TWI623572B - Cured film forming composition, alignment material and retardation material - Google Patents

Abstract

An object of the present invention is to provide a cured film forming composition for forming a cured film having excellent photoreaction efficiency, solvent resistance and high adhesion, and an alignment material for providing optical alignment and a phase difference material formed using the alignment material. .

The solution of the present invention is a cured film forming composition comprising (A) a photo-alignment group and one or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group, a trialkoxycarbonyl group, and an amine group. a compound having (B) a hydrophilic polymer having one or two or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group, (C) a compound having two or more trialkoxyfluorenyl groups, and (D) ) Cross-linking catalyst. The cured film is used to form a composition to form a cured film and an alignment material is formed by a photoalignment technique. A polymerizable liquid crystal is applied onto the alignment material to be cured to obtain a phase difference material.

Description

Hardened film forming composition, alignment material, and phase difference material

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

In the field of displays such as televisions using liquid crystal panels, in recent years, efforts have been made to develop 3D displays that can enjoy 3D images. In the 3D display, for example, by observing the right eye image of the observer's right eye, the observer's left eye can recognize the left eye image, and a stereoscopic image can be displayed.

There are many types of 3D displays that display 3D images. As a method that does not require special glasses, a lenticular lens method and a parallax barrier method are known.

In addition, as one of the ways in which the observer wears glasses to view the display of the 3D image, a circular polarized glasses method or the like is known (for example, refer to Patent Document 1).

In the case of a 3D display with a circular polarized glasses method, generally A phase difference material is disposed on a display element that forms an image such as a liquid crystal panel. In the phase difference material, the phase difference regions of the two types in which the phase difference characteristics are different are arranged in a plurality of rules, thereby forming a patterned phase difference material. Further, in the present specification, the phase difference material which is patterned by the phase difference region in which the plurality of phase difference characteristics are different in the configuration is referred to as a patterned phase difference material.

The patterned phase difference material can be produced by, for example, optically patterning a phase difference material composed of a polymerizable liquid crystal as disclosed in Patent Document 2. The optical patterning of the phase difference material composed of the polymerizable liquid crystal is a light alignment technique well known in the formation of an alignment material of a liquid crystal panel. In other words, a coating film made of a material having a light-aligning property is provided on the substrate, and two types of polarized light having different polarization directions are applied. Further, the optical alignment film was obtained as an alignment material in the liquid crystal alignment region in which the alignment control directions of the liquid crystals were different. A solution-like phase difference material containing a polymerizable liquid crystal is applied onto the light alignment film to realize alignment of the polymerizable liquid crystal. Thereafter, the aligned polymerizable liquid crystal is cured to form a patterned phase difference material.

In the formation of an alignment material using a photo-alignment technique of a liquid crystal panel, an acryl-based resin having a photodimerization site such as a cinnamyl group and a ketone group in a side chain is known as a material having an optical alignment property. Or polyimine resin, etc. Further, it has been reported that these resins exhibit the performance of controlling liquid crystal alignment by polarized UV irradiation (hereinafter also referred to as liquid crystal alignment) (see Patent Documents 3 to 5).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 10-232365

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-49865

[Patent Document 3] Japanese Patent No. 3171342

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-058584

[Patent Document 5] Japanese Patent Publication No. 2001-517719

However, as a result of investigation by the present inventors, it has been found that such an acryl-based resin having a photodimerization site such as a cinnabarinyl group or a ketone group in a side chain cannot be sufficiently characterized when it is applied to the formation of a phase difference material. The situation. In particular, in order to form an alignment material by irradiating the polarizing UV to the resin, and to use the alignment material to perform optical patterning of the phase difference material composed of the polymerizable liquid crystal, a large amount of polarized UV exposure is required. This polarized UV exposure amount is much more than the amount of sufficient polarized UV exposure (for example, about 100 mJ/cm ² ) required for alignment of a liquid crystal for a usual liquid crystal panel.

The reason why the amount of the polarized UV exposure is increased is as follows. When a phase difference material is formed, the coating material is coated on the alignment material and is different from the liquid crystal for the liquid crystal panel, and the polymerizable liquid crystal is used in a solution.

An acryl-based resin or the like having a photodimerization site such as a cinnabar base group in a side chain is used to form an alignment material, and a polymerizable liquid crystal is to be aligned. In the case of the acrylonitrile-based resin or the like, photocrosslinking by photodimerization reaction is carried out. Further, until the resistance to the polymerizable liquid crystal solution is found, it is necessary to continue the polarized light irradiation with a large exposure amount. In order to align the liquid crystal of the liquid crystal panel, it is usually only necessary to carry out a dimerization reaction on the surface of the photoalignment alignment material. However, when a conventional material such as the above-mentioned acryl-based resin is used and the alignment property is to exhibit solvent resistance, it is necessary to react it into the interior of the alignment material, which requires a large amount of exposure. As a result, there is a problem that the alignment sensitivity of the material has become very small.

Further, in order to exhibit the solvent resistance of the resin of the above-mentioned conventional materials, a technique of adding a crosslinking agent is known. However, it is known that after the thermosetting reaction by the crosslinking agent is carried out, the inside of the formed coating film forms a three-dimensional structure, resulting in a decrease in photoreactivity. That is, the alignment sensitivity is drastically lowered, and even if a crosslinking agent is added to a conventional material, the desired effect cannot be obtained.

Accordingly, there is a need for a photo-alignment technique that enhances the alignment sensitivity of an alignment material and reduces the amount of polarized UV exposure, and forms a composition with the cured film used for the formation of the alignment material. Moreover, there is a need for a technology that can efficiently provide patterned phase difference materials.

The present invention has been accomplished based on the above knowledge or findings. That is, an object of the present invention is to provide a cured film forming composition for providing an alignment material which has excellent photoreaction efficiency and has solvent resistance and can align a polymerizable liquid crystal with high sensitivity.

Further, another object of the present invention is to provide an excellent photoreaction efficiency and solvent resistance obtained by forming a composition from a cured film. An alignment material capable of aligning a polymerizable liquid crystal with high sensitivity and a phase difference material formed using the alignment material.

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

A first aspect of the present invention relates to a cured film forming composition comprising (A) a photoalignment group and one selected from the group consisting of a hydroxyl group, a carboxyl group, a trialkoxy group, and an amine group, or a compound having two or more substituents, (B) a hydrophilic polymer having one or two or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group, and (C) having two or more trialkoxycarbonyl groups a compound, and (D) a crosslinking catalyst.

In the first aspect of the present invention, the photo-alignment group of the component (A) is preferably a functional group having a structure of photodimerization or photoisomerization.

In the first aspect of the present invention, the photo-alignment group of the component (A) is preferably a cinnamyl group.

In the first aspect of the present invention, the photo-alignment group of the component (A) is preferably a azobenzen structure.

In the first aspect of the invention, the compound of the component (A) preferably has two or more hydroxyl groups.

In a first aspect of the invention, the component (B) is selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols. At least one hydrophilic polymer is preferred.

In the first aspect of the present invention, the component (B) is preferably cellulose or a derivative thereof.

In the first aspect of the invention, the component (B) is at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, and a carboxyl group and a phenolic hydroxyl group. At least one of the acrylonitrile-based polymers is preferred.

