KR20160075515A - Composition for forming cured film, alignment material, and retardation material - Google Patents

Abstract

로 표시되는 기로 이루어진 군으로부터 선택되는 하나를 갖는 저분자 화합물 그리고 광배향성기와, 하이드록시기, 카르복실기, 아미드기, 아미노기 및 알콕시실릴기 및 하기 식(2)로 표시되는 기로 이루어진 군으로부터 선택되는 치환기를 갖는 폴리머로부터 선택되는 적어도 1종, (B) 하이드록시기, 카르복실기, 아미노기, 알콕시실릴기 및 상기 식(2)로 표시되는 기로부터 선택되는 적어도 하나의 치환기를 갖는 폴리머, (C) 가교제, 그리고, (D) 1분자 중에 C=C이중결합을 포함하는 중합성기를 적어도 1개를 갖고 또한 N-알콕시메틸기를 적어도 1개 갖는 저분자 화합물을 함유한다. 이 경화막 형성 조성물을 이용하여, 경화막을 형성하고, 광배향기술을 이용하여 배향재를 형성한다. 배향재 상에 중합성 액정을 도포하고, 경화시켜 위상차재를 얻는다.[PROBLEMS] To provide a cured film-forming composition useful for forming a cured film having excellent liquid crystal alignability and close contact durability, to provide an alignment material, and to provide a retardation material using the alignment material.
A cured film-forming composition comprises (A) a photo-alignable group, a hydroxyl group, a carboxyl group, an amino group, an alkoxysilyl group,
[Chemical Formula 1]

And a group represented by the formula (2), and a group having a photo-orientable group and a substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group, and a group represented by the following formula (B) a polymer having at least one substituent selected from a hydroxyl group, a carboxyl group, an amino group, an alkoxysilyl group and a group represented by the formula (2), (C) a crosslinking agent, and , (D) a low-molecular compound having at least one polymerizable group containing at least one C = C double bond in one molecule and at least one N-alkoxymethyl group. The cured film-forming composition is used to form a cured film, and an alignment material is formed by using a photo-alignment technique. The polymerizable liquid crystal is applied on the alignment material and cured to obtain a retardation.

Description

COMPOSITION FOR FORMING CURED FILM, ALIGNMENT MATERIAL, AND RETARDATION MATERIAL < RTI ID = 0.0 >

The present invention relates to a cured film forming composition, an alignment material and a retardation material.

BACKGROUND ART [0002] In recent years, in the field of displays such as televisions using liquid crystal panels, development of a 3D display capable of enjoying 3D images has been proceeding with an attempt to achieve high performance. In the 3D display, for example, an image with a three-dimensional effect can be displayed by viewing an image for the right eye on the right eye of the observer and viewing an image for the left eye on the left eye of the observer.

There are various types of 3D display methods for displaying 3D images, and a lenticular lens method and a parallax barrier method are known as methods that do not require dedicated glasses.

One of the display methods for observers wearing glasses and observing a 3D image is a circular polarizing glasses method or the like (for example, refer to Patent Document 1).

In the case of a 3D display of a circular polarizing glasses system, a phase difference material is usually arranged on a display element forming an image of a liquid crystal panel or the like. This phase difference material has a plurality of two types of retardation regions with different retardation characteristics and is arranged regularly to constitute a patterned retardation material. Hereinafter, in the present specification, the retardation patterned to arrange a plurality of retardation regions having different retardation characteristics is referred to as a patterned retardation material.

The patterned retardation material can be produced, for example, by optical patterning a retardation material made of a polymerizable liquid crystal as disclosed in Patent Document 2. Optical patterning of a retardation material made of a polymerizable liquid crystal uses a photo-alignment technique known as alignment material formation of a liquid crystal panel. That is, a coating film made of a photo-orientable material is provided on a substrate, and two types of polarized light beams having different polarization directions are irradiated thereto. Then, a photo alignment film is obtained as an alignment material having two types of liquid crystal alignment regions in which alignment control directions of liquid crystals are different. A solution phase phase difference material containing a polymerizable liquid crystal is applied on the photo alignment layer to realize alignment of the polymerizable liquid crystal. Thereafter, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.

In the alignment reformation using the optical alignment technique of a liquid crystal panel, acrylic resin, polyimide resin, or the like having a photo-dimerization site such as a neomoyl group and a knocker on the side chain is known as a usable photo-orientable material. These resins have been reported to exhibit performance (hereinafter also referred to as liquid crystal alignability) for controlling alignment of liquid crystal by irradiating polarized UV (see Patent Documents 3 to 5).

Japanese Patent Application Laid-Open No. H10-232365 Japanese Patent Application Laid-Open No. 2005-49865 Japanese Patent No. 3611342 Specification Japanese Patent Application Laid-Open No. 2009-058584 Japanese Patent Publication No. 2001-517719

As described above, the patterned retardation material is constituted by laminating layers of cured polymerizable liquid crystals on a photo alignment film which is an alignment material. The patterned phase difference material having such a laminated structure can be used in the construction of the 3D display as it is in the laminated state.

The 3D display is sometimes used as a home television, and a high reliability, in particular, a long-term durability is required. Accordingly, durability is also required for the constituent members of the 3D display. Therefore, long-term durability is essential for patterned retardation materials as well as optical patterning with high accuracy (accuracy), high optical transmittance characteristics, and the like.

However, in the conventional patterned retardation material, there is a problem in adhesion between the photo alignment layer and the layer of the polymerizable liquid crystal. For example, there is a tendency that peeling easily occurs at the beginning of the formation between layers of the photo alignment film and the polymerizable liquid crystal, but the adhesiveness is excellent at the initial stage of formation, but the adhesion is decreased with time and the peeling is easily caused.

Among them, the peeling between the photo alignment film and the layer of the polymerizable liquid crystal, which occurs with the lapse of time, becomes a defect of the 3D display actually used, which causes the display quality of the 3D display to deteriorate. Therefore, there is a demand for a patterned retardation material which is capable of high-precision optical patterning, has excellent light transmission characteristics, and is excellent in durability. Particularly, the patterned phase retardation film having excellent adhesion between the photo-alignment film and the polymerizable liquid crystal in the initial stage of formation and durability maintaining the excellent adhesion for a long period of time (hereinafter, referred to as contact durability in the present specification) Ashes are being demanded.

The present invention is based on the above findings and the results of the examination. That is, an object of the present invention is to provide a cured film-forming composition having excellent liquid crystal alignability and light transmittance characteristics and being suitable for forming a cured film having excellent adhesion durability. Particularly, when a layer of a polymerizable liquid crystal is disposed thereon which is used as an alignment material and exhibits excellent liquid crystal alignability and light transmittance, it is possible to provide a cured film having excellent adhesion durability that can maintain adhesion between layers of the polymerizable liquid crystal for a long time Forming composition for forming a cured film.

An object of the present invention is to provide an alignment material excellent in liquid crystal alignment property and light transmission property and excellent in adhesion durability.

An object of the present invention is to provide a phase difference material capable of high-precision optical patterning and having excellent durability.

Other objects and advantages of the present invention will become apparent from the following description.

According to a first aspect of the present invention,

(A) a low molecular compound having a photo-orientable group and at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the following formula (2) A polymer having at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group, and a group represented by the following formula (2)

[Chemical Formula 1]

(Wherein R ⁶² represents an alkyl group, an alkoxy group or a phenyl group).

(B) a polymer having at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the formula (2)

(C) a crosslinking agent, and

(D) a low-molecular compound having at least one polymerizable group having at least one C = C double bond in one molecule and at least one N-alkoxymethyl group

And a curing-film-forming composition.

In the first aspect of the present invention, the component (A) is preferably one selected from a photo-orientable group, a low molecular compound having a hydroxyl group and / or a carboxyl group, and a polymer having a photo-orientable group and a hydroxyl group and / or a carboxyl group Do.

In the first aspect of the present invention, the compound of component (D) is preferably a compound having a structure represented by the following formula (1).

(2)

(Wherein R ¹ represents a hydrogen atom or a methyl group and R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms in a straight chain or branched chain)

In the first aspect of the present invention, the compound of component (D) is preferably a compound having a structure represented by the following formula (X2).

(3)

Wherein R ⁵¹ represents a hydrogen atom or a methyl group. Each R ⁵³ is independently a linear or branched alkylene group of 2 to 20 carbon atoms, a divalent group of an aliphatic ring having 5 to 6 carbon atoms, or a divalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms And may include an ether bond in the structure of these groups. R ⁵⁴ is a divalent to 9-valent group formed by removing 1 to 8 hydrogen atoms from a linear or branched alkyl group having 2 to 20 carbon atoms, a hydrogen atom from an aliphatic group having 5 to 6 carbon atoms, A divalent to ninth aliphatic group having 1 to 8 deleted structures or a divalent to 9-valent aliphatic group including an aliphatic ring having 5 to 6 carbon atoms, and may contain an ether bond in the structure. R ⁵² represents a linear or branched alkyl group having 1 to 20 carbon atoms, a monovalent group comprising an aliphatic ring having 5 to 6 carbon atoms, or a monovalent aliphatic group including an aliphatic ring having 5 to 6 carbon atoms, Or a plurality of non-adjacent methylene groups may be substituted for an ether bond. Z represents > NCOO- or -OCON < (where &quot; - &quot; represents one bonding hand, and & -CH ₂ OR ⁵² ). r is a natural number between 2 and 9 inclusive.]

In the first aspect of the present invention, it is preferable to contain a crosslinking catalyst (E).

A second aspect of the present invention relates to an alignment material characterized by being obtained by using the cured film forming composition of the first aspect of the present invention.

A third aspect of the present invention relates to a retarder characterized by having a cured film obtained from the cured film forming composition of the first aspect of the present invention.

According to the first aspect of the present invention, it is possible to provide a cured film-forming composition favorable for the formation of a cured film having excellent liquid crystal alignability and light transmittance and excellent adhesion durability.

According to the second aspect of the present invention, it is possible to provide an alignment material excellent in liquid crystal alignability and light transmittance and excellent in adhesion durability.

According to the third aspect of the present invention, it is possible to provide a phase difference material capable of high-precision optical patterning and having excellent durability.

As described above, in order to produce an excellent durability patterned retardation material, there is a demand for an alignment material excellent in close contact durability, particularly an alignment material excellent in adhesion durability between layers of a cured polymerizable liquid crystal. There is also a demand for a cured film forming composition favorable for the formation of an alignment material having such a performance.

The inventors of the present invention have conducted intensive studies in order to meet the above-mentioned demand. As a result, the inventors have found that a cured film obtained from a cured film-forming composition having a specific composition is excellent in light transmittance and liquid crystal orientation Indicating that it can be used as an alignment material. Furthermore, the inventors of the present invention have found that a cured film obtained from a cured film-forming composition having a specific composition exhibits excellent adhesion durability between layers of polymerized liquid crystal polymerized and cured thereon. That is, the cured film obtained from the cured film forming composition having the specific composition of the present invention can constitute a photo alignment film having excellent adhesion durability between the layers of the polymerizable liquid crystal.

Hereinafter, the cured film forming composition of the present invention will be described in detail with specific examples of components and the like. Then, the cured film and alignment material of the present invention using the cured film-forming composition of the present invention, the retardation formed by using the alignment material, and the liquid crystal display element are described.

