16, the trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (434 mg,2.52 mmol), the diisopropylcarbodiimide (1.00 g,7.92 mmol) as a condensing agent and the pyridine (6.3 mL) as a solvent were used as diol monomers.

Example 46-1

A film was obtained in the same manner as in example 1-1, except that the polymer 46 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 46-2

A film was obtained in the same manner as in example 1-1, except that the polymer 46 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 47

[ Chemical formula 251]

979Mg of a polymer 47 (yield: 61%) was obtained in the same manner as in example 28 except that the compound (1' -2-2) (218 mg,2.52 mmol) obtained in example 2, the compound (2 "A-1-1-HC) (586 mg,2.16 mmol) obtained in Synthesis example 17, the trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (434 mg,2.52 mmol), the diisopropylcarbodiimide (1.00 g,7.92 mmol) as a condensing agent and the pyridine (6.0 mL) as a solvent were used as dihydroxy compounds of the diol monomers.

Example 47-1

A film was obtained in the same manner as in example 1-1, except that polymer 47 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 48

[ Chemical formula 252]

1.03G of Polymer 48 (yield: 63%) was obtained in the same manner as in example 28 except that the compound (1' -2-2) (218 mg,2.52 mmol) obtained in example 2, the compound (2 "A-1-2-HC) (616 mg,2.16 mmol) obtained in Synthesis example 18, the trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (434 mg,2.52 mmol), the diisopropylcarbodiimide (1.00 g,7.92 mmol) as a condensing agent and the pyridine (6.2 mL) as a solvent were used as dihydroxy compounds of the diol monomers.

Example 48-1

A film was obtained in the same manner as in example 1-1, except that the polymer 48 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 48-2

A film was obtained in the same manner as in example 1-1, except that the polymer 48 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 49

[ Chemistry 253]

1.07G of Polymer 49 (yield: 66%) was obtained in the same manner as in example 28 except that the compound (1' -2-2) (708 mg,2.52 mmol) obtained in example 2, the compound (2 "A-1-46-HC) (611 mg,2.16 mmol) obtained in Synthesis example 19, the trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (434 mg,2.52 mmol), the diisopropylcarbodiimide (1.00 g,7.92 mmol) as a condensing agent and the pyridine (6.1 mL) as a solvent were used as dihydroxy compounds of the diol monomers.

Example 49-1

A film was obtained in the same manner as in example 1-1, except that polymer 49 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 49-2

A film was obtained in the same manner as in example 1-1, except that polymer 49 was used in place of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 50

[ Chemical formula 254]

738Mg of a polymer 50 (yield: 67%) was obtained in the same manner as in example 28 except that the compound (1' -6-2) (424 mg,1.74 mmol) obtained in example 11, the compound (2 "A-1-1-DH) (283 mg,1.16 mmol) obtained in Synthesis example 2, trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (500 mg,2.90 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (806 mg,6.39 mmol) as a condensing agent and pyridine (4.1 mL) as a solvent were used as dihydroxy compounds.

Examples 50 to 1

A film was obtained in the same manner as in example 1-1, except that the polymer 50 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 51

[ Chemical formula 255]

657Mg of polymer 51 (yield: 58%) was obtained in the same manner as in example 28 except that the compound (1' -6-3) (448 mg,1.74 mmol) obtained in example 12, the compound (2 "A-1-1-DH) (283 mg,1.16 mmol) obtained in Synthesis example 2, trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (500 mg,2.90 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (806 mg,6.39 mmol) as a condensing agent and pyridine (4.1 mL) as a solvent were used as dihydroxy compounds.

Example 51-1

A film was obtained in the same manner as in example 1-1, except that the polymer 51 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 150 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 52

[ Chemical formula 256]

966Mg of a polymer 52 (yield: 81%) was obtained in the same manner as in example 28 except that the compound (1' -2-10) (514 mg,1.74 mmol) obtained in example 8, the compound (2 "A-1-1-DH) (283 mg,1.16 mmol) obtained in Synthesis example 2, trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (500 mg,2.90 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (806 mg,6.39 mmol) as a condensing agent and pyridine (4.5 mL) as a solvent were used as dihydroxy compounds.

Example 52-1

A film was obtained in the same manner as in example 1-1, except that the polymer 52 was used in place of the polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 53

[ Chemistry type 257]

884Mg of Polymer 53 (yield: 74%) was obtained in the same manner as in example 28 except that the compound (1' -2-9) (514 mg,1.74 mmol) obtained in example 7, the compound (2 "A-1-1-DH) (283 mg,1.16 mmol) obtained in Synthesis example 2, trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (500 mg,2.90 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (806 mg,6.39 mmol) as a condensing agent and pyridine (4.5 mL) as a solvent were used as diol monomers.

Example 53-1

A film was obtained in the same manner as in example 1-1, except that polymer 53 was used instead of polymer 1. The obtained film (film thickness: 1 μm) was irradiated with 365nm polarized ultraviolet light at 100mJ/cm ² and then heated to 190 ℃. The phase difference and the wavelength dispersion are shown in table 4.

Example 54

[ Chemical formula 258]

483Mg of Polymer 54 (yield: 55%) was obtained in the same manner as in example 28 except that the compound (1' -2-11) (157 mg, 499. Mu. Mol) obtained in example 9, the compound (2 "A-1-1-DH) (243 mg, 999. Mu. Mol) obtained in Synthesis example 2, the compound (2"D-1-1) (138 mg, 999. Mu. Mol), the trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (430 mg,2.50 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (693 mg,5.49 mmol) as a condensing agent, and pyridine (3.2 mL) as a solvent were used as dihydroxy compounds of diol monomers.

Example 55

[ Chemical formula 259]

699Mg of a polymer 55 (yield: 74%) was obtained in the same manner as in example 28 except that the compound (1' -7-2) (225 mg, 499. Mu. Mol) obtained in example 10, the compound (2 "A-1-1-DH) (243 mg, 999. Mu. Mol) obtained in Synthesis example 2, the compound (2"D-1-1) (138 mg, 999. Mu. Mol), the trans-1, 4-cyclohexanedicarboxylic acid (2"D-7-3) (430 mg,2.50 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (693 mg,5.49 mmol) as a condensing agent, and pyridine (3.5 mL) as a solvent were used as dihydroxy compounds of diol monomers.

Example 56

[ Chemical formula 260]

1.21G of Polymer 56 (yield: 54%) was obtained in the same manner as in example 28 except that the dihydroxyl compound obtained in example 2 (1' -2-2) (946 mg,3.37 mmol), the compound (2"D-1-1) (233 mg,1.68 mmol), 2- (1, 3-tetramethylbutyl) hydroquinone (2"D-10-1) (214 mg,963 mmol), PEG20000 (60.3 mg, 3.01. Mu. Mol), terephthalic acid (1.00 g,1.68 mmol) as a dicarboxylic acid monomer, diisopropylcarbodiimide (693 mg,5.49 mmol) as a condensing agent and pyridine (3.5 mL) as a solvent were used as diol monomers.

Comparative example 1

[ Chemical formula 261]

In a 200mL three-necked flask equipped with a dropping funnel, ion-exchanged water (20 mL) was taken, and the compound (2 "-1-36-DH) (1.11 g,4.00 mmol) obtained in Synthesis example 1 and sodium hydroxide (320 mg,8.00 mmol) were added. After the matrix was dissolved by vigorous stirring (350 rpm), a 2% aqueous tetrabutylammonium bromide solution (1.6 mL) was added as a catalyst, and the inside of the apparatus was sufficiently replaced with argon. A solution of trans-1, 4-cyclohexanedicarboxylic acid dichloride in methylene chloride (20 mL) was taken in a dropping funnel and added to the system quickly. After the completion of the dropwise addition, the mixture was vigorously stirred at room temperature for 3 hours, and interfacial polymerization was carried out. After the reaction, the solution was added dropwise to methanol (200 mL), and the precipitate was separated by filtration, washed with water (100 mL) and methanol (100 mL), and dried under vacuum to give 1.04g of polymer 1' (yield: 63%) as a white solid.

