TWI724860B - Cured film forming composition, alignment material and retardation material - Google Patents

Abstract

The present invention provides an alignment material that has excellent vertical alignment and adhesion and can also align polymerizable liquid crystals vertically on a resin film with high sensitivity, and a phase difference material that uses such an alignment material. The cured film forms a composition.

The cured film forming composition of the present invention is characterized by containing (A) a polymer having a vertical alignment group and a functional group that can be thermally crosslinked, (B) a crosslinking agent, and (C) an adhesion promoter and ( D) Either one or both of the polymers with thermally crosslinkable groups; the alignment material characterized by the use of the composition, and the retardation material characterized by the use of the composition.

Description

Cured film forming composition, alignment material and retardation material

The present invention relates to a cured film forming composition suitable for a vertical alignment material for vertically aligning liquid crystal molecules. In particular, the present invention relates to the use of liquid crystal display devices (LCD) to improve liquid crystal display (LCD), specifically in the manufacture of IPS liquid crystal display devices filled with liquid crystals (△ε>0) with positive dielectric anisotropy ( In-plane Switching LCD (In-plane Switching LCD; In-plane alignment switch LCD) is useful for curing film forming composition, alignment material and phase difference material when using +C plate (positive C plate) for viewing angle characteristics.

Since IPS-LCD does not cause the vertical tilt of the liquid crystal molecules, it is characterized by less brightness change/color change due to the viewing angle. However, there are weaknesses that it is difficult to improve the relative contrast, brightness, and response speed. For example, Patent Document 1 discloses that in the IPS-LCD at the initial stage of the proposal, the compensation film for the viewing angle is not used. In the IPS-LCD that does not use the compensation film for the viewing angle, relatively Larger light leakage, so it has the disadvantage of showing low contrast value.

Patent Document 2 discloses an IPS-LCD compensation film using +C plate and +A plate (positive type A plate). The liquid crystal display element described in this document describes the following structure.

1) With electrodes that can apply an electric field parallel to the liquid crystal layer, a liquid crystal layer with horizontal alignment is sandwiched between the two supplied substrates.

2) More than one +A plate and +C plate are sandwiched between two polarizing plates.

3) The main optical axis of the +A plate is perpendicular to the main optical axis of the liquid crystal layer.

4) The liquid crystal layer retardation value R _LC, + C plate retardation value of R _{+ C, +} A-plate retardation value of R _{+ A} satisfy the following expression depends.

R _LC ：R _+C ：R _+A ≒1: 0.5: 0.25

5) Regarding the retardation value of the +A plate and the +C plate, the relationship of the retardation value (TAC, COP, PNB) in the thickness direction of the protective film of the polarizing plate is not shown.

In addition, it has a +A plate and +C for the purpose of providing an IPS-LCD with high contrast characteristics at the front and tilt angles and low color shift (Color Shift) by minimizing the light leakage in the dark state starting at the oblique angle. The panel IPS-LCD has been disclosed (Patent Document 3).

[Advanced Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2-256023

[Patent Document 2] Japanese Patent Application Laid-Open No. 11-133408

[Patent Document 3] JP 2009-122715 A

[Patent Document 4] Japanese Patent Application Publication No. 2001-281669

As proposed in the past, the +C plate can compensate for light leakage when the viewing angle of the polarizer is large, so it can be very useful as an optical compensation film for IPS-LCD. However, it is difficult to perform vertical alignment (positive C-plate) performance in the method performed by the generally known stretching process in the past.

In addition, to use the polyimide vertically aligned film proposed in the past, it is necessary to use a polyimide solvent such as N-methyl-2-pyrrolidone when forming the film. Therefore, it does not pose a problem for the glass substrate, but when the substrate is a thin film, there is a problem of imparting damage to the substrate when the alignment film is formed. In the vertical alignment film on which polyimide is used, firing at high temperature becomes a necessary step, and there is a problem that the film substrate cannot withstand high temperatures.

In addition, when the substrate is directly processed with a silane coupling agent with a long-chain alkyl group, a method that can form a vertical alignment film has also been proposed. However, it is difficult to process when the surface of the substrate is not hydroxyl, and the substrate is limited. Problem (Patent Document 4).

In addition, when using photo-alignment technology to manufacture patterned phase difference materials for 3D display, they used to be formed on a glass substrate. However, in recent years, in response to the demand for reduction in manufacturing costs, TAC (triacetyl cellulose) films, COP (cycloolefin polymer) films, etc., are inexpensive resin films, requiring so-called roll-to-roll production.

However, in the photo-alignment film formed of the past material as described above, the adhesion to the resin film is relatively weak, and it is difficult to manufacture on the resin film. High-reliability patterned phase difference material.

Therefore, it has excellent adhesion and can form highly reliable retardation materials even on resin films such as TAC films. It can be applied to the alignment materials of optical alignment technology and the cured film forming composition used to form such alignment materials. Look forward to.

The present invention is based on the above findings or the results of the review. The problem to be solved is to have excellent vertical alignment while providing a method for providing transparency or solvent resistance required for optical compensation films, even in resin films. The composition can also be formed into a cured film of an alignment material that stably aligns the polymerizable liquid crystal into a vertical alignment under the firing conditions at a low temperature and a short time.

Another object of the present invention is to provide a cured film-forming composition obtained from the above-mentioned cured film forming composition, which has excellent vertical alignment and solvent resistance, and can be stably used on a resin film under low-temperature and short-time firing conditions. The alignment material in which the polymerizable liquid crystal is vertically aligned and the +C plate formed by using the alignment material are useful retardation materials.

Other objects and advantages of the present invention can be understood from the following description.

In order to achieve the above-mentioned object, the inventors of the present invention, after repeated detailed reviews, found that by selecting an acrylic copolymer having a long-chain alkyl group in the side chain as the base material for the hardened film forming material, it is possible to form a hardened film regardless of the type of substrate A cured film with excellent vertical alignment, thus completing the present invention.

That is, as the first viewpoint of the present invention, it relates to a cured film forming composition;

A cured film forming composition which contains

(A) Polymers with vertical alignment groups and functional groups that can be thermally crosslinked,

Either or both of (B) a crosslinking agent, (C) an adhesion promoter, and (D) a polymer having a thermally crosslinkable group, characterized in that the aforementioned vertical alignment group is the following formula [1] The base shown.

(In formula [1],

* Indicates the position of the bond,

Y ¹ represents a single bond or a bonding group,

Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms or -CH ₂ -CH(OH)-CH ₂ -, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, Any hydrogen atom on the aforementioned cyclic group can be an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, a fluorine-containing alkyl group with 1 to 3 carbon atoms, and one with 1 to 3 carbon atoms. Substituted by fluorine-containing alkoxy or fluorine atom,

Y ³ represents a single bond or an alkylene group with 1 to 15 carbon atoms,

Y ⁴ represents a single bond, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a divalent organic group having a steroid skeleton with 17 to 30 carbon atoms, any of the aforementioned cyclic groups The hydrogen atom can be an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, a fluorinated alkyl group with 1 to 3 carbon atoms, a fluorinated alkoxy group with 1 to 3 carbon atoms, or fluorine. Replaced by atoms,

Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring. Any hydrogen atom on these cyclic groups can be an alkyl group with 1 to 3 carbon atoms and an alkane with 1 to 3 carbon atoms. Substituted by oxy group, fluorine-containing alkyl group with 1 to 3 carbon atoms, fluorine-containing alkoxy group with 1 to 3 carbon atoms or fluorine atom,

n represents an integer from 0 to 4, and when n is 2 or more, Y ⁵ may be the same or different from each other,

Y ⁶ represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms, a fluorinated alkyl group with 1 to 18 carbon atoms, an alkoxy group with 1 to 18 carbon atoms or a fluorinated alkoxy group with 1 to 18 carbon atoms ,

The alkylene group as Y ² and Y ³ , and the alkyl group, fluorine-containing alkyl group, alkoxy group, and fluorine-containing alkoxy group as the substituent on the cyclic group or Y ^{6 may be linear, branched,} Or any one or a combination of these,

In addition, the alkylene group ^{as Y 2} and Y ³ , and the alkyl group, fluorine-containing alkyl group, alkoxy group, and fluorine-containing alkoxy group ^{as Y 6 can be from 1 to 3 as long as the bonding groups are not adjacent to each other.} The bond base is interrupted,

And Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, or Y ⁴ represents a divalent organic group with a steroid skeleton, or Y ² represents -CH ₂ -CH(OH)-CH ₂ -, or Y ² or When Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or a fluorine-containing alkyl group, the divalent cyclic group, the divalent organic group having the steroid skeleton, the -CH ₂ -CH(OH)-CH _2- , The alkylene group, the alkyl group and the fluorine-containing alkyl group may be bonded to the bonding group via the adjacent group,

The above-mentioned bonding group means a group selected from the group consisting of -O-, -CH ₂ O-, -COO-, -OCO-, -NHCO-, -NH-CO-O- and -NH-CO-NH- ,

However, each of Y ² to Y ⁶ represents an alkylene group having 1 to 15 carbon atoms, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent organic group having a steroid skeleton, and -CH ₂ -CH(OH) -CH ₂ -, C1-C18 alkyl group, C1-C18 fluoroalkyl group, C1-C18 alkoxy group and C1-C18 fluoroalkoxy group The total number of carbon atoms is 6-30).

The second aspect is the cured film forming composition described in the first aspect, wherein the thermally crosslinkable functional group of the component (A) is a hydroxyl group, a carboxyl group, an amino group, or an alkoxysilyl group.

The third aspect is the cured film forming composition described in the first aspect or the second aspect, wherein the crosslinking agent of the component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group.

As a fourth viewpoint, the cured film forming composition described in any one of the first viewpoint to the third viewpoint further contains (E) a crosslinking catalyst.

As a fifth viewpoint, the cured film forming composition described in any one of the first to fourth viewpoints contains 1 part by mass to 300 parts by mass based on 100 parts by mass of the (A) component. )ingredient.

As a sixth viewpoint, the cured film forming composition described in any one of the first to fifth viewpoints, wherein the total amount of the polymer of the component (A) and the crosslinking agent of the component (B) is 100 parts by mass In terms, it contains 0.1 parts by mass to 100 parts of (C) and 1 part by mass to 400 parts by mass of (D) Either or both of the ingredients.

As a seventh viewpoint, the cured film forming composition described in any one of the fourth viewpoint to the sixth viewpoint contains 0.01 parts by mass to 20 parts by mass of the (E) component.

The eighth viewpoint relates to an alignment material characterized by curing the cured film forming composition described in any one of the first to seventh viewpoints.

The ninth viewpoint relates to the retardation material, which is characterized by using a cured film obtained from the cured film forming composition described in any one of the first viewpoint to the seventh viewpoint.

According to the first aspect of the present invention, it is possible to provide an alignment material with excellent vertical alignment properties that can stably align polymerizable liquid crystals in vertical alignment even on a resin film under low-temperature and short-time firing conditions. The useful cured film forming composition.

According to the second aspect of the present invention, it is possible to provide an alignment material that has excellent vertical alignment properties and can stably align the polymerizable liquid crystals in a vertical alignment under the firing conditions at a low temperature and a short time.

According to the third aspect of the present invention, it is possible to provide a retardation material that can be formed on a resin film with high efficiency, is highly transparent and has high solvent resistance and adhesion to the substrate (also called base material) and liquid crystal film .

[The form of implementing the invention]

<Cured film forming composition>

The cured film forming composition of the present invention contains (A) a polymer having a vertical alignment group and a functional group that can be thermally crosslinked, (B) a crosslinking agent, and (C) an adhesion promoter and (D) having Either or both of the thermally crosslinkable polymers. In addition to the above-mentioned (A) component, (B) component, (C) component, and (D) component, the cured film forming composition of the present invention may further contain a crosslinking catalyst as the (E) component. Other additives may be contained within a range that does not impair the effects of the present invention.