&Lt; Cured film forming composition >

The cured film-forming composition of the present embodiment of the present invention is a cured film-forming composition comprising (A) a photo-alignable group and at least a group selected from the group consisting of hydroxyl group, carboxyl group, amide group, amino group, alkoxysilyl group, A low molecular compound having one substituent and a polymer having at least one substituent selected from the group consisting of a photo-orienting group and a group represented by a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group, and a group represented by the formula (2) (B) a polymer having at least one substituent selected from a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the formula (2), a crosslinking agent as the component (C) And (D) a low molecular weight compound having at least one polymerizable group containing a C = C double bond in one molecule and having at least one N-alkoxymethyl group Curing the film forming composition of the thermosetting containing compound. Further, in addition to the component (A), the component (B), the component (C) and the component (D), a crosslinking catalyst may be contained as the component (E). Further, other additives may be added as long as the effect of the present invention is not impaired. Further, it may contain a solvent.

Hereinafter, the details of each component will be described.

[Component (A)] [

The component (A) of the cured film-forming composition of the present embodiment is at least one member selected from a low molecular weight light component and a high molecular component. First, the case where the component (A) is a low-molecular photo-alignment component will be described below. (A) is a component which imparts photo-alignment property to the cured film of the present embodiment obtained from the cured film forming composition of the present embodiment, and is a low molecular weight component that is a low molecular weight component Of the photo-alignment component.

In the cured film-forming composition of the present embodiment, the low molecular weight photo-aligned component as the component (A) is preferably a photo-aligned group, a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, A group having at least one substituent selected from the group consisting of a group represented by the following formula:

In the present invention, the photo-orientable group means a functional group at a structural site where the photo-dimerization or photo-isomerization occurs.

The structural moiety where the low molecular compound of component (A) can have a light-diminishable light as a photo-orientable group is a moiety that forms a dimer by light irradiation. Specific examples thereof include a cinnamoyl group, , Anthracene group and the like. Of these, a neomoyl group is preferred because of high transparency in the visible light region and high light quantization reactivity.

The photo-isomerizable structural moiety that the low-molecular compound of the component (A) may have as a photo-orientable group refers to a structural moiety which is converted into a cis body and a trans-isomer by light irradiation. Specific examples thereof include an azobenzene structure, And the like. Among them, the azobenzene structure is preferable in view of high reactivity.

Further, examples of the alkoxysilyl group in the present embodiment include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group , A methoxydimethylsilyl group, and an ethoxydimethylsilyl group.

The low molecular weight compound having a photo aligning group and any one of a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a substituent selected from the group represented by the formula (2) can be obtained by, for example, to be.

[Chemical Formula 4]

Wherein A ¹ and A ² each independently represent a hydrogen atom or a methyl group and X ¹¹ represents a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, , A phenyl group, a biphenyl group, or a combination of two or more substituents selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a combination thereof. X ¹² represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group. Here, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, an amide bond, a urethane bond, a carbonyl bond or an urea bond.

X ¹³ represents a hydroxyl group, a mercapto group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a phenoxy group, a biphenyloxy group or a phenyl group. X ¹⁴ each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group. The alkylene group having 1 to 20 carbon atoms may be branched or straight-chain. X ¹⁵ represents a hydroxyl group, a carboxyl group, an amino group, an alkoxysilyl group or a group represented by the formula (2). Provided that when X ¹⁴ is a single bond, X ¹⁵ is a hydroxyl group or an amino group. X ⁰ represents a single bond, an oxygen atom or a sulfur atom. However, when X ¹⁴ is a single bond, X ^{0 is} also a single bond.

When the substituent contains a benzene ring, the benzene ring may be the same or different 1 or 2 selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group and a cyano group. Or may be substituted by a plurality of substituents.

Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms A halogen atom, a trifluoromethyl group or a cyano group.

Examples of the alkyl group having 1 to 18 carbon atoms as defined above include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl- Butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, Dimethyl-n-butyl group, a 2-ethyl-n-butyl group, a 2-ethyl- N-propyl group, 1-ethyl-2-methyl-n-propyl group, Methyl-n-hexyl group, 1, 1-dimethyl-n-pentyl group, 1,2- Dimethyl-n-pentyl group, 1,3-dimethyl-n N-pentyl group, a 1-ethyl-n-pentyl group, a 2-ethyl-n-pentyl group, ethyl-n-butyl group, 1-ethyl-2-methyl-n-butyl group, Ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-heptyl group, 2-methyl- Dimethyl-n-hexyl group, 1, 3-dimethyl-n-hexyl group, 2,2-dimethyl- ethyl-n-hexyl group, 3-ethyl-n-hexyl group, 3-ethyl-n-hexyl group, Ethyl-n-pentyl group, 1-methyl-3-ethyl-n-pentyl group, 2-methyl- methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group N-heptadecyl group, n-heptadecyl group, n-octadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group. Examples of the alkyl group having 1 to 4 carbon atoms likewise include groups having the same number of carbon atoms as the above groups.

Examples of the alkoxy group having 1 to 10 carbon atoms, the alkoxy group having 1 to 4 carbon atoms, and the alkylthio group having 1 to 10 carbon atoms include the groups having the corresponding carbon atoms in the groups in which the above alkyl groups are oxidized or thioated .

Further, examples of the alkylene group having 1 to 20 carbon atoms include a divalent group obtained by removing one hydrogen atom from an alkyl group having 19 to 20 carbon atoms such as the above alkyl group and n-nonadecyl group and n-eicosyl group.

Examples of the alkyl group represented by R ⁶² in the formula (2) include an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, And a group of the corresponding carbon atom number in the alkyl group. Examples of the alkoxy group represented by R ⁶² include an alkoxy group having 1 to 10 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, A group of the carbon atom number corresponding to the group represented by the formula

The group represented by the formula (2) includes, for example, the following structures and the like.

[Chemical Formula 5]

Specific examples of the low-molecular compound having a photo-orientable group and a hydroxy group, which are the component (A), include, for example, 4- (8-hydroxyoctyloxy) cinnamic acid methyl ester, 4- (6- (4-hydroxybutyloxy) cinnamic acid methyl ester, 4- (3-hydroxypropyloxy) cinnamic acid methyl ester, 4- (2-hydroxyethyloxy) cinnamic acid methyl ester, 4- Hydroxyoctyloxy) cinnamic acid ethyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid ethyl ester, 4- (4-hydroxy- (3-hydroxypropyloxy) cinnamic acid ethyl ester, 4- (2-hydroxyethyloxy) cinnamic acid ethyl ester, 4-hydroxymethyloxy cinnamic acid ethyl ester, 4-hydroxy cinnamic acid ethyl ester, Ethyl ester, phenyl 4- (8-hydroxyoctyloxy) cinnamate 4- (2-hydroxybutyloxy) cinnamate phenyl ester, 4- (3-hydroxypropyloxy) cinnamate phenyl ester, 4- (2-hydroxybutyloxy) cinnamate phenyl ester, 4- 4-hydroxymethyloxycinnamic acid phenyl ester, 4- (8-hydroxyoctyloxy) cinnamic acid biphenyl ester, 4- (6-hydroxy- (3-hydroxypropyloxy) cinnamic acid biphenyl ester, 4- (2-hydroxyethyloxy) cinnamic acid biphenyl ester, 4- Biphenyl ester, 4-hydroxymethyloxy cinnamic acid biphenyl ester, 4-hydroxycinnamic acid biphenyl ester, cinnamic acid 8-hydroxyoctyl ester, cinnamic acid 6-hydroxyhexyl ester, cinnamic acid 4-hydroxybutyl ester, cinnamic acid 3 - hydroxypropyl ester, cinnamon 4- (4-hydroxybutyloxy) chalcone, 4- (2-hydroxybutyloxy) chalcone, 4- 4-hydroxymethyloxycalone, 4-hydroxycalcone, 4 '- (8-hydroxyoctyloxy) chalcone, 4- , 4 '- (3-hydroxypropyloxy) chalcone, 4' - (2-hydroxyethyl) chalcone, Hydroxyquinoxalyl) coumarin, 7- (4-hydroxyoxycyclohexyl) coumarin, 7- (4-hydroxyoxycyclohexyl) Hydroxypropyloxy) coumarin, 7- (2-hydroxyethyloxy) coumarin, 7-hydroxymethyloxycoumarin, 7-hydroxycoumarin, 6-hydroxyoctyl Oxycumarin, 6-hydroxyhexyloxy coumarin, (2-hydroxyethyloxy) coumarin, 6-hydroxymethyloxycoumarin, 6-hydroxybutyryloxy coumarin, 6- (4-hydroxybutyloxy) coumarin, 6- Benzoyl] cinnamic acid methyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (6- hydroxyhexyloxy) Oxy] benzoyl] cinnamic acid methyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (2-hydroxyethyloxy) 4- (4-hydroxybenzoyl) cinnamic acid methyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid Ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid ethyl ester, 4- - [4- (4- (4-hydroxyhexyloxy) benzoyl] cinnamic acid tert-butyl ester, 4- [4- (6- Benzoyl] cinnamic acid tert-butyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid tert-butyl ester, 4- [4- (2- hydroxyethyloxy) (4-hydroxymethyloxybenzoyl) cinnamic acid tert-butyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- Benzoyl] cinnamic acid phenyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid phenyl ester and 4- [4- (3- hydroxypropyloxy) benzoyl] Phenyl phenyl ester of 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamate, phenyl ester of 4- [4-hydroxymethyloxybenzoyl] cinnamate, phenyl ester of 4- Benzoyl] cinnamic acid biphenyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (4- (2-hydroxyethyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- Esters, biphenyl ester of 4- [4-hydroxymethyloxybenzoyl] cinnamic acid, biphenyl ester of 4- [4-hydroxybenzoyl] cinnamic acid, 8-hydroxyoctyl ester of 4-benzoyl cinnamic acid, Hydroxyhexyl ester, 4-benzoyl cinnamic acid 4-hydroxybutyl ester, 4-benzoyl cinnamic acid 3-hydroxypropyl ester, Benzoyl cinnamate hydroxymethyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] chalcone, 4- [4- (6- hydroxyhexyloxy) benzoyl] Benzoyl] chalcone, 4- [4- (3-hydroxypropyloxy) benzoyl] chalcone, 4- [4- (2-hydroxyethyloxy) benzoyl] (4-hydroxymethyloxybenzoyl) chalcone, 4- (4-hydroxybenzoyl) chalcone, 4 '- [4- (8- hydroxyoctyloxy) benzoyl] - (6- hydroxyhexyloxy) benzoyl] chalcone, 4 '- [4- (4-hydroxybutyloxy) benzoyl] chalcone, 4' - [4- (3- hydroxypropyloxy) 4'- [4- (2-hydroxyethyloxy) benzoyl] chalcone, 4 '- (4-hydroxymethyloxybenzoyl) chalcone and 4' - (4-hydroxybenzoyl) chalcone.

Specific examples of the low-molecular compound having a photo-aligning group and a carboxyl group, which are the component (A), include cinnamic acid, ferulic acid, 4-nitro cinnamic acid, 4-methoxy cinnamic acid, 3,4-dimethoxy cinnamic acid, coumarin- 4- (6-acryloxyhexyl-1-oxy) cinnamic acid, 4- (6-acryloxyhexyl- 4- (4- (3-methacryloxypropyl-1-oxy) acryloxy) benzoic acid, 4- (4- Benzoyloxy) cinnamic acid and the like.

Specific examples of the low-molecular compound having photo-alignment group and amide group as component (A) include cinnamic acid amide, 4-methyl cinnamic acid amide, 4-ethyl cinnamic acid amide, 4-methoxy cinnamic acid amide, 4-ethoxy cinnamic acid amide 4 (6-methacryloxyhexyl-1-oxy) -N- (4-cyanophenyl) cinnamamide, 4- Oxyhexyl-1-oxy) -N-bishydroxyethylcinnamamide and the like.