6.0 Mass% of the polymer 1' was dissolved in 94.0 mass% of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated, and dried in an oven at 60℃for 30 minutes to obtain a thin film (film thickness: 1 μm). The film thus obtained was irradiated with polarized ultraviolet light of 248nm at 500mJ/cm ² and then heated to 250 ℃. The phase difference and the wavelength dispersion are shown in table 5.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

In tables 1, 2, 3, 4 and 5, R (450)/R (550) represents the ratio of the in-plane retardation at 450nm to the in-plane retardation at 550 nm.

Re 10 μm shows the value of the phase difference in terms of film thickness of 10 μm. ]

As shown in tables 1,2,3, and 4, the polymers of examples 1 to 53 exhibited a retardation of inverse wavelength dispersibility by irradiation with ultraviolet light and heat treatment.

The polymer of the present invention having the photoreactive inverse wavelength dispersion unit a more significantly expresses the retardation of the inverse wavelength dispersion than comparative example 1 shown in table 5.

[ Dihydroxy Compound example 14]

After 2, 5-dihydroxybenzaldehyde (57.5 g,416 mmol) and acetophenone (50.0 g,416 mmol) were dissolved in methanol (200 mL), a 50% aqueous sodium hydroxide solution (120 mL,2.25 mol) was added dropwise with ice water cooling. After the reaction system was stirred at room temperature for 12 hours, acetic acid (167 mL,2.91 mmol) was added with ice water cooling. After the obtained reaction mixture was added to water (300 mL), toluene (30 mL), isopropyl alcohol (2 mL) and methylene chloride (100 mL) were added and stirred vigorously. The resulting solid was taken out by filtration and washed with dichloromethane (50 mL) and distilled water (50 mL). The resulting solid was dried in vacuo to give 14.8g of compound (1' -1-1) as a yellow solid (yield ：15％).¹H-NMR(400MHz,DMSO-d₆)δ9.90-8.39(br,2H),8.04(d,J＝8.2Hz,2H),7.94(d,J＝15.4Hz,1H),7.67(d,J＝15.4Hz,1H),7.61(t,J＝7.4Hz,1H),7.52(t,J＝7.4Hz,2H),7.15(s,1H),6.76-6.67(m,2H).

[ Chemical formula 262]

Synthesis example 20-1

1, 2-Dimethylhydrazine dihydrochloride (2.66 g,20.0 mmol) and N, N-diisopropylethylamine (17.0 mL,100 mmol) were suspended in tetrahydrofuran (40 mL) under argon. The pre-prepared tetrahydrofuran solution of 4-acetoxybenzoyl chloride was slowly added with ice water cooling, warmed to room temperature and stirred overnight. The solvent was distilled off under reduced pressure, 1M hydrochloric acid (100 mL) was added, and the mixture was extracted with ethyl acetate (2X 100 mL). The combined organic layers were washed with saturated aqueous sodium hydrogencarbonate (100 mL) and saturated brine (100 mL) in this order, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was suspended in methanol (75 mL), and a solution of sodium hydroxide (4.16 g,104 mmol) in water (25 mL) was added thereto, followed by stirring at room temperature for 1 hour. The solvent was distilled off under reduced pressure, 2M hydrochloric acid (75 mL) was added, and extracted with ethyl acetate (2X 100 mL). The combined organic layers were washed with saturated aqueous sodium hydrogencarbonate (2X 100 mL) and saturated brine (100 mL) in this order, and dried over anhydrous sodium sulfate. The solvent was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography, and the obtained solid was recrystallized from a mixed solvent of ethanol/hexane to give compound (2"C-2-13) as a white solid (yield: 3.02g, yield) ：50％).¹H-NMR(400MHz,(CD₃)₂SO):δ9.95(brs,2H),7.58-6.87(brm,4H),6.87-6.61(brm,4H),3.13(brs,6H).

[ Chemical formula 263]

Example 57

To a reaction vessel were added a dihydroxy compound (1 '-2-2) (4.0 g,14.3 mmol) obtained in example 2, a compound (2 "A-1-1-DH) (1.9 g,7.7 mmol) obtained in Synthesis example 2, trans-1, 4-cyclohexanedicarboxylic acid (3.8 g,21.9 mmol), pyridine (8.2 mL) and N-methyl-2-pyrrolidone (8.2 mL) under a nitrogen atmosphere, and the reaction system was stirred at 40℃for 1 hour to dissolve the compound, and then N, N' -diisopropylcarbodiimide (6.1 g,48.2 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 40℃for 3 hours, acetic anhydride (2.2 g,21.9 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 40℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 57 (yield: 6.4g, yield: 72%).

[ Chemical formula 264]

13.0 Mass% of the polymer 57 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 2000rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 58

To a reaction vessel were added a dihydroxy compound (1 '-2-2) (4.0 g,14.3 mmol) obtained in example 2, a compound (2 "A-1-1-DH) (1.9 g,7.7 mmol) obtained in Synthesis example 2, trans-1, 4-cyclohexanedicarboxylic acid (3.8 g,21.9 mmol), pyridine (8.2 mL) and N-methyl-2-pyrrolidone (8.2 mL) under a nitrogen atmosphere, and the reaction system was stirred at 40℃for 1 hour to dissolve the compound, and then N, N' -diisopropylcarbodiimide (6.1 g,48.2 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 40℃for 3 hours, cyclohexane carbonyl chloride (3.2 g,21.9 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 40℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 58 (yield: 6.6g, yield: 75%).

[ Chemical formula 265]

13.0 Mass% of the polymer 58 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1600rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 5.

Example 59

To a reaction vessel were added a dihydroxy compound (1 '-2-2) (4.0 g,14.3 mmol) obtained in example 2, a compound (2 "A-1-1-DH) (1.9 g,7.7 mmol) obtained in Synthesis example 2, trans-1, 4-cyclohexanedicarboxylic acid (3.8 g,21.9 mmol), pyridine (8.2 mL) and N-methyl-2-pyrrolidone (8.2 mL) under a nitrogen atmosphere, and the reaction system was stirred at 40℃for 1 hour to dissolve the compound, and then N, N' -diisopropylcarbodiimide (6.1 g,48.2 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 40℃for 3 hours, a solution in which chloroacetic anhydride (3.7 g,21.9 mmol) as a monocarboxylic acid derivative compound was dissolved in N-methyl-2-pyrrolidone (3.0 mL) was added. After the reaction system was stirred at 40℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 59 (yield: 6.5g, yield: 73%).

[ Chemical formula 266]

13.0 Mass% of the polymer 59 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 60

To a reaction vessel were added a dihydroxy compound (1 '-2-2) (4.0 g,14.3 mmol) obtained in example 2, a compound (2 "A-1-1-DH) (1.9 g,7.7 mmol) obtained in Synthesis example 2, trans-1, 4-cyclohexanedicarboxylic acid (3.8 g,21.9 mmol), pyridine (8.2 mL) and N-methyl-2-pyrrolidone (8.2 mL) under a nitrogen atmosphere, and the reaction system was stirred at 40℃for 1 hour to dissolve the compound, and then N, N' -diisopropylcarbodiimide (6.1 g,48.2 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 40℃for 3 hours, p-methylbenzoyl chloride (3.4 g,21.9 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 40℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 60 (yield: 7.7g, yield: 87%).