In the first aspect of the invention, the component (B) is at least one of a monomer comprising a monomer having a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms. One of them is preferably a propylene-based copolymer obtained by subjecting a monomer having at least one of a monomer having a carboxyl group and a monomer having a phenolic hydroxyl group to polymerization.

In the first aspect of the present invention, the component (B) is preferably a cyclodextrin or a derivative thereof.

In the first aspect of the present invention, the component (D) is preferably an acid or a thermal acid generator.

In the first aspect of the invention, the ratio of the component (A) to the component (B) is preferably 5:95 to 65:35 by mass ratio.

In the first aspect of the present invention, it is preferred to contain 10 parts by mass to 100 parts by mass of the component (C) based on 100 parts by mass of the total of the components (A) and (B).

In the first aspect of the present invention, it is preferred to contain the component (D) in an amount of from 0.5 part by mass to 20 parts by mass based on 100 parts by mass of the total of the components (A) and (B).

A second aspect of the present invention relates to an alignment material which is produced by forming a composition of a thermosetting film according to a first aspect of the present invention.

A third aspect of the present invention relates to a phase difference material characterized by using a cured film obtained by forming a composition of a cured film according to a first aspect of the present invention.

According to the first aspect of the present invention, there is provided a cured film forming composition for providing an alignment material which has excellent photoreaction efficiency and has solvent resistance and can align a polymerizable liquid crystal with high sensitivity.

According to the second aspect of the present invention, it is possible to provide an alignment material which has excellent photoreaction efficiency and solvent resistance and can align a polymerizable liquid crystal with high sensitivity.

According to the third aspect of the present invention, it is possible to provide a phase difference material which can be formed with high efficiency and which can be optically patterned.

<Cured film forming composition>

The cured film formation composition of the present embodiment contains (A) a low molecular light alignment component, a hydrophilic polymer of the component (B), a compound having two or more trialkoxyfluorenyl groups of the component (C), and D) cross-linking catalyst for the ingredients. The cured film forming composition of the present embodiment contains (A) In addition to the component (B), the component (C), and the component (D), other additives may be contained without impairing the effects of the present invention.

Hereinafter, each component will be described in detail.

<(A) component>

The component (A) contained in the cured film formation composition of the present embodiment is a photo-alignment group, and one or two or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group, a trialkoxycarbonyl group, and an amine group. Compound.

Further, in the compound of the component (A), the photo-alignment group reacts with light to form a hydrophobic photo-alignment portion, and on the other hand, a substituent selected from a carboxyl group, a trialkoxyfluorenyl group and an amine group constitutes hydrophilicity. Thermal reaction unit. That is, the component (A) is a component which imparts light alignability to the cured film, and in the present specification, the component (A) is also referred to as a photoalignment component or a low molecular light alignment component.

Further, in the present invention, the photo-alignment group means a functional group at a structural site where photodimerization or photoisomerization is carried out.

The structural site where photodimerization is carried out refers to a site where a dimer is formed by light irradiation, and specific examples thereof include a cinnamyl group, a ketone group, a coumarin group, and a fluorenyl group. Among these, cassia base which has high transparency and photodimerization reactivity in the visible light region is preferred. In addition, the structural part which carried out photoisomerization is a structural site which converted into a cis isomer and a trans isomer by light irradiation, and a specific example is azobenzene structure, a 茋 structure, etc. The part of the composition. Among these, from the viewpoint of high reactivity, the azobenzene structure is preferred. A compound having a photo-alignment group and a hydroxyl group is, for example It is represented by the following formula. Specific examples of such a compound are as shown in the following formula [A1] to formula [A5].

In the above formula, X ¹ represents a single bond, an ether bond, an ester bond, a guanamine bond, a urethane bond, a guanamine bond, or a bond of one or more selected from the group consisting of these, and A structure in which it is bonded to an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a substituent selected from the group consisting of 1 to 3 in combination. X ² represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group. In this case, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, and a cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, a guanamine bond, or a urea bond. X ³ represents a hydroxyl group, a phenyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkoxy group. The X ^{4 group} each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, an aromatic cyclic group, or an aliphatic cyclic group. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear. X ⁵ represents a hydroxyl group, a carboxyl group, an amine group or an alkoxy group. X represents a single bond, an oxygen atom or a sulfur atom.

Further, in the substituents, the phenyl group and the biphenyl group may be selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group and a cyano group. Substituting one or more substituents of the same or different.

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. Alkoxy group, halogen atom, trifluoromethyl group or cyano group.

Further, in the above formula, A ¹ represents a hydrogen atom or a methyl group. A2 represents a hydrogen atom or a methyl group.