Specific examples of the low-molecular compound having photo-aligning group and amino group, which are the component (A), include 4-amino cinnamic acid methyl ester, 4-amino cinnamic acid ethyl ester, 3-amino cinnamic acid methyl ester, 3- .

Specific examples of the low-molecular compound having a photo-orienting group and an alkoxysilyl group, which are components (A), include 4- (3-trimethoxysilylpropyloxy) cinnamate methyl ester, 4- (3-triethoxysilylpropyloxy) Methyl ester, 4- (3-trimethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3-triethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- Ester, 4- (3-triethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylhexyloxy) cinnamic acid ethyl ester and 4- (3-triethoxysilylhexyloxy) Ethyl ester and the like.

Specific examples of the low molecular weight compound having a photo-orientable group and the group represented by the formula (2), which is the component (A), include compounds represented by the following formulas (wherein Me represents a methyl group).

[Chemical Formula 6]

As the component (A), a low-molecular compound in which a polymerizable group is bonded via a spacer to a group in which a photo-orientable region and a thermally reactive site are combined, represented by the following formula (1a), is preferable.

(7)

Wherein R ¹⁰¹ is a group selected from the group consisting of a hydroxyl group, an amino group, a hydroxyphenoxy group, a carboxylphenoxy group, an aminophenoxy group, an aminocarbonylphenoxy group, a phenylamino group, a hydroxyphenylamino group, a carboxyphenylamino group, A hydroxyalkylamino group or a bis (hydroxyalkyl) amino group, X ¹⁰¹ represents a phenylene group which may be substituted with an arbitrary substituent, and the benzene ring in the definition of these substituents may be substituted with a substituent.

Examples of the substituent when the benzene ring may be substituted with a substituent include alkyl groups such as a methyl group, ethyl group, propyl group, butyl group and isobutyl group; A haloalkyl group such as a trifluoromethyl group; An alkoxy group such as a methoxy group or an ethoxy group; Halogen atoms such as iodine, bromine, chlorine and fluorine; Cyano; Nitro group and the like.

Among the R &lt; ¹⁰¹ &gt; s, a hydroxyl group and an amino group are preferable, and a hydroxy group is particularly preferable.

The spacer is a bivalent group selected from the group consisting of straight chain alkylene, branched alkylene, cyclic alkylene and phenylene, or a group formed by combining a plurality of the bivalent groups. In this case, examples of the bond between the bivalent groups constituting the spacer, the bond between the spacer and the group represented by the formula (1a), and the bond between the spacer and the polymerizable group include single bonds, ester bonds, amide bonds, urea bonds, A bond, a carbonyl or an ether bond. When the above-mentioned bivalent groups are plural, the bivalent groups may be the same or different, and when there are a plurality of the bonds, the bonds may be the same or different.

Specific examples of the monomer to which the polymerizable group is bonded to the group in which the photo-orientable portion and the thermally reactive portion, which are the component (A), are bonded are 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid, 4- (4- (3-methacryloxypropyl-1-oxy) acryloxy) benzoic acid, 4- (4-methoxy- 4- (6-methacryloxyhexyl-1-oxy) - cinnamic acid, 4- (6-methacryloxyhexyl- N- (4-cyanophenyl) cinnamamide, 4- (6-methacryloxyhexyl-1-oxy) -N-bishydroxyethylcinnamamide and the like.

Examples of the low molecular weight photo-alignment component as the component (A) include the specific examples described above, but are not limited thereto.

Next, details of the case where the component (A) is a polymer, that is, a polymer having a high molecular weight will be described below.

When the component (A) contained in the cured film-forming composition of the present invention is a high molecular weight polymer, the component (A) is a polymer having a photo-orientable group, that is, a photo- , In particular an acrylic copolymer having at least a light dimerization site. Further, in addition to the photo-dimerization site, at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the formula (2) Crosslinking site).

In the present invention, the acrylic copolymer refers to a copolymer obtained by polymerizing a monomer having an unsaturated double bond such as an acrylate ester, a methacrylate ester, or styrene.

(Hereinafter also referred to as a specific copolymer) having a photo-dimerization site and a thermal crosslinking site of the component (A) may be any acrylic copolymer having such a structure, and the backbone skeleton of the polymer constituting the acrylic copolymer And the kind of the side chain.

Examples of the light dimerization site include a cinnamoyl group, a chalcone group, a coumarin group, and an anthracene group. Among them, a neomoyl group is preferable because of high transparency in the visible light region and high light quantization reactivity. More preferred examples of the substituent containing a cinnamoyl group and a cinnamoyl structure include a structure represented by the following formula [1] or [2]. In the present specification, the group in which the benzene ring in the nenamoyl group is a naphthalene group is also included in the &quot; nenamoyl group &quot; and the &quot; substituent group having a cinnamoyl structure &quot;.

[Chemical Formula 8]

In the formula [1], X ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. At this time, the phenyl group and the biphenyl group may be substituted by either a halogen atom or a cyano group.

In the formula [2], X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. The alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group and the cyclohexyl group may be selected from a covalent bond, an ether bond, an ester bond, an amide bond, an urea bond, a urethane bond, an amino bond, a carbonyl group or a combination thereof Or a plurality of types of bonds may be bonded via one or more kinds of bonds.

In the above formulas [1] and [2], A represents any one of the formula [A1], the formula [A2], the formula [A3], the formula [A4], the formula [A5] and the formula [A6].

In the formula [A1], formula [A2], formula [A3], formula [A4], formula [A5] and formula ^{[A6], R 31, R} 32, R 33, R 34, R 35, R 36, R ³⁷ and R ³⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group or a cyano group.

Examples of the thermal crosslinking site include a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and a group represented by the formula (2) have.

The acrylic copolymer of component (A) preferably has a weight average molecular weight of 3,000 to 200,000. On the other hand, if the weight average molecular weight is less than 3,000 and the weight average molecular weight is less than 3,000, curing will be insufficient at the time of heat curing, There is a case where the resistance is lowered or the heat resistance is lowered.

As a method of synthesizing an acrylic copolymer having a photo-dimerization site and a thermal crosslinking site of the component (A), a method of copolymerizing a monomer having a photo-dimerization site and a monomer having a thermal crosslink site is simple.

Examples of the monomer having a photo-dimerization moiety include monomers having a cinnamoyl group, a chalcone group, a coumarin group, and an anthracene group. Of these, monomers having a nenamoyl group from the high transparency and high photo-dimerization reactivity in the visible light region are particularly preferable.

Among them, a monomer having a substituent including a neomoyl group and a cinnamoyl structure having the structure represented by the above formula [1] or [2] is more preferable. Specific examples of such a monomer are the monomer represented by the following formula [3] or formula [4].

[Chemical Formula 9]

In the formula [3], X ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. At this time, the phenyl group and the biphenyl group may be substituted by either a halogen atom or a cyano group.

L ¹ and L ² each independently represent a covalent bond, an ether bond, an ester bond, an amide bond, an urea bond or a urethane bond.

In the formula [4], X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. In this case, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded through a covalent bond, an ether bond, an ester bond, an amide bond, or an urea bond.

In the formulas [3] and [4], X ³ and X ⁵ each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group or a divalent aliphatic ring group. The alkylene group having 1 to 20 carbon atoms may be branched or straight-chain.

In the formulas [3] and [4], X ⁴ and X ⁶ represent a polymerizable group. Specific examples of the polymerizable group include an acryloyl group, a methacryloyl group, a styrene group, a maleimide group, an acrylamide group, and a methacrylamide group.

In the above formulas [3] and [4], A is a group represented by the formula [A1], the formula [A2], the formula [A3], the formula [A4] And formula [A6].

Examples of the above alkyl group and alkylene group as the alkyl group having 1 to 18 carbon atoms and the alkyl group having 1 to 20 carbon atoms in the definitions of the groups in the above formulas [1] to [4] include the above-

The monomer having a thermal crosslinking site includes, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, Hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate Caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxy norbornene-2-carboxyl-6-lactone, 5-methacryloyloxy-6-hydroxy norbornene- Monomers having a hydroxy group; Acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N - (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, and the like; (Hydroxyphenyl) maleimide, N- (hydroxyphenyl) maleimide and the like such as N- (hydroxyphenyl) methacrylamide, N- A monomer having a group; Monomers having an amide group such as acrylamide and methacrylamide; Monomers having an alkoxysilyl group such as methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, acryloyloxypropyltrimethoxysilane, and acryloyloxypropyltriethoxysilane; Monomers having an amino group such as dimethylaminoethyl methacrylate, diethylaminomethacrylate and tert-butylaminoethyl methacrylate; And monomers having a group represented by the formula (2) such as 2-acetoacetoxyethyl acrylate and 2-acetoacetoxyethyl methacrylate.

The amount of the monomer having the photo-dimerizing moiety and the monomer having the thermally crosslinking moiety used for obtaining the specific copolymer is preferably 40 to 40% by weight based on the total amount of the total monomers used for obtaining the specific copolymer, By mass to 95% by mass, and a monomer having a thermal crosslinking site in an amount of 5% by mass to 60% by mass. When the content of the monomer having the photo-dimerization site is 40 mass% or more, high sensitivity and good liquid crystal alignability can be given. On the other hand, when it is 95 mass% or less, sufficient thermosetting property can be imparted, and high sensitivity and good liquid crystal alignability can be maintained.

In the composition for forming a cured film of the present invention, a monomer copolymerizable with a monomer having a photo-dimerization site and a thermal crosslinking site (hereinafter also referred to as a specific functional group) (hereinafter referred to as a monomer having a non-reactive functional group Also referred to as a monomer) can be used in combination.

Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

Hereinafter, specific examples of the monomer are mentioned, but the present invention is not limited thereto.

Examples of the acrylic ester compound include acrylic esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, Acrylates such as glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate 2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methoxybutyl acrylate, 2- Methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl Methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, Methoxyethyl methacrylate, 2-methoxyethyl methacrylate, methoxy triethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, Adamantyl methacrylate,? -Butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8- Tricyclodecyl methacrylic And the like.

Examples of the above-mentioned vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

Examples of the above-mentioned styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

Examples of the maleimide compound described above include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The method for obtaining the specific copolymer used in the cured film-forming composition of the present invention is not particularly limited. For example, a monomer having a specific functional group (a monomer having a light dimerization site and a monomer having a thermal crosslinking site) In a solvent in which a monomer having a non-reactive functional group and a polymerization initiator are coexisted, at a temperature of 50 ° C to 110 ° C. The solvent to be used at this time is not particularly limited as long as it can dissolve monomers having specific functional groups, monomers having non-reactive functional groups to be used as needed, and polymerization initiators. Specific examples include the solvents described in the below-mentioned solvents.

The specific copolymer thus obtained is usually in the form of a solution dissolved in a solvent and can be used as it is as a solution of the component (A) in the present invention.

The solution of the specific copolymer thus obtained may be re-precipitated by the addition of diethyl ether, water or the like with stirring, and the resultant precipitate may be filtered and washed and then dried at room temperature or under reduced pressure or by heating and drying, It can be a powder of a specific copolymer. By this operation, the polymerization initiator coexisting with the specific copolymer and the unreacted monomer can be removed, and as a result, the purified specific copolymer powder can be obtained. When the powder can not be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

In the cured film-forming composition of the present invention, the powder of the specific copolymer may be used as the component (A) as it is, or the powder may be used as a solution in a solvent, for example, as described below.

Further, in the present embodiment, the acrylic copolymer of component (A) may be a mixture of plural kinds of specific copolymers.