[ Chemical formula 267]

13.0 Mass% of the polymer 60 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 250℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 61

To a reaction vessel, a dihydroxy compound (1 '-1-1) (1.0 g,4.2 mmol) obtained in example 14, a compound (2 "A-1-1-DH) (0.55 g,2.2 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.1 g,6.4 mmol), pyridine (2.2 mL) and N-methyl-2-pyrrolidone (2.2 mL) were added under a nitrogen atmosphere, and the reaction system was stirred at 40℃for 1 hour to dissolve the compound, and then N, N' -diisopropylcarbodiimide (1.8 g,14.1 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 40℃for 3 hours, acetic anhydride (0.65 g,6.4 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 40℃for 30 minutes, the mixture in the system was added to methanol (100 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 61 (yield: 1.3g, yield: 54%).

[ Chemical formula 268]

13.0 Mass% of the polymer 61 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 250℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 62

To a reaction vessel, a dihydroxyl compound (1 ' -2-2) (2.5 g,9.1 mmol), 4' -dicyclohexyl (0.69 g,3.5 mmol), 4- (2-hydroxyethyl) phenol (0.67 g,4.9 mmol), trans-1, 4-cyclohexanedicarboxylic acid (3.0 g,17.4 mmol) and pyridine (16.2 mL) obtained in example 2 were added under a nitrogen atmosphere, and the reaction system was stirred at 30℃for 1 hour to dissolve the compounds, and then N, N ' -diisopropylcarbodiimide (4.8 g,38.3 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (1.8 g,17.4 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 62 (yield:

4.3g, yield: 69%).

[ Chemical formula 269]

13.0 Mass% of the polymer 62 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 63

To a reaction vessel were added a dihydroxy compound (1 '-2-2) (1.1 g,4.1 mmol) obtained in example 2, a compound (2 "A-1-1-DH) (7.1 g,0.3 mmol) obtained in Synthesis example 2, 4- (2-hydroxyethyl) phenol (0.20 g,1.5 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol) and pyridine (8.2 mL) under a nitrogen atmosphere, and the reaction system was stirred at 30℃for 1 hour to dissolve the compound, and then N, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.59 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 63 (yield: 1.7g, yield: 80%).

[ Chemical formula 270]

10.0 Mass% of polymer 63 was dissolved in 90.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1000rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 64

To a reaction vessel were added a dihydroxy compound (1 '-2-2) (1.1 g,4.1 mmol) obtained in example 2, a compound (2 "A-1-1-DH) (0.07 g,0.3 mmol) obtained in Synthesis example 2,4- (2-hydroxyethyl) phenol (0.20 g,1.5 mmol), polyethylene glycol 20000 (manufactured by Tokyo chemical industries, inc., 0.11 g), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol) and pyridine (8.7 mL) under a nitrogen atmosphere, and the reaction system was stirred at 30℃for 1 hour to dissolve the mixture, and then N, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.59 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 64 (yield: 1.6g, yield: 68%).

[ Chemical formula 271]

10.0 Mass% of the polymer 64 was dissolved in 90.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1000rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 65

To a reaction vessel, a dihydroxyl compound (1 '-2-2) (1.3 g,4.7 mmol), bis (4-hydroxybenzoic acid) hexamethylene (0.10 g,0.3 mmol), 4- (2-hydroxyethyl) phenol (0.12 g,0.9 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol) and pyridine (8.7 mL) obtained in example 2 were added under a nitrogen atmosphere, and the reaction system was stirred at 30℃for 1 hour to dissolve the compounds, and then N, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.59 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give a polymer 65 (yield: 1.9g, yield: 81%).

[ Chemical formula 272]

10.0 Mass% of the polymer 65 was dissolved in 90.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1000rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 66

To a reaction vessel, a dihydroxyl compound (1 ' -2-2) (0.91 g,3.3 mmol), 4' -dicyclohexyl (0.18 g,0.9 mmol), 4- (2-hydroxyethyl) phenol (0.23 g,1.6 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol) and pyridine (7.8 mL) obtained in example 2 were added under a nitrogen atmosphere, and the reaction system was stirred at 30℃for 1 hour to dissolve the compounds, and then N, N ' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, isobutyric anhydride (0.92 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 66 (yield: 1.4g, yield: 66%).

[ Chemical formula 273]

13.0 Mass% of the polymer 66 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 67

To a reaction vessel, a dihydroxyl compound (1 ' -2-2) (0.91 g,3.3 mmol), 4' -dicyclohexyl (0.18 g,0.9 mmol), 4- (2-hydroxyethyl) phenol (0.23 g,1.6 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol) and pyridine (7.8 mL) obtained in example 2 were added under a nitrogen atmosphere, and the reaction system was stirred at 30℃for 1 hour to dissolve the compounds, and then N, N ' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, hexanoic anhydride (1.3 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 67 (yield: 1.4g, yield: 65%).

[ Chemical formula 274]

13.0 Mass% of the polymer 67 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 68

To a reaction vessel, a dihydroxyl compound (1 ' -2-2) (0.91 g,3.3 mmol), 4' -dicyclohexyl (0.18 g,0.9 mmol), 4- (2-hydroxyethyl) phenol (0.23 g,1.6 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol) and pyridine (7.8 mL) obtained in example 2 were added under a nitrogen atmosphere, and the reaction system was stirred at 30℃for 1 hour to dissolve the compounds, and then N, N ' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, decanoic anhydride (1.9 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give a polymer 68 (yield: 1.4g, yield: 67%).

[ Chemical formula 275]

13.0 Mass% of the polymer 68 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 69

To a reaction vessel, a dihydroxyl compound (1 ' -2-2) (0.91 g,3.3 mmol), 4' -dicyclohexyl (0.18 g,0.9 mmol), 4- (2-hydroxyethyl) phenol (0.23 g,1.6 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol) and pyridine (7.8 mL) obtained in example 2 were added under a nitrogen atmosphere, and the reaction system was stirred at 30℃for 1 hour to dissolve the compounds, and then N, N ' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, cyclohexane carboxylic anhydride (1.4 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 69 (yield: 1.4g, yield: 66%).

[ Chemical formula 276]

13.0 Mass% of the polymer 69 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 70

To a reaction vessel were added a dihydroxy compound (1 '-2-2) (37.3 g,133.0 mmol) obtained in example 2, a compound (2 "A-1-1-DH) (9.9 g,40.8 mmol) obtained in Synthesis example 2, polyethylene glycol 20000 (7.9 g, manufactured by Tokyo chemical industry Co., ltd.), trans-1, 4-cyclohexanedicarboxylic acid (30.0 g,174.2 mmol), pyridine (74.7 mL) and N-methyl-2-pyrrolidone (74.7 mL) under a nitrogen atmosphere, and the reaction system was stirred at 40℃for 1 hour to dissolve the compounds, and then N, N' -diisopropylcarbodiimide (48.4 g,383.3 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 40℃for 3 hours, acetic anhydride (17.8 g,174.2 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (1320 mL). The resulting solid was taken out by filtration, washed with methanol (3000 mL), and dried in vacuo to give polymer 70 (yield: 39.2g, yield: 50%).

[ Chemical formula 277]

13.0 Mass% of the polymer 70 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 71

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxy compound (1' -2-2) (0.91 g,3.3 mmol), 4- (2-hydroxyethyl) phenol (0.29 g,2.1 mmol), hydroquinone (0.05 g, 0.5 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol), pyridine (7.5 mL) obtained in example 2. After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.59 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 71 (yield: 1.6g, yield: 76%).

[ Chemical formula 278]

13.0 Mass% of the polymer 71 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 72

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxy compound (1' -2-2) (0.91 g,3.3 mmol), 4- (2-hydroxyethyl) phenol (0.29 g,2.1 mmol), methyl hydroquinone (0.06 g, 0.5 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol), and pyridine (7.6 mL) obtained in example 2. After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.59 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 72 (yield: 1.5g, yield: 71%).