Each component is explained in detail below.

<(A) Ingredient>

The (A) component contained in the cured film forming composition of the present invention is a polymer having a vertical alignment group and a thermally crosslinkable functional group (hereinafter also referred to as a thermally crosslinkable group) as a side chain.

The polymer of component (A) of the present invention is not particularly limited, but it is preferably a copolymer obtained by polymerizing monomers having unsaturated double bonds such as acrylate, methacrylate, styrene, maleimide, etc. .

That is, the polymer of component (A) of the present invention contains a vertical alignment group and a functional group that can be thermally crosslinked in the side chain. For example, it is only an acrylic polymer (hereinafter, only the polymer of component (A) is referred to as specific Copolymer), there are no particular restrictions on the types of the backbone of the main chain and other side chains of the polymer constituting the acrylic copolymer.

(A) The weight average molecular weight of the polymer of the component is 1,000 It is preferably 200,000, more preferably 2,000 to 150,000, and more preferably 3,000 to 100,000. If the weight average molecular weight exceeds 200,000, the solubility to the solvent will decrease and the handling properties will be reduced. If the weight average molecular weight is less than 1,000, the hardening will be insufficient during thermal curing and the solvent will be reduced. The endurance and heat resistance are reduced.

The polymer of component (A) is a method for synthesizing an acrylic copolymer having a specific group such as a vertical alignment group in the side chain. The method of polymerizing a monomer having a vertical alignment group described later, or a reaction The method of bonding the acrylic polymer of the free group and the compound having the vertical alignment group in the polymer reaction is simple.

Among them, the polymer having a vertical alignment group and a thermally crosslinkable group of component (A) is a copolymer obtained by copolymerizing a monomer having a vertical alignment group and a monomer having a thermally crosslinkable group. It is easy to use the above-mentioned vertical alignment group or thermally crosslinkable group of acrylate, methacrylate, styrene, maleimide and other monomers with unsaturated double bonds obtained by polymerization. Things.

In this specification, the term "vertical alignment group" means, for example, a group containing a hydrocarbon group having about 6 to 20 carbon atoms, and specifically means a group represented by formula [1] described later.

Therefore, as a monomer having a vertical alignment group, for example, a monomer having a hydrocarbon group with about 6 to 20 carbon atoms can be cited. Examples of the hydrocarbon group having 6 to 20 carbon atoms include a hydrocarbon group having 6 to 20 carbon atoms containing a linear, branched, or cyclic alkyl group or aromatic group having 6 to 20 carbon atoms. because Here, as specific examples of monomers containing a hydrocarbon group with 6 to 20 carbon atoms, they are acrylic acid alkyl ester, methacrylic acid alkyl ester, alkyl vinyl ether, 2-alkylstyrene, 3- Alkyl styrene, 4-alkyl styrene, N-alkyl maleimide, and the alkyl group has 6 to 20 carbon atoms.

The vertical alignment group is more specifically a group represented by the following formula [1], that is, a monomer having a vertical alignment group, and more specifically, an acrylate, methacrylate, benzene containing a group represented by the following formula [1] Monomers with unsaturated double bonds such as ethylene and maleimide.

(In the formula, * represents the bonding position).

In formula [1], Y ¹ represents a single bond or a bonding group.

In the formula [1], Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms, or -CH ₂ -CH(OH)-CH ₂ -.

In addition, Y ² includes a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring. Any hydrogen atom on these cyclic groups can be an alkyl group with 1 to 3 carbon atoms, and the number of carbon atoms. Substitution with 1 to 3 alkoxy groups, fluorinated alkyl groups with 1 to 3 carbon atoms, fluorinated alkoxy groups with 1 to 3 carbon atoms, or fluorine atoms.

Examples of the heterocyclic ring include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, and purine Ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimid Azole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc., preferably pyrrole ring, imidazole ring, Pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring.

The alkyl group mentioned as the above-mentioned substituent includes methyl, ethyl, n-propyl, isopropyl, and cyclopropyl. As the above-mentioned alkoxy group, the aforementioned alkyl group can be mentioned as specific examples. The oxygen atom -O- is bonded to the group. As the above-mentioned fluorine-containing alkyl group and fluorine-containing alkoxy group, any hydrogen atom in the aforementioned alkyl group and alkoxy group is substituted with a fluorine atom.

Among them, from the viewpoint of ease of synthesis, Y ² is preferably a benzene ring or a cyclohexane ring.

In the above formula [1], Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms.

In the above formula [1], Y ⁴ represents a single bond, or represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups can be carbon atoms of 1 to 3 Is substituted with an alkyl group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom.

Examples of the above-mentioned heterocyclic ring and the alkyl group as the substituent include those listed for Y ² described above.

In addition, Y ⁴ may be a divalent organic group selected from organic groups having 17 to 30 carbon atoms and having a steroid skeleton. The preferred example is one having selected from cholesterol, androsterol, β-cholesterol, epiandrosterol, ergosterol, Estoril, 11α-hydroxymethyl sterol, 11α-progesterol, lanosterol, Meratoranyl, methyl ester The structure of testosterol, norethisterol, pregnasterol, β-sitosterol, stigmasterol, testosterol, and cholesteryl acetate is a divalent group in which two hydrogen atoms are taken out. More specifically, for example, it is as follows.

(In the formula, * represents the bonding position ^{with Y 3} and Y ⁵ (or Y ^{6 )).}

Among them, from the viewpoint of ease of synthesis, Y ^{4 is} preferably a benzene ring, a cyclohexane ring, or a divalent organic group having a steroid skeleton with 17 to 30 carbon atoms.

In formula [1], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring. Any hydrogen atom on these cyclic groups can be an alkyl group with 1 to 3 carbon atoms or carbon atoms It is substituted with alkoxy groups having 1 to 3, fluorinated alkyl groups having 1 to 3 carbon atoms, fluorinated alkoxy groups having 1 to 3 carbon atoms, or fluorine atoms. The alkyl group and the like exemplified as the heterocyclic ring and the substituent may be those exemplified ^{in Y 4 described above.}

Among these, Y ⁵ is preferably a benzene ring or a cyclohexane ring.

In addition, in formula [1], n represents an integer of 0 to 4, and when n represents 2 or more, Y ⁵ may be the same group or different groups. Among them, from the viewpoint of availability of raw materials or ease of synthesis, n is preferably 0~3. Preferably it is 0~2.

In formula [1], Y ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a carbon number of 1~ 18 fluorine-containing alkoxy group.

Among them, Y ^{6 is} also an alkyl group with 1 to 18 carbon atoms, a fluorinated alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 18 carbon atoms or a fluorinated alkoxy group with 1 to 10 carbon atoms. The one is better. Preferably, Y ⁶ is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. It is particularly preferable that Y ⁶ is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

In addition, when Y ⁴ is a divalent organic group having a steroid skeleton, Y ⁶ is preferably a hydrogen atom.

The alkylene group, alkyl group, fluorine-containing alkyl group, alkoxy group or fluorine-containing alkoxy group mentioned in the definition in the above formula [1] may be any of linear, branched, or cyclic, or It can also be a combination of these.

For example, the above-mentioned alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1- Methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n -Propyl, 2,2-Dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl , 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3 -Dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1 -Ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1 -Ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n- Hexyl, 3-methyl-n-hexyl, 1,1-dimethyl-n-pentyl, 1,2-dimethyl-n-pentyl, 1,3-dimethyl-n-pentyl, 2,2-Dimethyl-n-pentyl, 2,3-dimethyl-n-pentyl, 3,3-dimethyl-n-pentyl, 1-ethyl-n-pentyl, 2 -Ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1-ethyl-n-butyl, 1-methyl-2-ethyl-n-butyl, 1 -Ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n-butyl, n-octyl, 1 -Methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1,1-dimethyl-n-hexyl, 1,2-dimethyl-n -Hexyl, 1,3-dimethyl-n-hexyl, 2,2-dimethyl-n-hexyl, 2,3-dimethyl-n-hexyl, 3,3-dimethyl-n-hexyl , 1-ethyl-n-hexyl, 2-ethyl-n-hexyl, 3-ethyl-n-hexyl, 1-methyl-1-ethyl-n-pentyl, 1-methyl-2- Ethyl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2-ethyl-n-pentyl, 2-methyl-3-ethyl-n- Pentyl, 3-methyl-3-ethyl-n-pentyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n -Tetradecyl group, n-fiveteen Alkyl and so on.

As said alkylene group, the divalent group which removed one arbitrary hydrogen atom from the said alkyl group is mentioned.

Examples of the above-mentioned alkoxy group include a group in which an oxygen atom -O- is bonded to the group mentioned as a specific example of the aforementioned alkyl group.

In addition, as the above-mentioned fluorine-containing alkyl group and fluorine-containing alkoxy group, any hydrogen atom in the aforementioned alkyl group and alkoxy group may be substituted with a fluorine atom.

As the above-mentioned Y ² and Y ³ alkylene, the group as well as cyclic alkyl substituent or Y ^6, fluorine-containing alkyl, alkoxy and fluorine-containing group may be linear, branched , Or any one of cyclic or a combination of these.

In addition, the alkylene group ^{as Y 2} and Y ³ , and the alkyl group, fluorine-containing alkyl group, alkoxy group, and fluorine-containing alkoxy group ^{as Y 6 can be from 1 to 3 as long as the bonding groups are not adjacent to each other.} The bond base is interrupted.

And Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, Y ⁴ represents a divalent organic group with a steroid skeleton, Y ² represents -CH ₂ -CH(OH)-CH ₂ -, Y ² or Y ³ represents When an alkylene group or Y ⁶ represents an alkyl group or a fluorine-containing alkyl group, the divalent cyclic group, the divalent organic group having the steroid skeleton, the -CH ₂ -CH(OH)-CH ₂ -, the The alkyl group, the alkyl group, and the fluorine-containing alkyl group may be bonded via a group adjacent to each other and a bonding group.

In addition, the above-mentioned bonding group means selected from the group consisting of -O-, -CH ₂ O-, -COO-, -OCO-, -NHCO-, -NH-CO-O- and -NH-CO-NH- base.

In addition, each of Y ² to Y ⁶ represents an alkylene group having 1 to 15 carbon atoms, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent organic group having a steroid skeleton, and -CH ₂ -CH(OH)- CH ₂ -, an alkyl group with 1 to 18 carbon atoms, a fluorinated alkyl group with 1 to 18 carbon atoms, an alkoxy group with 1 to 18 carbon atoms, and a fluorinated alkoxy group with 1 to 18 carbon atoms The total number of carbon atoms is 6-30, for example, 6-20.

Among them, when considering the vertical alignment properties and the coating properties of the polymerizable liquid crystal, the vertical alignment groups preferably contain 7-18 carbon atoms, especially those containing 8-15 alkyl groups.

As a preferable vertical alignment group, for example, a hydrocarbon group having about 6 to 20 carbon atoms is mentioned. Examples of the hydrocarbon group having 6 to 20 carbon atoms include linear, branched or cyclic hydrocarbon groups containing 6 to 20 carbon atoms or aromatic groups having 6 to 20 carbon atoms.

As the vertical alignment group, for example, the aforementioned Y ¹ to Y ⁴ are single bonds, Y ³ is a single bond or an alkylene group having 1 to 15 carbon atoms, n is 0, and Y ⁶ is an alkyl group having 1 to 18 carbon atoms. Examples of the group include a vertical alignment group (a-1) in which the group represented by the formula [1] is an alkyl group with a total of 6 to 20 carbon atoms. As a specific example of such an alkyl group, among the aforementioned alkyl groups, an alkyl group having 6 to 20 carbon atoms in total can be mentioned.