As described above, in the present invention, as the component (A), a compound having a low molecular weight or a specific copolymer having a high molecular weight can be used. Further, the component (A) may be a mixture of one or more kinds of low molecular weight compounds and specific copolymers of high molecular weight.

[Component (B)] [

The component (B) contained in the cured film-forming composition of the present embodiment is at least one substituent selected from a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and the group represented by the formula (2) , A specific functional group). Examples of the alkoxysilyl group in the component (B) include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group , A methoxydimethylsilyl group, and an ethoxydimethylsilyl group.

Examples of the polymer as the component (B) include polymers such as acrylic polymers, polyamic acids, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylic acids, polyether polyols, polyester polyols, polycarbonate polyols, A cyclic polymer such as a polymer having a straight chain structure or a branched chain structure such as a polyol, a polyalkyleneimine, a polyallylamine, a cellulose (a cellulose or a derivative thereof), a phenol novolac resin or a melamine formaldehyde resin, .

Specific examples of the specific polymer as the component (B) include an acrylic polymer, a hydroxyalkylcyclodextrin, a cellulose, a polyether polyol, a polyester polyol, a polycarbonate polyol and a polycaprolactone polyol.

(B) is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, or a vinyl compound, and is preferably a polymer obtained by polymerizing a monomer containing a monomer having a specific functional group Or a mixture thereof, and is not particularly limited as to the skeleton of the main chain of the polymer constituting the acrylic polymer and the kind of the side chain.

Examples of the monomer having a specific functional group include monomers having a polyethylene glycol ester group, monomers having a hydroxyalkyl ester group having 2 to 5 carbon atoms, monomers having a phenolic hydroxy group, monomers having a carboxyl group, monomers having an amide group, A monomer, an alkoxysilyl group and a monomer having a group represented by the formula (2).

Examples of the above-mentioned monomer having a polyethylene glycol ester group include monoacrylate or monomethacrylate of H- (OCH ₂ CH ₂ ) n -OH. The value of n is 2 to 50, preferably 2 to 10.

Examples of the monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms as described above include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2 -Hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate.

Examples of the above-mentioned monomer having a phenolic hydroxy group include p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene.

Examples of the above-mentioned monomer having a carboxyl group include acrylic acid, methacrylic acid and vinylbenzoic acid.

Examples of the monomer having the above-described amino group in the side chain include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate.

Examples of the monomer having the above-described alkoxysilyl group in the side chain include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, and the like.

Examples of the monomer having a group represented by the above-described formula (2) in the side chain include 2-acetoacetoxyethyl acrylate and 2-acetoacetoxyethyl methacrylate.

In the present embodiment, in the synthesis of the acrylic polymer, which is an example of the component (B), a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, ) Can be used in combination.

Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2 , 2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2- Methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate , And 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, ethyl methacrylate, ethyl methacrylate, butyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, Methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl methacrylate, 2-ethylhexyl methacrylate, Adamantyl methacrylate, 2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

The amount of the monomer having a specific functional group used for obtaining the acrylic polymer which is an example of the component (B) is preferably from 2 mol% to 98 mol% based on the total amount of all the monomers used for obtaining the acrylic polymer as the component (B) Do. When the monomer having a specific functional group is too small, the liquid crystal alignability of the obtained cured film tends to become insufficient, and in the case of excess, the compatibility with the component (A) tends to deteriorate.

The method for obtaining the acrylic polymer which is an example of the component (B) is not particularly limited. For example, a method in which a monomer containing a monomer having a specific functional group, a monomer having no specific functional group, In the range of 50 to 110 캜. The solvent to be used at this time is not particularly limited as long as it dissolves the monomer having a specific functional group, the monomer having no specific functional group to be used, if necessary, and the polymerization initiator. Specific examples are described in the section [solvent] described later.

The acrylic polymer which is an example of the component (B) obtained by the above method is usually in the state of a solution dissolved in a solvent.

Further, a solution of an acrylic polymer, which is an example of the component (B) obtained by the above-mentioned method, is re-precipitated by being added to diethyl ether or water under stirring, and the resultant precipitate is filtered and washed and then dried at room temperature or reduced pressure And dried by heating to obtain a powder of an acrylic polymer which is an example of the component (B). By the above-described operation, the polymerization initiator coexisting with the acrylic polymer serving as the component (B) and the unreacted monomer can be removed. As a result, a powder of an acrylic polymer which is an example of the purified component (B) is obtained. When the powder can not be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above-described operation may be repeated.

The acrylic polymer, which is a preferred example of the component (B), has a weight average molecular weight of preferably from 3,000 to 200,000, more preferably from 4,000 to 150,000, and still more preferably from 5,000 to 100,000. If the weight-average molecular weight is more than 200,000, the solubility in the solvent is lowered and the handling property may be lowered. If the weight-average molecular weight is less than 3,000 and the weight average molecular weight is excessively small, curing becomes insufficient during heat curing, The heat resistance may be lowered. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as standard data. Hereinafter, the same shall apply in the present specification.

Polyether polyol, which is a preferable example of the specific polymer of the component (B), may, for example, be a polyol such as polyethylene glycol, polypropylene glycol, propylene glycol or polyhydric alcohols such as bisphenol A, triethylene glycol, sorbitol, Glycol, and the like. Specific examples of polyether polyols include ADEKA polyether P series, G series, EDP series, BPX series, FC series, CM series manufactured by ADEKA, UNIOX (registered trademark) HC-40, HC- TG-1000, TG-3000, TG-4000, HS-1600D, DA-60, ST-30E, ST-40E, G-450, G-750, UNIOL (registered trademark) 400, DA-700, DB-400, NONION (registered trademark) LT-221, ST-221 and OT-221.

Examples of the polyester polyol which is a preferable example of the specific polymer of the component (B) include polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol and the like in addition to adipic acid, sebacic acid and isophthalic acid. Followed by reaction with diol. Specific examples of the polyester polyol include POLYLITE (POLYLITE) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD- X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD- P-510, P-1010, P-2010, P-3010, P-4010 and P-5010 manufactured by Kuraray Co., , P-6010, F-510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010 and PNNA-2016.

Examples of the polycaprolactone polyol which is a preferable example of the specific polymer of the component (B) include those obtained by ring-opening polymerization of ε-caprolactone using initiators such as trimethylolpropane and ethylene glycol. Specific examples of the polycaprolactone polyol include POLYLITE (registered trademark) OD-X-2155, OD-X-640, OD-X-2568 manufactured by DIC, PLACCEL (registered trademark) 205, L205AL, , 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, and the like.

Examples of the polycarbonate polyol which is a preferable example of the specific polymer of the component (B) include those obtained by reacting a polyalcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like. Specific examples of the polycarbonate polyol include PLACCEL (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel Corporation, C-590, C-1050, C-2050, C- 3090 and the like.

Examples of the cellulose which is a preferable example of the specific polymer of component (B) include hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxyethylethylcellulose and the like Hydroxyalkylcelluloses such as hydroxyethylcellulose, hydroxypropylcellulose and the like are preferable, and hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose are preferred.

Examples of the cyclodextrin which is a preferable example of the specific polymer of the component (B) include cyclodextrins such as -cyclodextrin, -cyclodextrin and -cyclodextrin, methyl-? -Cyclodextrin, methyl? -Cyclodextrin and methyl- hydroxymethyl-? -cyclodextrin, hydroxymethyl-? -cyclodextrin, 2-hydroxyethyl-? -cyclodextrin, 2- methylethyl-? -cyclodextrin and? -cyclodextrin, Hydroxypropyl-? -Cyclodextrin, 2-hydroxyethyl-? -Cyclodextrin, 2-hydroxypropyl-? -Cyclodextrin, 2-hydroxypropyl- Cyclodextrin, 3-hydroxypropyl-? -Cyclodextrin, 3-hydroxypropyl-? -Cyclodextrin, 3-hydroxypropyl-? -Cyclodextrin, 2,3-dihydroxypropyl-? Lin host, and the like can be mentioned 2,3-di-hydroxypropyl -β- cyclodextrin, 2,3-di-hydroxypropyl -γ- cycloalkyl hydroxyalkyl cyclodextrin, such as cyclodextrin.

The melamine formaldehyde resin, which is a preferable example of the specific polymer of component (B), is a resin obtained by polycondensation of melamine and formaldehyde, and is represented by the following formula.

[Chemical formula 10]

In the formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is a natural number representing the number of repeating units. Examples of the alkyl group having 1 to 4 carbon atoms include groups having the same number of carbon atoms as the alkyl groups exemplified above or below.

In the melamine formaldehyde resin as the component (B), it is preferable that the methylol group formed at the time of polycondensation of melamine and formaldehyde is alkylated from the viewpoint of storage stability.

The method for obtaining the melamine formaldehyde resin as the component (B) is not particularly limited. Generally, melamine and formaldehyde are mixed and made weakly alkaline by using sodium carbonate, ammonia or the like, and then heated at 60 ° C to 100 ° C, do. Further, the methylol group can be alkoxylated by reacting with an alcohol.

The melamine formaldehyde resin as the component (B) preferably has a weight average molecular weight of 250 to 5000, more preferably 300 to 4000, and still more preferably 350 to 3500. If the weight-average molecular weight is over 5000, the solubility in a solvent is lowered and the handling property is lowered. If the weight-average molecular weight is less than 250 and the weight average molecular weight is less than 250, hardening becomes insufficient during thermal curing, The effect of improving the heat resistance may not be sufficiently exhibited.

In the embodiment of the present invention, the melamine formaldehyde resin as the component (B) may be in a liquid form or may be used in the form of a solution in which the purified liquid is redissolved in a solvent described later.

In the embodiment of the present invention, the melamine formaldehyde resin as the component (B) may be a mixture of plural kinds of the melamine formaldehyde resin as the component (B).

Examples of the phenol novolak resin which is a preferable example of the specific polymer of component (B) include phenol-formaldehyde polycondensate and the like.

In the cured film forming composition of the present embodiment, the polymer of component (B) may be in the form of a powder, or the purified powder may be used in the form of a solution which is redissolved in a solvent to be described later.

Further, in the cured film-forming composition of the present embodiment, the component (B) may be a mixture of plural kinds of the polymers exemplified as the component (B).

[Component (C)] [

The cured film forming composition of the present embodiment contains, as a component (C), a crosslinking agent. More specifically, the component (C) reacts with the aforementioned component (A), component (B) and component (D) described below, and when component (A) is a low molecular photo- It is a crosslinking agent which reacts at a lower temperature than the sublimation temperature of the component (A). The component (C) is a compound having a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group of the low molecular compound and / or polymer as the component (A) at a temperature lower than the sublimation temperature of the component (A) A substituent selected from a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the formula (2) contained in the component (B), a compound (D) Lt; / RTI &gt; As a result, sublimation of the component (A) can be suppressed when the component (A), the component (B) and the component (D) are thermally reacted with the crosslinking agent as the component (C). The cured film forming composition of the present embodiment can form an alignment material having a high photoreaction efficiency as a cured film.

Examples of the crosslinking agent as the component (C) include compounds such as epoxy compounds, methylol compounds and isocyanato compounds, preferably methylol compounds.

Specific examples of the methylol compounds described above include, for example, compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

Specific examples of the alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) (Methoxymethyl) urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis ) -4,5-dimethoxy-2-imidazolidinone. As a commercial product, a compound such as a glycoluril compound (trade name: CYMEL (registered trademark) 1170, POWDERLINK (registered trademark) 1174) manufactured by Mitsui Cytec Ltd., a methylation urea resin (trade name: UFR U-VAN10S60, U-VAN10R, U-VAN11HV) manufactured by Dainippon Ink and Chemicals, Inc. Urethane / formaldehyde resin (high condensation type, Trade name: BECKAMINE (registered trademark) J-300S, BECKAMINE P-955, BECKAMINE N).