[ Chemical formula 279]

13.0 Mass% of the polymer 72 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 73

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxy compound (1' -2-2) (0.91 g,3.3 mmol), 4- (2-hydroxyethyl) phenol (0.29 g,2.1 mmol), 2-tert-butylhydroquinone (0.08 g, 0.5 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol), and pyridine (7.6 mL) obtained in example 2. After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.59 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 73 (yield: 1.5g, yield: 70%).

[ Chemical formula 280]

13.0 Mass% of the polymer 73 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 74

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxy compound (1' -2-2) (0.91 g,3.3 mmol), 4- (2-hydroxyethyl) phenol (0.22 g,1.6 mmol), 2- (1, 3-tetramethylbutyl) hydroquinone (0.21 g, 0.9 mmol), polyethylene glycol 20000 (manufactured by tokyo chemical industry Co., ltd., 0.1 g), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol), and pyridine (8.4 mL). After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.59 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 74 (yield: 1.3g, yield: 59%).

[ Chemical formula 281]

13.0 Mass% of the polymer 74 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 75

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxy compound (1' -2-2) (0.91 g,3.3 mmol), 4- (2-hydroxyethyl) phenol (0.22 g,1.6 mmol), 2, 5-di-tert-butylhydroquinone (0.21 g, 0.9 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol), pyridine (7.9 mL) obtained in example 2. After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.59 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give a polymer 75 (yield: 1.5g, yield: 68%).

[ Chemical formula 282]

13.0 Mass% of the polymer 75 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 76

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxy compound (1' -2-2) (0.91 g,3.3 mmol), 4- (2-hydroxyethyl) phenol (0.22 g,1.6 mmol), 2, 5-di-t-amylhydroquinone (0.23 g, 0.9 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol), pyridine (8.0 mL) obtained in example 2. After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.59 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 76 (yield: 1.4g, yield: 66%).

[ Chemical formula 283]

13.0 Mass% of the polymer 76 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 77

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxy compound (1' -2-2) (0.91 g,3.3 mmol), 4- (2-hydroxyethyl) phenol (0.22 g,1.6 mmol), 2, 5-bis (1, 3-tetramethylbutyl) hydroquinone (0.31 g,0.9 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol), and pyridine (8.3 mL). After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.59 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give a polymer 77 (yield: 1.4g, yield: 63%).

[ Chemical formula 284]

13.0 Mass% of the polymer 77 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 78

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxy compound (1' -2-2) (0.85 g,3.0 mmol), 4- (2-hydroxyethyl) phenol (0.19 g,1.4 mmol), 2- (1, 3-tetramethylbutyl) hydroquinone (0.31 g,1.4 mmol), polyethylene glycol 20000 (manufactured by tokyo chemical industry Co., ltd., 0.1 g), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol) and pyridine (8.4 mL). After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, decanoic anhydride (1.9 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 78 (yield: 1.2g, yield: 53%).

[ Chemical formula 285]

13.0 Mass% of the polymer 78 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 79

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxy compound (1' -2-2) (0.85 g,3.0 mmol), 4- (2-hydroxyethyl) phenol (0.06 g,0.5 mmol), 2-tert-butylhydroquinone (0.39 g, 2.3 mmol), polyethylene glycol 20000 (manufactured by Tokyo chemical industry Co., ltd., 0.1 g), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol), and pyridine (5.7 mL). After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, decanoic anhydride (1.9 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 79 (yield: 1.2g, yield: 56%).

[ Chemical formula 286]

13.0 Mass% of the polymer 79 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 80

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxy compound (1' -2-2) (1.0 g,3.7 mmol), 4- (2-hydroxyethyl) phenol (0.22 g,1.6 mmol), methyl hydroquinone (0.06 g, 0.5 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol), and pyridine (7.8 mL) obtained in example 2. After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, hexanoic anhydride (1.2 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 80 (yield: 1.7g, yield: 78%).

[ Chemical formula 287]

13.0 Mass% of the polymer 80 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 81

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxy compound (1' -2-2) (1.0 g,3.7 mmol) obtained in example 2, a compound (2"C-2-2) (0.1 g,0.5 mmol) obtained in Synthesis example 11, 4- (2-hydroxyethyl) phenol (0.22 g,1.6 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol), and pyridine (8.1 mL). After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.6 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give a polymer 81 (yield: 1.7g, yield: 79%).

[ Chemical formula 288]

13.0 Mass% of the polymer 81 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 82

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxy compound (1' -2-2) (1.0 g,3.7 mmol) obtained in example 2, a compound (2"C-2-13) (0.1 g,0.5 mmol) obtained in Synthesis example 20-1, 4- (2-hydroxyethyl) phenol (0.22 g,1.6 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol), and pyridine (8.2 mL). After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.6 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 82 (yield: 1.7g, yield: 78%).

[ Chemical formula 289]

13.0 Mass% of the polymer 82 was dissolved in 87.0 mass% of hexafluoro-2-propanol. This was cast on a quartz substrate, spin-coated at 1800rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to obtain a film (film thickness 5 μm). The film was evaluated by measuring the Yellowness Index (YI) of the resulting film and visually inspecting the appearance of the film. The obtained film was irradiated with polarized ultraviolet light of 365nm at 100mJ/cm ², and then subjected to heat treatment at 150℃for 10 minutes, whereby the retardation property and the wavelength dispersion property were evaluated. The results are shown in Table 6.

Example 83

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxy compound (1' -2-2) (0.91 g,3.3 mmol), 4- (2-hydroxyethyl) phenol (0.22 g,1.6 mmol), 2- (1, 3-tetramethylbutyl) hydroquinone (0.21 g, 0.9 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol), and pyridine (7.9 mL). After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.6 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 83 (yield: 1.4g, yield: 63%).

[ Chemical formula 290]

Example 84

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxy compound (1' -2-2) (0.91 g,3.3 mmol), 1, 4-cyclohexanedimethanol (0.13 g,0.87 mmol), 4- (2-hydroxyethyl) phenol (0.23 g, 1.7 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol), and pyridine (7.6 mL) obtained in example 2. After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.6 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 84 (yield: 1.6g, yield: 77%).

[ Chemical formula 291]

6.0 Mass% of the polymer 84 was dissolved in 94.0 mass% of 1, 3-hexafluoroisopropanol. After casting it on a quartz glass substrate, it was spin-coated and dried in an oven at 60 ℃ for 30 minutes to obtain a thin film. The obtained film (film thickness 1 μm) was irradiated with 365nm polarized ultraviolet light 500mJ/cm ² and then heated to 150℃to exhibit a retardation Re=46.8 nm and a wavelength dispersibility Re (450)/Re (550) =0.89.

Example 85

To the reaction vessel were added, under a nitrogen atmosphere, a dihydroxyl compound (1' -2-2) (0.93 g,3.3 mmol), tricyclodecane dimethanol (0.13 g,0.64 mmol), 4- (2-hydroxyethyl) phenol (0.26 g, 1.7 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.0 g,5.8 mmol) and pyridine (7.8 mL). After the reaction system was stirred at 30℃for 1 hour to dissolve, N' -diisopropylcarbodiimide (1.6 g,12.8 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.6 g,5.8 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 85 (yield: 1.5g, yield: 70%).

[ Chemical formula 292]

6.0 Mass% of the polymer 85 was dissolved in 94.0 mass% of 1, 3-hexafluoroisopropanol. After casting it on a quartz glass substrate, it was spin-coated and dried in an oven at 60 ℃ for 30 minutes to obtain a thin film. The obtained film (film thickness 1 μm) was irradiated with 365nm polarized ultraviolet light 500mJ/cm ² and then heated to 150℃to exhibit a retardation Re=39.9 nm and a wavelength dispersibility Re (450)/Re (550) =0.88.