As the vertical alignment group, in addition to the above, for example, the above Y ¹ to Y ⁴ are single bonds, n is 2 to 3, Y ⁵ is a group selected from a benzene ring and a cyclohexane ring, and Y ⁶ is a carbon number of 1 to The vertical alignment group (a-2) of the alkyl group of 18 is preferable. As such a group (a-2), the following (a-2-1) to (a-2-6), etc. are preferable.

(In the formula, Y ⁶ is an alkyl group having 1 to 18 carbon atoms. Also * represents the bonding position).

As the vertical alignment group, in addition to the above, for example, the above Y ¹ to Y ³ are single bonds, Y ⁴ is a steroid skeleton, n is 0, and Y ⁶ is a vertical alignment group (a-3) of a hydrogen atom. Examples of such groups (a-3) include vertical alignment groups (a-3-1) to (a-3-8) represented by the following formulae.

(In the formula, * represents the bonding position).

Examples of thermally crosslinkable groups include hydroxyl, carboxyl, and amine Groups, blocked isocyanate groups, vinyl groups, allyl groups, acrylic groups, methacrylic groups, alkoxysilyl groups. From the viewpoint that a thermally cured film can be formed at a low temperature in a short time, the preferred thermally crosslinkable group includes a hydroxyl group, a carboxyl group, an amino group, and an alkoxysilyl group.

Examples of monomers having the above-mentioned hydroxyl, carboxyl, amino, and alkoxysilyl groups as thermally crosslinkable groups include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxy Propyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl Methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2-(acryloxy) ethyl ester, caprolactone 2-(methacryloxy) Ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5-propenoxy-6-hydroxynorbornene-2-carboxylic acid-6 -Lactone and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone and other monomers having hydroxyl groups; acrylic acid, methacrylic acid, crotonic acid, mono-(2-( Acrylonyloxy)ethyl)phthalate, mono-(2-(methacryloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, Monomers with carboxyl groups such as N-(carboxyphenyl)acryloyl and N-(carboxyphenyl)methacryloyl; hydroxystyrene, N-(hydroxyphenyl)acryloyl, N-(hydroxybenzene) Monomers with phenolic hydroxyl groups such as methacrylic acid group and N-(hydroxyphenyl) maleimide; amino ethyl acrylate, amino ethyl methacrylate, amino propyl acrylic acid Ester and aminopropyl methacrylate and other monomers with amine groups; and acryloxypropyl trimethoxysilane, methacryloxypropyl trimethoxysilane, acryloxypropyl trimethoxysilane Monomers with alkoxysilyl groups such as ethoxysilane and methacryloxypropyl triethoxysilane.

In addition, within the range that does not impair the effect of the present invention, when obtaining an acrylic polymer (specific copolymer) containing a vertical alignment group and a thermally crosslinkable group in the present invention, the monomer having the above vertical alignment group, In addition to monomers with thermally crosslinkable groups (preferably at least one substituent selected from hydroxyl, carboxyl, amine, and alkoxysilyl groups), those that can be copolymerized with these monomers that do not have the above-mentioned specific Other monomers for functional groups (vertical alignment groups and thermally crosslinkable groups).

Specific examples of such other monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acryl-based compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

Specific examples of other monomers can be given below, but they are not limited to these.

Examples of the acrylate compound include methacrylate, ethacrylate, isopropyl acrylate, benzyl methacrylate, naphthalene acrylate, anthracenyl acrylate, anthryl methacrylate, and phenyl methacrylate. Acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, Methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, etc.

As the aforementioned methacrylate compound, for example, Methmethacrylate, Ethyl Methacrylate, Isopropyl Methacrylate, Benzyl Methacrylate, Naphthalene Methacrylate, Anthryl Methacrylate, Anthryl Methacrylate Ester, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methylacrylate Methyl acrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3 -Methoxybutyl methacrylate, γ-butyrolactone methacrylate, etc.

As said maleimide compound, maleimide, N-methylmaleimide, N-ethylmaleimide, etc. are mentioned, for example.

As said styrene compound, styrene, methylstyrene, chlorostyrene, bromostyrene, etc. are mentioned, for example.

Examples of the aforementioned vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, and 3-vinyl-7-hexaring. [4.1.0] Heptane, 1,2-epoxy-5-hexene and 1,7-octadiene monoepoxide, etc.

As shown above, the polymer as the component (A), that is, a specific copolymer (acrylic copolymer with a vertical alignment group and a thermally crosslinkable group) is selected from monomers with a vertical alignment group. The method of copolymerizing at least one monomer and at least one monomer selected from monomers having a thermally crosslinkable group with other monomers as required is simple.

The usage amount of each monomer used to obtain a specific copolymer, based on the total amount of all monomers, has a sag of 3 to 90 mol% Monomers with straight alignment groups, monomers with 3 to 90 mol% of thermally crosslinkable groups (hydroxyl, carboxyl, amine, alkoxysilyl), without 0 to 94 mol% of the above specific Other monomers of functional groups (however, the total of these monomers is 100 mol%) is preferable.

If the content of the monomer having a vertical alignment group is less than 3 mol%, it is difficult to impart good vertical liquid crystal alignment. When the content of the monomer having a vertical alignment group is more than 90 mol%, the coatability of the polymerizable liquid crystal will deteriorate and it is difficult to form a uniform retardation film.

In addition, if the content of the monomer having a thermally crosslinkable group (preferably at least one substituent selected from a hydroxyl group, a carboxyl group, an amino group, and an alkoxysilyl group) is less than 3 mol%, it is difficult to provide sufficient It is difficult to maintain good vertical liquid crystal alignment due to thermosetting properties.

The method for obtaining the specific copolymer used in the present invention is not particularly limited. For example, a monomer having a vertical alignment group and a monomer having a thermally crosslinkable group are combined, and the combination required will not have the above specific functional group. The monomer is obtained by polymerizing the monomer in a solvent coexisting with a polymerization initiator and the like at a temperature of 50 to 110°C. At this time, the solvent used can only dissolve monomers with vertical alignment groups and monomers with thermally crosslinkable groups, and the monomers that do not have the above-mentioned specific functional groups and polymerization initiators that need to be used It is not particularly limited as long as they are the same. As specific examples thereof, those listed in the below-mentioned <solvent> can be used.

The specific copolymer obtained by the aforementioned method is usually in the state of a solution dissolved in a solvent. As described later, the obtained specific copolymer solution can be used as it is (A) component (solution).

In addition, the solution of the specific copolymer obtained by the above method is poured into diethyl ether or water under stirring to re-precipitate, and the resulting precipitate is filtered and washed, and then placed under normal pressure or reduced After pressing, drying at room temperature or heating and drying, it can become a powder of a specific copolymer. Through the foregoing operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If it is not sufficiently purified after one operation, redissolve the obtained powder in a solvent and repeat the above operation.

In the present invention, the specific copolymer can be used in the form of a powder or in the form of a solution in which the purified powder is re-dissolved in the solvent described below.

In addition, in the present invention, the specific copolymer of the component (A) may be a mixture of a plurality of specific copolymers.

<(B) Ingredient>

The (B) component in the cured film forming composition of the present invention is a crosslinking agent.

The crosslinking agent of the component (B) has a group capable of forming a crosslink with the thermally crosslinkable functional group of the component (A), for example, a crosslinking agent having a methylol group or an alkoxymethyl group is preferred.

Examples of compounds having these groups include methylol compounds such as alkoxymethylated glycol urea, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

As a specific example of alkoxymethylated glycol urea, for example, 1,3,4,6-four (methoxymethyl) glycol urea, 1,3,4,6-four ( Butoxymethyl) glycol urea, 1,3,4,6-four (hydroxymethyl) glycol urea, 1,3- Bis (hydroxymethyl) urea, 1,1,3,3-four (butoxymethyl) urea, 1,1,3,3-four (methoxymethyl) urea, 1,3-bis( Hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone, etc. As commercially available products, compounds such as ethylene glycol urea compounds (trade names: Cymel (registered trademark) 1170, Powder link (registered trademark) 1174) manufactured by Nihon Cytec Industry Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) can be mentioned. , Methylated urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC (stock ) (Old Dainippon Ink Chemical Industry Co., Ltd.) Urea/formaldehyde resin (high condensation type, trade name: BECKAMINE (registered trademark) J-300S, same as P-955, same as N), etc.

As a specific example of alkoxymethylated benzoguanamine, tetramethoxymethyl benzoguanamine etc. are mentioned. Commercially available products include Nihon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) (trade name: Cymel (registered trademark) 1123), and Sanwa Chemical Co., Ltd. (trade name: NIKALAC (registered) Trademark) BX-4000, same as BX-37, same as BL-60, same as BX-55H) etc.

As a specific example of alkoxymethylated melamine, hexamethoxymethyl melamine etc. are mentioned, for example. As commercially available products, methoxymethyl melamine compounds (trade name: Cymel (registered trademark) 300, the same 301, the same 303, the same 350), butoxymethyl melamine compound (trade name: Mycoat (registered trademark) 506, the same as 508), (stock) Sanwa Chemical's methoxymethyl melamine compound (trade name: NIKALAC (registered trademark) MW-30, same MW-22, same MW-11, same MS-001, same MX- 002, the same MX-730, the same MX-750, the same MX-035), butoxymethyl melamine compound (trade name: NIKALAC (registered trademark) MX-45, the same MX-410, the same MX-302), etc. .

In addition, it may also be a compound obtained by condensation of a melamine compound, a urea compound, a glycol urea compound, and a benzoguanamine compound in which the hydrogen atom of the amino group is replaced by a methylol group or an alkoxymethyl group. For example, a high molecular weight compound produced from a melamine compound and a benzoguanamine compound as described in U.S. Patent No. 6,323,310 can be mentioned. Commercial products of the aforementioned melamine compound include trade name: Cymel (registered trademark) 303, etc., and commercial products of the aforementioned benzoguanamine compound include trade name: Cymel (registered trademark) 1123 (the above are Japan Cytec Industry Co., Ltd. (formerly manufactured by Mitsui Cytec Co., Ltd.), etc.

In addition, as the crosslinking agent of component (B), the following polymers can also be used. The polymer is based on N-hydroxymethacryloyl, N-methoxymethylmethacryloyl, and N-ethoxy Methacrylic acid group, N-butoxymethyl methacrylic acid group and other hydroxymethyl (i.e. hydroxymethyl) or alkoxymethyl substituted acryloyl compounds or methacryloyl compounds Manufactured polymers.

Examples of such polymers include poly(N-butoxymethacryloyl), copolymers of N-butoxymethacryloyl and styrene, and N-hydroxymethylmethacryloyl Copolymer with methacrylate, copolymer of N-ethoxymethylmethacrylic acid and benzyl methacrylate, and N-butoxymethacrylic acid and benzyl Copolymers of methacrylate and 2-hydroxypropyl methacrylate, etc. Of such a polymer The weight average molecular weight (polystyrene conversion value) is 1,000 to 500,000, preferably 2,000 to 200,000, preferably 3,000 to 150,000, and more preferably 3,000 to 50,000.

Such a crosslinking agent can be used individually or in combination of 2 or more types. In addition, the crosslinking agent as the component (B) is also the unit structure exemplified in the component (C) described later, and a polymer having an N-alkoxymethyl group and a polymerizable group containing a C=C double bond can also be used (Specific copolymer 2).

The content of the crosslinking agent of component (B) in the cured film forming composition of the present invention is based on 100 parts by mass of the polymer of component (A), preferably 1 part by mass to 300 parts by mass, preferably 5 Parts by mass ~ 200 parts by mass. When the content of the crosslinking agent is too small, the solvent resistance of the cured film obtained from the cured film forming composition will decrease, resulting in a decrease in vertical alignment. On the other hand, if the content is too large, the vertical alignment and storage stability will decrease.

<(C) Ingredient>

The cured film forming composition of the present invention contains either or both of the component (C): an adhesion promoter and the component (D) described later: a polymer having a thermally crosslinkable group.

The (C) component of the present invention is a component that can improve the adhesiveness of the formed cured film (hereinafter also referred to as an adhesion promoting component).

And when using the specific copolymer 2 which is the said (B) component as mentioned later, (C) component may be the same as (B) component.

When the cured film formed from the cured film forming composition of the present embodiment containing the component (C) is used as an alignment material, the alignment material can be improved The adhesion to the layer of the polymerizable liquid crystal, the crosslinking reaction site of the polymerizable functional group of the polymerizable liquid crystal and the alignment material can be connected by a covalent bond. As a result, the retardation material of the present embodiment formed by laminating the hardened polymerizable liquid crystal on the alignment material of the present embodiment can maintain strong adhesion even under the conditions of high temperature and high humidity, showing high resistance to peeling, etc. Durability.

As the (C) component, monomers and polymers selected from the group consisting of a hydroxyl group and an N-alkoxymethyl group, and a polymerizable group are preferred.

As such (C) component, a compound having a hydroxyl group and a (meth)acrylic group, a compound having a (meth)acrylic group of an N-alkoxymethyl group, and a compound having an N-alkoxymethyl group and ( Meth) acrylic-based polymers, etc. Specific examples are shown below.

As an example of (C) component, the polyfunctional acrylate containing a hydroxyl group (hereinafter also referred to as a polyfunctional acrylate containing a hydroxyl group) is mentioned.

(C) Examples of the hydroxyl group-containing polyfunctional acrylate as an example of the component include, for example, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like.

As an example of (C) component, the compound which has 1 acrylic group and 1 or more hydroxyl groups is mentioned. In this way, preferred examples of compounds having one acrylic group and one or more hydroxyl groups can be given. In addition, the compound of the component (C) is not limited to the following compound examples.

(In the above formula, R ¹¹ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10).

Moreover, as a compound of (C)component, the compound which has at least 1 polymerizable group containing a C=C double bond in 1 molecule, and at least 1 N-alkoxymethyl group is mentioned.

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

Regarding the N of N-alkoxymethyl group, that is, as the nitrogen atom, it can include the nitrogen atom of amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen of urethane The nitrogen atom, the nitrogen atom bonded to the adjacent position of the nitrogen atom of the nitrogen-containing heterocyclic ring, etc. Therefore, as the N-alkoxymethyl group, it can be selected from the nitrogen atom of amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of urethane, Nitrogen-containing heterocycle A structure in which an alkoxymethyl group is bonded to a nitrogen atom such as a nitrogen atom adjacent to the nitrogen atom.

As the (C) component, it is only necessary to have the above-mentioned group. For example, a compound represented by the following formula (X1) is preferably used.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms).

Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1, 2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2- Methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n -Butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl -n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl -n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl, 3-methyl-n-hexyl, 1,1-dimethyl-n-pentyl, 1,2-di Methyl-n-pentyl, 1,3-dimethyl-n-pentyl, 2,2-dimethyl-n-pentyl, 2,3-dimethyl-n-pentyl, 3,3 -Dimethyl-n-pentyl, 1-ethyl-n-pentyl, 2-ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1-ethyl- n-butyl, 1-methyl-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n-butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1,1-dimethyl-n-hexyl, 1,2-dimethyl-n-hexyl, 1,3-dimethyl-n-hexyl, 2,2-dimethyl-n-hexyl, 2, 3-dimethyl-n-hexyl, 3,3-dimethyl-n-hexyl, 1-ethyl-n-hexyl, 2-ethyl-n-hexyl, 3-ethyl-n-hexyl, 1 -Methyl-1-ethyl-n-pentyl, 1-methyl-2-ethyl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2 -Ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl, 3-methyl-3-ethyl-n-pentyl, n-nonyl, n-decyl, etc.

As specific examples of the compound represented by the above formula (X1), N-hydroxymethyl (meth)acryloyl, N-methoxymethyl (meth)acryloyl, N-ethoxymethyl Acrylic compounds or methacrylic compounds substituted with hydroxymethyl or alkoxymethyl, such as methacrylic acid group and N-butoxymethyl(meth)acrylic acid group. In addition, the (meth)acryloyl group means both a methacryloyl group and an acrylic group.

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

In the formula, R ⁵¹ represents a hydrogen atom or a methyl group. R ⁵² and R ⁵³ each independently represent a straight chain or branched alkylene group having 2 to 20 carbon atoms, aliphatic cyclic group having 5 to 6 carbon atoms, or aliphatic ring having 5 to 6 carbon atoms The group group may contain ether bonds in the structure. R ⁵⁴ represents an aliphatic group containing a linear or branched alkyl group having 1 to 20 carbon atoms, an aliphatic ring group having 5 to 6 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms, one of these groups One methylene group or a plurality of non-adjacent methylene groups may be substituted with ether linkages. Z means >NCOO-, or -OCON< (where "-" means that there is one bond. Also, ">" and "<" mean that there are two bonds, and it means that any one of the bonds is bound to an alkane. Oxymethyl). R is a natural number of 2 or more and 9 or less.

As a ^{specific example of the alkylene group having 2 to 20 carbon atoms in the definition of R 53} and R ⁵⁴ , there can be exemplified the divalent to 9 of the alkyl group having 2 to 20 carbon atoms and 1 to 8 hydrogen atoms. Price base.

Specific examples of the alkyl group having 2 to 20 carbon atoms include ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl , N-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, n -Hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1-ethyl-n-butyl, 1,1, 2-Trimethyl-n-propyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-decyl Monoalkyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl Alkyl, n-nonadecyl, n-eicosyl, cyclopentyl, cyclohexyl, one or more of these groups bonded in the range of carbon atoms to 20, and the extension of one of these groups Methyl groups or groups in which a plurality of non-adjacent methyl groups are substituted with ether bonds are all examples.

Among them, an alkylene group having 2 to 10 carbon atoms is preferred, when R ⁵³ is an ethylidene group, and R ⁵⁴ is a pentyl group, it is particularly preferred from the viewpoint of availability of raw materials.

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 in the definition of ^{R 53} and R ^{54 and methyl group.} Among them, an alkyl group having 1 to 6 carbon atoms is preferred, and a methyl group, an ethyl group, an n-propyl group or an n-butyl group is particularly preferred.

Examples of r include natural numbers of 2 or more and 9 or less, but among them, 2 to 6 are also preferred.

Compound (X2) is obtained by the production method shown in the following reaction scheme. That is, a urethane compound having an acrylic or methacrylic group represented by the following formula (X2-1) (hereinafter also referred to as compound (X2-1)) is added to trimethylsilyl chloride and Formaldehyde (generally represented by the chemical formula (CH ₂ O) n) is reacted in a solvent to synthesize the intermediate represented by the following formula (X2-2), and the alcohol represented by ^{R 52 -OH is added to the reaction solution to react} And manufacturing.

In the formula, R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , Z and r represent the aforementioned meanings, and X represents -NHCOO- or -OCONH-.

There are no particular restrictions on the amount of trimethylsilyl chloride and formaldehyde used in compound (X2-1). To terminate the reaction, use trimethylsilyl for one urethane bond in the molecule. 1.0 to 6.0 equivalent times of base chloride and 1.0 to 3.0 equivalent times of formaldehyde are preferred, and the use equivalent of trimethylsilyl chloride is better than that of formaldehyde.

The reaction solvent is not particularly limited as long as it is inert to the reaction. Examples include hydrocarbons such as hexane, cyclohexane, benzene, and toluene; dichloromethane, carbon tetrachloride, chloroform, and , 2-Dichloroethane and other halogen-based hydrocarbons; diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran and other ethers; acetonitrile, propionitrile and other nitriles; N,N-di Methylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone and other nitrogen-containing aprotic polar solvents; Pyridines such as pyridine and picoline. These solvents may be used alone, or two or more of these solvents may be mixed and used. Dichloromethane and chloroform are preferred, and dichloromethane is more preferred.

The use amount (reaction concentration) of the above-mentioned solvent is not particularly limited, and the reaction can be carried out without using a solvent, and when a solvent is used, the compound (X2- 1) 0.1 to 100 times the mass of the solvent can be used. It is preferably 1 to 30 times by mass, more preferably 2 to 20 times by mass.

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

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

The reaction can be carried out under normal pressure or under pressure, and can be divided into batches or continuous methods.

During the reaction, a polymerization inhibitor can be added. As such a polymerization inhibitor, BHT (2,6-di-tert-butyl-p-cresol), hydroquinone, p-methoxyphenol, etc. can be used, which only hinder the polymerization of acrylic and methacrylic groups. There may also be no particular limitation.

The addition amount when adding the polymerization inhibitor is not particularly limited, and the total usage (mass) of the compound (X2-1) is 0.0001 to 10 wt%, preferably 0.01 to 1 wt%. In this specification, wt% means mass%.

For the step of reacting the alcohol with the intermediate (X2-2), a base can be added to suppress hydrolysis under acidic conditions. Examples of the base include pyridines such as pyridine and picoline, or tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, and tributylamine. Preferred are triethylamine and diisopropylethylamine, and more preferred is triethylamine. The addition amount when adding the base is not particularly limited. For the addition amount of the trimethylsilyl chloride used in the reaction, it is only necessary to use 0.01 to 2.0 equivalent times, preferably 0.5 to 1.0 equivalent.

Moreover, after obtaining the intermediate (X2-2) from the compound (X2-1), it is not necessary to isolate the intermediate (X2-2), and an alcohol may be added to perform the reaction.

The method for synthesizing compound (X2-1) is not particularly limited, but it can be achieved by reacting (meth)acryloxyalkyl isocyanate with a polyol compound, or by reacting a hydroxyalkyl (meth)acrylate compound with The polyisocyanate compound is produced by reacting.

As a specific example of (meth)acryloxyalkyl isocyanate, for example, 2-methacryloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., trade name: Karenz MOI [registered trademark]), 2 -Acrylic oxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., trade name: Karenz AOI [registered trademark]), etc.

Specific examples of polyol compounds include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl Diol compounds such as 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, triol compounds such as glycerol, trimethylolpropane, pentaerythritol, di Pentaerythritol, diglycerol, etc.

Specific examples of hydroxyalkyl (meth)acrylate compounds include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl acrylate. Base acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, poly(ethylene glycol) ethyl ether acrylate, Monomers having hydroxyl groups such as poly(ethylene glycol) ethyl ether methacrylate.

As a specific example of the polyisocyanate compound, one can cite Aliphatic diisocyanates such as hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4'-methylidene Alicyclic diisocyanates such as bis(cyclohexyl isocyanate), ω,ω'-diisocyanate dimethylcyclohexane, lysine triisocyanate, 1,6,11-undecane triisocyanate, 1,8- Triisocyanates such as diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, etc.

These (meth)acryloxyalkyl isocyanate compounds, polyol compounds, hydroxyalkyl (meth)acrylate compounds, and polyisocyanate compounds are generally sold products, and they can be synthesized by known methods.

In addition, as an example of the component (C), as a unit structure, a polymer having an N-alkoxymethyl group and a C=C double bond-containing polymerizable group (hereinafter also referred to as specific copolymer 2) . This is the crosslinking agent that can be used as the component (B) as described above, that is, the component (C) and the component (B) may be the same at this time.

The above-mentioned specific copolymer can be the following two kinds of polymers. One of the polymers contains the following repeating unit structure. The repeating unit structure is a two-group containing N-alkoxymethyl group and a polymerizable group containing a C=C double bond Repeating unit structure, the other polymer contains the following two repeating unit structures, one of which is a repeating unit structure containing N-alkoxymethyl group, and the other is a repeating unit containing a polymerizable group with a C=C double bond It can also be a polymer containing at least one of the following two repeating unit structures, one of which is a polymerizable group containing N-alkoxymethyl groups and C=C double bonds In the case of both groups, the other repeating unit structure is a repeating unit containing a repeating unit structure having an N-alkoxymethyl group and a polymerizable group containing a C=C double bond. Among them, as the specific copolymer 2, a polymer containing the following repeating unit structure is applicable. The repeating unit structure is a repeating unit containing an N-alkoxymethyl group and a polymerizable group having a C=C double bond By.

The specific copolymer 2 (also referred to as the polymer of the (C) component) as an example of the (C) component will be described below.

As the N of the N-alkoxymethyl group, the nitrogen atom includes the nitrogen atom of amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, and the nitrogen atom of carbamate. , The nitrogen atom bonded to the adjacent position of the nitrogen atom of the nitrogen-containing heterocyclic ring, etc. Therefore, the N-alkoxymethyl group may be selected from the group consisting of nitrogen atom of amide, nitrogen atom of thioamide, nitrogen atom of urea, nitrogen atom of thiourea, nitrogen atom of urethane, nitrogen-containing A structure in which an alkoxymethyl group is bonded to a nitrogen atom such as a nitrogen atom bonded to a nitrogen atom adjacent to the nitrogen atom of the heterocyclic ring.

The N-alkoxymethyl group-imparting monomer (hereinafter also referred to as the specific monomer X1) may only have the above-mentioned groups. For example, the compound represented by the above-mentioned formula (X1) (in the formula R ² represents a compound of a linear or branched alkyl group having 1 to 10 carbon atoms).

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

The above-mentioned polymerizable group containing C=C double bond is obtained by inserting into the side chain of the main skeleton of the polymer, that is, as having C=C double bond The specific side chain of the polymerizable group is inserted into the side chain of the polymer of the component (C).

(C) The number of carbon atoms in the specific side chain of the polymerizable group containing the C=C double bond of the component is 3-16, preferably having an unsaturated bond at the end, and the specific side represented by the following formula (b2) The chain is especially good. The specific side chain represented by the formula (b2) is, for example, as represented by the formula (b2-1), which is bonded to the ester bond portion of the acrylic polymer.

In formula (b2), the ^{number of carbon atoms in R 61} is 1 to 14, selected from the group consisting of aliphatic groups, cyclic structure-containing aliphatic groups and aromatic groups, or plural organic groups selected from the group An organic base formed by a combination of bases. R ⁶¹ may also contain an ester bond, ether bond, amide bond, or urethane bond.

For the specific side chain represented by the formula (b2), R ⁶² is a hydrogen atom or a methyl group, and ^{it is particularly preferable that R 62 is} a specific side chain of a hydrogen atom. Preferably, it is a specific side chain whose terminal is an acryloyl group, a methacryloyl group or a vinyl phenyl group.

In the formula (b2-1), R ⁶³ is a hydrogen atom or a methyl group.

To obtain a polymer with specific side chains as described above It is not particularly limited.

To give an example, an acrylic polymer having a specific functional group described later (hereinafter also referred to as a polymer having a specific functional group) is produced by a polymerization method such as prepolymerization of free radicals (and, a polymer having the specific functional group) (N-alkoxymethyl) can be introduced into the acrylic copolymer as described later. Secondly, after the specific functional group reacts with a compound having an unsaturated bond (C=C double bond) at the end (hereinafter referred to as a specific compound) to form a specific side chain, the polymerizability containing the C=C double bond is introduced Base, the polymer of component (C) can be obtained.

Here, the specific functional group means a functional group such as a carboxyl group, a glycidyl group, a hydroxyl group, an amine group having active hydrogen, a phenolic hydroxyl group, or an isocyanate group, or a plurality of functional groups selected from these.

For the reaction to generate the above-mentioned specific side chain, the preferred combination of the specific functional group and the functional group of the specific compound (generating the characteristic side chain), that is, the relevant group of the reaction, is a carboxyl group and an epoxy group, a hydroxyl group and an isocyanate group, and a phenolic hydroxyl group. With epoxy groups, carboxyl groups and isocyanate groups, amine groups and isocyanate groups, or hydroxyl groups and acid chlorides. And the preferred combination is carboxyl group and glycidyl methacrylate, or hydroxyl group and isocyanate ethyl methacrylate.

In addition, the polymer having a specific functional group used in the reaction for generating the specific side chain is preferably a polymer having an N-alkoxymethyl group and a specific functional group. That is, it is preferable that the polymer having the aforementioned specific functional group is such that the specific monomer X1, which is a monomer imparting an N-alkoxymethyl group, and has an unsaturated bond (C=C double bond) at the end ) Is the functional group (specific functional group) of the compound that reacts with the specific compound "monomers with carboxyl group, glycidyl group, hydroxyl group, amine group with active hydrogen, phenolic A copolymer obtained by using monomers such as a hydroxyl group or an isocyanate group (hereinafter also referred to as a specific monomer X3) as an essential component, and the number average molecular weight is preferably 2,000-25,000. Among them, the monomer having a specific functional group used in the polymerization can be used alone, and if it does not react during the polymerization, a plurality of types can be combined and used.

The monomers necessary to obtain a polymer having a specific functional group are listed below, and specific examples of the specific monomer X3 can be cited. But it is not limited to this.

As the monomer having a carboxyl group, for example, acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacrylic acid) ((Oxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacryloyl and N-(carboxyphenyl)acryloyl, etc. .

Examples of monomers having a glycidyl group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and 3-vinyl-7-hexaring [4.1.0] Heptane, 1,2-epoxy-5-hexene and 1,7-octadiene monoepoxide, etc.

Examples of monomers having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 4-hydroxyethyl methacrylate. Butyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol mono Methacrylate, caprolactone 2-(acryloxy) ethyl ester, caprolactone 2-(methacryloxy) ethyl ester, poly(ethylene glycol) ethyl ether propylene Ester, poly(ethylene glycol) ethyl ether methacrylate, 5-propenoxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone and 5-methacryloxy-6 -Hydroxynorbornene-2-carboxylic acid-6-lactone and the like.

Examples of monomers having an amino group include 2-aminoethyl acrylate, 2-aminomethyl methacrylate, and the like.

Examples of monomers having a phenolic hydroxyl group include hydroxystyrene, N-(hydroxyphenyl)acryloyl, N-(hydroxyphenyl)methacryloyl, and N-(hydroxyphenyl)maleic group. Diimines and so on.

Examples of the monomer having an isocyanate group include acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m-tetramethyl xylene isocyanate, and the like.

As described above, for the specific side chain represented by the formula (b2) obtained by the reaction with the specific functional group ^{, specific examples of R 61} include the following formulas (B-1) to (B- 11) etc.

(In the formula, * represents the ^{number of bonding places between R 62} and the carbon atom forming a double bond).

Furthermore, in the present invention, when obtaining the polymer of the component (C), the specific monomer X1 can be copolymerized with the monomer other than the specific monomer X3, and it can be used in combination without the component (A), which can be thermally crosslinked. The functional group (ie, hydroxyl, carboxyl, amine, alkoxysilyl, etc.) monomers.

As specific examples of such monomers, specific monomers X1, and acrylate compounds or methacrylate compounds having a structure different from that of specific monomer X3, maleimide compounds, acryl-based compounds, propylene Nitriles, maleic anhydride, styrene compounds, vinyl compounds, etc. (hereinafter also referred to as monomer X4).

Although specific examples of the aforementioned monomer X4 are given below, it is not limited to these.

Examples of acrylate compounds as examples of the aforementioned monomer X4 include methacrylate, ethacrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and isobutyl acrylate. Esters, t-butyl acrylate, benzyl acrylate, naphthalene acrylate, anthracenyl acrylate, anthryl methacrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoro Ethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl Acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl Acrylate and 8-ethyl-8-tricyclodecyl acrylate, etc.

The methacrylate compound as an example of the aforementioned monomer X4 includes, for example, methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n -Butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, naphthalene methacrylate, anthryl methacrylate, anthryl methacrylate, benzene Methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl Methyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2 -Methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl Methacrylate and 8-ethyl-8-tricyclodecyl methacrylate, etc.

Examples of vinyl compounds as examples of the aforementioned monomer X4 include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-vinyl -7-hexacyclo[4.1.0]heptane, 1,2-epoxy-5-hexene and 1,7-octadiene monoepoxide, etc.

Examples of styrene compounds that are examples of the aforementioned monomer X4 include styrene, methylstyrene, chlorostyrene, and bromostyrene.

Examples of the maleimide compound as an example of the aforementioned monomer X4 include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylimine. Leimine and so on.

In the polymer of component (C), the proportion of N-alkoxymethyl is 40 mol%~90 mol% for the total repeating unit of the polymer 100 mol, and 50 mol% %~85mol% is better.

That is, the amount of the specific monomer X1 (N-alkoxymethyl-imparting monomer) used to obtain the specific copolymer 2 of the component (C) is determined by the specific copolymer 2 of the component (C). The total amount of all monomers used is the basis, preferably 40 mol%~90 mol%, and more preferably 50 mol%~85 mol%.

If the total is less than 40 mol%, the curing by thermal cross-linking with component (A) may be insufficient. If it is greater than 90 mol%, it will have an effect on the adhesion to the liquid crystal layer. A bad influence situation will occur.

(C) The proportion of polymerizable groups containing C=C double bonds in the polymer of the component is 10 mol% to 60 mol% for the total repeating unit of the polymer 100 mol, preferably 15 mol% Moear%~50mol% is better.

That is, to be used to obtain the specific monomer X3 of the specific copolymer 2 of the component (C) (having a functional group (specific functional group) to react with a specific compound of a compound having an unsaturated bond (C=C double bond) at the end The usage amount of the monomer) is preferably 10 mol% to 60 mol% based on the total amount of all monomers used when the specific copolymer 2 of component (C) is to be obtained, and 15 Moear%~50mol% is better.

If the total is less than 10 mol%, the adhesion to the liquid crystal layer may be insufficient. If it is greater than 60 mol%, the curing by thermal cross-linking with the component (A) may be insufficient. The situation arises.

The method for obtaining the specific copolymer 2 as an example of the component (C) is not particularly limited. For example, the specific monomer X1, the specific monomer X3, and other monomers (for example, the monomer X4) and the It can be obtained by polymerization reaction at a temperature of 50°C to 110°C in a solvent such as a polymerization initiator. At this time, the solvent to be used is only one that can dissolve the above-mentioned specific monomer X1, specific monomer X3, other monomers and polymerization initiators used as needed, and is not particularly limited. As a specific example, it is as described in the item of [solvent] mentioned later.

The acrylic polymer as an example of the component (C) obtained by the above method is generally in the state of a solution dissolved in a solvent, and can be used directly as a solution of the component (C) in the present invention.

In addition, the acrylic polymer solution, which is an example of component (C) obtained by the above method, is poured into diethyl ether or water under stirring to re-precipitate, and the resulting precipitate is filtered and washed, It can be made into the powder of the specific copolymer 2 of the component (C) by performing room temperature drying or heat drying under normal pressure or reduced pressure. By the above operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer 2 of the component (C) can be removed. As a result, a purified specific copolymer 2 of the example of the component (C) can be obtained Powder. If it is not possible to purify sufficiently in one operation, dissolve the obtained powder in the solvent again and repeat the above operation.

For the composition forming the surface cured film in the optical film of the present invention, the specific copolymer 2 of the component (C) can be used in the form of a powder or a solution in which the purified powder is re-dissolved in the solvent described below.

In addition, for the hard surface of the optical film of the present invention In the composition of the chemical film, the specific copolymer 2 of the component (C) may be a mixture of plural kinds.

The weight average molecular weight of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, preferably 3,000 to 150,000, and more preferably 3,000 to 50,000.

The content of the (C) component in the cured film forming composition of the embodiment of the present invention is 0.1 parts by mass relative to 100 parts by mass of the total amount of the polymer of the component (A) and the crosslinking agent of the (B) component ~100 parts by mass is better, more preferably 5 parts by mass to 70 parts by mass. When the content of the component (C) is 0.1 parts by mass or more, sufficient adhesiveness can be imparted to the cured film formed. However, if it is more than 100 parts by mass, the liquid crystal alignment tends to decrease.

And, when the component (B) is the above-mentioned specific copolymer 2, and the component (C) and the component (B) are the same (the same compound), the compounding quantity of the component (C) is regarded as the compounding quantity of the component (B) (in this case Regarding the blending, the blending amount of the component (C) is regarded as 0).

In addition, in the cured film forming composition of the present embodiment, the component (C) may be a mixture of plural kinds of compounds of the component (C).

<(D) Ingredients>

The cured film forming composition of the present invention contains either or both of the aforementioned (C) component: adhesion promoter and (D) component: a polymer having a thermally crosslinkable group.

As the polymer of the component (D) of the present invention (hereinafter also referred to as a specific polymer), for example, acrylic polymer, polyamide acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylate Acid, polyether polyol, polyester polyol Alcohol, polycarbonate polyol, polycaprolactone polyol, polyalkyleneimine, polyallylamine, cellulose (cellulose or its derivatives), phenol novolak resin, melamine formaldehyde resin, etc. Linear or branched polymers, cyclic polymers such as cyclodextrins, etc.

The specific polymer of (D) component preferably includes acrylic polymers, hydroxyalkyl cyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone. Ester polyol.

The acrylic polymer, which is a preferable example of the specific polymer of the component (D), is a polymer obtained by polymerizing monomers having unsaturated double bonds such as acrylic acid, methacrylic acid, styrene, and vinyl compounds. It is only The polymer can be obtained by polymerizing a monomer or a mixture containing a monomer having the following specific functional group D. The main chain skeleton and side chain types of the polymer constituting the acrylic polymer are combined There is no particular limitation.

Examples of monomers having a specific functional group D include monomers having polyethylene glycol ester groups, monomers having hydroxyalkyl ester groups with 2 to 5 carbon atoms, monomers having phenolic hydroxyl groups, and monomers having phenolic hydroxyl groups. Monomers with carboxyl groups, monomers with amine groups, monomers with alkoxysilyl groups, monomers with acetyl acetoxy groups, monomers with amide groups, etc.

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

Examples of monomers having the above-mentioned hydroxyalkyl ester group having 2 to 5 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl methacrylate. , 2-Hydroxypropyl propylene Acid ester, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate.

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

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

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

As the monomer having an alkoxysilyl group on the side chain, for example, 3-propenyloxypropyltrimethoxysilane, 3-propenyloxypropyltriethoxysilane, 3-methyl Acrylic oxypropyl trimethoxy silane, 3-methacryloxy propyl trimethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, allyl trimethoxy silane and alkene Propyl triethoxysilane and so on.

Examples of the monomer having an acetylacetoxy group in the side chain include 2-acetylacetoxyethyl acrylate, 2-acetylacetoxyethyl methacrylate, and the like.

In addition, in this embodiment, when synthesizing the acrylic polymer as an example of component (D), in order not to impair the effects of the present invention, monomers that do not have the above-mentioned specific functional group D, for example, can be used in combination without a hydroxyl group, a carboxyl group, or a glutamate. A monomer of any one of amine group, amine group, alkoxysilyl group and acetyl acetoxy group.

As specific examples of such monomers, acrylate compounds, methacrylate compounds, maleimide compounds, acrylic Nitriles, maleic anhydride, styrene compounds and vinyl compounds, etc.

Examples of acrylate compounds include methacrylate, ethacrylate, isopropyl acrylate, benzyl methacrylate, naphthalene acrylate, anthracenyl acrylate, anthryl methacrylate, and phenyl acrylate. Esters, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol Acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2- Adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, etc.

As the methacrylate compound, for example, methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthalene methacrylate, anthrylmethyl Methyl acrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, iso Bornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate Ester, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tri Cyclodecyl methacrylate and 8-ethyl-8-tricyclodecyl methacrylate, etc.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-ring Hexyl maleimide and so on.

Examples of styrene compounds include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

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

The usage amount of the monomer having the specific functional group D used when obtaining the acrylic polymer of the example of the component (D) is based on the total amount of all monomers used when obtaining the acrylic polymer of the component (D) , Preferably 2 mol%~98 mol%. If the monomer having the specific functional group D is too small, the liquid crystal alignment of the cured film obtained will tend to be insufficient, and if it is too large, the compatibility with the component (A) will tend to decrease.

The method for obtaining the acrylic polymer as an example of the component (D) is not particularly limited. For example, in the coexistence of a monomer containing a monomer having a specific functional group D, a monomer that does not have a specific functional group D as required, and polymerization The initiator is equal to the solvent and is obtained by polymerization at a temperature of 50°C to 110°C. At this time, the solvent used can only dissolve the monomer having the specific functional group D, the monomer without the specific functional group D and the polymerization initiator used as needed, and is not particularly limited. As a specific example, it is as described in the item of [solvent] mentioned later.

The acrylic polymer as an example of the component (D) obtained by the above method is generally in the state of a solution dissolved in a solvent.

In addition, the acrylic polymer solution, which is an example of the component (D) obtained by the above method, is poured into diethyl ether or water under stirring to make After re-precipitation, the resulting precipitate is filtered and washed, dried at room temperature or heated under normal pressure or reduced pressure, and can become acrylic polymer powder as an example of component (D). By the above operation, the polymerization initiator and unreacted monomers coexisting with the acrylic polymer of the example of the component (D) can be removed. As a result, a purified powder of the acrylic polymer of the example of the (B) component can be obtained. body. If it is not possible to fully purify in one operation, re-dissolve the obtained powder in a solvent and repeat the above operation.

(D) The weight average molecular weight of the acrylic polymer of the preferred example of the component is preferably 3,000 to 200,000, preferably 4,000 to 150,000, and more preferably 5,000 to 100,000. If the weight average molecular weight exceeds 200,000, the solubility to the solvent will be reduced and the handling properties will decrease. If the weight average molecular weight is less than 3,000 but too small, the curing during thermal curing becomes insufficient. There are cases where solvent resistance and heat resistance are reduced. In addition, the weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample. The following is the same for this manual.

Next, as a preferable example of the specific polymer of the component (D), polyether polyols include polyols such as polyethylene glycol, polypropylene glycol, propylene glycol, or bisphenol A, triethylene glycol, and sorbitol. Adding propylene oxide, polyethylene glycol, polypropylene glycol, etc. Specific examples of polyether polyols include Adeka polyether P series, G series, EDP series, BPX series, FC series, CM series, and Uniox (registered trademark) HC manufactured by ADEKA. -40, HC-60, ST-30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG- 4000, HS-1600D, DA-400, DA-700, DB-400, non-ionic (registered trademark) LT-221, ST-221, OT-221, etc.

As a preferred example of the specific polymer of the component (D), polyester polyols include polyvalent carboxylic acids such as adipic acid, sebacic acid, and isophthalic acid, ethylene glycol, propylene glycol, butane Diol, polyethylene glycol, polypropylene glycol and other glycols are reacted. Specific examples of polyester polyols include POLYLITE (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X- 240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD-X-2555, OD-X-2560, (stock) Kuraray polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P -6010, F-510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, etc.

The polycaprolactone polyol, which is a preferable example of the specific polymer of the component (D), uses a polyol such as trimethylolpropane or ethylene glycol as an initiator to carry out ring-opening polymerization of ε-caprolactone Those can be cited. Specific examples of polycaprolactone polyols include POLYLITE (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, PLACCEL manufactured by DIC (Stock) Registered trademark) 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, etc.

As a preferable example of the specific polymer of the component (D), polycarbonate polyols include polyols such as trimethylolpropane or ethylene glycol and Reactors such as diethyl carbonate, diphenyl carbonate, and ethylene carbonate. Specific examples of polycarbonate polyols include PLACCEL (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel Corporation, and C-590, C-1050, C-2050, C-2050 manufactured by Kuraray -2090, C-3090, etc.

As a preferable example of the specific polymer of the component (D), cellulose includes hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyethyl methyl cellulose, and hydroxypropyl cellulose. Hydroxyalkylalkylcelluloses, such as hydroxymethylcellulose and hydroxyethylethylcellulose, and cellulose, etc., for example, hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose are preferred.

Cyclodextrin as a preferred example of the specific polymer of the component (D) includes cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, and methyl-α-cyclodextrin. Methylated cyclodextrin, methyl-β-cyclodextrin and methyl-γ-cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl -γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxyethyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α -Cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-ring Dextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2,3-dihydroxypropyl-β-cyclodextrin, 2,3-di Hydroxyalkyl cyclodextrins such as hydroxypropyl-γ-cyclodextrin and the like.

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

In the above formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and q represents a natural number of the number of repeating units.

(D) The melamine formaldehyde resin of the component, from the viewpoint of storage stability, the methylol formed during the polycondensation of melamine and formaldehyde is preferably alkylated.

The method for obtaining the melamine-formaldehyde resin of component (D) is not particularly limited. Generally, it is to mix melamine and formaldehyde, use sodium carbonate or ammonia to make it weakly alkaline, and then heat it at 60°C to 100°C to synthesize it. . And by reacting with alcohol, hydroxymethyl can be alkoxylated.

(D) The weight average molecular weight of the melamine formaldehyde resin of the component is preferably 250 to 5,000, preferably 300 to 4,000, and more preferably 350 to 3,500. If the weight average molecular weight exceeds 5,000, the solubility to the solvent will be reduced and the handling properties will be reduced. If the weight average molecular weight is less than 250, there will be insufficient curing during thermal curing, and There may be cases where the effect of improving solvent resistance and heat resistance cannot be fully expressed.

For the embodiment of the present invention, the melamine of component (D) The formaldehyde resin can be used in a liquid form or in a solution form in which a purified liquid is re-dissolved in a solvent described below.

As a phenol novolak resin which is a preferable example of the specific polymer of (D) component, a phenol-formaldehyde polycondensate etc. are mentioned, for example.

Regarding the cured film forming composition of this embodiment, the polymer of the component (D) can be used in the form of a powder or in the form of a solution in which the purified powder is redissolved in the solvent described below.

The content of component (D) in the cured film forming composition of the present invention is preferably 400 parts by mass or less based on 100 parts by mass of the total amount of the polymer of component (A) and the crosslinking agent of component (B) , Preferably 10 parts by mass to 380 parts by mass, more preferably 40 parts by mass to 360 parts by mass. When the content of the component (D) is too large, the liquid crystal alignment tends to decrease, and when it is too small, the adhesion tends to decrease.

In addition, in the cured film forming composition of the present embodiment, the component (D) may be a mixture of plural kinds of polymers exemplified as the component (D).

<(E) Ingredient>

In addition to the aforementioned (A) component, (B) component, (C) component and/or (D) component, the cured film forming composition of the present invention may further contain a crosslinking catalyst as the (E) component.

As the crosslinking catalyst of the component (E), for example, an acid or a thermal acid generator can be applied. The (E) component is effective for promoting the thermal curing reaction of the cured film forming composition of the present invention.

(E) In specific examples of the component, examples of the acid include a compound containing a sulfonic acid group, hydrochloric acid or a salt thereof. As the above-mentioned thermal acid generator, only a compound that generates an acid by thermal decomposition during heat treatment, that is, a compound that generates an acid by thermal decomposition at a temperature of 80°C to 250°C, is not particularly limited.

As specific examples of the above acid, for example, hydrochloric acid or its salt; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluene Sulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, tritoluenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1- Sulfonic acid group-containing compounds such as sulfonic acid and dodecylbenzenesulfonic acid, or hydrates or salts thereof.

Further, as a compound that generates an acid by heat, for example, bis(toluene xanthoxy) ethane, bis(toluene xanthoxy) propane, bis(toluene xanthoxy) butane, p-nitro Benzyl toluene sulfonate, o-nitrobenzyl toluene sulfonate, 1,2,3-phenyl ginseng (methyl sulfonate), p-pyridinium toluene sulfonate, p-toluene Morpholinium sulfonate, p-ethyl toluenesulfonate, p-propyl toluenesulfonate, p-butyl toluenesulfonate, p-isobutyl toluenesulfonate, p-methyl toluenesulfonate Base ester, p-phenethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate Acid salt, N-ethyl-p-toluenesulfonimide and the compound represented by the following formula:

等。

Wait.

The content of the (E) component in the cured film forming composition of the present invention is 0.01 to 20 parts by mass relative to 100 parts by mass of the total amount of the polymer of the component (A) and the crosslinking agent of the component (B) Preferably, it is preferably 0.1 parts by mass to 15 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass. (E) When the content of the component is 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance cannot be imparted. However, if it exceeds 20 parts by mass, the storage stability of the composition may decrease.

<Solvent>

The cured film forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used at this time can only dissolve (A) component, (B) component, (C) component and/or (D) component, as required (E) component and/or other additives described later, It can be of any type and structure, and there is no particular limitation set.

As specific examples of solvents, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone , Isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxypropionic acid Ethyl ester, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, Ethyl lactate, butyl lactate, cyclopentyl methyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, etc.

When using the cured film forming composition of the present invention to form a cured film on a resin film to produce an alignment material, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol, It is preferable that 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. are solvents showing resistance to the resin film.

These solvents can be used individually by 1 type or in combination of 2 or more types.

<Other additives>

In addition, the cured film forming composition of the present invention may contain adhesion promoters, silane coupling agents, surfactants, rheology modifiers, pigments, dyes, storage stabilizers, Defoamer, antioxidant, etc.

<Preparation of cured film forming composition>

The cured film forming composition of the present invention contains the polymer of component (A), the crosslinking agent of component (B), the adhesion promoter of component (C), and/or the thermally crosslinkable group of component (D) The polymer may contain the cross-linking catalyst of the component (E) as required, and the composition of other additives may be contained within the range that does not further impair the effect of the present invention. Generally, these are used in the form of a solution dissolved in a solvent.

Preferred examples of the cured film forming composition of the present invention are shown below.

[1]: A cured film forming composition containing (A) component, 1 part by mass to 300 parts by mass of (B) component based on 100 parts by mass of (A) component, and relative to (A) component The total amount of the crosslinking agent of the polymer and (B) component 100 parts by mass is at least one of 0.1 part by mass to 100 parts by mass of the (C) component and 1 part by mass to 400 parts by mass of the (D) component.

[2]: A cured film forming composition containing (A) component, 1 part by mass to 300 parts by mass of (A) component based on 100 parts by mass of (A) component, for polymerization of (A) component The total amount of the crosslinking agent of the component (B) and 100 parts by mass is at least one of 0.1 parts by mass to 100 parts by mass of the (C) component and 1 part by mass to 400 parts by mass of the (D) component, and a solvent .

[3]: A cured film forming composition containing (A) component, 1 part by mass to 300 parts by mass of (A) component based on 100 parts by mass of (A) component, for polymerization of (A) component The total amount of the crosslinking agent of component (B) and 100 parts by mass is at least one of 0.1 parts by mass to 100 parts by mass of (C) component and 1 part by mass to 400 parts by mass of (D) component, for ( The total amount of the polymer of the component A) and the crosslinking agent of the component (B) is 0.01 parts by mass to 20 parts by mass of the (E) component and the solvent for 100 parts by mass.

[4]: A cured film forming composition containing (A) component, 1 part by mass to 300 parts by mass of (A) component based on 100 parts by mass of (A) component, for polymerization of (A) component The total amount of the crosslinking agent of component and (B) component is 0.1 to 100 parts by mass of component (C) for 100 parts by mass, for the polymer of component (A) and the crosslinking agent of component (B) The total amount of 100 parts by mass is 1 to 400 parts by mass of component (D), and the total amount of the polymer of (A) component and the crosslinking agent of (B) component is 0.01 to 20 parts by mass for 100 parts by mass. Parts by mass of (E) component and solvent.

The mixing ratio and preparation method when using the cured film forming composition of the present invention as a solution will be described in detail below.

The ratio of the solid content in the cured film forming composition of the present invention is only required to uniformly dissolve each component in the solvent, and is not particularly limited, but it is 1% by mass to 60% by mass, and 2% by mass to 50% by mass is used as More preferably, it is preferably 2% by mass to 20% by mass. Here, the term "solid content" means that the solvent is removed from all components of the cured film forming composition.

The method of preparing the cured film forming composition of the present invention is not particularly limited. As a preparation method, for example, component (A) dissolved in a solvent (B) component, (C) component and/or (D) component, further to (E) component, etc. are mixed in the solution in a predetermined ratio to form a uniform solution, or at the appropriate stage of the preparation method, if necessary The method of adding and mixing other additives.

For the preparation of the cured film forming composition of the present invention, a solution of a specific copolymer (polymer) obtained by a polymerization reaction in a solvent can be used as it is. At this time, for example, the same (B) component, (C) component, (D) component, and further (E) component and the like as described above are put into the solution of (A) component to form a uniform solution. At this time, for the purpose of concentration adjustment, a solvent can be further added. At this time, the solvent used in the production process of the component (A) and the solvent used for the concentration adjustment of the cured film forming composition may be the same or different.

In addition, the prepared solution of the cured film forming composition is preferably filtered with a filter having a pore size of about 0.2 μm before use.

<Cured film, alignment material and retardation material>

Apply the solution of the cured film forming composition of the present invention to a substrate (e.g., silicon/silicon dioxide coated substrate, silicon nitride substrate, metal, such as a substrate coated with aluminum, molybdenum, chromium, etc., glass substrate, quartz substrate, ITO Substrate, etc.) or film substrate (e.g. triacetyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalic acid Ethylene glycol ester (PET) film, acrylic film, polyethylene film and other resin films), etc., by bar coating, rotary coating, flow coating, roll coating, slit coating, and slit coating. Rotate Coating, inkjet coating, printing, etc. are applied to form a coating film, and then heated and dried with a hot plate or oven, etc., to form a cured film. The hardened film can be used directly as an alignment material.

As the conditions for heating and drying, the composition of the cured film (alignment material) is such that the polymerizable liquid crystal solution coated on it does not dissociate, and the crosslinking reaction can be carried out only by the crosslinking agent. For example, the temperature is 60°C~ 200°C, the heating temperature and heating time are appropriately selected in the range of 0.4 minutes to 60 minutes. The heating temperature and heating time are preferably 70°C to 160°C, 0.5 minutes to 10 minutes.

The thickness of the cured film (alignment material) formed by using the curable composition of the present invention is, for example, 0.05 μm to 5 μm, which can be appropriately selected in consideration of the step difference or optical and electrical properties of the substrate used.

Since the alignment material formed by the cured film composition of the present invention has solvent resistance and heat resistance, it can be aligned on the alignment material by coating the alignment material with a phase difference material such as a polymerizable liquid crystal solution with vertical alignment. By directly hardening the phase difference material in the aligned state, the phase difference material can be formed as a layer with optical anisotropy. If the substrate on which the alignment material is formed is a thin film, it is useful as a retardation film.

In addition, using the two substrates with the alignment material of the present invention formed as described above, the alignment materials on the two substrates can face each other through the spacers, and then the liquid crystal is injected between these substrates to become liquid crystal Aligned liquid crystal display element.

In this way, the cured film forming composition of the present invention can be applied to the production of various retardation materials (retardation films), liquid crystal display elements, and the like.

[Example]

Examples are given below to explain the present invention in more detail, but the present invention is not limited to these embodiments.

[Abbreviation used in the examples]

The meanings of the abbreviations used in the following examples are as follows.

<Polymer Raw Material>

LAA: Lauryl Acrylate

PAA: hexadecyl acrylate

LAMA: Lauryl Methacrylate

HEMA: 2-hydroxyethyl methacrylate

MMA: Methmethacrylate

BzMA: Benzyl methacrylate

BMAA: N-butoxymethacryloyl

GMA: Glycidyl methacrylate

AIBN: α,α’-Azobisisobutyronitrile

A1: 2-(((4-(4'-pentyl-[1,1'-bis(cyclohexane)]-4-yl)phenoxy)carbonylamino)ethyl methacrylate

A2: 6-(4-(4-heptylcyclohexyl)phenoxy)hexyl methacrylate

<(B) Ingredient>

HMM: Melamine crosslinking agent represented by the following structural formula [Cymel (CYMEL) (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.)]

<(C) Ingredient>

BMAA: N-butoxymethacryloyl

DM-1:

<(D) Ingredients>

PUA: Polyurethane grafted acrylic polymer [ACRIT (registered trademark) 8UA-146 (manufactured by Dacheng Fine Chemical Co., Ltd.)]

PCDO: Polycarbonate diol [C-590 (manufactured by Kuraray)]

PEPO: Polyester polyol polymer (adipic acid/diethylene glycol copolymer with the following structural unit. Molecular weight 4,800).

(In the above formula, R represents an alkylene group).

<(E) Ingredient>

PTSA: p-toluenesulfonic acid‧monohydrate

<Solvent>

PM: Propylene glycol monomethyl ether

BA: Butyl acetate

MEK: Methyl ethyl ketone

CPME: Cyclopentyl methyl ether

The number-average molecular weight and weight-average molecular weight of the acrylic copolymer obtained according to the following synthesis example are GPC equipment (Shodex (registered trademark) column KF803L and KF804L) manufactured by Japan Branch The measurement is carried out under the conditions of dissociating in the column (column temperature 40°C). In addition, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) represent values in terms of polystyrene.

<Synthesis of component (A) (1)>

<Synthesis Example 1>

Dissolve 4.0 g of LAA, 12.0 g of MMA, 4.0 g of HEMA, 0.3 g of AIBN as a polymerization catalyst in 60.9 g of PM, and react at 80°C for 20 hours to obtain an acrylic copolymer solution (solid content 25% by mass) ( PA1). The Mn of the obtained acrylic copolymer was 12,000 and the Mw was 26,000.

<Synthesis example 2>

4.0 g of PAA, 12.0 g of MMA, 4.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 60.9 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid content concentration 25% by mass) (PA2). The Mn of the obtained acrylic copolymer is 6,000, and the Mw is 12,000.

<Synthesis Example 3>

4.0 g of LAMA, 12.0 g of MMA, 4.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 60.9 g of PM, and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid content concentration 25% by mass) (PA3). The Mn of the obtained acrylic copolymer was 14,000 and the Mw was 31,000.

<Synthesis Example 4>

4.0 g of LAA, 12.0 g of BzMA, 4.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 60.9 g of PM, and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid content concentration 25% by mass) (PA4). The Mn of the obtained acrylic copolymer was 10,000 and the Mw was 24,000.

<Synthesis Example 5>

LAA 2.0g, MMA 14.0g, HEMA 4.0g, and AIBN 0.3g as a polymerization catalyst were dissolved in PM 60.9g, and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid content concentration 25% by mass) (PA5). The Mn of the obtained acrylic copolymer was 12,000 and the Mw was 27,000.

<Synthesis Example 6>

6.0 g of LAA, 10.0 g of MMA, 4.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 60.9 g of PM, and the reaction was carried out at 80°C for 20 hours to obtain an acrylic copolymer solution (solid content concentration 25% by mass) (PA6). The Mn of the obtained acrylic copolymer was 14,000 and the Mw was 31,000.

<(B) Synthesis of ingredients>

<Synthesis Example 7>

100.0 g of BMAA and 4.2 g of AIBN as a polymerization catalyst were dissolved in 193.5 g of PM and reacted at 90° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration 35% by mass) (PB1). The Mn of the obtained acrylic copolymer was 2,700 and the Mw was 3,900.

<(C) Synthesis of ingredients>

<Synthesis Example 8>

32.0 g of BMAA, 8.0 g of GMA, and 0.8 g of AIBN as a polymerization catalyst were dissolved in 204.0 g of tetrahydrofuran and reacted at 60° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was slowly dropped into 1000.0 g of hexane, and a solid was precipitated. After filtration and drying under reduced pressure, an acrylic copolymer (PC1) was obtained. The Mn of the obtained acrylic copolymer was 7,000, and the Mw was 18,000.

<Synthesis Example 9>

10.0 g of the acrylic copolymer (PC1) obtained in Synthesis Example 8, 2.2 g of acrylic acid, 0.2 g of dibutylhydroxytoluene, and 10 mg of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 60 g of PM and heated at 90°C The reaction was carried out for 20 hours. This solution was slowly dropped into 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PC2) having an acryl group. After ¹ H-NMR analysis, it was confirmed that the acrylic copolymer (PC2) had an acryl group.

In addition, PC2 can also function as the B component in the present invention.

<Compound Synthesis Example 1> Synthesis of Compound [DM-1]

Under nitrogen flow, in a 2L four-necked flask, 500 g of ethyl acetate, 35.5 g (0.300 mol) of 1,6-hexanediol, 1,8-diazabicyclo[5.4.0]-7-undecane Ene (DBU) 1.80g (11.8mmol), 2,6-di-tert-butyl-p-cresol (BHT) 0.45g (2.04mmol) were charged at room temperature, and heated to 55°C. 95.9 g (0.679 mol) of 2-isocyanatoethyl acrylate was dropped into the reaction liquid, and after 2 hours of stirring, the reaction liquid was analyzed by high-speed liquid chromatography. When the area percentage of the intermediate became less than 1%, End the reaction. After adding 328 g of hexane and cooling to room temperature, the precipitated solid was washed twice with 229 g of hexane to obtain a dried compound [A-a] (104 g, 0.260 mol, yield 86.7%).

In a nitrogen stream, a 2L four-necked flask was charged with 1330g of methylene chloride, 100g (0.250mol) of compound [Aa], 22.5g (0.749mol) of p-formaldehyde, and 122g of trimethylsilyl chloride was dropped into an ice bath. (1.12mol). 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, transfer to a 5L separatory funnel, add 1500 g of water, and perform liquid separation operation. The obtained organic layer was dried with magnesium sulfate, and the magnesium sulfate was removed by filtration. The resulting filtrate was concentrated and dried to obtain compound [DM-1] (110 g, 0.226 mol, yield 90.3%). The structure of compound [DM-1] can be ^{confirmed by 1} H-NMR analysis to obtain the following spectral data.

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, 6H J=12.8), 1.67 (m, 4H), 1.40 (m, 4H).

<(D) Synthesis of ingredients>

<Synthesis Example 10>

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° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration 20% by mass) (PD1). The Mn of the obtained acrylic copolymer was 4,200, and the Mw was 7,600.

<(A) Synthesis of component (2)>

<Synthesis Example 11>

4.0 g of A1, 12.0 g of MMA, 4.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 60.9 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid content concentration 25% by mass) (PA7). The Mn of the obtained acrylic copolymer was 12,000 and the Mw was 23,000.

<Synthesis Example 12>

A2 4.0g, MMA 12.0g, HEMA 4.0g, and AIBN 0.3g as a polymerization catalyst were dissolved in PM 60.9g, and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid content concentration 25% by mass) (PA8). The Mn of the obtained acrylic copolymer was 15,000 and the Mw was 29,000.

<Synthesis Example 13>

Dissolve 13.8g of MAA, 14.1g of LAA, 7.2g of HEMA, and 0.68g of AIBN as a polymerization catalyst in PM 107.0g, After 16 hours of reaction, an acrylic copolymer solution (solid content concentration 25% by mass) (PA9) was obtained. The Mn of the obtained acrylic copolymer was 13,300 and the Mw was 27,800.

<Making of Base Film>

The acrylic film used as the base material can be produced by the following method, for example. That is, raw material pellets made of copolymers containing methacrylate as the main component are melted at 250°C in an extruder, and passed through a T-nozzle, and can be made into a thickness of 40μm through a casting roll, a drying roll, etc. The acrylic film.

<Examples, Comparative Examples>

In the composition shown in Table 1, each cured film forming composition of the example and the comparative example was prepared. In addition, the blending amounts of the components (A) to (E) in Table 1 are in terms of total solid content (when obtained as a solution at the time of preparation, the solvent is removed). Next, each retardation material forming composition was used to form a cured film, and the vertical alignment and adhesion of the obtained cured film were evaluated.

[Evaluation of vertical alignment]

<Example 1, Comparative Example 1>

Using a UV ozone treatment device (UV-312) manufactured by Techno Vision, UV ozone treatment was applied to the surface of the substrate shown in Table 2 for 5 minutes. Yu Gaiji Each cured film forming composition of Example 1 and Comparative Example 1 was applied on the material to a Wet film thickness of 4 μm using bar coating. Thereafter, heating and drying in a thermal cycle oven at the temperature of 110°C for 60 seconds were performed to form each cured film on the substrate.

On the cured film, a vertical alignment polymerizable liquid crystal solution RMS03-015 manufactured by Merck (Stocks) was applied using a bar to a Wet film thickness of 6 μm. The coating film on the substrate ^{was exposed at 600 mJ/cm 2} to produce a retardation material.

These produced retardation materials were measured using a retardation measuring device RETS100 manufactured by Otsuka Electronics Co., Ltd., to measure the incident angle dependence of the in-plane retardation. The in-plane phase difference value is 0 at the incident angle of 0 degrees, and the in-plane phase difference is within the range of 38±5 nm at the incident angle of ±50 degrees. It is judged as a vertical alignment. The evaluation results are summarized as "Vertical Orientation" in Table 2 below.

<Examples 2 to 18, Comparative Examples 2 to 5>

Except that the UV ozone treatment was not performed, the evaluation was performed under the same conditions as in Example 1 above. The evaluation results of Examples 2 to 17 and Comparative Examples 2 and 3 are shown in "Vertical Orientation" in Table 2, and the evaluation results of Example 18, Comparative Example 4 and Comparative Example 5 are shown in Table 3.

[Assessment of Adhesion]

<Example 1, Comparative Example 1>

Using a UV ozone treatment device (UV-312) manufactured by Techno Vision, as shown in Table 2, UV ozone treatment was applied to the surface of the substrate for 5 minutes. Yu Gaiji Each cured film forming composition of the Examples and Comparative Examples was applied on the material to a Wet film thickness of 4 μm using bar coating. After that, heating and drying in a thermal cycle oven at each temperature of 110°C for 60 seconds were performed to form each cured film on the substrate.

On the cured film, a polymerizable liquid crystal solution RMS03-015 for vertical alignment manufactured by Merck (Stocks) was applied to a Wet film thickness of 6 μm using bar coating. The coating film on the substrate ^{was exposed at 600 mJ/cm 2} to produce a retardation material.

The phase difference material was cut into 5×5 mass with a dicing knife at an interval of 1 mm in the vertical and horizontal directions. Scotch tape was used on the cut to perform a scotch tape peel test. In the evaluation system, those without peeling in 25 masses are evaluated as ○, and those with only 1 mass peeling are evaluated as ×. The evaluation results are summarized in "Adhesion" in Table 2 below.

<Examples 2 to 17, Comparative Examples 2 to 3>

The evaluation was carried out under the same conditions as in Example 1 above except that it was not subjected to UV ozone treatment. The evaluation results are summarized as "adhesion" in Table 2 below.

As shown in Table 2, the alignment material obtained by using the cured film forming composition of Examples 1 to 17 and the cured film formed of Comparative Examples 1 to 3 The alignment material obtained from the composition also shows good vertical alignment. In addition, as shown in Table 3, the alignment material obtained by using the cured film forming composition of Example 18 compared with the alignment material obtained by using the cured film forming composition of Comparative Examples 4 and 5 showed good vertical alignment for various substrates. Sex.

In addition, the cured films obtained by using the cured film forming compositions of Examples 1 to 17 showed excellent adhesion. In contrast, the cured films obtained using the cured film forming compositions of Comparative Examples 1 to 3 are difficult to obtain adhesion.

[Industrial availability]

The cured film forming composition of the present invention is very suitable as a material for forming a liquid crystal alignment film of a liquid crystal display element, or as a material for an alignment material used when a liquid crystal display element forms an optically anisotropic thin film installed inside or outside, and is particularly suitable as IPS-LCD is used as a material for optical compensation films.

Claims (9)

A cured film forming composition characterized by containing (A) Polymers with vertical alignment groups and functional groups that can be thermally crosslinked, (B) Crosslinking agent, and Either or both of (C) adhesion promoter and (D) polymer with thermally crosslinkable group The cured film forming composition, The aforementioned vertical alignment group is a group represented by the following formula [1];

In formula [1], * represents the bonding position, Y ¹ to Y ⁴ all represent single bonds, n is 2 to 3, Y ⁵ represents a group selected from a benzene ring and a cyclohexane ring, and Y ⁶ represents the number of carbon atoms 1. ~18 alkyl group. According to the cured film forming composition of claim 1, wherein the thermally crosslinkable functional group of the component (A) is a hydroxyl group, a carboxyl group, an amino group or an alkoxysilyl group. The cured film forming composition of claim 1 or claim 2, wherein the crosslinking agent of the component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group. The cured film forming composition of claim 1 or claim 2, which further contains (E) a crosslinking catalyst. Such as the cured film forming composition of claim 1 or claim 2, which contains 1 part by mass based on 100 parts by mass of component (A) ~300 parts by mass of (B) component. For example, the cured film forming composition of claim 1 or claim 2, which contains 0.1 parts by mass to 100 parts by mass for 100 parts by mass of the polymer of component (A) and crosslinking agent of component (B) Either or both of the (C) component and 1 to 400 parts by mass of the (D) component. The cured film forming composition of claim 4, which contains 0.01 to 20 parts by mass relative to 100 parts by mass of the polymer of component (A) and crosslinking agent of component (B) (E) ingredient. An alignment material characterized by hardening the cured film-forming composition of any one of claims 1 to 7. A retardation material characterized by being formed by using a cured film obtained from the cured film forming composition of any one of claims 1 to 7.