Specific examples of the alkoxymethylated benzoguanamine include, for example, tetramethoxymethylbenzoguanamine. (Trade name: CYMEL (registered trademark) 1123) manufactured by Mitsui Cytec Ltd., NIKALAC (registered trademark) BX-4000, NIKALAC BX-37 manufactured by Sanwa Chemical Co., NIKALAC BL-60, NIKALAC BX-55H).

Specific examples of the alkoxymethylated melamine include, for example, hexamethoxymethylmelamine and the like. As a commercial product, a methoxymethyl type melamine compound (trade name: CYMEL (registered trademark) 300, CYMEL 301, CYMEL 303, CYMEL 350 manufactured by Mitsui Cytec Ltd.), butoxymethyl type melamine compound (trade name: MYCOAT NIKALAC MW-30, NIKALAC MW-22, NIKALAC MW-11, NIKALAC MS-001 manufactured by Sanwa Chemical Industrial Co., Ltd. (trade name: NIKALAC MX-45, NIKALAC MX-410, NIKALAC MX-302), butoxymethyl type melamine compounds (trade names: NIKALAC MX-002, NIKALAC MX-730, NIKALAC MX- And the like.

A compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, a high molecular weight compound prepared from a melamine compound and a benzoguanamine compound described in U.S. Patent 6,323,310 can be mentioned. CYMEL (registered trademark) 303 (manufactured by Mitsui Cytec Ltd.) and the like can be used as a commercially available product of the above-mentioned melamine compound. Commercially available products of the above benzoguanamine compound include CYMEL (registered trademark) 1123 Ltd.).

Examples of the component (C) include hydroxymethyl groups such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide and N-butoxymethylmethacrylamide, or alkoxymethyl groups Or a polymer prepared by using a methacrylamide compound may also be used.

Such polymers include, for example, poly (N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methylmethacrylate, A copolymer of N-ethoxymethylmethacrylamide and benzylmethacrylate, and a copolymer of N-butoxymethylacrylamide and benzylmethacrylate and 2-hydroxypropylmethacrylate. The weight average molecular weight of such a polymer is 1000 to 500000, preferably 2000 to 200000, more preferably 3000 to 150000, and still more preferably 3000 to 50000.

These crosslinking agents may be used alone or in combination of two or more.

The content of the crosslinking agent in the component (C) in the cured film-forming composition of the present embodiment is preferably 100 parts by mass or more, more preferably 100 parts by mass or less, , More preferably 15 parts by mass to 80 parts by mass. When the content of the crosslinking agent is too low, the solvent resistance and heat resistance of the cured film obtained from the cured film-forming composition are lowered, and the orientation sensitivity at the time of photo curing is lowered. On the other hand, when the content is excessive, the photoalignment property and the storage stability may be deteriorated.

[Component (D)] [

The component (D) contained in the cured film-forming composition of the present embodiment is a low molecular compound having at least one polymerizable group containing a C═C double bond in one molecule and at least one N-alkoxymethyl group.

When the cured film formed from the cured film forming composition of the present embodiment containing the component (D) is used as the alignment material, the polymerizable functional group of the polymerizable liquid crystal and the alignment material Linking reaction sites can be linked by covalent bonds. As a result, the retarder of the present embodiment, which is obtained by laminating the cured polymerizable liquid crystal on the alignment material of the present embodiment, can maintain strong adhesion even under high-temperature and high-quality conditions and exhibit high durability against peeling and the like .

Examples of the polymerizable group containing a C = C double bond include an acryl group, a methacryl group, a vinyl group, an allyl group, and a maleimide group.

The N, i.e., nitrogen atom of the N-alkoxymethyl group is bonded to the nitrogen atom of the amide, the nitrogen atom of the thioamide, the nitrogen atom of the urea, the nitrogen atom of the thiourea, the nitrogen atom of the urethane, or the nitrogen atom of the nitrogen hetero- Nitrogen atom and the like. Accordingly, examples of the N-alkoxymethyl group include nitrogen atom bonded to the adjacent position of the nitrogen atom of the amide, the nitrogen atom of the thioamide, the nitrogen atom of the urea, the nitrogen atom of the thiourea, the nitrogen atom of the urethane, and the nitrogen atom of the nitrogen hetero- Is bonded to an alkoxymethyl group.

As the component (D), those having the above-mentioned groups may be used. Preferable examples thereof include compounds represented by the following formula (1).

(11)

(Wherein R ¹ represents a hydrogen atom or a methyl group and R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms in a straight chain or branched chain)

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-butyl group, n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2- Butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-butyl group, Propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1-methyl methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1,3- Dimethyl-n-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3- Pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n-pentyl group, Butyl group, 1-methyl-2-ethyl-n-butyl group, 1-ethyl- methyl-n-heptyl group, 1, 1-dimethyl-n-hexyl group, 1-methyl-n-hexyl group, Dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-pentyl group, 1-methyl-2-pentyl group, 2-ethyl-n-hexyl group, Ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl- 3-ethyl-n-pentyl group, n-nonyl group, and n-decyl group.

Specific examples of the compound represented by the formula (1) include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N- Methylol acrylamide, and the like.

As another embodiment of the compound having an N-alkoxymethyl group and a polymerizable group containing a C = C double bond in the component (D), for example, a compound represented by the following formula (X2) can be preferably used .

[Chemical Formula 12]

Wherein R ⁵¹ represents a hydrogen atom or a methyl group. R ⁵³ represents a bivalent group consisting of an alkylene group having 2 to 20 carbon atoms in the straight chain or branched chain, an aliphatic ring having 5 to 6 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms, May include an ether linkage. R &lt; ⁵⁴ &gt; is a divalent to 9-valent group formed by removing 1 to 8 hydrogen atoms from a linear or branched alkyl group having 2 to 20 carbon atoms, an aliphatic group having 5 to 6 carbon atoms, A divalent to ninth aliphatic group having 8 or more eliminated structures or a divalent to 9-valent aliphatic group including an aliphatic ring having 5 to 6 carbon atoms, and may contain an ether bond in the structure. R ⁵² represents a linear or branched alkyl group having 1 to 20 carbon atoms, a monovalent group comprising an aliphatic ring having 5 to 6 carbon atoms, or a monovalent aliphatic group including an aliphatic ring having 5 to 6 carbon atoms, Or a plurality of non-adjacent methylene groups may be substituted for an ether bond. Z represents > NCOO- or -OCON < (where &quot; - &quot; represents one bonding hand, and & -CH ₂ OR ⁵² ). r is a natural number between 2 and 9 inclusive.]

An alkylene group having 2 to 20 carbon atoms in the definition of R ⁵³ , and a divalent to twenty-one having a structure in which 1 to 8 hydrogen atoms are removed from an alkyl group having 2 to 20 carbon atoms in the straight chain or branched chain in the definition of R ⁵⁴ . Specific examples of the 9-valent group include 2 to 9-valent groups obtained by removing 1 to 8 hydrogen atoms from an alkyl group having 2 to 20 carbon atoms shown below.

Specific examples of the alkyl group having 2 to 20 carbon atoms in the alkyl group include an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, Methyl-n-butyl group, a 1-methyl-n-propyl group, an n-hexyl group, Butyl group, a 1-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, an n-heptyl group, n-pentyl group, n-hexadecyl group, n-hexadecyl group, n-hexadecyl group, n-octadecyl group, N-octadecyl group, n-nonadecyl group, and n-eicosyl group, and one or more of these groups may be bonded to each other in a range of up to 20 carbon atoms, and one of these groups, methylene Or a group in which a plurality of non-neighboring methylene groups are substituted by an ether bond.

Of these, an alkylene group having 2 to 10 carbon atoms is preferable, R ⁵³ is an ethylene group, and R ⁵⁴ is a hexylene group, from the viewpoint of the availability of raw materials and the like.

Specific examples of the alkyl group having 1 to 20 carbon atoms in the definition of R ⁵² include specific examples of the alkyl group having 2 to 20 carbon atoms and methyl group in the definition of R ⁵³ and R ⁵⁴ . Of these, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group or an n-butyl group is particularly preferable.

Examples of the aliphatic ring group having 5 to 6 carbon atoms in the definition of R ⁵² , R ⁵³ and R ⁵⁴ include a group based on a cyclopentyl group and a cyclohexyl group. In addition to a cyclopentyl group and a cyclohexyl group which are monovalent groups, A divalent to 9-valent group formed by removing 1 to 8 further hydrogen atoms from the aliphatic ring group having 5 to 6 carbon atoms and a monovalent or divalent group containing an aliphatic ring having 5 to 6 carbon atoms, A group in which one or more of the 9-valent aliphatic groups is bonded in a range of up to 20 carbon atoms, and further one of these groups, methylene or a group in which a plurality of non-adjacent methylene groups are substituted by an ether bond .

As r, natural numbers of 2 or more and 9 or less are exemplified. Of these, 2 to 6 are preferable.

Compound (X2) is obtained by the production method shown by the following reaction scheme. Namely, a carbamate compound (hereinafter also referred to as a compound (X2-1)) having an acrylic or methacryl group represented by the following formula (X2-1) is reacted in a solvent containing trimethylsilyl chloride and paraformaldehyde to obtain Is synthesized by synthesizing an intermediate represented by the formula (X2-2), adding an alcohol represented by R &lt; ⁵² &gt; -OH to the reaction solution and reacting.

[Chemical Formula 13]

In the formula, R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , Z and r have the same meanings as above, and X represents -NHCOO- or -OCONH-.

The amount of the trimethylsilyl chloride and the paraformaldehyde to be used for the compound (X2-1) is not particularly limited. To complete the reaction, 1.0 to 6.0 equivalents of trimethylsilyl chloride is added to one carbamate bond in the molecule, The formaldehyde is preferably used in an amount of 1.0 to 3.0 equivalents, and the use equivalent of trimethylsilyl chloride is more preferably greater than the equivalent amount of paraformaldehyde.

The reaction solvent is not particularly limited as long as it is inert to the reaction, and for example, hydrocarbons such as hexane, cyclohexane, benzene, and toluene; Halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, chloroform, and 1,2-dichloroethane; Ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane and tetrahydrofuran; Nitriles such as acetonitrile and propionitrile; Protonic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone; And pyridine such as pyridine and picoline. These solvents may be used alone or in combination of two or more of them. It is preferably methylene chloride or chloroform, more preferably methylene chloride.

The amount of the solvent to be used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent. When a solvent is used, 0.1 to 100 times by mass of the solvent may be used relative to the compound (X2-1) have. Preferably 1 to 30 times by mass, and more preferably 2 to 20 times by mass.

The reaction temperature is not particularly limited, but is, for example, from -90 to 200 캜, preferably from -20 to 100 캜, more preferably from -10 to 50 캜.

The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.

The reaction may be carried out under atmospheric pressure or under pressure, and may be carried out in a batch or a continuous manner.

In the reaction, a polymerization inhibitor may be added. Examples of such a polymerization inhibitor include BHT (2,6-di-tertiarybutyl-para-cresol), hydroquinone, para-methoxyphenol and the like, and they are particularly limited as long as they inhibit polymerization of an acryl group or a methacryl group It does not.