TABLE 6

	Polymer	YI(％)	Film appearance	Re(nm)	Re(450)/Re(550)
						Example 57	Polymer 57	2.7	A	36	0.96
Example 58	Polymer 58	2.5	A	48	0.96
						Example 59	Polymer 59	4.9	B	36	0.94
Example 60	Polymer 60	2.8	A	52	0.88
						Example 61	Polymer 61	3.6	B	270	0.88
Example 62	Polymer 62	1.8	A	16	0.92
						Example 63	Polymer 63	1.7	A	9	0.86
Example 64	Polymer 64	3.8	B	19	0.82
						Example 65	Polymer 65	1.4	A	16	0.84
Example 66	Polymer 66	2.8	A	7	0.87
						Example 67	Polymer 67	2.4	A	12	0.87
Example 68	Polymer 68	2.3	A	7	0.88
						Example 69	Polymer 69	2.7	A	6	0.87
Example 70	Polymer 70	3.2	B	10	0.87
						Example 71	Polymer 71	2.7	A	7	0.96
Example 72	Polymer 72	2.4	A	9	0.88
						Example 73	Polymer 73	2.5	A	7	0.87
Example 74	Polymer 74	3.0	B	3	0.83
						Example 75	Polymer 75	3.0	B	5	0.89
Example 76	Polymer 76	3.5	B	11	0.88
						Example 77	Polymer 77	2.7	A	10	0.91
Example 78	Polymer 78	2.7	A	6	0.86
						Example 79	Polymer 79	3.3	B	11	0.83
Example 80	Polymer 80	3.2	B	10	0.84
						Example 81	Polymer 81	3.0	B	5	0.84
Example 82	Polymer 82	3.2	B	7	0.88

As shown in table 6, films produced using the polymers of examples 57 to 82 exhibited low Yellowness Index (YI) and expressed a phase difference due to inverse wavelength dispersibility of the irradiation of ultraviolet light and the heat treatment.

Polymers 57-82 exhibit a low Yellowness Index (YI).

Polymerization example 1

Chemical formula 293

To a reaction vessel were added a solution of the compound (2 "A-1-1-DH) (1.16 g,4.78 mmol) obtained in Synthesis example 2 and the compound (1' -2-1) (1.77 g,7.16 mmol) obtained in example 1 as diol monomers in water (114 mL) and a 2wt% aqueous tetrabutylammonium bromide solution (4.75 mL) under a nitrogen stream, followed by stirring. Further, trans-1, 4-cyclohexanedicarboxylic acid dichloride (2.50 g,12.0 mmol) as a dicarboxylic acid dichloride monomer was dissolved in chloroform (119 mL), and the solution was added to the reaction system. After the reaction system was stirred for 3 hours, the mixture in the system was added to methanol (500 mL). The resulting solid was taken out by filtration, washed with methanol (200 mL) and water (200 mL), and dried under vacuum to obtain 4.13g of polymer 86 (yield: 91%).

Polymerization example 2

[ Chemical formula 294]

The compound (2 "A-1-DH) (1.44 g,5.92 mmol) obtained in Synthesis example 2, the compound (1 '-2-2) (3.22 g,11.5 mmol) obtained in dihydroxyl compound example 2, trans-1, 4-cyclohexanedicarboxylic acid (3.00 g,17.4 mmol), PEG20000 (0.801 mg) and pyridine (29.6 mL) were charged into a reaction vessel under a nitrogen atmosphere, and after dissolving the mixture by stirring at 30℃for 1 hour, N' -diisopropylcarbodiimide (4.84 g,38.3 mmol) was added dropwise. After the reaction system was stirred at 30℃for 3 hours, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give a polymer 87 (yield: 4.53g, yield: 58%).

Polymerization example 3

[ Chemical formula 295]

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxyl compound (1 '-2-2) (21 g,74 mmol), 4-dicyclohexyl (1.8 g,9.3 mmol), 4- (2-hydroxyethyl) phenol (4.5 g,33 mmol), trans-1, 4-cyclohexanedicarboxylic acid (20 g,120 mmol) and pyridine (119 mL), and the reaction system was stirred at 30℃for 30 minutes to dissolve the compounds, and then N, N' -diisopropylcarbodiimide (32 g,260 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (12 g,120 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (1400 mL). The resulting solid was taken out by filtration, washed with methanol (2000 mL), and dried in vacuo to give polymer 88 (yield: 31.6g, yield: 73%).

Polymerization example 4

[ Chemistry 296]

To a reaction vessel, a dihydroxyl compound (1 '-2-2) (0.98 g,3.49 mmol), 2- (tert-butyl) benzene-1, 4-diol (0.15 g,0.93 mmol), 4- (2-hydroxyethyl) phenol (0.19 g,1.39 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.00 g,5.81 mmol) and pyridine (7.8 mL) obtained in example 2 were added under a nitrogen atmosphere, and the reaction system was stirred at 30℃for 30 minutes to dissolve the compounds, and then N, N' -diisopropylcarbodiimide (1.61 g,12.78 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.6 g,5.81 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give a polymer 89 (yield: 1.49g, yield: 70%).

Polymerization example 5

[ Chemical formula 297]

To a reaction vessel, a dihydroxyl compound (1 '-2-2) (0.98 g,3.49 mmol), 2- (tert-butyl) benzene-1, 4-diol (0.19 g,1.16 mmol), 4- (2-hydroxyethyl) phenol (0.16 g,1.16 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.00 g,5.81 mmol) and pyridine (7.8 mL) obtained in example 2 were added under a nitrogen atmosphere, and the reaction system was stirred at 30℃for 30 minutes to dissolve the compounds, and then N, N' -diisopropylcarbodiimide (1.61 g,12.78 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.6 g,5.81 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 90 (yield: 1.47g, yield: 69%).

Polymerization example 6

[ Chemical formula 298]

To a reaction vessel were added, under a nitrogen atmosphere, a dihydroxyl compound (1 '-2-2) (0.91 g,3.25 mmol), 2- (2, 4-trimethylpentan-2-yl) benzene-1, 4-diol (0.27 g,0.93 mmol), 4- (2-hydroxyethyl) phenol (0.22 g,1.63 mmol), trans-1, 4-cyclohexanedicarboxylic acid (1.00 g,5.81 mmol) and pyridine (7.9 mL), and the reaction system was stirred at 30℃for 30 minutes to dissolve the compounds, and then N, N' -diisopropylcarbodiimide (1.61 g,12.78 mmol) as an ester bond-forming condensing agent was added dropwise to start polymerization. After the reaction system was stirred at 30℃for 3 hours, acetic anhydride (0.6 g,5.81 mmol) was added as a monocarboxylic acid derivative compound. After the reaction system was stirred at 30℃for 30 minutes, the mixture in the system was added to methanol (300 mL). The resulting solid was taken out by filtration, washed with methanol (500 mL), and dried in vacuo to give polymer 91 (yield: 1.35g, yield: 63%).

Example 86

5.4% By weight of polymer 86 and 0.6% by weight of dimethyl phthalate (molecular weight: 194) as a thermal reorientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 4000rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.004 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 7.

Example 87

5.4% By weight of polymer 86 and 0.6% by weight of diisodecyl phthalate (molecular weight: 447) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate and spin-coated at 5000rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.948 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 7.

Example 88

A thin film (film thickness: 1.121 μm) was obtained in the same manner as in example 86, except that ditridecyl phthalate (molecular weight: 531) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 7.

Example 89

A film (film thickness: 1.098 μm) was obtained in the same manner as in example 86, except that tributyl trimellitate (molecular weight: 378) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 7.

Example 90

A film (film thickness: 1.155 μm) was obtained in the same manner as in example 86, except that trihexyl orthobutyryl citrate (molecular weight: 515) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 7.

Example 91

5.7% By weight of polymer 86 and 0.3% by weight of diisodecyl adipate (molecular weight: 427) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 5000rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.021 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 7.

Example 92

A film (film thickness: 0.943 μm) was obtained in the same manner as in example 87 except that diisodecyl adipate (molecular weight: 427) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 7.