Specific examples of the compound having a photo-alignment group and a hydroxyl group as the component (A) include, for example, 4-(8-hydroxyoctyloxy)cinnamic acid methyl ester and 4-(6-hydroxyhexyloxy group). ) cinnamic acid methyl ester, 3-methoxy-4-(6-hydroxyhexyloxy) cinnamic acid methyl ester, 4-(4-hydroxybutyloxy) cinnamic acid methyl ester, 4-(3) -hydroxypropyloxy)methyl cinnamate, methyl 4-(2-hydroxyethyloxy) cinnamate, methyl 4-hydroxymethyloxycinnamate, methyl 4-hydroxycinnamate Ester, ethyl 4-(8-hydroxyoctyloxy) cinnamate, ethyl 4-(6-hydroxyhexyloxy) cinnamate, ethyl 4-(4-hydroxybutyloxy) cinnamate Ester, ethyl 4-(3-hydroxypropyloxy) cinnamate, ethyl 4-(2-hydroxyethyloxy) cinnamate, ethyl 4-hydroxymethyloxycinnamate, 4 -hydroxycinnamic acid ethyl Ester, 4-(8-hydroxyoctyloxy) cinnamic acid phenyl ester, 4-(6-hydroxyhexyloxy) cinnamic acid phenyl ester, 4-(4-hydroxybutyloxy) cinnamic acid phenyl Ester, 4-(3-hydroxypropyloxy) cinnamic acid phenyl ester, 4-(2-hydroxyethyloxy) cinnamic acid phenyl ester, 4-hydroxymethyloxycinnamic acid phenyl ester, 4 - hydroxy cinnamic acid phenyl ester, 4-(8-hydroxyoctyloxy) cinnamic acid biphenyl ester, 4-(6-hydroxyhexyloxy) cinnamic acid biphenyl ester, 4-(4-hydroxybutyl) Benzyloxy)biphenyl cinnamate, 4-(3-hydroxypropyloxy) cinnamic acid biphenyl ester, 4-(2-hydroxyethyloxy) cinnamic acid biphenyl ester, 4-hydroxyl Methyloxycinnamate biphenyl ester, 4-hydroxycinnamic acid biphenyl ester, cinnamic acid 8-hydroxyoctyl ester, cinnamic acid 6-hydroxyhexyl ester, cinnamic acid 4-hydroxybutyl ester, cinnamic acid 3 -hydroxypropyl ester, 2-hydroxyethyl cinnamic acid, hydroxymethyl cinnamate, 4-(8-hydroxyoctyloxy)azobenzene, 4-(6-hydroxyhexyloxy)azobenzene , 4-(4-hydroxybutyloxy)azobenzene, 4-(3-hydroxypropyloxy)azobenzene, 4-(2-hydroxyethyloxy)azobenzene, 4-hydroxyl Alkoxyazobenzene 4-hydroxyazobenzene, 4-(8-hydroxyoctyloxy)chaconazole, 4-(6-hydroxyhexyloxy)chalcone, 4-(4-hydroxybutyloxy)chalcone, 4- (3-hydroxypropyloxy)chaconazole, 4-(2-hydroxyethyloxy)chaconazole, 4-hydroxymethyloxychalcone, 4-hydroxychalcone, 4'-(8-hydroxyoctyl) Benzyloxy)chaconazole, 4'-(6-hydroxyhexyloxy)chalcone, 4'-(4-hydroxybutyloxy)chalcone, 4'-(3-hydroxypropyloxy)chalcone , 4'-(2-hydroxyethyloxy)chalcone, 4'-hydroxymethyloxychalcone, 4'-hydroxychalcone, 7-(8-hydroxyoctyloxy)coumarin, 7 -(6-hydroxyhexyloxy)coumarin, 7-(4-hydroxybutyloxy)coumarin, 7-(3-hydroxypropyloxy)coumarin, 7- (2-hydroxyethyloxy)coumarin, 7-hydroxymethyloxycoumarin, 7-hydroxycoumarin, 6-hydroxyoctyloxycoumarin, 6-hydroxyhexyloxycoumarin 6,6-(4-hydroxybutyloxy)coumarin, 6-(3-hydroxypropyloxy)coumarin, 6-(2-hydroxyethyloxy)coumarin, 6-hydroxyl Methyloxycoumarin, 6-hydroxycoumarin, 4-[4-(8-hydroxyoctyloxy)benzylindolyl] cinnamic acid methyl ester, 4-[4-(6-hydroxyhexyloxy) Benzyl benzyl] cinnamic acid methyl ester, 4-[4-(4-hydroxybutyloxy)benzyl hydrazide] cinnamic acid methyl ester, 4-[4-(3-hydroxypropyloxy) Benzyl hydrazide] methyl cinnamate, 4-[4-(2-hydroxyethyloxy)benzylidene] cinnamic acid methyl ester, 4-[4-hydroxymethyloxybenzylidene] cinnamic acid Methyl ester, 4-[4-hydroxybenzylidene] cinnamic acid methyl ester, 4-[4-(8-hydroxyoctyloxy)benzylindolyl] cinnamic acid ethyl ester, 4-[4-( 6-Hydroxyhexyloxy)benzylhydrazone]ethyl cinnamate, 4-[4-(4-hydroxybutyloxy)benzylidene]ethyl cinnamate, 4-[4-(3-hydroxyl) Propyloxy)benzylidene]ethyl cinnamate, 4-[4-(2-hydroxyethyloxy)benzylidene]ethyl cinnamate, 4-[4-hydroxyl Ethoxybenzyl benzyl] cinnamic acid ethyl ester, 4-[4-hydroxybenzylidene] cinnamic acid ethyl ester, 4-[4-(8-hydroxyoctyloxy)benzyl hydrazino] cinnamic acid 3-butyl ester, 4-[4-(6-hydroxyhexyloxy)benzylidene] cinnamic acid, tert-butyl ester, 4-[4-(4-hydroxybutyloxy)benzylidene] cinnamic acid Third butyl ester, 4-[4-(3-hydroxypropyloxy)benzylidene] cinnamic acid, tert-butyl ester, 4-[4-(2-hydroxyethyloxy)benzylidene] Tributyl cinnamate, 4-[4-hydroxymethyloxybenzylidene] cinnamic acid 3 butyl ester, 4-[4-(8-hydroxyoctyloxy)benzyl hydrazide] cinnamic acid Phenyl ester, 4-[4-(6-hydroxyhexyloxy)benzylidene] cinnamic acid phenyl ester, 4-[4-(4-hydroxybutyloxy)benzylidene] cinnamic acid phenyl Ester, 4-[4-(3-hydroxypropyloxy)benzylidene] cinnamic acid phenyl ester, 4-[4-(2-hydroxyethyloxy)benzylidene] cinnamic acid phenyl ester, 4-[4-Hydroxymethyloxybenzylidene] phenyl cinnamate, 4-[4-hydroxybenzylidene] phenyl cinnamate, 4-[4-(8-hydroxyoctyloxy) Benzyl hydrazide] biphenyl cinnamate, 4-[4-(6-hydroxyhexyloxy)benzylidene] phenyl cinnamate, 4-[4-(4-hydroxybutyloxy)benzyl Mercapto]biphenyl cinnamate, 4-[4-(3-hydroxypropyloxy)benzylidene]biphenyl cinnamate, 4-[4-(2-hydroxyethyloxy)benzyl Mercapto] biphenyl cinnamate, 4-[4-hydroxymethyloxybenzylidene] phenyl cinnamate, 4-[4-hydroxybenzylindolyl] phenyl cinnamate, 4- Benzyl cinnamic acid 8-hydroxyoctyl ester, 4-benzyl phenyl cinnamate 6-hydroxyhexyl ester, 4-benzyl cinnamic acid 4-hydroxybutyl ester, 4-benzyl cinnamic acid 3-hydroxypropyl Base ester, 4-hydroxyethyl benzyl cinnamic acid, 4-benzyl benzyl cinnamic acid hydroxymethyl ester, 4-[4-(8-hydroxyoctyloxy)benzyl hydrazino] 4-[4-(6-hydroxyhexyloxy)benzylindenyl]chalcone, 4-[4-(4-hydroxybutyloxy)benzylindenyl]chalcone 4-[4-(3-hydroxypropyloxy)benzylidene]chaconazole, 4-[4-(2-hydroxyethyloxy)benzylidene]chaconazole, 4-(4-hydroxymethyl) Oxybenzyl)chaconazole, 4-(4-hydroxybenzylidene)chaconazole, 4'-[4-(8-hydroxyoctyloxy)benzylidene]chalcone, 4'-[4- (6-Hydroxyhexyloxy)benzylindenyl]chalcone, 4'-[4-(4-hydroxybutyloxy)benzylidene]chalcone, 4'-[4-(3-hydroxypropyloxy) Base benzyl ketone, 4'-[4-(2-hydroxyethyloxy)benzylidene] ketone, 4'-(4-hydroxymethyloxybenzylidene) ketone, 4 '-(4-Hydroxybenzylidene) ketone.

Specific examples of the compound having a photo-alignment group and a carboxyl group include cinnamic acid, ferulic acid, 4-nitrocinnamic acid, and 4-methoxy group. Cinnamic acid, 3,4-dimethoxycinnamic acid, coumarin-3-carboxylic acid, 4-(N,N-dimethylamino)cinnamic acid, and the like.

Specific examples of the compound having a photo-alignment group and a carboxyl group and an amine group include methyl-4-amino cinnamic acid, ethyl-4-amino cinnamic acid, and methyl-3-amino cinnamic acid. , ethyl-3-amino cinnamic acid, and the like.

Specific examples of the compound having a photo-alignment group and an amine group as the component (A) include, for example, 4-amino cinnamic acid methyl ester, 4-amino cinnamic acid ethyl ester, and 3-amino cinnamic acid. Methyl ester, ethyl 3-amino cinnamate, and the like.

Specific examples of the compound having a photo-alignment group and a trialkoxyfluorenyl group as the component (A) include, for example, methyl 4-(3-trimethoxydecylpropyloxy) cinnamate, 4-(3-triethoxymercaptopropyloxy) cinnamic acid methyl ester, 4-(3-trimethoxydecylpropyloxy) cinnamic acid ethyl ester, 4-(3-triethyl) Ethyl methoxypropyloxy) cinnamic acid ethyl ester, 4-(3-trimethoxydecylhexyloxy) cinnamic acid methyl ester, 4-(3-triethoxydecylhexyloxy) Methyl cinnamate, ethyl 4-(3-trimethoxydecylhexyloxy) cinnamate, and ethyl 4-(3-triethoxydecylhexyloxy) cinnamate.

The low molecular light alignment component of the component (A) is exemplified by the above specific examples, but is not limited thereto.

Further, when the photo-alignment component of the component (A) is a compound having a photo-alignment group and a hydroxyl group, the component (A) can be used for a compound having two or more photo-alignment groups and/or two or more hydroxyl groups in the molecule. . Specifically, the component (A) can be used for having one hydroxyl group in the molecule and having 2 A compound having one or more photo-alignment groups, a compound having one photo-alignment group in the molecule and having two or more hydroxyl groups, or a compound having two or more photo-alignment groups and a hydroxyl group in the molecule. For example, a compound having two or more photo-alignment groups and a hydroxyl group in each molecule may be exemplified as a compound represented by the following formula.

By selecting such a compound, it becomes possible to control the molecular weight of the photoalignment component of the component (A). As a result, as will be described later, when the photo-alignment component of the component (A) and the polymer of the component (B) are thermally reacted with the crosslinking agent of the component (C), the sublimation of the optical alignment component of the component (A) can be suppressed. . Further, the cured film of the present embodiment forms a composition, and as the cured film, an alignment material having high photoreaction efficiency can be formed.

Further, the compound of the component (A) in the cured film formation composition of the present embodiment may be a mixture of a plurality of compounds having a photo-alignment group and any one of a substituent selected from a hydroxyl group, a carboxyl group and an amine group. .

<(B) component>

The component (B) contained in the cured film formation composition of the present embodiment is a hydrophilic polymer.

Further, the hydrophilic polymer of the component (B) can be a polymer (hereinafter also referred to as a specific polymer) having one or two or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group.

In the cured film forming composition of the present embodiment, the specific polymer as the component (B) is preferably hydrophilic compared to the compound of the component (A), and it is preferred to select a highly hydrophilic polymer having high hydrophilicity. . Further, the specific polymer is preferably a polymer having a hydrophilic group such as a hydroxyl group or a carboxyl group or an amine group, and specifically, one or two or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group. The polymer is preferred. That is, the "hydrophilic" in the hydrophilic polymer of the component (B) of the present specification means that it is at least hydrophilic than the compound of the component (A).

Examples of the hydrophilic polymer as the component (B) include an acrylonitrile-based polymer, a poly-proline, a polyimine, a polyvinyl alcohol, a polyester, a polyester polycarboxylic acid, a polyether polyol, and a poly Ester polyalcohol, polycarbonate polyol, polycaprolactone polyalcohol, polyalkyleneimine, polyallylamine, cellulose (cellulose or its derivatives), phenol novolac resin, melamine formaldehyde resin, etc. A polymer having a linear structure or a branched structure, a cyclic polymer such as a cyclodextrin, or the like.

Here, as the acrylonitrile-based polymer, a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylate, methacrylate or styrene can be used.

The specific polymer as the component (B) preferably has a hydroxyl group At least one of an alkylcyclodextrin, a cellulose, a polyethylene glycol ester group, and a hydroxyalkyl ester group having 2 to 5 carbon atoms and at least one of a carboxyl group and a phenolic hydroxyl group An acrylonitrile-based polymer, an acrylonitrile-based polymer having an aminoalkyl group in a side chain, a polyether polyol, a polyester polyol, a polycarbonate polyol, and a polycaprolactone polyol.

Preferably, the specific polymer of the component (B) has at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, and a carboxyl group and a phenolic hydroxyl group. The acryl-based polymer of at least one of them is not particularly limited as long as it has an acryl-based polymer having such a structure, and the skeleton of the main chain of the polymer constituting the acryl-based polymer and the type of the side chain.

The structural unit of at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms is preferably a structural unit represented by the following formula [B1].

The structural unit having at least one of a carboxyl group and a phenolic hydroxyl group is preferably a structural unit represented by the following formula [B2].

In the above formula [B1] and formula [B2], X ¹¹ and X ¹² each independently represent a hydrogen atom or a methyl group, and Y ¹ represents an H-(OCH ₂ CH ₂ ) _n - group (here, the value of n is 2) To 50, preferably 2 to 10) or a hydroxyalkyl group having 2 to 5 carbon atoms, and Y ² represents a carboxyl group or a phenolic hydroxyl group.

The propylene fluorenyl polymer of the component (B) preferably has a weight average molecular weight of 3,000 to 200,000, preferably 4,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is more than 200,000, the solubility in a solvent is lowered and the workability is lowered. If the weight average molecular weight is less than 3,000, the hardening becomes insufficient at the time of thermosetting. Solvent resistance and heat resistance are reduced. Further, the weight average molecular weight is a value obtained by using gel permeation chromatography (GPC) using polystyrene as a standard sample. Hereinafter, the same is true in the present specification.

a method for synthesizing an acrylonitrile-based polymer as an example of the component (B), wherein at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms is used (hereinafter, The method of copolymerizing a monomer having at least one of a carboxyl group and a phenolic hydroxyl group (hereinafter also referred to as a b2 monomer) is a simple one.

The monomer having a polyethylene glycol ester group may, for example, be a monoacrylate or a monomethacrylate such as H-(OCH ₂ CH ₂ ) _n -OH. The value of n is 2 to 50, preferably 2 to 10.

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

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

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

Further, in the present embodiment, in the case of synthesizing the acrylonitrile-based polymer of the component (B), a monomer other than the b1 monomer and the b2 monomer may be used in combination without impairing the effects of the present invention. For example, a monomer having no one of a hydroxyl group and a carboxyl group.

Examples of such a monomer include methacrylate, ethacrylate, propyl acrylate, isopropyl acrylate, butyl methacrylate, butyl acrylate, isobutyl acrylate, and t- Acrylate compound such as butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylic acid a methacrylate compound such as an ester, a maleic imine, an N-methyl maleimide, an N-phenyl maleimide, and a N-cyclohexyl maleimide, etc. An imine compound, an acrylamide compound, acrylonitrile, maleic anhydride, a styrene compound, a vinyl compound, and the like.

The total amount of the b1 monomer and the b2 monomer used for obtaining the acrylonitrile-based polymer of the component (B) is based on the total amount of the all monomers used for obtaining the propylene fluorenyl polymer of the component (B). The amount is preferably from 2 mol% to 95 mol% of the b1 monomer, and from 5 mol% to 98 mol% of the b2 monomer.

When the monomer having only a carboxyl group is used in the b2 single system, the total amount of the all monomers used for obtaining the propylene fluorenyl polymer of the component (B) is 60 mol% to 95 mol of the b1 monomer. The ear %, b2 monomer is preferably from 5 mol% to 40 mol%.

On the other hand, when a monomer having only a phenolic hydroxyl group is used in the b2 single system, it is 2 mol% to 80 mol% of the b1 monomer, and 20 mol% to 98 mol% of the b2 monomer. good. When the amount of the b2 monomer is too small, the liquid crystal alignment property tends to be insufficient, and when it is too large, the compatibility with the component (A) is liable to lower.

The method for obtaining the acryl-based polymer of the component (B) is not particularly limited. For example, a monomer other than the b1 monomer, the b2 monomer, the b1 monomer and the b2 monomer may be present together. In the solvent such as a polymerization initiator, the acrylonitrile-based polymer is obtained by a polymerization reaction at a temperature of from 50 ° C to 110 ° C. In this case, the solvent to be used is not particularly limited as long as it can dissolve the b1 monomer, the b2 monomer, the b1 monomer and the monomer other than the b2 monomer, and the polymerization initiator. Specific examples thereof are described in the term "solvent" to be described later.

A preferred example of the specific polymer of the component (B) is an acrylonitrile-based polymer having an aminoalkyl group in the side chain, and examples thereof include an aminoethyl acrylate, an aminoethyl methacrylate, and an amine group. a polymer obtained by polymerizing an aminoalkyl ester monomer such as propyl acrylate or aminopropyl methacrylate, or the aminoalkyl group monomer and the acryl-based monomer selected from the above One or two or more monomers are copolymerized.

The acrylonitrile-based polymer of the component (B) obtained by the above method is usually in a solution state dissolved in a solvent.

Further, a solution of the acrylonitrile-based polymer of the component (B) obtained by the above method is placed in diethyl ether or water under stirring to reprecipitate, and the resulting precipitate is filtered and washed. It can be dried at room temperature or dried under reduced pressure or under reduced pressure to form a powder of an acrylonitrile-based polymer as an example of the component (B). By the above operation, the polymerization initiator and the unreacted monomer which coexist with the acryl-based polymer of the component (B) can be removed, and as a result, the propylene sulfhydryl group of the purified component (B) can be obtained. Powder of polymer. When the purification is not sufficiently performed in one operation, the obtained powder may be redissolved in a solvent, and the above operation may be repeated.

The polyether polyol which is a preferable example of the specific polymer of the component (B) may, for example, be a polyhydric alcohol such as polyethylene glycol, polypropylene glycol, propylene glycol or bisphenol A, triethylene glycol or sorbitol. Addition of propylene oxide, polyethylene glycol, polypropylene glycol, etc. Specific examples of the polyether polyol include ADEKA polyether P series, G series, EDP series, BPX series, FC series, CM series, and Uniox (registered trademark) HC-40, HC-made by ADEKA. 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, Nonion (registered trademark) LT-221, ST-221, OT-221, etc.

The polyester polyol which is a preferable example of the specific polymer of the component (B) may, for example, be a polyvalent carboxylic acid such as adipic acid, sebacic acid or isodecanoic acid, and ethylene glycol or diethylene glycol. A diol such as propylene glycol, butylene glycol, polyethylene glycol or polypropylene glycol is reacted. Specific examples of the polyester polyol include Polylite (registered trademark) OD-X-286 and OD-X-made by DIC. 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, Polyola P-510, P-1010, P-2010 by Kuraray , 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.

As a polycaprolactone polyol which is a preferable example of the specific polymer of the component (B), ε-caprolactone is used as a starting agent such as a polyol such as trimethylolpropane or ethylene glycol. The open loop polymerization is carried out. Specific examples of the polycaprolactone polyol include Polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568 manufactured by DIC, and Placcel (registered trademark) 205 manufactured by Dale Chemicals Co., Ltd. L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, and the like.

Preferred examples of the polycarbonate polyol which is a specific polymer of the component (B) include a polyol such as trimethylolpropane or ethylene glycol, diethyl carbonate, diphenyl carbonate, and carbonic acid. Ethyl ester or the like is reacted. Specific examples of the polycarbonate polyol include Placcel (registered trademark) CD205, CD205PL, CD210, CD220, and Kuraray C-590, C-1050, C-2050, C-2090, C. -3090 and so on.

The cellulose which is a preferred example of the specific polymer of the component (B) may, for example, be hydroxyethylcellulose or hydroxypropylcellulose. a hydroxyalkylalkylcellulose such as an alkylcellulose, a hydroxyethylmethylcellulose, a hydroxypropylmethylcellulose or a hydroxyethylethylcellulose, and a cellulose, etc., for example, a hydroxyethyl group A hydroxyalkylcellulose such as cellulose or hydroxypropylcellulose is preferred.

Preferred examples of the cyclodextrin which is a specific polymer of the component (B) include cyclodextrin such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, and methyl-α-. Cyclodextrin, methyl-β-cyclodextrin, methylated cyclodextrin such as 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-hydroxyl Propyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl -β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2,3-dihydroxypropyl-β-cyclodextrin, 2 a hydroxyalkyl cyclodextrin or the like such as 3-dihydroxypropyl-γ-cyclodextrin.

A melamine-formaldehyde resin which is a preferred example of the specific polymer of the component (B), such as a resin obtained by polycondensation of melamine and formaldehyde, is represented by the following formula.

In the above formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n-table A natural number indicating the number of repeating units.

The melamine-formaldehyde resin of the component (B) is preferably alkylated by a methylol group formed during the condensation polymerization of melamine and formaldehyde from the viewpoint of preservation stability.

The method for obtaining the melamine-formaldehyde resin of the component (B) is not particularly limited. Usually, melamine and formaldehyde are mixed, and after making a weak alkalinity using sodium carbonate or ammonia, the mixture is heated at 60 to 100 ° C to be synthesized. The methylol group can be alkoxylated by reacting it with an alcohol.

The weight average molecular weight of the melamine formaldehyde resin of the component (B) is preferably from 250 to 5,000, more preferably from 300 to 4,000, still more preferably from 350 to 3,500. When the weight average molecular weight is more than 5,000, the solubility in a solvent is lowered and the workability is lowered. If the weight average molecular weight is too small to be less than 250, the hardening becomes insufficient at the time of heat curing. And the solvent resistance and heat resistance are lowered.

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

Further, in the present invention, the melamine formaldehyde resin of the component (B) may be a mixture of a plurality of melamine formaldehyde resins of the component (B).

The phenol phenol resin which is a preferable example of the specific polymer of the component (B) is, for example, a phenol-formaldehyde condensed polymer.

In the cured film formation composition of the present embodiment, the polymer of the component (B) may be used in the form of a powder, or may be a powder obtained by purifying the powder. It is used in the form of a solution which is dissolved in a solvent to be described later.

Further, in the cured film formation composition of the present embodiment, the polymer of the component (B) may be a mixture of a plurality of polymers of the component (B).

<(C) component>

The component (C) contained in the cured film formation composition of the present embodiment is a compound having two or more trialkoxyfluorenyl groups. It may also be a polymer having a trialkoxyfluorenyl group.

Specific examples of the compound having two or more trialkoxyfluorenyl groups include, for example, 1,4-bis(trimethoxyindenyl)benzene and 1,4-bis(triethoxyindenyl)benzene. 4,4'-bis(trimethoxyindenyl)biphenyl, 4,4'-bis(triethoxyindenyl)biphenyl, bis(trimethoxyindenyl)ethane, bis(triethoxy) Mercapto) ethane, bis(trimethoxyindenyl)methane, bis(triethoxyindenyl)methane, bis(trimethoxyindenyl)ethylene, bis(triethoxyindenyl)ethylene, 1, 3-bis(trimethoxydecylethyl)tetramethyldioxane, 1,3-bis(triethoxydecylethyl)tetramethyldioxane, bis(triethoxyhydrazine) Methyl)amine, bis(trimethoxydecylmethyl)amine, bis(triethoxymethylpropyl)amine, bis(trimethoxydecylpropyl)amine, bis(3-trimethoxy) Mercaptopropyl)carbonate, bis(3-triethoxydecylpropyl)carbonate, bis[(3-trimethoxyindolyl)propyl]disulfide, disulfide double[(3-tri-B) Oxycarbonyl)propyl], bis[(3-trimethoxyindolyl)propyl]thiourea, bis[(3-triethoxyindolyl)propyl]thiourea, bis[(3-trimethyl) Oxyfluorenyl)propyl]urea, bis[(3-three) Ethoxymercapto)propyl]urea, 1,4-bis(trimethoxydecylmethyl)benzene, 1,4-bis(triethoxydecylmethyl)benzene, ginseng (trimethoxyanthracene) Alkyl)amine, ginseng (triethoxymercaptopropyl)amine, 1,1,2-paraxyl (trimethoxydecyl)ethane, 1,1,2-paran (triethoxyindenyl) a compound such as ethane, ginseng (3-trimethoxymercaptopropyl)isocyanate, ginseng (3-triethoxydecylpropyl)isocyanate, or methacryl A separate polymer or copolymer of oxypropyltrimethoxydecane, acryloxypropyltriethoxydecane.

These compounds having two or more trialkoxyfluorenyl groups may be used singly or in combination of two or more kinds.

The content of the compound having two or more trialkoxyfluorenyl groups of the component (C) in the cured film formation composition of the present embodiment, and the total amount of the compound based on the component (A) and the component (B) The amount is 100 parts by mass, preferably 10 parts by mass to 100 parts by mass, preferably 15 parts by mass to 80 parts by mass. When the content of the compound having two or more trialkoxyfluorenyl groups in the component (C) is too small, the solvent resistance and heat resistance of the cured film obtained by forming the composition from the cured film are lowered, and the sensitivity at the time of photoalignment is lowered. . On the other hand, if the content is too large, the optical alignment property and the storage stability may be lowered.

<(D) component>

The cured film formation composition of the present embodiment contains the component (A), the component (B) and the component (C), and further contains the component (D) as a crosslinking catalyst.

The crosslinking catalyst as the component (D) can be used, for example, as an acid or a thermal acid generator. In the formation of the cured film using the cured film forming composition of the present embodiment, the component (D) can effectively promote the thermosetting reaction.

When the component (D) is an acid or a thermal acid generator, the component (D) is a compound which is a compound containing a sulfonic acid group, hydrochloric acid or a salt thereof, which is thermally decomposed during prebaking or postbaking to produce an acid. That is, a compound which thermally decomposes at a temperature of 80 ° C to 250 ° C to generate an acid, that is, it is not particularly limited.

Examples of such a compound include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and camphor. Sulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-indole-2-sulfonic acid, m-indole-2-sulfonic acid, 4-ethylbenzene Sulfonic acid, 1H, 1H, 2H, 2H-perfluorooctane sulfonic acid, perfluoro(2-ethoxy ethane) sulfonic acid, pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, hydrazine A sulfonic acid such as a benzenesulfonic acid or a hydrate or a salt thereof.

Further, examples of the compound which generates an acid by heat include bis(toluenesulfonyloxy)ethane, bis(toluenesulfonyloxy)propane, bis(toluenesulfonyloxy)butane, and p- Nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylene (methylsulfonate), pyridinium p-toluenesulfonate, p-toluene Sulfonate sulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, p-toluenesulfonic acid Base ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate Acid ester, N-ethyl-4-toluenesulfonamide, And a compound represented by the following formula [TAG-1] to the formula [TAG-41].

The content of the component (D) in the cured film formation composition of the embodiment of the present invention is 0.5 mass by mass based on 100 parts by mass of the total of the polymer of the component (A) and the component (B). Preferably, it is 20 parts by mass, preferably 0.8 parts by mass to 15 parts by mass, more preferably It is 0.8 parts by mass to 6 parts by mass. By setting the content of the component (D) to 0.5 parts by mass or more, sufficient thermosetting property and solvent resistance can be imparted, and high sensitivity to exposure can be imparted. Moreover, by setting it in 20 mass parts or less, the storage stability of the cured film formation composition can be improved.

<solvent>

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

Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethylene glycol alone. Methyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, hydrazine, methyl ethyl ketone, cyclopentane Ketone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, 2-hydroxy-2 -ethyl methacrylate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl ester, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N , N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

These solvents may be used alone or in combination of two or more. Used in combination.

<Other additives>

Further, the cured film forming composition of the present embodiment may contain a polymerization initiator, a sensitizer, a decane coupling agent, a surfactant, a rheology modifier, and the like, without damaging the effects of the present invention. Pigments, dyes, preservatives, defoamers, antioxidants, etc.

For example, a sensitizer can effectively promote a photoreactor after forming a thermosetting film using the cured film forming composition of the present embodiment.

Examples of the sensitizer which is one of the other additives include benzophenone, anthracene, anthracene, thioxanthone, and the like, and a nitrophenyl compound. Among these, a benzophenone derivative and a nitrophenyl compound are preferred. Specific examples of preferred compounds include N,N-diethylaminobenzophenone, 2-nitroguanidine, 2-nitrofluorenone, 5-nitroguanidine, 4-nitro group. Biphenyl, 4-nitrocinnamic acid, 4-nitroguanidine, 4-nitrobenzophenone, 5-nitroindole, and the like. In particular, N,N-diethylaminobenzophenone, which is a derivative of benzophenone, is preferred.

These sensitizers are not limited to the above. Further, the sensitizer may be used singly or in combination of two or more kinds of compounds.

The use ratio of the sensitizer in the cured film formation composition of the present embodiment is preferably 0.1 parts by mass to 20 parts by mass based on 100 parts by mass of the total mass of the component (A) and the component (B). It is preferably 0.2 parts by mass to 10 parts by mass. If the ratio is too small, there is a case where the effect as a sensitizer cannot be sufficiently obtained, and when it is too large, the penetration rate is lowered. Low and uneven film formation.

<Modulation of a cured film forming composition>

The cured film formation composition of the present embodiment contains the low molecular light alignment component of the component (A) and the ratio (B) component. The photoalignment component of the component (A) further has a hydrophilic polymer and a component (C). A compound having two or more trialkoxyfluorenyl groups and a crosslinking catalyst of the component (D). Further, other additives may be contained within the range not impairing the effects of the present invention.

The compounding ratio of the component (A) to the component (B) is preferably 5:95 to 65:35 by mass ratio. When the content of the component (B) is too large, the liquid crystal alignment property is liable to lower, and when it is too small, the solvent resistance is liable to lower, and the alignment property is liable to lower.

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

[1]: The compounding ratio of the component (A) to the component (B) is 5:95 to 65:35 by mass ratio, and 10 parts by mass based on the total amount of the component (A) and the component (B), and 10 The component (C) is formed in a mass ratio of 100 parts by mass to 0.5 to 20 parts by mass of the cured film of the component (D).

[2]: The compounding ratio of the component (A) to the component (B) is 5:95 to 65:35 by mass ratio, and 10 parts by mass based on the total amount of the component (A) and the component (B), and 10 The component (C) in an amount of from 100 parts by mass to the component (D) in an amount of from 0.5 to 20 parts by mass is formed into a composition with a cured film of a solvent.

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

The ratio of the solid content in the cured film formation composition of the present embodiment is not particularly limited as long as the components are uniformly dissolved in the solvent, that is, from 1% by mass to 80% by mass, preferably 3% by mass. From 5% to 60% by mass, more preferably from 5% by mass to 40% by mass. Here, the solid fraction refers to a solvent which removes the solvent from the entire composition of the cured film forming composition.

The method for preparing the cured film forming composition of the present embodiment is not particularly limited. The preparation method may be a method in which a component (A), a component (C), and a component (D) are mixed with a solution of the component (B) dissolved in a solvent in a predetermined ratio to prepare a homogeneous solution, or In the appropriate stage of this modulation method, a method of adding other additives for mixing is required.

In the preparation of the cured film formation composition of the present embodiment, a solution of a specific polymer obtained by a polymerization reaction in a solvent can be used as it is. In this case, for example, at least one of a monomer having a polyethylene glycol ester group and a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms, a monomer having a carboxyl group and having a phenolic hydroxyl group The solution of the component (B) obtained by copolymerizing at least one of the monomers is added in the same manner as described above, and the component (A), the component (C) and the component (D) are added to form a homogeneous solution. At this time, it is also possible to add a solvent further for the purpose of adjusting the concentration adjustment. In this case, the solvent used in the formation of the component (B) may be the same as or different from the solvent used for adjusting the concentration of the cured film-forming composition.

Further, the prepared cured film forms a solution of the composition It is preferred to use a filter having a pore size of about 0.2 μm for filtration.

<hardened film, alignment material, and phase difference material>

The cured film of the present embodiment is formed into a solution of a composition on a substrate (for example, a ruthenium/yttrium oxide-coated substrate, a tantalum nitride substrate, a substrate coated with a metal, for example, aluminum, molybdenum, chromium, or the like, a glass substrate, or quartz. a substrate, an ITO substrate, or the like, or a film (for example, a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, a resin film such as an acrylic film), or the like Bar coating, spin coating, cast coating, roll coating, slit coating, spin coating, spin coating, inkjet coating, printing, etc., coating to form a coating film, followed by coating A cured film can be formed by heating and drying a hot plate or an oven.

As a condition of heat drying, the crosslinking reaction by the crosslinking agent may be carried out to such an extent that the component of the alignment material formed of the cured film does not precipitate to the polymerizable liquid crystal solution coated thereon, for example, A heating temperature and a heating time which are suitably selected in the range of 60 ° C to 200 ° C and a time period of 0.4 minutes to 60 minutes are employed. The heating temperature and heating time are preferably from 70 ° C to 160 ° C for from 0.5 minutes to 10 minutes.

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

The cured film formed thereby can be made to function as an alignment material after being irradiated by polarized UV, that is, a member capable of aligning a compound having liquid crystallinity such as liquid crystal.

As the irradiation method of the polarized UV, ultraviolet light of a wavelength of 150 nm to 450 nm is usually used to obtain visible light, and linear polarized light is irradiated from a vertical or oblique direction at room temperature or in a heated state.

Since the alignment material formed of the cured film composition of the present embodiment has solvent resistance and heat resistance, the phase difference material composed of the polymerizable liquid crystal solution can be applied to the alignment material, and then heated to the liquid crystal. The phase difference material is made into a liquid crystal state by phase transfer temperature, and is aligned on the alignment material. Further, the phase difference material which has become the alignment state is directly cured in this state, whereby a phase difference material which is a layer having optical anisotropy can be formed.

As the phase difference material, for example, a liquid crystal monomer having a polymerizable group, a composition containing the same, or the like can be used. Further, when the substrate on which the alignment material is formed is a film, the film having the phase difference material of the present embodiment can be used as a retardation film. The phase difference material forming the phase difference material has an alignment state such as horizontal alignment, cholesteric alignment, vertical alignment, and mixed alignment on the alignment material after being in a liquid crystal state, and can be adapted to the phase difference required for each. Use differently.

Further, in the case of producing a patterned phase difference material used for a 3D display, the cured film composition of the present embodiment is hardened by the above method from a predetermined standard via a mask having a line width and a line pattern. The film, for example, is subjected to polarized UV exposure from a direction of +45 degrees, and then the polarized UV exposure is performed from the direction of -45 degrees after removing the mask, and the liquid crystal alignment field in which the alignment control direction in which the liquid crystal is formed is different is obtained. Orientation material. Thereafter, a phase difference material composed of a polymerizable liquid crystal solution is applied Thereafter, by heating to the phase transition temperature of the liquid crystal, the phase difference material is made into a liquid crystal state to be aligned on the alignment material. Further, the phase difference material which has become the alignment state is directly cured in this state, and it is possible to obtain a pattern phase difference material in which the phase difference characteristics are different in the phase difference characteristics, which are plural and regularly arranged.

Further, two substrates having the alignment material of the present embodiment formed by the above-described method are used, and the alignment materials on the two substrates are faced to each other via a spacer, and the liquid crystal is injected between the substrates. It can also be used as a liquid crystal display element in which liquid crystals are aligned.

Therefore, the cured film forming composition of the present embodiment can be suitably used for the production of various phase difference materials (phase difference films) or liquid crystal display elements.

[Examples]

Hereinafter, the present embodiment will be described in more detail by way of examples, but this embodiment is not limited by the examples.

[Omitted symbols used in the examples]

The meaning of the omission marks used in the following examples is as follows.

<Compound having a photo-alignment group and a hydroxyl group>

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

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

<Specific polymer raw materials>

MAA: Methacrylic acid

MMA: Methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

AIBN: α,α'-azobisisobutyronitrile

HPCEL: Hydroxypropyl cellulose

AADEG: Polyester (adipic acid / diethylene glycol)

<Alkoxydecane compound>

TTMSI: ginseng (3-trimethoxymercaptopropyl) isomeric cyanurate

BTMSE: bis(trimethoxyindenyl)ethane

<crosslinking catalyst>

PTSA: p-toluenesulfonic acid. 1 hydrate

PPTS: p-toluenesulfonic acid pyridinium salt

<solvent>

PM: propylene glycol monomethyl ether

The number average molecular weight and the weight average molecular weight of the acrylonitrile-based copolymer obtained by the following synthesis examples were determined by using a GPC apparatus (Shodex (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation, in the presence of a tetrahydrofuran as a solvent. The flow rate was measured under a condition that the flow rate of 1 mL/min was poured into the column (column temperature: 40 ° C) to be dissolved. Still, the following number The average molecular weight (hereinafter referred to as Mn) and the weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

<Synthesis Example 1>

0.2 g of MAA 2.5 g, MMA 9.2 g, HEMA 5.0 g, and AIBN of a polymerization catalyst were dissolved in 50.7 g of PM, and the reaction was carried out at 70 ° C for 20 hours to obtain a propylene-based copolymer solution (solid content concentration). 25 mass%) (P1). The obtained acrylonitrile-based copolymer had an Mn of 19,600 and a Mw of 45,200.

<Examples 1 to 5, Comparative Examples 1, 2>

According to the composition shown in Table 1, each of the cured films of the examples and the comparative examples was used to form a composition, and the adhesion, the alignment sensitivity, the pattern formation property, and the transmittance were evaluated individually.

[Evaluation of adhesion]

Each of the cured film forming compositions of the examples and the comparative examples was spin-coated on an alkali-free glass at 2000 rpm for 30 seconds using a spin coater, and then dried by heating at a temperature of 130 ° C for 120 seconds in a heat cycle oven. And a cured film is formed. The cured film was vertically irradiated with linear polarized light of 313 nm at 50 mJ/cm ² . The horizontal alignment of the Merck Co., Ltd. was applied to the surface of the cured film formed on the exposed substrate by a spin coater, and then pre-baked on a hot plate at 60 ° C. The film was baked for 60 seconds to form a film having a film thickness of 1.0 μm. The coating film was exposed at 1000 mJ/cm ² , and a phase difference material having a polymerizable liquid crystal layer was formed on the cured film. Using a cutting knife, the intersection of the phase difference material on the obtained substrate is cut out (1 mm × 1 mm × 100 squares), and then the adhesive tape is attached, and then, after peeling off the adhesive tape, the phase on the substrate is counted. The number of squares in which the difference material (hardened film and polymerizable liquid crystal layer) is not peeled off. When the retardation material was not peeled off and the remaining squares were 90 or more, it was judged that the adhesion was good.

[Evaluation of alignment sensitivity]

Each of the cured film forming compositions of the examples and the comparative examples was spin-coated on an alkali-free glass at 2000 rpm for 30 seconds using a spin coater, and then dried by heating at a temperature of 130 ° C for 120 seconds in a heat cycle oven. And a cured film is formed. The cured film was vertically irradiated with 303 nm linearly polarized light to form an alignment material. The horizontal alignment of the Merck Co., Ltd. was applied to the surface of the alignment material on the substrate by a spin coater, and then pre-baked on the hot plate at 60 ° C for 60 seconds. A coating film having a film thickness of 1.0 μm was formed. The coating film was exposed at 1000 mJ/cm ² to form a phase difference material having a polymerizable liquid crystal layer on the alignment material. The phase difference material on the substrate is sandwiched between a pair of polarizing plates, and the phase difference characteristic in the phase difference material is observed, and the exposure amount of the polarized light UV required for the alignment material to exhibit liquid crystal alignment is measured. An alignment material having a high alignment sensitivity exhibits an alignment property to a polymerizable liquid crystal layer on an alignment material at a low exposure amount.

[Evaluation of pattern formation]

Each of the cured film forming compositions of the examples and the comparative examples was spin-coated on an alkali-free glass at 2000 rpm for 30 seconds using a spin coater, and then dried by heating at a temperature of 130 ° C for 120 seconds in a heat cycle oven. And a cured film is formed. This cured film was vertically irradiated with 313 nm linearly polarized light at 30 mJ/cm ² via a line width of 100 μm and a line spacing mask. After removing the mask and rotating the substrate by 90 degrees, the linearly polarized light of 313 nm was vertically irradiated at 15 mJ/cm ² to obtain an alignment material in which two types of liquid crystal alignment directions in which the alignment control direction of the liquid crystal was different were obtained. The horizontal alignment of the Merck Co., Ltd. was applied to the alignment material on the substrate by a spin coater using a polymerizable liquid crystal solution RMS03-013C, and then pre-baked at 60 ° C for 60 seconds on a hot plate. A coating film having a film thickness of 1.0 μm was formed. The coating film was exposed at 1000 mJ/cm ² to polymerize the polymerizable liquid crystal, and a patterning phase difference material having a regular arrangement of two types of fields having different phase difference characteristics was prepared. The patterned phase difference material on the prepared substrate was observed with a polarizing microscope, and the phase difference pattern was formed without the alignment defect, and was evaluated as ○, and the alignment defect was evaluated as ×.

[Evaluation of light transmittance (transparency)]

Each of the cured film forming compositions of the examples and the comparative examples was spin-coated on a quartz substrate at 2000 rpm for 30 seconds using a spin coater, and then heat-dried and baked on a hot plate at a temperature of 130 ° C for 120 seconds. A cured film having a film thickness of 300 nm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. The transmittance of this cured film to light having a wavelength of 400 nm was measured using an ultraviolet-visible spectrophotometer (SHIMADZU UV-2550 model manufactured by Shimadzu Corporation).

[Results of evaluation]

The results of the above evaluations are shown in Table 2.

The alignment materials obtained by using the thermosetting film prepared in Examples 1 to 5 to form a composition exhibit liquid crystal alignment at an exposure amount of less than 100 mJ/cm ² , which can be understood as having a high alignment sensitivity. Also, optical patterning has been successfully performed. Also, it exhibits high transparency.

In Comparative Examples 1 and 2, it was difficult to align the image, and the patterning could not be performed.

[Industrial Applicability]

The cured film forming composition of the present invention is useful as a liquid crystal alignment film for a liquid crystal display element or an alignment material for an optical anisotropic film provided inside or outside the liquid crystal display element, and is particularly suitable as a 3D. A material for forming a patterned phase difference material of a display.

Claims (12)

A cured film-forming composition comprising (A) a compound having a photo-alignment group and one or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group, a trialkoxyfluorenyl group, and an amine group, (B) a hydrophilic polymer having one or two or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group, (C) a compound having two or more trialkoxyfluorenyl groups, and (D) a crosslinked contact a medium; wherein the ratio of the component (A) to the component (B) is 5:95 to 65:35 by mass ratio, and 10 parts by mass based on the total amount of the component (A) and the component (B); The component (C) of the component (C) is contained in an amount of from 0.5 part by mass to 20 parts by mass based on 100 parts by mass of the total of the components (A) and (B). The cured film forming composition of claim 1, wherein the photo-alignment group of the component (A) is a functional group having a photodimerization or photoisomerization structure. A cured film forming composition according to claim 1 or 2, wherein the photo-alignment group of the component (A) is cinnamyl. A cured film forming composition according to claim 1 or claim 2, wherein the photoalignment group of the component (A) is a azobenzene structure. The cured film forming composition of claim 1 or claim 2, wherein the compound of the component (A) has two or more hydroxyl groups. A cured film forming composition according to claim 1 or claim 2, wherein The component (B) is a polymer selected from at least one selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols. The cured film forming composition of claim 1 or claim 2, wherein the component (B) is cellulose or a derivative thereof. The cured film forming composition of claim 1 or claim 2, wherein the component (B) is at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, and An acrylonitrile-based polymer of at least one of a carboxyl group and a phenolic hydroxyl group. The cured film forming composition of claim 1 or claim 2, wherein the component (B) is a cyclodextrin or a derivative thereof. The cured film forming composition of claim 1 or claim 2, wherein the component (D) is an acid or a thermal acid generator. An alignment material produced by the cured film forming composition according to any one of Claims 1 to 10. A phase difference material formed by using a cured film obtained by forming a composition of the cured film according to any one of Claims 1 to 10.