The addition amount of the polymerization inhibitor is not particularly limited, but it is 0.0001 to 10 wt%, preferably 0.01 to 1 wt%, based on the total amount (mass) of the compound (X2-1). In the present specification, wt% means mass%.

In the step of reacting the intermediate (X2-2) with an alcohol, a base may be added to suppress hydrolysis under acidic conditions. Examples of the base include pyridine such as pyridine and picoline, and tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine and tributylamine. Preferably triethylamine or diisopropylethylamine, and more preferably triethylamine. The amount of the base to be added is not particularly limited, but may be 0.01 to 2.0 equivalents, more preferably 0.5 to 1.0 equivalents, based on the amount of trimethylsilyl chloride used in the reaction.

Alternatively, after the intermediate (X2-2) is obtained from the compound (X2-1), the intermediate (X2-2) may be reacted by adding alcohol without isolation.

The method of synthesizing the compound (X2-1) is not particularly limited, but may be produced by reacting a (meth) acryloyloxyalkyl isocyanate with a polyol compound or by reacting a hydroxyalkyl (meth) acrylate compound with a polyisocyanate compound .

Specific examples of the (meth) acryloyloxyalkyl isocyanate include 2-methacryloyloxyethyl isocyanate (trade name: KARENZ (trade name), manufactured by Showa Denko KK), 2-acryloyloxyethyl isocyanate And monoethyl isocyanate (trade name: KARENZ AOI [registered trademark]) manufactured by Showa Denko KK.

Specific examples of the polyol compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl- Diol compounds such as 6-hexanediol and 1,4-cyclohexanedimethanol, triol compounds such as glycerin and trimethylolpropane, pentaerythritol, dipentaerythritol, diglycerin and the like.

Specific examples of the hydroxyalkyl (meth) acrylate compound include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4 Diethylene glycol monomethacrylate, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, diethylene glycol monomethacrylate, And hydroxyl group-containing monomers such as a carboxylate and a carboxylate.

Specific examples of the polyisocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and dimer acid diisocyanate, isophorone diisocyanate, 4,4'-methylene bis (cyclohexyl Alicyclic diisocyanate such as ω, ω'-diisocyanate dimethylcyclohexane, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, , Triisocyanates such as 3,6-hexamethylene triisocyanate and bicycloheptane triisocyanate, and the like.

These (meth) acryloyloxyalkyl isocyanate compounds, polyol compounds, hydroxyalkyl (meth) acrylate compounds and polyisocyanate compounds are generally commercially available and can be synthesized by a known method.

The content of the component (D) in the cured film-forming composition of the embodiment of the present invention is preferably such that the content of the component (A) is at least one selected from a low molecular compound and a polymer, a polymer of the component (B) Is preferably from 0.1 to 40 parts by mass, and more preferably from 5 to 35 parts by mass based on 100 parts by mass of the total amount of When the content of the component (D) is 0.1 part by mass or more, sufficient adhesion can be imparted to the cured film to be formed. However, if it is more than 40 parts by mass, the storage stability of the cured film-forming composition may be deteriorated.

In the cured film-forming composition of the present embodiment, the component (D) may be a mixture of a plurality of compounds of the component (D).

[Component (E)] [

The cured film forming composition of the present embodiment can further contain a crosslinking catalyst as the component (E) in addition to the components (A), (B), (C) have.

The crosslinking catalyst as the component (E) may be, for example, an acid or a thermal acid generator. This component (E) is effective for promoting the thermosetting reaction in the formation of the cured film using the cured film-forming composition of the present embodiment.

When an acid or a thermal acid generator is used as the component (E), the component (E) is a compound capable of generating an acid by thermal decomposition at a sulfonic acid group-containing compound, hydrochloric acid or its salt, prebake or postbake, It is not particularly limited as long as it is a compound which generates an acid by pyrolysis at 250 ° C.

Such compounds include, for example, inorganic acids such as hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p- toluenesulfonic acid, P-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, p-toluenesulfonic acid, But are not limited to, 1H, 1H, 2H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethanesulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane- Or a hydrate thereof or a salt thereof.

Examples of the compound capable of generating an acid by the action of heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p- P-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid ethyl ester, Toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenetyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-tosylate, N-ethyl-4-toluenesulfonamide and compounds represented by the following formulas [TAG-1] to [TAG-41] .

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

The content of the component (E) in the cured film-forming composition according to the embodiment of the present invention is preferably such that the content of the component (A) is at least one selected from a low molecular compound and a polymer, a polymer of the component (B) Preferably from 0.01 to 10 parts by mass, more preferably from 0.05 to 8 parts by mass, further preferably from 0.1 to 6 parts by mass, based on 100 parts by mass of the total amount of the low-molecular compounds of the component (D) Wealth. When the content of the component (E) is 0.01 part by mass or more, sufficient thermosetting property and solvent resistance can be imparted, and high sensitivity to exposure can be given. When the amount is 10 parts by mass or less, the storage stability of the cured film forming composition can be improved.

[Other additives]

The cured film forming composition of the embodiment of the present invention may contain other additives as long as the effect of the present invention is not impaired.

Other additives may include, for example, sensitizers. The sensitizer is effective in promoting the photoreaction when the cured film of the embodiment of the present invention is formed from the cured film forming composition of the present embodiment.

Examples of the sensitizer include derivatives such as benzophenone, anthracene, anthraquinone and thioxanthone, and nitrophenyl compounds. Of these, N, N-diethylaminobenzophenone, which is a benzophenone derivative, and nitrophenyl compounds such as 2-nitrofluorene, 2-nitrofluorenone, 5-nitroesenaphthene, 4-nitrobiphenyl, Nitrostevanone, 4-nitrobenzophenone and 5-nitroindole are particularly preferred.

These sensitizers are not particularly limited to those described above. These can be used alone or in combination of two or more compounds.

In the embodiment of the present invention, the use ratio of the sensitizer is 0.1 part by mass to 20 parts by mass relative to 100 parts by mass of the total amount of the component (A), the component (B), the component (C) and the component (D) And more preferably 0.2 parts by mass to 10 parts by mass. If the ratio is too small, the effect as a sensitizer may not be sufficiently obtained. In the case where the ratio is excessive, the transmittance of the formed cured film may be lowered or the coating film may be roughened.

The cured film-forming composition of the embodiment of the present invention may contain, as other additives, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, a defoaming agent, And the like.

[solvent]

The cured film-forming composition of the embodiment of the present invention is often used in the form of a solution dissolved in a solvent. The solvent to be used at this time is to dissolve the component (A), the component (B), the component (C) and the component (D), and optionally the component (E) and / or other additives. The type and structure thereof are not particularly limited.

Specific examples of the solvent include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene Propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, cyclopentyl methyl ether, isopropyl alcohol, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butane Butanone, ethyl, 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl ethoxyacetate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and the like can be given as examples of the organic peroxide such as methyl ethyl ketone, methyl ethyl ketone, methyl lactate, methyl lactate, methyl pyruvate, ethyl pyruvate, ethyl acetate, have.

These solvents may be used singly or in combination of two or more. Of these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate are more preferred because of good film forming properties and high safety.

&Lt; Preparation of cured film forming composition >

The cured film-forming composition of the embodiment of the present invention is a thermosetting cured film-forming composition having photo-alignment property. As described above, the cured film-forming composition of the present embodiment comprises at least one selected from the group consisting of a low-molecular compound as the component (A) and a polymer, and a hydroxyl group, a carboxyl group, an amide group, an amino group, A polymer having at least one substituent selected from the group represented by the formula (2), a crosslinking agent as the component (C), and a polymerizable group containing a C═C double bond in one molecule, which is a component (D) And a low molecular weight compound having at least one N-alkoxymethyl group and at least one N-alkoxymethyl group. Further, as the component (E), a crosslinking catalyst may be contained. As long as the effect of the present invention is not impaired, other additives may be contained, and further, a solvent may be contained.

The blending ratio of the component (A) and the component (B) is preferably 5:95 to 80:20 in terms of the mass ratio. When the content of the component (B) is excessive, the liquid crystal alignability tends to deteriorate. If the content of the component (B) is too low, the solvent resistance tends to decrease.

Preferred examples of the cured film forming composition of the present embodiment are as follows.

[1] A photosensitive resin composition comprising a photo-aligned group which is a component (A) and a low-molecular compound having at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the formula (2) Wherein the compounding ratio of the hydroxyl group, the carboxyl group, the amide group, the amino group, the alkoxysilyl group and the polymer having at least one substituent selected from the group represented by the formula (2) 10 to 100 parts by mass based on 100 parts by mass of the total amount of the polymer (A) and at least one polymer selected from the polymer (B) and (B) ) And 0.1 to 40 parts by mass of a crosslinking agent per 100 parts by mass of the total amount of the crosslinking agent of the component (A), the polymer of the component (B) and the crosslinking agent of the component (C) mass Of the component (D) in a molecule in the C = C double bonds having a polymerizable group containing at least one N- also an alkoxymethyl group and at least one low molecular weight compound to form a cured film having a composition containing.

(2), wherein the mixing ratio of the component (A) to the component (B) is 5:95 to 80:20 in terms of a mass ratio, and the ratio of the component (A) (C) component and at least one member selected from the group consisting of a low molecular weight compound and a polymer as the component (A), a polymer of the component (B), and a polymer of the component (C) in an amount of 10 parts by mass to 100 parts by mass based on 100 parts by mass of the total amount (D) component and a solvent in an amount of 0.1 to 40 parts by mass based on 100 parts by mass of the total amount of the cross-linking agent.

[3] The positive resist composition according to any one of [1] to [3], wherein the mixing ratio of the component (A) to the component (B) is 5:95 to 80:20 in mass ratio, Based on 100 parts by mass of the total amount of the component (A), at least one member selected from the group consisting of (A) a low molecular weight compound and a polymer, (B) a polymer of component (B) (D) component and at least one member selected from the group consisting of the low molecular weight compound and the polymer as the component (A), the polymer of the component (B), and the polymer of the component (C) in an amount of 0.1 part by mass to 40 parts by mass with respect to 100 parts by mass of the total amount (E) component and a solvent in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the total amount of the crosslinking agent and the compound of the component (D).

The mixing ratio, preparation method and the like when the cured film forming composition of the present embodiment is used as a solution will be described in detail below.

The proportion of the solid content in the cured film forming composition of the present embodiment is not particularly limited as long as each component is uniformly dissolved in a solvent, but it is preferably 1% by mass to 80% by mass, more preferably 3% By mass to 60% by mass, and more preferably 5% by mass to 40% by mass. Here, the solid content refers to the solvent excluding the entire components of the cured film forming composition.

The method of preparing the cured film forming composition of the present embodiment is not particularly limited. (A), the component (C), the component (D), and further the component (E) are mixed in a predetermined ratio, for example, in a solution of the component Or a method in which other additives are further added and mixed in an appropriate step of this preparation method, if necessary.

In the preparation of the cured film-forming composition of the present embodiment, the solution of the specific copolymer obtained by the polymerization reaction in a solvent can be used as it is. In this case, for example, the component (A), the component (C), the component (D), and further the component (E) are added to a solution prepared by mixing the component (B) At this time, a solvent may be added again for the purpose of concentration adjustment. At this time, the solvent used in the preparation of the component (B) and the solvent used to adjust the concentration of the cured film forming composition may be the same or different.

The solution of the prepared cured film-forming composition is preferably filtered after using a filter having a pore diameter of about 0.2 탆 or the like.

As described above, the cured film-forming composition of the present embodiment of the present invention is a cured film-forming composition of the present invention comprising (A) a photo-aligning group and a group selected from a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, (B) at least one member selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the formula (2), at least one member selected from the group consisting of a low molecular compound having at least one substituent, Of a polymer having a substituent. (A), the photo-orientable group constitutes a photoreactive portion having a hydrophobic property, and the hydrophilic group is a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the formula (2) The at least one substituent selected from the group to be displayed constitutes a hydrophilic thermal reaction part. At least one substituent selected from the hydroxyl group, carboxyl group, amide group, amino group, alkoxysilyl group and the group represented by the formula (2) in the polymer of the component (B) is also hydrophilic.

Therefore, the cured film formed from the cured film-forming composition of the present embodiment is formed so that its interior becomes hydrophilic due to the nature of the component (B) so that the film structure is stabilized. At least one kind selected from a low-molecular compound of the component (A) and a polymer in the cured film is localized near the surface of the cured film. More specifically, at least one kind selected from the low-molecular compounds of the component (A) and the polymer has a structure in which the hydrophilic thermoreaction part faces the inside of the cured film and the hydrophobic light reaction part faces the surface side, And is localized in the vicinity of the surface. As a result, the cured film of the present embodiment realizes a structure in which the ratio of the photoreactive group of the component (A) present near the surface is increased. When the cured film of the present embodiment is used as an alignment material, it is possible to improve the efficiency of light reaction for photo alignment and have excellent alignment sensitivity. Furthermore, the alignment material becomes a favorable alignment material for forming the patterned retardation material, and the patterned retardation material produced using the material can have excellent pattern forming properties.

The cured film forming composition of the present embodiment contains, as described above, a crosslinking agent as the component (C). Accordingly, in the cured film obtained from the cured film-forming composition of the present embodiment, before the light reaction by the at least one photo-orienting group selected from the low-molecular compound of the component (A) and the polymer, (C) A crosslinking reaction can be carried out. As a result, when used as an alignment material, the resistance to the polymerizable liquid crystal applied thereon and the solvent thereof can be improved.

The cured film-forming composition of the present embodiment of the present invention is a cured film-forming composition of the present invention, which comprises (A), (B) and (C) A low-molecular compound having at least one maleic acid group and at least one N-alkoxymethyl group. When the cured film obtained from the cured film-forming composition of the present embodiment is used as an alignment material, the compound serving as the component (D) functions to enhance the adhesion between the layers of the cured polymerizable liquid crystal formed thereon.

<Cured film, alignment material and retardation material>

The solution of the cured film-forming composition of the present embodiment may be applied to a substrate (e.g., a substrate coated with a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a metal such as aluminum, molybdenum, chromium, A spin coating, a spin coating, a spin coating, a spin coating, a spin coating, a spin coating, a spin coating, or a spin coating) on a film (e.g., a quartz substrate, an ITO substrate, etc.) The cured film can be formed by coating, roll coating, slit coating, rotary coating followed by slit coating, inkjet coating, printing or the like to form a coating film, and then heating and drying with a hot plate or oven.

As the conditions of the heating and drying, the curing reaction proceeds so that the components of the alignment material formed from the cured film do not dissolve in the polymerizable liquid crystal solution applied thereon. For example, The heating temperature and the heating time appropriately selected from the range of 1 minute to 60 minutes are employed. The heating temperature and the heating time are preferably 70 to 160 DEG C for 0.5 to 10 minutes.

The film thickness of the cured film formed using the curable composition of the present embodiment is, for example, 0.05 탆 to 5 탆, and can be appropriately selected in consideration of the step difference of the substrate to be used and the optical and electrical properties.

The cured film thus formed can function as a member for orienting an alignment material, that is, a liquid crystalline compound including a polymerizable liquid crystal, by performing polarized UV irradiation.

As a method of irradiating polarized UV, ultraviolet light or visible light having a wavelength of 150 nm to 450 nm is usually used and irradiated with linearly polarized light in a vertical or inclined direction at room temperature or in a heated state.

Since the alignment material formed from the cured film composition of this embodiment has a solvent resistance and a heat resistance, a phase difference material comprising a polymerizable liquid crystal solution is coated on the alignment material, and then heated to the phase transition temperature of the liquid crystal, , And is oriented on the alignment material. Then, the retardation material having the optically anisotropic layer can be formed by directly curing the retardation material in the desired alignment state.

As the retardation material, for example, a liquid crystal monomer having a polymerizable group and a composition containing the liquid crystal monomer are used. When the substrate on which the alignment material is formed is a film, the film having the retardation film of the present embodiment is useful as a retardation film. The retardation material forming such a retardation material is in a liquid crystal state and has an alignment state such as a horizontal alignment, a cholesteric alignment, a vertical alignment, and a hybrid alignment on the alignment material. Can be used.

In the case of producing a patterned retardation material for use in a 3D display, a cured film formed by the above-described method from the cured film composition of the present embodiment is subjected to a patterning process using a line- Polarized UV exposure is performed in the direction of +45 degrees, then the mask is removed, and then the polarized UV is exposed in the direction of -45 degrees to form an alignment material having two types of liquid crystal alignment regions in which alignment control directions of liquid crystals are different . Thereafter, the retardation material made of the polymerizable liquid crystal solution is coated, and then heated to the phase transition temperature of the liquid crystal to bring the retardation material into a liquid crystal state. The polymerizable liquid crystal in a liquid crystal state is oriented on an alignment material having two kinds of liquid crystal alignment regions, and forms an alignment state corresponding to each liquid crystal alignment region. The patterned retardation material in which the retardation material realizing such an alignment state is intact and the above-described alignment state is fixed and a plurality of two types of retardation regions having different retardation characteristics are arranged in a regular pattern can be obtained .

The alignment material formed from the cured film composition of the present embodiment can also be used as a liquid crystal alignment film of a liquid crystal display element. For example, two substrates having the alignment material of the present embodiment formed as described above are used, and the alignment materials on both substrates face each other with a spacer interposed therebetween. Then, liquid crystal is injected between these substrates , A liquid crystal display element in which liquid crystals are aligned can be manufactured.

Accordingly, the cured film-forming composition of the present embodiment can be suitably used for the production of various retardation films (phase difference films) and liquid crystal display elements.

[Example]

Hereinafter, the present embodiment will be described in more detail by way of examples. However, the present invention is not limited to these examples.

[Composition components used in Examples and the like]

The composition components used in the following examples and comparative examples are as follows. In the formula, Me represents a methyl group, and t-Bu represents a tert-butyl group.

&Lt; Component (A): low molecular light orientation component >

CIN1: 4- (6-hydroxyhexyloxy) cinnamic acid methyl ester

[Chemical Formula 21]

CIN2: 3-Methoxy-4- (6-hydroxyhexyloxy) cinnamic acid methyl ester

[Chemical Formula 22]

CIN3: 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid tert-butyl ester

(23)

CIN4: 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid

&Lt; EMI ID =

CIN5: 4-propyloxy cinnamic acid

(25)

&Lt; Specific polymer raw material >

MAA: methacrylic acid

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

CIN4: 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid

AIBN: α, α'-azobisisobutyronitrile

<Component (B)>

PEPO: polyester polyol polymer (adipic acid / diethylene glycol copolymer having the following structural unit, molecular weight: 4,800.)

(26)

(Wherein R represents alkylene).

&Lt; Component (C): Crosslinking agent >

HMM: hexamethoxymethyl melamine

&Lt; Component (E): Crosslinking catalyst >

PTSA: Paratoluenesulfonic acid

(27)

&Lt; Component (D): N-alkoxymethyl group and low molecular compound having polymerizable group >

D-1: N-methoxymethyl methacrylamide

(28)

D-2: N-methoxymethylacrylamide

[Chemical Formula 29]

D-3: N-n-Butoxymethylacrylamide (BMAA)

(30)

D-4: N-isobutoxymethylacrylamide

(31)

D-5:

(32)

D-6:

(33)

<Other reagents>

BHT: 2,6-di-tert-butyl-para-cresol

DBU: 1,8-diazabicyclo [5.4.0] -7-undecene

<Solvent>

Each of the cured film forming compositions of Examples and Comparative Examples contained a solvent, and propylene glycol monomethyl ether (PM), butyl acetate (BA), and methyl ethyl ketone (MEK) were used as the solvent.

&Lt; Measurement of molecular weight of polymer &

The molecular weight of the polyimide, polyamic acid or acrylic polymer in the synthesis examples was measured using a gel permeation chromatograph (GPC-101), Shodex (KD-803, KD-805) Were measured as follows.

Column temperature: 50 ° C

Eluent: 30 mmol / L of lithium bromide-hydrate (LiBr.H ₂ O), 30 mmol / L of phosphoric acid-anhydrous crystal (o-phosphoric acid) and 30 mmol / L of tetrahydrofuran (THF) 10 mL / L)

Flow rate: 1.0 mL / min

Standard sample for calibration curve: Tosoh Corporation TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, 30,000) and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) manufactured by Polymer Laboratory.

&Lt; Examples and Comparative Examples &

&Lt; Polymerization Example 1 &

3.5 g of MAA, 7.0 g of MMA, 7.0 g of HEMA and 0.5 g of AIBN as a polymerization catalyst were dissolved in 53.9 g of PM and reacted at 70 DEG C for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 25 mass%) (P1). The obtained acrylic copolymer had Mn of 10,300 and Mw of 24,600.

&Lt; Polymerization Example 2 &

100.0 g of MMA, 11.1 g of HEMA and 5.6 g of AIBN as a polymerization catalyst were dissolved in 450.0 g of PM and reacted at 80 占 폚 for 20 hours to obtain an acrylic copolymer solution (solid content concentration 20 mass%) (P2). The obtained acrylic copolymer had Mn of 4,200 and Mw of 7,600.

&Lt; Polymerization Example 3 &

100 g of N-butoxymethyl acrylamide (BMAA) and 4.2 g of AIBN as a polymerization catalyst were dissolved in 193.5 g of PM and reacted at 90 DEG C for 20 hours to obtain an acrylic polymer solution (solid content concentration: 35 mass%) (P3). The obtained acrylic copolymer had 2,700 Mn and 3,900 Mw.

&Lt; Polymerization Example 4 &

4.0 g of CIN 4, 4.0 g of styrene, 2.0 g of HEMA and 0.1 g of AIBN as a polymerization catalyst were dissolved in 90.9 g of PM and reacted at 80 DEG C for 20 hours to obtain an acrylic polymer solution (solid concentration 10 mass%) (CIN6). The obtained acrylic copolymer had Mn of 20,000 and Mw of 55,000.

Synthesis of Compound [D-5]

(34)

In a 2 L four-necked flask under nitrogen gas flow, 500 g of ethyl acetate, 35.5 g (0.300 mol) of 1,6-hexanediol, 1.80 g of 1,8-diazabicyclo [5.4.0] 0.45 g (2.04 mmol) of 2,6-di-tertiarybutyl-para-cresol (BHT) was added at room temperature and the temperature was raised to 55 ° C under magnetic stirrer stirring. 95.9 g (0.679 mol) of 2-isocyanatoethyl acrylate was added dropwise to the reaction mixture, and the mixture was stirred for 2 hours. The reaction mixture was analyzed by high performance liquid chromatography and the reaction was carried out when the proportion of the intermediate was 1% . 328 g of hexane was added and the mixture was cooled to room temperature. The precipitated solid was washed twice with 229 g of hexane and dried to obtain Compound (Aa) (104 g, 0.260 mol, yield 86.7%).

(35)

1330 g of dichloromethane, 100 g (0.250 mol) of the compound [Aa] and 22.5 g (0.749 mol) of paraformaldehyde were placed in a 2 L four-necked flask under a nitrogen gas stream and 122 g (1.12 mol) of trimethylsilyl chloride . After stirring for 2 hours, a mixture of 63.2 g (0.625 mol) of triethylamine and 240 g of methanol was added dropwise. After stirring for 30 minutes, the mixture was transferred to a separatory funnel of 5 L, and 1500 g of water was added to perform liquid separation. The obtained organic layer was dried with magnesium sulfate, and magnesium sulfate was removed by filtration. The resulting filtrate was concentrated and dried to obtain Compound [D-5] (110 g, 0.226 mol, yield 90.3%). The following spectral data were obtained by ¹ H-NMR analysis of the structure of the compound [D-5].

_{^{1 H-NMR (CDCl 3)}} : δ6.42 (d, 2H J = 17.2), 6.17-6.08 (m, 2H), 5.86 (d, 2H J = 10.0), 4.77 (d, 4H J = 19.6), 4.30 (m, 4H), 4.12 (t, 4H J = 6.4), 3.61 (m, 4H), 3.30 (d, 6HJ = 12.8), 1.67 (m, 4H), 1.40 (m, 4H).

Synthesis of Compound [D-6]

(36)

(50.0 mmol) of hexamethylene diisocyanate, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) in a 500 ml four-necked flask under nitrogen gas stream, 35.0 g of ethyl acetate, 87.0 g of toluene, (0.318 mmol) of 2,6-di-tertiarybutyl-para-cresol (BHT) were added at room temperature, and the temperature was raised to 60 ° C under magnetic stirrer stirring. To the reaction solution, a mixed solution of 12.8 g (111 mmol) of 2-hydroxyethyl acrylate and 26.0 g of toluene was added dropwise, and the mixture was stirred for 1 hour and then stirred at room temperature for 24 hours. 131 g of hexane was added and the solution was cooled in an ice bath. The precipitated crystals were filtered and dried to obtain a compound [Ab] (15.0 g, 37.4 mmol, yield: 74.8%).

(37)

200 g of dichloromethane, 14.6 g (36.4 mmol) of the compound [Ab] and 3.28 g (0.109 mmol) of paraformaldehyde were added to a 300-mL four-necked flask under a nitrogen gas stream, and trimethylsilyl chloride (23.7 g ). After stirring for 1 hour, 35.6 g of methanol was added dropwise and stirred for 1 hour. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution (300 mL), and the aqueous layer was washed again with 200 g of dichloromethane. The solution obtained by mixing the two kinds of organic layers was further washed with 170 g of brine, and the obtained organic layer was dried with magnesium sulfate. Magnesium sulfate was removed by filtration, and the obtained dichloromethane solution was concentrated and dried to obtain the aimed product [D-6] (16.2 g, 33.1 mmol, yield 91.0%).

The structure of the compound [D-6] was confirmed by ¹ H-NMR analysis and the following spectral data were obtained.

_{^{1 H-NMR (CDCl 3)}} : δ6.33 (d, 2H J = 17.2), 6.20-6.14 (m, 2H), 5.96 (d, 2H J = 10.4), 4.63 (s, 4H), 4.33 (m , 4H), 4.27 (m, 4H), 3.16-3.14 (br, 10H), 1.47 (m, 4H), 1.20 (m, 4H).

&Lt; Preparation of base film &

The acrylic film used as the substrate can be prepared, for example, by the following method. That is, a raw material pellet composed of a copolymer mainly composed of methyl methacrylate is melted at 250 ° C. by an extruder, passed through a T-die, and an acrylic film having a thickness of 40 μm can be produced through a casting roll and a drying roll. TAC films can also be made in the same way.

&Lt; Examples 1 to 18, Comparative Examples 1 and 2 >

Each of the cured film forming compositions of the examples and comparative examples was prepared with the composition shown in Table 1, and the orientation property, the pattern forming property, and the adhesion property were evaluated.

[Table 1]

[Evaluation of orientation]

Each of the cured film forming compositions of Examples and Comparative Examples was applied to a film using a bar coater and then heated and dried at a temperature of 110 캜 for 2 minutes in a thermocycling oven to form a cured film. Each of the cured films was vertically irradiated with linearly polarized light of 313 nm at an exposure dose of 10 mJ / cm ² to form an alignment material. The polymerizable liquid crystal solution for horizontal orientation was coated on the alignment material on the substrate using a bar coater and then prebaked on a hot plate at 70 DEG C for 60 seconds to form a coating film having a thickness of 1.0 mu m . The coating film on the substrate was exposed at 300 mJ / cm ² to prepare a retardation film. The retardation on the produced substrate was sandwiched between a pair of polarizing plates and the appearance of the retardation characteristics in the retardation was observed to see that the retardation was expressed without defects as? &Quot; Orientation &quot;.

[Evaluation of pattern formation property]

Each of the cured film forming compositions of Examples and Comparative Examples was coated on an acrylic film or a TAC film using a bar coater and then heated and dried in a thermocycling oven at a temperature of 110 DEG C for 2 minutes to form a cured film. This cured film was vertically irradiated with linearly polarized light of 313 nm at 20 mJ / cm ^{2 through} a line-and-space mask of 350 m. Subsequently, the mask was removed, and the substrate was rotated by 90 degrees. Thereafter, linearly polarized light of 313 nm was radiated vertically at 10 mJ / cm ² to obtain an alignment material having two kinds of liquid crystal alignment regions in which alignment control directions of liquid crystals were different by 90 degrees . The polymerizable liquid crystal solution for horizontal orientation was coated on the alignment material on the substrate using a bar coater and then prebaked on a hot plate at 70 DEG C for 60 seconds to form a coating film having a thickness of 1.0 mu m . The coating film on the substrate was exposed at 300 mJ / cm ² to prepare a patterned retardation material in which two kinds of regions having different retardation characteristics were regularly arranged. The patterned phase difference material on the produced substrate was observed using a polarizing microscope to find that no alignment defect and phase difference pattern were formed, and that having alignment defect was indicated as &quot; x &quot; Respectively.

[Evaluation of adhesion]

Each of the cured film forming compositions of Examples and Comparative Examples was coated on an acrylic film or a TAC film using a bar coater and then heated and dried in a thermocycling oven at a temperature of 110 DEG C for 2 minutes to form a cured film. This cured film was vertically irradiated with linearly polarized light of 313 nm at 20 mJ / cm ^{2 through} a line-and-space mask of 350 m. Subsequently, the mask was removed, and the substrate was rotated by 90 degrees. Thereafter, linearly polarized light of 313 nm was radiated vertically at 10 mJ / cm ² to obtain an alignment material having two kinds of liquid crystal alignment regions in which alignment control directions of liquid crystals were different by 90 degrees . The polymerizable liquid crystal solution for horizontal orientation was coated on the alignment material on the substrate using a bar coater and then prebaked on a hot plate at 70 DEG C for 60 seconds to form a coating film having a thickness of 1.0 mu m . The coating film on the substrate was exposed at 300 mJ / cm ² to prepare a patterned retardation material in which two kinds of regions having different retardation characteristics were regularly arranged.

The patterned retardation material was cut with a cutter knife so as to have a 5 × 5 scale in the longitudinal and transverse directions at intervals of 1 mm. A cellophane tape peeling test was carried out on this sheath using a scotch tape. The evaluation result was &quot; initial &quot;, and all of the 25 graduations were left without being peeled off. The evaluation results are summarized in Table 2 later.

[Evaluation of Durability of Adhesion]

The retardation on the acrylic film or the TAC film produced by the same method as the evaluation of the adhesion described above was put in an oven set at a temperature of 80 DEG C and a humidity of 90% and allowed to stand for at least 72 hours. Thereafter, the retardation material was taken out, and the adhesion property was evaluated in the same manner as the evaluation of the above-described adhesion. The evaluation results are shown collectively in Table 2 as &quot; durability &quot;.

[Results of evaluation]

The results of the above evaluation are shown in Table 2 as described above.

[Table 2]

The alignment materials obtained using the cured film forming compositions of Examples 1 to 18 exhibited good alignment properties as in the alignment materials obtained using the cured film forming composition of the comparative example.

In addition, the alignment materials obtained using the cured film forming compositions of Examples 1 to 18 exhibited good pattern formability, as in the alignment material obtained using the cured film forming composition of the comparative example.

Further, the cured films obtained by using the cured film forming compositions of Examples 1 to 18 maintained high adhesiveness even when subjected to high temperature and high humidity treatment, and exhibited excellent adhesion durability.

On the contrary, the cured film obtained by using the cured film-forming composition of the comparative example was difficult to maintain the initial adhesion after the high temperature and high humidity treatment.

[Industrial Availability]

The cured film-forming composition according to the present invention is very useful as a liquid crystal alignment film of a liquid crystal display element or an alignment material for forming an optically anisotropic film provided inside or outside a liquid crystal display element. Particularly, As a material for forming the ash. Furthermore, a material for forming a cured film such as a protective film, a planarizing film and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element, particularly, a material for forming an interlayer insulating film of a TFT type liquid crystal element, Or as a material for forming an insulating film of an organic EL element or the like.

Claims (7)

(A) a low molecular compound having a photo-orientable group and at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group, and a group represented by the following formula (2) A polymer having at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group, and a group represented by the following formula (2)
[Chemical Formula 1]

(Wherein R ⁶² represents an alkyl group, an alkoxy group or a phenyl group).
(B) a polymer having at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the formula (2)
(C) a crosslinking agent, and
(D) a low-molecular compound having at least one polymerizable group having at least one C = C double bond in one molecule and at least one N-alkoxymethyl group
Wherein the cured film-forming composition is a cured film-forming composition.
The method according to claim 1,
Wherein the component (A) is one selected from a photo-orientable group, a low-molecular compound having a hydroxyl group and / or a carboxyl group, and a polymer having a photo-orientable group and a hydroxyl group and / or a carboxyl group.
3. The method according to claim 1 or 2,
(D) is a compound having a structure represented by the following formula (1).
(2)

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms in a straight chain or branched chain.)
3. The method according to claim 1 or 2,
(D) is a compound having a structure represented by the following formula (X2).
(3)

Wherein R ⁵¹ represents a hydrogen atom or a methyl group. Each R ⁵³ is independently a linear or branched alkylene group of 2 to 20 carbon atoms, a divalent group of an aliphatic ring having 5 to 6 carbon atoms, or a divalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms And may include an ether bond in the structure of these groups. R ⁵⁴ is a divalent to 9-valent group formed by removing 1 to 8 hydrogen atoms from a linear or branched alkyl group having 2 to 20 carbon atoms, a hydrogen atom from an aliphatic group having 5 to 6 carbon atoms, A divalent to ninth aliphatic group having 1 to 8 deleted structures or a divalent to 9-valent aliphatic group including an aliphatic ring having 5 to 6 carbon atoms, and may contain an ether bond in the structure. R ⁵² represents a linear or branched alkyl group having 1 to 20 carbon atoms, a monovalent group comprising an aliphatic ring having 5 to 6 carbon atoms, or a monovalent aliphatic group including an aliphatic ring having 5 to 6 carbon atoms, Or a plurality of non-adjacent methylene groups may be substituted for an ether bond. Z represents > NCOO- or -OCON < (where &quot; - &quot; represents one bonding hand, and & -CH ₂ OR ⁵² ). r is a natural number between 2 and 9 inclusive.]
5. The method according to any one of claims 1 to 4,
(E) a crosslinking catalyst.
An alignment material obtained by using the cured film forming composition according to any one of claims 1 to 5.
A retardation film having a cured film obtained from the cured film-forming composition according to any one of claims 1 to 5.