Example 93

5.1% By weight of polymer 86 and 0.9% by weight of diisodecyl adipate (molecular weight: 427) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2500rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.981 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 7.

Example 94

4.5% By weight of polymer 86 and 1.5% by weight of diisodecyl adipate (molecular weight: 427) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate and spin-coated at 5000rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.896 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 7.

Example 95

A film (film thickness: 1.019 μm) was obtained in the same manner as in example 86, except that trimethyl phosphate (molecular weight: 140) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 7.

Example 96

A film (film thickness: 1.025 μm) was obtained in the same manner as in example 87, except that a polyester-based plasticizer (ADK CIZER P-300 (molecular weight: 3000)) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 7.

Example 97

A thin film (film thickness: 1.052 μm) was obtained in the same manner as in example 87, except that polyethylene glycol 4000 (molecular weight: 4000) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 7.

Example 98

A film (film thickness: 1.077 μm) was obtained in the same manner as in example 87 except that polyethylene glycol 11000 (molecular weight: 11000) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 7.

Example 99

A thin film (film thickness: 1.141 μm) was obtained in the same manner as in example 87, except that polyethylene glycol 20000 (molecular weight: 20000) was used as a thermal reorientation promoting agent. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 7.

Example 100

A thin film (film thickness: 0.975 μm) was obtained in the same manner as in example 87, except that bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid ] [ ethylenebis (ethylene oxide) ] (molecular weight: 587) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 8.

Example 101

4.5% By weight of polymer 86 and 0.5% by weight of tetrakis [3- (3 ',5' -di-tert-butyl-4 ' -hydroxyphenyl) propionate ] (molecular weight: 1178) as a thermal reorientation promoter were dissolved in 95% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 3000rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.986 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 8.

Example 102

A thin film (film thickness: 1.067 μm) was obtained in the same manner as in example 87 except that bis [3- [3- (tert-butyl) -4-hydroxy-5-methylphenyl ] propionic acid ]2,4,8, 10-tetraoxaspiro [5,5] undecane-3, 9-diylbis (2-methylpropan-2, 1-diyl) ester (molecular weight: 741) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 8.

Example 103

A thin film (film thickness: 0.969 μm) was obtained in the same manner as in example 87, except that triisodecyl phosphite (molecular weight: 503) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 8.

Example 104

A thin film (film thickness: 0.970 μm) was obtained in the same manner as in example 87, except that didodecyl 3,3' -thiodipropionate (molecular weight: 515) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 8.

Example 105

A thin film (film thickness: 1.033 μm) was obtained in the same manner as in example 87, except that bis (1, 2, 6-pentamethyl-4-piperidyl) sebacate (molecular weight: 509) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 190℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 8.

Example 106

5.4% By weight of polymer 87 and 0.6% by weight of dihexylphthalate (molecular weight: 224) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2200rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.033 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 9.

Example 107

A thin film (film thickness: 1.084 μm) was obtained in the same manner as in example 106, except that diphenyl phthalate (molecular weight: 318) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 9.

Example 108

A film (film thickness: 1.042 μm) was obtained in the same manner as in example 106, except that diisodecyl phthalate (molecular weight: 447) was used as the thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 9.

Example 109

A thin film (film thickness: 1.079 μm) was obtained in the same manner as in example 106, except that ditridecyl phthalate (molecular weight: 531) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm, the film was heated to 150℃to obtain a film having a good appearance and exhibiting a high retardation value. The phase difference amounts are shown in table 9.

Example 110

A film (film thickness: 1.018 μm) was obtained in the same manner as in example 106, except that diisodecyl adipate (molecular weight: 427) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 9.

Example 111

A thin film (film thickness: 1.036 μm) was obtained in the same manner as in example 106, except that trihexyl phosphate (molecular weight: 350) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 9.

Example 112

A thin film (film thickness: 1.057 μm) was obtained in the same manner as in example 106, except that triphenyl phosphate (molecular weight: 326) was used as the thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 9.

Example 113

5.7 Wt% of polymer 88 and 0.3 wt% of diisodecyl phthalate (molecular weight: 447) as a thermal re-orientation promoter were dissolved in 94 wt% of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2600rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.996 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 10.

Example 114

5.4% By weight of polymer 88 and 0.6% by weight of diisodecyl phthalate (molecular weight: 447) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2400rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.015 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 10.

Example 115

5.1% By weight of polymer 88 and 0.9% by weight of diisodecyl phthalate (molecular weight: 447) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2300rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.006 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 10.

Example 116

4.8% By weight of polymer 88 and 1.2% by weight of diisodecyl phthalate (molecular weight: 447) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2000rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.125 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 10.

Example 117

A thin film (film thickness: 1.015 μm) was obtained in the same manner as in example 114, except that ditridecyl phthalate (molecular weight: 531) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 10.

Example 118

A thin film (film thickness: 0.995 μm) was obtained in the same manner as in example 114, except that bis (2-ethylhexyl) phthalate (molecular weight: 391) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 10.

Example 119

A thin film (film thickness 1.021 μm) was obtained in the same manner as in example 114, except that tris (2-ethylhexyl) trimellitate (molecular weight: 547) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 10.

Example 120

A film (film thickness: 0.997 μm) was obtained in the same manner as in example 114, except that diisodecyl adipate (molecular weight: 427) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 10.

Example 121

A film (film thickness: 1.019 μm) was obtained in the same manner as in example 114, except that tris (2-ethylhexyl) phosphate (molecular weight: 435) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 10.

Example 122

A thin film (film thickness: 1.027 μm) was obtained in the same manner as in example 114, except that bis (2-ethylhexyl) terephthalate (molecular weight: 391) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 10.

Example 123

A thin film (film thickness: 1.005 μm) was obtained in the same manner as in example 114, except that 2-ethylhexyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate (molecular weight: 394) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 10.

Example 124

A thin film (film thickness: 1.005 μm) was obtained in the same manner as in example 114, except that bis (2-ethylhexyl) 4-cyclohexene-1, 2-dicarboxylate (molecular weight: 395) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 10.

Example 125

5.94% By weight of polymer 89 and 0.06% by weight of diisodecyl phthalate (molecular weight: 447) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2700rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.991 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 11.

Example 126

5.7% By weight of polymer 89 and 0.3% by weight of diisodecyl phthalate (molecular weight: 447) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2600rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.972 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 11.

Example 127

5.4% By weight of polymer 89 and 0.6% by weight of diisodecyl phthalate (molecular weight: 447) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2500rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.009 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 11.

Example 128

5.1% By weight of polymer 89 and 0.9% by weight of diisodecyl phthalate (molecular weight: 447) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2300rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.033 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 11.

Example 129

4.8% By weight of polymer 89 and 1.2% by weight of diisodecyl phthalate (molecular weight: 447) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2000rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.096 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 11.

Example 130

A thin film (film thickness: 0.969 μm) was obtained in the same manner as in example 103, except that bis (2-ethylhexyl) phthalate (molecular weight: 391) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 11.

Example 131

A thin film (film thickness: 0.991 μm) was obtained in the same manner as in example 127, except that di (undecyl) phthalate (molecular weight: 475) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 11.

Example 132

A thin film (film thickness 1.034 μm) was obtained in the same manner as in example 127, except that ditridecyl phthalate (molecular weight: 531) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 11.

Example 133

A thin film (film thickness: 0.992 μm) was obtained in the same manner as in example 127, except that tris (2-ethylhexyl) trimellitate (molecular weight: 547) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 11.

Example 134

A film (film thickness: 0.958 μm) was obtained in the same manner as in example 127, except that diisodecyl adipate (molecular weight: 427) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 11.

Example 135

A film (film thickness: 1.025 μm) was obtained in the same manner as in example 127, except that tris (2-ethylhexyl) phosphate (molecular weight: 435) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 11.

Example 136

A thin film (film thickness: 0.950 μm) was obtained in the same manner as in example 127, except that bis (2-ethylhexyl) terephthalate (molecular weight: 391) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 11.

Example 137

A thin film (film thickness: 0.980 μm) was obtained in the same manner as in example 127, except that 2-ethylhexyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate (molecular weight: 394) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 11.

Example 138

A thin film (film thickness: 0.990 μm) was obtained in the same manner as in example 127, except that bis (2-ethylhexyl) 4-cyclohexene-1, 2-dicarboxylate (molecular weight: 395) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 11.

Example 139

5.4% By weight of polymer 90 and 0.6% by weight of diisodecyl phthalate (molecular weight: 447) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2500rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.010 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 12.

Example 140

5.7% By weight of polymer 90 and 0.3% by weight of diisodecyl adipate (molecular weight: 427) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2600rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.978 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 12.

Example 141

5.1% By weight of polymer 90 and 0.9% by weight of diisodecyl adipate (molecular weight: 427) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2300rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.002 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 12.

Example 142

5.1% By weight of polymer 90 and 0.9% by weight of bis (2-ethylhexyl) terephthalate (molecular weight 391) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2300rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.962 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 12.

Example 143

5.7% By weight of polymer 90 and 0.3% by weight of bis (2-ethylhexyl) 4-cyclohexene-1, 2-dicarboxylate (molecular weight: 395) as a thermal reorientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2600rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.953 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 12.

Example 144

5.1% By weight of polymer 90 and 0.9% by weight of bis (2-ethylhexyl) 4-cyclohexene-1, 2-dicarboxylate (molecular weight: 395) as a thermal reorientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2300rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.967 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 12.

Example 145

5.94% By weight of polymer 91 and 0.06% by weight of diisodecyl phthalate (molecular weight: 447) as thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2700rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.035 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 146

5.7% By weight of polymer 91 and 0.3% by weight of diisodecyl phthalate (molecular weight: 447) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2600rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.931 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 147

5.4% By weight of polymer 91 and 0.6% by weight of diisodecyl phthalate (molecular weight: 447) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2500rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.994 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 148

5.1% By weight of polymer 91 and 0.9% by weight of diisodecyl phthalate (molecular weight: 447) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2300rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.049 μm). After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 149

A thin film (film thickness: 0.952 μm) was obtained in the same manner as in example 147, except that bis (2-ethylhexyl) phthalate (molecular weight: 391) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 150

A thin film (film thickness: 0.970 μm) was obtained in the same manner as in example 147, except that ditridecyl phthalate (molecular weight: 531) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 151

A film (film thickness: 0.954 μm) was obtained in the same manner as in example 147, except that tris (2-ethylhexyl) trimellitate (molecular weight: 547) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 152

A film (film thickness: 0.973 μm) was obtained in the same manner as in example 145, except that diisodecyl adipate (molecular weight: 427) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 153

A film (film thickness: 0.999 μm) was obtained in the same manner as in example 146, except that diisodecyl adipate (molecular weight: 427) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 154

A film (film thickness: 0.953 μm) was obtained in the same manner as in example 147, except that diisodecyl adipate (molecular weight: 427) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 155

A film (film thickness: 1.020 μm) was obtained in the same manner as in example 148, except that diisodecyl adipate (molecular weight: 427) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 156

A film (film thickness: 0.980 μm) was obtained in the same manner as in example 147, except that tris (2-ethylhexyl) phosphate (molecular weight: 435) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 157

A thin film (film thickness: 0.989 μm) was obtained in the same manner as in example 145, except that bis (2-ethylhexyl) terephthalate (molecular weight: 391) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 158

A thin film (film thickness: 0.966 μm) was obtained in the same manner as in example 146, except that bis (2-ethylhexyl) terephthalate (molecular weight: 391) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 159

A thin film (film thickness: 1.037 μm) was obtained in the same manner as in example 147, except that bis (2-ethylhexyl) terephthalate (molecular weight: 391) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 160

A thin film (film thickness: 1.025 μm) was obtained in the same manner as in example 148, except that bis (2-ethylhexyl) terephthalate (molecular weight: 391) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 161

A thin film (film thickness: 0.966 μm) was obtained in the same manner as in example 145, except that bis (2-ethylhexyl) 4-cyclohexene-1, 2-dicarboxylate (molecular weight: 395) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 162

A thin film (film thickness: 0.943 μm) was obtained in the same manner as in example 146, except that bis (2-ethylhexyl) 4-cyclohexene-1, 2-dicarboxylate (molecular weight: 395) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 163

A thin film (film thickness: 1.000 μm) was obtained in the same manner as in example 147, except that bis (2-ethylhexyl) 4-cyclohexene-1, 2-dicarboxylate (molecular weight: 395) was used as a thermal reorientation accelerator. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Example 164

A thin film (film thickness: 1.011 μm) was obtained in the same manner as in example 148, except that bis (2-ethylhexyl) 4-cyclohexene-1, 2-dicarboxylate (molecular weight: 395) was used as a thermal reorientation promoter. After the obtained film was irradiated with linearly polarized ultraviolet light of 365nm at 100mJ/cm ², the film was heated to 150℃to obtain a film having a good appearance and showing a high retardation amount. The phase difference amounts are shown in table 13.

Comparative example 3

6.0 Wt% of polymer 86 was dissolved in 94 wt% 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 5700rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.974 μm). After irradiation of 365nm linearly polarized ultraviolet light at 100mJ/cm ², the resulting film was heated to 190℃and, although the appearance was good, a film exhibiting a high retardation value could not be obtained. The amount of phase difference is shown in table 14.

Comparative example 4

3.9% By weight of polymer 86 and 2.1% by weight of diisodecyl adipate (molecular weight: 427) as a thermal re-orientation promoter were dissolved in 94% by weight of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2500rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.167 μm). After irradiation of 365nm linearly polarized ultraviolet light at 100mJ/cm ², the resulting film was heated to 190℃to obtain a film exhibiting a high retardation but having a poor appearance. The amount of phase difference is shown in table 14.

Comparative example 5

6.0 Wt% of polymer 87 was dissolved in 94 wt% of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate and spin-coated at 3000rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 0.945 μm). After irradiation of 365nm linearly polarized ultraviolet light at 100mJ/cm ², the film was heated to 150℃and, although the appearance was good, a film exhibiting a high retardation value could not be obtained. The amount of phase difference is shown in table 14.

Comparative example 6

6.0 Wt% of polymer 88 was dissolved in 94 wt% 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2700rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.017 μm). After irradiation of 365nm linearly polarized ultraviolet light at 100mJ/cm ², the film was heated to 150℃and, although the appearance was good, a film exhibiting a high retardation value could not be obtained. The amount of phase difference is shown in table 14.

Comparative example 7

6.0 Wt% of polymer 89 was dissolved in 94 wt% of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2700rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.031 μm). After irradiation of 365nm linearly polarized ultraviolet light at 100mJ/cm ², the film was heated to 150℃and, although the appearance was good, a film exhibiting a high retardation value could not be obtained. The amount of phase difference is shown in table 14.

Comparative example 8

6.0 Wt% of polymer 90 was dissolved in 94 wt% of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2700rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.000 μm). After irradiation of 365nm linearly polarized ultraviolet light at 100mJ/cm ², the film was heated to 150℃and, although the appearance was good, a film exhibiting a high retardation value could not be obtained. The amount of phase difference is shown in table 14.

Comparative example 9

6.0 Wt% of polymer 91 was dissolved in 94 wt% of 1, 3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 2700rpm for 60 seconds, and dried in an oven at 60℃for 30 minutes to give a thin film (film thickness 1.006 μm). After irradiation of 365nm linearly polarized ultraviolet light at 100mJ/cm ², the film was heated to 150℃and, although the appearance was good, a film exhibiting a high retardation value could not be obtained. The amount of phase difference is shown in table 14.

TABLE 7

TABLE 8

TABLE 9

TABLE 10

TABLE 11

TABLE 12

TABLE 13

TABLE 14

In tables 7 to 14, re (450)/Re (550) represents the ratio of the in-plane retardation at 450nm to the in-plane retardation at 550 nm. ]

Industrial applicability

By using the polymer of the present invention, a retardation film having inverse wavelength dispersibility can be formed without requiring an alignment film. Therefore, the present invention has high industrial applicability.

Claims

1. A main chain polymer having a photoreactive inverse wavelength dispersion unit in the polymer main chain, the photoreactive inverse wavelength dispersion unit having two functions of photoreactivity and birefringence,

The photoreactive inverse wavelength dispersion unit has a structure represented by the following chemical formula (1):

[ chemical formula 1]

In the chemical formula (1), L ¹、L², which may be the same or different, represents a carbonyl group, an ester bond, an amide bond, an ether bond, or a single bond;

* Represents bonding positions to other structures in the main chain polymer;

Ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, or the condensed ring aromatic ring may have a substituent;

R ⁰、R¹、R²、R³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a group represented by the following formula (Z1);

[ chemical formula 2]

In the chemical formula (Z1), rz ³ and Rz ⁴ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms;

Arz represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, or the condensed ring aromatic ring may have a substituent; the wavy line means a bonding position to a portion other than R ⁰、R¹、R²、R³ or R ⁴ in the formula (1).

2. The main chain polymer according to claim 1, wherein in the chemical formula (1), ar is any one of the following chemical formulas (Ar-1) to (Ar-7):

[ chemical formula 3]

In the chemical formulas (Ar-1) to (Ar-7), X ¹、X²、X³、X⁴、X⁵、X⁶、X⁷ and X ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group, an alkylthio group having 1 to 6 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms;

r ^e represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;

* Represents a bonding position to the other part except Ar in the chemical formula (1).

3. The main chain type polymer according to claim 1, further having at least one structure selected from the group consisting of the following chemical formulas (2A), (2B), (2C) and (2D):

[ chemical formula 4]

In the chemical formula (2A), the ring C, the ring D, and the ring E each independently represent a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, a condensed ring aromatic ring, and an aliphatic hydrocarbon ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, the condensed ring aromatic ring, and the aliphatic hydrocarbon ring may have a substituent;

R ⁵ and R ⁶, which may be the same or different, each represent a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, and an optionally substituted aromatic group having 3 to 12 carbon atoms;

n is 0 or 1;

L ³ and L ⁴, which may be the same or different, represent a carbonyl group, an ester bond, an amide bond, an ether bond, or a single bond;

* Represents bonding positions to other structures in the backbone polymer;

[ chemical formula 5]

In the chemical formula (2B), L ⁹ and L ¹⁰, which may be the same or different, represent a carbonyl group, an ester bond, an amide bond, an ether bond, or a single bond;

* Represents bonding positions to other structures in the backbone polymer;

[ chemical formula 6]

In the chemical formula (2C), X ⁹ represents an alkylene chain having 1 to 10 carbon atoms or a single bond;

X ¹⁰ represents-O-, -N (R ^c) -;

X ¹¹ represents-O-, -N (R ^d) -;

R ^c、R^d, which may be the same or different, represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;

L ¹¹ and L ¹², which may be the same or different, represent a carbonyl group, an ester bond, an amide bond, an ether bond, or a single bond;

* Represents bonding positions to other structures in the backbone polymer;

[ chemical formula 7]

In the chemical formula (2D), the ring G represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, a condensed ring aromatic ring, a spiro ring, and an aliphatic hydrocarbon ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, the condensed ring aromatic ring, the spiro ring, and the aliphatic hydrocarbon ring may have a substituent;

L ¹³ and L ¹⁴, which may be the same or different, represent a single bond or an alkylene chain having 1 to 6 carbon atoms;

L ¹⁵ and L ¹⁶, which may be the same or different, represent a carbonyl group, an ester bond, an amide bond, an ether bond, or a single bond;

* Represents bonding positions to other structures in the backbone polymer.

4. The main chain polymer according to any one of claims 1 to 3, wherein at least one of the main chain polymers is terminated with a monocarboxylic acid ester represented by the following chemical formula (2');

[ chemical formula 8]

In the chemical formula (2'), R ¹⁰ represents a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms which may be substituted, a cycloalkyl group having 3 to 8 carbon atoms which may be substituted, and an aromatic group having 3 to 12 carbon atoms which may be substituted;

* Represents bonding positions to other structures in the backbone polymer.

5. A resin composition comprising 70 to 99.99% by weight of the main chain polymer according to any one of claims 1 to 3 and 0.01 to 30% by weight of a thermal reorientation promoter.

6. A resin composition comprising 70 to 99.99% by weight of the main chain polymer according to claim 4 and 0.01 to 30% by weight of a thermal reorientation promoter.

7. A method for producing the main chain polymer according to any one of claims 1 to 3, comprising polymerizing a raw material composition comprising a dihydroxy compound represented by the following chemical formula (1'):

[ chemical formula 9]

In the chemical formula (1'), R ⁰、R¹、R²、R³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a group represented by the following chemical formula (Z1); ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, or the condensed ring aromatic ring may have a substituent;

[ chemical formula 10]

8. A method for producing a main chain polymer according to claim 4, wherein a monocarboxylic acid derivative compound represented by any one of the following formulas (2-1) and (2-2) is further added in polymerizing a raw material composition containing a dihydroxy compound represented by formula (1'):

[ chemical formula 11]

In the chemical formula (2-1) or (2-2), R ^5a、R^6a and R ⁷ each independently represent a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms which may be substituted, a cycloalkyl group having 3 to 8 carbon atoms which may be substituted, and an aromatic group having 3 to 12 carbon atoms which may be substituted.

9. An optical film comprising the main chain polymer according to any one of claims 1 to 3 or the resin composition according to claim 5.

10. An optical film comprising the main chain polymer according to claim 4 or the resin composition according to claim 6.

11. The optical film according to claim 9 or 10, wherein the phase difference (Re) satisfies the following formula (I):

Re(450)≤Re(550)…(I)

In the formula (I), re (450) represents the in-plane phase difference value measured at a wavelength of 450nm, and Re (550) represents the in-plane phase difference value measured at a wavelength of 550 nm.

12. The optical film according to claim 10, wherein the Yellowness Index (YI) of the film thickness of 5 μm is 5% or less.

13. A method for producing an optical film according to any one of claims 9 to 12, wherein any one of polarized ultraviolet rays and oblique incident ultraviolet rays is irradiated.

14. The method for producing an optical film according to claim 13, further comprising a heat treatment step.

15. A multilayer film provided with the optical film of any one of claims 9 to 12.

16. A dihydroxy compound represented by the following chemical formula (1'):

[ chemical formula 12]

[ chemical formula 13]

17. A process for producing a dihydroxy compound, wherein a dihydroxy compound represented by the following formula (3) is reacted with a ketone represented by the following formula (4 ') to obtain a dihydroxy compound represented by the following formula (1'):

[ chemical formula 14]

In the chemical formula (3), R ⁰、R¹ and R ⁷ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms;

R ^2f represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a formyl group;

[ chemical formula 15]

In the chemical formula (4'), R ⁸ represents an alkyl group having 1 to 8 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms;

Ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, and the condensed ring aromatic ring may have a substituent;

[ chemical formula 16]

In the chemical formula (1'), ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed ring type aromatic ring, wherein an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is taken as a ring constituting atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, and the condensed ring type aromatic ring may have a substituent;

r ⁰、R¹、R²、R³、R⁴ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a group represented by the following formula (Z1);

[ chemical formula 17]

In the formula (Z1), rz ³ and Rz ⁴ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms;