JPWO2014171376A1 - Cured film forming composition, alignment material and retardation material - Google Patents

Abstract

Provided is a cured film forming composition for forming a cured film having excellent photoreaction efficiency, solvent resistance, and high adhesion, and is formed using an alignment material for photo-alignment and the alignment material. A phase difference material is provided. A cured film-forming composition comprises (A) a compound having a photo-alignment group and one or more substituents selected from a hydroxy group, a carboxyl group, a trialkoxysilyl group, and an amino group, (B) a hydrophilic polymer having one or more substituents selected from a hydroxy group, a carboxyl group and an amino group, (C) a compound having two or more trialkoxysilyl groups, and (D) a crosslinking catalyst. contains. Using this cured film forming composition, a cured film is formed, and an alignment material is formed using a photo-alignment technique. A polymerizable liquid crystal is applied on the alignment material and cured to obtain a retardation material. [Selection figure] None

Description

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

  In recent years, in the field of displays such as a television using a liquid crystal panel, development of a 3D display capable of enjoying 3D images has been promoted as an effort toward high performance. In the 3D display, for example, a right-eye image is visually recognized by an observer's right eye, and a left-eye image is visually recognized by an observer's left eye, whereby a stereoscopic image can be displayed.

There are various 3D display methods for displaying 3D images, and lenticular lens methods, parallax barrier methods, and the like are known as methods that do not require dedicated glasses.
And as one of the display systems in which an observer wears glasses and observes a 3D image, a circularly polarized glasses system or the like is known (see, for example, Patent Document 1).

  In the case of a circularly polarized glasses type 3D display, a retardation material is usually disposed on a display element that forms an image, such as a liquid crystal panel. In this retardation material, a plurality of two types of retardation regions having different retardation characteristics are regularly arranged, thereby forming a patterned retardation material. Hereinafter, in the present specification, a retardation material patterned so as to arrange a plurality of retardation regions having different retardation characteristics is referred to as a patterned retardation material.

  For example, as disclosed in Patent Document 2, the patterned retardation material can be produced by optically patterning a retardation material made of a polymerizable liquid crystal. Optical patterning of a retardation material made of a polymerizable liquid crystal utilizes a photo-alignment technique known for forming an alignment material for a liquid crystal panel. That is, a coating film made of a photo-alignment material is provided on a substrate, and two types of polarized light having different polarization directions are irradiated on the coating film. Then, a photo-alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed. A solution-like retardation material containing a polymerizable liquid crystal is applied on the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Thereafter, the aligned polymerizable liquid crystal is cured to form a patterned retardation material.

  In the formation of alignment materials using the photo-alignment technology of liquid crystal panels, acrylic resins and polyimide resins having photodimerization sites such as cinnamoyl groups and chalcone groups in the side chain are known as usable photo-alignment materials. . These resins have been reported to exhibit the ability to control the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment) by irradiation with polarized UV (see Patent Documents 3 to 5).

Japanese Patent Laid-Open No. 10-232365 JP 2005-49865 A Japanese Patent No. 3611342 JP 2009-058584 A JP-T-2001-517719

However, the present inventors have confirmed that acrylic resins having photodimerization sites such as cinnamoyl groups and chalcone groups in such side chains do not provide sufficient characteristics when applied to the formation of retardation materials. ing. In particular, in order to form an alignment material by irradiating these resins with polarized UV and to perform optical patterning of a retardation material composed of a polymerizable liquid crystal using the alignment material, a large amount of polarized UV exposure is required. . The polarized UV exposure amount is much larger than the polarized UV exposure amount (for example, about 100 mJ / cm ² ) sufficient to align the liquid crystal for a normal liquid crystal panel.

  The reason why the amount of polarized UV exposure increases is that, in the case of forming a retardation material, unlike a liquid crystal for a liquid crystal panel, a polymerizable liquid crystal is used in a solution state and applied onto an alignment material.

  When an alignment material is formed using an acrylic resin having a photodimerization site such as a cinnamoyl group in the side chain, and the polymerizable liquid crystal is to be aligned, the acrylic resin is subjected to photocrosslinking by a photodimerization reaction. . And it is necessary to continue the irradiation of polarized light with a large exposure amount until resistance to the polymerizable liquid crystal solution is developed. In order to align the liquid crystal of the liquid crystal panel, it is usually only necessary to dimerize only the surface of the photo-alignment alignment material. However, if a conventional material such as the above-mentioned acrylic resin is used to cause the alignment material to exhibit solvent resistance, it is necessary to cause the alignment material to react, and a larger amount of exposure is required. As a result, there is a problem that the orientation sensitivity of the conventional material becomes very small.

  In addition, a technique of adding a crosslinking agent is known in order to develop such solvent resistance in the above-described conventional resin. However, it has been found that after a thermosetting reaction with a crosslinking agent, a three-dimensional structure is formed inside the formed coating film, and the photoreactivity decreases. That is, the orientation sensitivity is greatly reduced, and the desired effect is not obtained even when a conventional material is added with a crosslinking agent.

  From the above, there is a need for a photo-alignment technique that can improve the alignment sensitivity of an alignment material and reduce the amount of polarized UV exposure, and a cured film forming composition used for the formation of the alignment material. And the technique which can provide a patterned phase difference material with high efficiency is calculated | required.

  The present invention has been made based on the above knowledge and examination results. That is, an object of the present invention is to provide a cured film forming composition for providing an alignment material having excellent photoreaction efficiency and solvent resistance, and capable of aligning a polymerizable liquid crystal with high sensitivity. It is.

  Another object of the present invention is an alignment material obtained from the cured film-forming composition, having an excellent photoreaction efficiency and having solvent resistance, and capable of aligning a polymerizable liquid crystal with high sensitivity, and its The object is to provide a retardation material formed using an alignment material.

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

The first aspect of the present invention is:
(A) a compound having a photo-alignment group and one or more substituents selected from a hydroxy group, a carboxyl group, a trialkoxysilyl group, and an amino group,
(B) a hydrophilic polymer having one or more substituents selected from a hydroxy group, a carboxyl group and an amino group;
The present invention relates to a cured film-forming composition comprising (C) a compound having two or more trialkoxysilyl groups and (D) a crosslinking catalyst.

  In the first aspect of the present invention, it is preferable that the photoalignable group of the component (A) is a functional group having a structure that undergoes photodimerization or photoisomerization.

  In the first aspect of the present invention, the photoalignable group of the component (A) is preferably a cinnamoyl group.

  In the first aspect of the present invention, the photoalignable group of the component (A) is preferably a group having an azobenzene structure.

  1st aspect of this invention WHEREIN: It is preferable that the compound of (A) component has a 2 or more hydroxy group.

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

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

  In the first embodiment of the present 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 at least one of a carboxyl group and a phenolic hydroxy group. It is preferable that it is an acrylic polymer which has.

  In the first embodiment of the present invention, the component (B) includes 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 An acrylic copolymer obtained by a polymerization reaction of a monomer containing at least one of monomers having a phenolic hydroxy group is preferable.

  In the first aspect of the present invention, the component (B) is preferably 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.

  1st aspect of this invention WHEREIN: It is preferable that the ratio of (A) component and (B) component is 5:95 thru | or 65:35 by mass ratio.

  1st aspect of this invention WHEREIN: It is preferable to contain (C) component of 10 mass parts thru | or 100 mass parts based on 100 mass parts of the component total amount of (A) component and (B).

  1st aspect of this invention WHEREIN: It is preferable to contain (D) component of 0.5 mass part thru | or 20 mass parts based on 100 mass parts of the component total amount of (A) component and (B). .

  A second aspect of the present invention relates to an alignment material made from the thermosetting film-forming composition of the first aspect of the present invention.

  A third aspect of the present invention relates to a retardation material characterized by being formed using a cured film obtained from the cured film forming composition of the first aspect of the present invention.

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

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

  According to the third aspect of the present invention, it is possible to provide a phase difference material that can be formed with high efficiency and is capable of optical patterning.

<Curing film forming composition>
The cured film forming composition of the present embodiment includes (A) a low molecular photo-alignment component, (B) a hydrophilic polymer as a component, and a compound having two or more trialkoxysilyl groups as a component (C), And (D) a crosslinking catalyst as a component. In addition to the component (A), the component (B), the component (C) and the component (D), the cured film forming composition of the present embodiment contains other additives as long as the effects of the present invention are not impaired. Can be contained.

Hereinafter, details of each component will be described.
<(A) component>
(A) component contained in the cured film forming composition of this Embodiment is 1 type, or 2 or more types of substitution chosen from a photo-alignment group and a hydroxy group, a carboxyl group, a trialkoxysilyl group, and an amino group And a compound having a group.

In the compound of component (A), the photoalignable group reacts with light to form a hydrophobic photoalignment portion, while the substituent selected from a carboxyl group, trialkoxysilyl group and amino group is hydrophilic. The thermal reaction part is configured. That is, the component (A) is a component that imparts photoalignment to the cured film, and the component (A) is also referred to as a photoalignment component or a low molecular photoalignment component in the present specification.
In the present invention, the photo-alignment group means a functional group at a structural site that undergoes photodimerization or photoisomerization.

  The structural site to be photodimerized is a site that forms a dimer by light irradiation, and specific examples thereof include a cinnamoyl group, a chalcone group, a coumarin group, and an anthracene group. Among these, a cinnamoyl group having high transparency in the visible light region and photodimerization reactivity is preferable. In addition, the structural site that undergoes photoisomerization refers to a structural site that changes into a cis form and a trans form upon irradiation with light, and specific examples thereof include a site comprising an azobenzene structure, a stilbene structure, or the like. Of these, an azobenzene structure is preferred because of its high reactivity. The compound having a photo-alignment group and a hydroxy group is represented by the following formula, for example. Specific examples of such a compound are shown in the following formulas [A1] to [A5].

In the above formula, X ¹ has 1 to 18 carbon atoms via one or more bonds selected from a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, an amino bond, or a combination thereof. It represents a structure in which 1 to 3 substituents selected from an alkyl group, a phenyl group, a biphenyl group, or a combination thereof are bonded. 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, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded through a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond. X ³ represents a hydroxy 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. X ⁴ each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, an aromatic ring group, or an aliphatic ring group. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear. X ⁵ represents a hydroxy group, a carboxyl group, an amino group or an alkoxysilyl group. X represents a single bond, an oxygen atom or a sulfur atom.
In these substituents, the phenyl group and the biphenyl group are the same or 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. It may be substituted with one or more different substituents.

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom. Represents an alkoxy group, a halogen atom, a trifluoromethyl group, or a 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 (A) component compound having a photo-alignable group and a hydroxy group include, for example, 4- (8-hydroxyoctyloxy) cinnamic acid methyl ester, 4- (6-hydroxyhexyloxy) silicate. Cinnamic acid methyl ester, 3-methoxy-4- (6-droxyhexyloxy) cinnamic acid methyl ester, 4- (4-hydroxybutyloxy) cinnamic acid methyl ester, 4- (3-hydroxypropyloxy) silicic acid Cinnamic acid methyl ester, 4- (2-hydroxyethyloxy) cinnamic acid methyl ester, 4-hydroxymethyloxycinnamic acid methyl ester, 4-hydroxycinnamic acid methyl ester, 4- (8-hydroxyoctyloxy) silicic acid Cinnamic acid ethyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid ethyl ester, 4- (4 Hydroxybutyloxy) cinnamic acid ethyl ester, 4- (3-hydroxypropyloxy) cinnamic acid ethyl ester, 4- (2-hydroxyethyloxy) cinnamic acid ethyl ester, 4-hydroxymethyloxy cinnamic acid ethyl ester 4-hydroxycinnamic acid ethyl ester, 4- (8-hydroxyoctyloxy) cinnamic acid phenyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid phenyl ester, 4- (4-hydroxybutyloxy) cinnamic acid Cinnamic acid phenyl ester, 4- (3-hydroxypropyloxy) cinnamic acid phenyl ester, 4- (2-hydroxyethyloxy) cinnamic acid phenyl ester, 4-hydroxymethyloxy cinnamic acid phenyl ester, 4-hydroxy cinnamic acid Cinnamic acid phenyl ester, 4- (8- Roxyoctyloxy) cinnamic acid biphenyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid biphenyl ester, 4- (4-hydroxybutyloxy) cinnamic acid biphenyl ester, 4- (3-hydroxypropyloxy) silicic acid Cinnamic acid biphenyl ester, 4- (2-hydroxyethyloxy) cinnamic acid biphenyl ester, 4-hydroxymethyloxycinnamic acid biphenyl ester, 4-hydroxycinnamic acid biphenyl ester, cinnamic acid 8-hydroxyoctyl ester, cinnamic acid Cinnamic acid 6-hydroxyhexyl ester, cinnamic acid 4-hydroxybutyl ester, cinnamic acid 3-hydroxypropyl ester, cinnamic acid 2-hydroxyethyl ester, cinnamic acid hydroxymethyl ester, 4- (8-hydroxyoctyloxy) Azo Benzene, 4- (6-hydroxyhexyloxy) azobenzene, 4- (4-hydroxybutyloxy) azobenzene, 4- (3-hydroxypropyloxy) azobenzene, 4- (2-hydroxyethyloxy) azobenzene, 4-hydroxymethyl Oxyazobenzene, 4-hydroxyazobenzene, 4- (8-hydroxyoctyloxy) chalcone, 4- (6-hydroxyhexyloxy) chalcone, 4- (4-hydroxybutyloxy) chalcone, 4- (3-hydroxypropyloxy) Chalcone, 4- (2-hydroxyethyloxy) chalcone, 4-hydroxymethyloxychalcone, 4-hydroxychalcone, 4 ′-(8-hydroxyoctyloxy) chalcone, 4 ′-(6-hydroxyhexyloxy) chalcone, 4 '-(4 Hydroxybutyloxy) chalcone, 4 ′-(3-hydroxypropyloxy) chalcone, 4 ′-(2-hydroxyethyloxy) chalcone, 4′-hydroxymethyloxychalcone, 4′-hydroxychalcone, 7- (8-hydroxy) Octyloxy) 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- (4-hydroxybutyloxy) coumarin, 6- (3-hydroxypropyloxy) coumarin, 6- ( 2-hydroxy Tiloxy) coumarin, 6-hydroxymethyloxycoumarin, 6-hydroxycoumarin, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] Cinnamic acid methyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid methyl ester, 4- [4 -(2-hydroxyethyloxy) benzoyl] cinnamic acid methyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid methyl ester, 4- [4-hydroxybenzoyl] cinnamic acid methyl ester, 4- [4 -(8-Hydroxyoctyloxy) benzoyl] cinnamic acid ethyl ester 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (3- Hydroxypropyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid ethyl ester, 4- [4-Hydroxybenzoyl] cinnamic acid ethyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic Acid tertiary butyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl Cinnamic acid tertiary butyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid tertiary butyl Ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid tertiary butyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (6-hydroxyhexyl) Oxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] Cinnamic acid phenyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid phenyl ester, 4- [4-hydroxybenzoyl] cinnamic acid phenyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] Cinnamic acid biphenyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4 -(3-hydroxypropyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid biphenyl ester Ester, 4- [4-hydroxybenzoyl] silica Cinnamic acid biphenyl ester, 4-benzoylcinnamic acid 8-hydroxyoctyl ester, 4-benzoyl cinnamic acid 6-hydroxyhexyl ester, 4-benzoyl cinnamic acid 4-hydroxybutyl ester, 4-benzoyl cinnamic acid 3-hydroxy Propyl ester, 4-benzoylcinnamic acid 2-hydroxyethyl ester, 4-benzoyl cinnamic acid hydroxymethyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] chalcone, 4- [4- (6-hydroxy Hexyloxy) benzoyl] chalcone, 4- [4- (4-hydroxybutyloxy) benzoyl] chalcone, 4- [4- (3-hydroxypropyloxy) benzoyl] chalcone, 4- [4- (2-hydroxyethyloxy) ) Benzoyl] chalcone, 4- (4-hydride) Xymethyloxybenzoyl) chalcone, 4- (4-hydroxybenzoyl) chalcone, 4 ′-[4- (8-hydroxyoctyloxy) benzoyl] chalcone, 4 ′-[4- (6-hydroxyhexyloxy) benzoyl] chalcone 4 '-[4- (4-hydroxybutyloxy) benzoyl] chalcone, 4'-[4- (3-hydroxypropyloxy) benzoyl] chalcone, 4 '-[4- (2-hydroxyethyloxy) benzoyl] Examples include chalcone, 4 ′-(4-hydroxymethyloxybenzoyl) chalcone, and 4 ′-(4-hydroxybenzoyl) chalcone.

Specific examples of the compound having a photo-alignment group and a carboxyl group include cinnamic acid, ferulic acid, 4-nitrocinnamic acid, 4-methoxy cinnamic acid, 3,4-dimethoxy cinnamic acid, coumarin-3- Carboxylic acid, 4- (N, N-dimethylamino) cinnamic acid and the like can be mentioned.
Specific examples of the compound having a photo-alignment group and a carboxyl group and an amino group include methyl-4-aminocinnamic acid, ethyl-4-aminocinnamic acid, methyl-3-aminocinnamic acid, ethyl-3- Examples include aminocinnamic acid.

  Specific examples of the compound having a photoalignable group and an amino group as component (A) include 4-aminocinnamic acid methyl ester, 4-aminocinnamic acid ethyl ester, 3-amino cinnamic acid methyl ester, Examples include 3-aminocinnamic acid ethyl ester.

  Specific examples of the compound having a photo-alignable group and trialkoxysilyl group as component (A) include 4- (3-trimethoxysilylpropyloxy) cinnamic acid methyl ester, 4- (3-triethoxy Silylpropyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3-triethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3-tri Methoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-triethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylhexyloxy) cinnamic acid ethyl ester and 4- (3- And triethoxysilylhexyloxy) cinnamic acid ethyl ester.

  Specific examples of the low molecular photo-alignment component (A) are not limited to these.

  Further, when the photo-alignment component as the component (A) is a compound having a photo-alignment group and a hydroxy group, as the component (A), two or more photo-alignment groups and / or hydroxy are present in the molecule. It is possible to use compounds having two or more groups. Specifically, as the component (A), a compound having two or more photoalignable groups with one hydroxy group in the molecule, or two or more hydroxy groups with one photoalignable group in the molecule Or a compound having two or more photo-alignable groups and two hydroxyl groups in the molecule can be used. For example, a compound represented by the following formula can be shown as an example of a compound having two or more photoalignable groups and hydroxy groups in the molecule.

  By appropriately selecting such a compound, it is possible to control to increase the molecular weight of the photo-alignment component as the component (A). As a result, as will be described later, when the photo-alignment component (A) and the polymer (B) component and the cross-linking agent (C) are thermally reacted, the photo-alignment component (A) It can suppress that a component sublimates. And the cured film formation composition of this Embodiment can form alignment material with high photoreaction efficiency as a cured film.

  Moreover, as a compound of (A) component in the cured film formation composition of this Embodiment, it has multiple types which have a photo-alignment group and any one substituent chosen from a hydroxyl group, a carboxyl group, and an amino group. A mixture of these compounds may also be used.

<(B) component>
The component (B) contained in the cured film forming composition of the present embodiment is a hydrophilic polymer.
The hydrophilic polymer as the component (B) is a polymer having one or more substituents selected from a hydroxy group, a carboxyl group and an amino group (hereinafter also referred to as a specific polymer). it can.

  In the cured film forming composition of the present embodiment, as the specific polymer as the component (B), selection of a highly hydrophilic polymer having high hydrophilicity so as to be more hydrophilic than the compound of the component (A) Is preferred. And it is preferable that a specific polymer is a polymer which has hydrophilic groups, such as a hydroxyl group, a carboxyl group, and an amino group, Specifically, 1 type or 2 types chosen from a hydroxy group, a carboxyl group, and an amino group A polymer having the above substituents is preferred. That is, “hydrophilicity” in the hydrophilic polymer of the component (B) in the present specification means that it is more hydrophilic than the compound of the component (A).

  Examples of the hydrophilic polymer (B) include acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, and polyalkyleneimine. , Polymers having linear or branched structures such as polyallylamine, celluloses (cellulose or derivatives thereof), phenol novolac resins, melamine formaldehyde resins, and cyclic polymers such as cyclodextrins.

  Among these, as the acrylic polymer, a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic ester, methacrylic ester or styrene can be applied.

  The specific polymer as component (B) is preferably at least one of hydroxyalkylcyclodextrins, celluloses, polyethylene glycol ester groups and hydroxyalkyl ester groups having 2 to 5 carbon atoms, a carboxyl group, and An acrylic polymer having at least one of phenolic hydroxy groups, an acrylic polymer having an aminoalkyl group in the side chain, a polyether polyol, a polyester polyol, a polycarbonate polyol, and a polycaprolactone polyol.

  (B) It is a preferred example of the specific polymer of the component, and has at least one of 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 hydroxy group. The acrylic polymer may be an acrylic polymer having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the acrylic polymer.

As a structural unit having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, a preferred structural unit is represented by the following formula [B1].
As a structural unit having at least one of a carboxyl group and a phenolic hydroxy group, a preferred structural unit is represented by the following formula [B2].

In the above formulas [B1] and [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 (where n The value 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 hydroxy group.

  The acrylic polymer as an example of the component (B) preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and 5,000 to 100,000. More preferably, it is 000. If the weight average molecular weight is over 200,000, the solubility in the solvent may be reduced and the handling property may be reduced. If the weight average molecular weight is less than 3,000, When cured, it may become insufficiently cured and solvent resistance and heat resistance may decrease. The weight average molecular weight is a value obtained by using gel as a standard sample by gel permeation chromatography (GPC). Hereinafter, the same applies to this specification.

  As a method for synthesizing the acrylic polymer which is an example of the component (B), a monomer having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms (hereinafter also referred to as b1 monomer) is used. A method of copolymerizing a monomer having at least one of a carboxyl group and a phenolic hydroxy group (hereinafter also referred to as b2 monomer) is simple.

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

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

Examples of the monomer having a carboxyl group described above include acrylic acid, methacrylic acid, and vinyl benzoic acid.
Examples of the monomer having a phenolic hydroxy group described above include p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene.

  In this embodiment, when synthesizing an acrylic polymer as an example of the component (B), a monomer other than the b1 monomer and the b2 monomer, specifically a hydroxy group, unless the effects of the present invention are impaired. And a monomer having neither of the carboxyl groups can be used in combination.

  Examples of such a monomer include acrylic acid ester compounds such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl methacrylate, butyl acrylate, isobutyl acrylate, and t-butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, Methacrylic acid ester compounds such as isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide, acrylamide compounds, acrylonitrile, maleic anhydride, styrene Examples thereof include compounds and vinyl compounds.

  The amount of the b1 monomer and b2 monomer used to obtain the acrylic polymer which is an example of the component (B) is based on the total amount of all monomers used to obtain the acrylic polymer which is the component (B). It is preferable that the monomer is 2 mol% to 95 mol% and the b2 monomer is 5 mol% to 98 mol%.

When a monomer having only a carboxyl group is used as the b2 monomer, the b1 monomer is 60 mol% to 95 mol% and the b2 monomer is based on the total amount of all monomers used to obtain the acrylic polymer as the component (B). 5 mol% to 40 mol% is preferable.
On the other hand, when a monomer having only a phenolic hydroxy group is used as the b2 monomer, it is preferable that the b1 monomer is 2 mol% to 80 mol% and the b2 monomer is 20 mol% to 98 mol%. When the b2 monomer is too small, the liquid crystal orientation tends to be insufficient, and when it is too large, the compatibility with the component (A) tends to decrease.

  (B) Although the method to obtain the acrylic polymer which is an example of a component is not specifically limited, For example, in the solvent which coexisted the monomer other than b1 monomer and b2 monomer with the monomer other than b1 monomer and the polymerization initiator etc. if desired The acrylic polymer is obtained by a polymerization reaction at a temperature of 50 ° C. to 110 ° C. In this case, the solvent used is not particularly limited as long as it dissolves the b1 monomer and the b2 monomer, the monomer other than the b1 monomer and the b2 monomer used as desired, a polymerization initiator, and the like. Specific examples are described in the <Solvent> section below.

  The acrylic polymer having an aminoalkyl group in the side chain, which is a preferred example of the specific polymer of component (B), includes aminoalkyl ester monomers such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate. What polymerized or what copolymerized the said aminoalkyl ester monomer and 1 type, or 2 or more types of monomers chosen from said acrylic monomer are mentioned.

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

  In addition, the acrylic polymer solution, which is an example of the component (B) obtained by the above method, is poured into diethyl ether or water under stirring to cause reprecipitation, and the generated precipitate is filtered and washed. Under normal pressure or reduced pressure, it can be dried at room temperature or dried to obtain an acrylic polymer powder as an example of the component (B). By the above operation, the polymerization initiator and unreacted monomer coexisting with the acrylic polymer as an example of the component (B) can be removed. As a result, the purified acrylic polymer as an example of the component (B) A powder is obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

  (B) Polyether polyol which is a preferred example of the specific polymer of component is polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, polyhydric alcohol such as sorbitol, propylene oxide, polyethylene glycol, polypropylene glycol, etc. Is added. Specific examples of the polyether polyol include ADEKA Adeka Polyether P Series, G Series, EDP Series, BPX Series, FC Series, CM Series, NOF UNIOX (registered trademark) HC-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 Nonion (registered trademark) LT-221, ST-221, OT-221 and the like.

  As a polyester polyol which is a preferable example of the specific polymer of the component (B), polyvalent carboxylic acid such as adipic acid, sebacic acid, isophthalic acid, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, etc. And those obtained by reacting these diols. Specific examples of the polyester polyol include DIC 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, Kuraray polyols 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 and the like.

  Examples of the polycaprolactone polyol which is a preferred example of the specific polymer of the component (B) include those obtained by ring-opening polymerization of ε-caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of the polycaprolactone polyol include DIC polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, Daicel Chemical's Plaxel (registered trademark) 205, L205AL, 205U, 208, 210. 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, and the like.

  (B) As a polycarbonate polyol which is a preferable example of the specific polymer of a component, what reacted polyhydric alcohols, such as a trimethylol propane and ethylene glycol, diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc. is mentioned. Specific examples of the polycarbonate polyol include Placel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel Chemical Industries, and C-590, C-1050, C-2050, C-2090, C-3090 manufactured by Kuraray, and the like.

  Examples of cellulose that is a preferred example of the specific polymer of component (B) include hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyalkylalkylcelluloses such as hydroxyethylmethylcellulose, hydroxypropylmethylcellulose and hydroxyethylethylcellulose, and cellulose. For example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.

  As a cyclodextrin which is a preferable example of the specific polymer of component (B), cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, methyl-α-cyclodextrin, methyl-β-cyclodextrin And methylated cyclodextrins 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-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl Lopyr-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2 , 3-dihydroxypropyl-β-cyclodextrin, and hydroxyalkylcyclodextrins such as 2,3-dihydroxypropyl-γ-cyclodextrin.

上記式中、Ｒは水素原子または炭素原子数１乃至４のアルキル基を表し、ｎは繰り返し単位の数を表す自然数である。
（Ｂ）成分のメラミンホルムアルデヒド樹脂は、保存安定性の観点からメラミンとホルムアルデヒドの重縮合の際に生成したメチロール基がアルキル化されていることが好ましい。The melamine formaldehyde resin which is a preferable example of the specific polymer of the component (B) is a resin obtained by polycondensation of melamine and formaldehyde, and 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, and n is a natural number representing the number of repeating units.
In the melamine formaldehyde resin as the component (B), it is preferable that the methylol group generated during the polycondensation of melamine and formaldehyde is alkylated from the viewpoint of storage stability.

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

  The component (B) melamine formaldehyde resin preferably has a weight average molecular weight of 250 to 5,000, more preferably 300 to 4,000, and still more preferably 350 to 3,500. If the weight average molecular weight is over 5,000, the solubility in the solvent may be lowered and the handling property may be lowered. If the weight average molecular weight is less than 250 and the weight is too small, Insufficient curing may reduce solvent resistance and heat resistance.

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

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

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

  In the cured film forming composition of the present embodiment, the polymer of component (B) may be used in the form of a powder or in the form of a solution obtained by re-dissolving the purified powder in a solvent described later.

  Moreover, in the cured film forming composition of this Embodiment, the polymer of (B) component may be a mixture of multiple types of the polymer of (B) component.

<(C) component>
Component (C) contained in the cured film forming composition of the present embodiment is a compound having two or more trialkoxysilyl groups. A polymer having a trialkoxysilyl group may also be used.

  Specific examples of the compound having two or more trialkoxysilyl groups include 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, and 4,4′-bis (trimethoxysilyl). Biphenyl, 4,4′-bis (triethoxysilyl) biphenyl, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri Methoxysilyl) ethylene, bis (triethoxysilyl) ethylene, 1,3-bis (trimethoxysilylethyl) tetramethyldisiloxane, 1,3-bis (triethoxysilylethyl) tetramethyldisiloxane, bis (triethoxysilyl) Methyl) amine, bis (trimethoxysilylmethyl) amine, (Triethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) carbonate, bis (3-triethoxysilylpropyl) carbonate, bis [(3-trimethoxysilyl) propyl] Disulfide, bis [(3-triethoxysilyl) propyl] disulfide, bis [(3-trimethoxysilyl) propyl] thiourea, bis [(3-triethoxysilyl) propyl] thiourea, bis [(3-trimethoxysilyl) Propyl] urea, bis [(3-triethoxysilyl) propyl] urea, 1,4-bis (trimethoxysilylmethyl) benzene, 1,4-bis (triethoxysilylmethyl) benzene, tris (trimethoxysilylpropyl) Amine, Tris (Triet Cysilylpropyl) amine, 1,1,2-tris (trimethoxysilyl) ethane, 1,1,2-tris (triethoxysilyl) ethane, tris (3-trimethoxysilylpropyl) isocyanurate, tris (3- And a homopolymer or copolymer of a compound such as triethoxysilylpropyl) isocyanurate, methacryloyloxypropyltrimethoxysilane, and acryloyloxypropyltriethoxysilane.

  These compounds having two or more trialkoxysilyl groups can be used alone or in combination of two or more.

  In the cured film forming composition of the present embodiment, the content of the compound having two or more trialkoxysilyl groups as the component (C) is the total amount of the compound as the component (A) and the polymer as the component (B). The amount is preferably 10 parts by mass to 100 parts by mass based on 100 parts by mass, and more preferably 15 parts by mass to 80 parts by mass. When the content of the compound having two or more trialkoxysilyl groups as component (C) is too small, the solvent resistance and heat resistance of the cured film obtained from the cured film forming composition are reduced, and the photo-alignment Sensitivity decreases. On the other hand, when the content is excessive, the photo-alignment property and the storage stability may be lowered.

<(D) component>
The cured film forming composition of this Embodiment contains a crosslinking catalyst as (D) component in addition to (A) component, (B) component, and (C) component mentioned above.
As a crosslinking catalyst which is (D) component, it can be set as an acid or a thermal acid generator, for example. This component (D) is effective in promoting a thermosetting reaction in the formation of a cured film using the cured film forming composition of the present embodiment.

  When an acid or a thermal acid generator is used as the component (D), the component (D) is a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof, a compound that generates heat by pre-baking or post-baking to generate an acid, that is, a temperature of 80 The compound is not particularly limited as long as it is a compound capable of generating an acid by thermal decomposition at from 250C to 250C.

  Examples of such compounds include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoro. L-methanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H, 2H, Sulfonic acids such as 2H-perfluorooctane sulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzene sulfonic acid or the hydrates and salts thereof Is mentioned.

  Examples of the compound that generates an acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2, 3-phenylene tris (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydride Kishibuchiru p- tosylate, N- ethyl-4-toluenesulfonamide, and the following formula [TAG-1] to may be mentioned a compound represented by such formula [TAG-41].

  The content of the component (D) in the cured film forming composition of the embodiment of the present invention is preferably 0 with respect to 100 parts by mass of the total amount of the compound as the component (A) and the polymer as the component (B). 0.5 to 20 parts by mass, more preferably 0.8 to 15 parts by mass, and even more preferably 0.8 to 6 parts by mass. By setting the content of component (D) to 0.5 parts by mass or more, sufficient thermosetting and solvent resistance can be imparted, and high sensitivity to exposure can also be imparted. Moreover, the storage stability of a cured film forming composition can be made favorable by setting it as 20 mass parts or less.

<Solvent>
The cured film forming composition of the present embodiment is mainly used in a solution state dissolved in a solvent. The solvent used in that case should just be able to melt | dissolve (A) component, (B) component, (C) component and (D) component, and / or the other additive mentioned later, and the kind and structure are especially limited. It is not what is done.

  Specific examples of the solvent include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate. , Propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate , Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, pyruvate Examples include ethyl, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

  These solvents can be used singly or in combination of two or more.

<Other additives>
Furthermore, the cured film forming composition of the present embodiment, as long as the effects of the present invention are not impaired, as necessary, a polymerization initiator, a sensitizer, a silane coupling agent, a surfactant, a rheology modifier, Pigments, dyes, storage stabilizers, antifoaming agents, antioxidants and the like can be contained.

  For example, the sensitizer is effective in promoting the photoreaction after forming a thermosetting film using the cured film forming composition of the present embodiment.

  Examples of other sensitizers as additives include benzophenone, anthracene, anthraquinone, thioxanthone, and derivatives thereof, and nitrophenyl compounds. Of these, benzophenone derivatives and nitrophenyl compounds are preferred. Specific examples of preferred compounds include N, N-diethylaminobenzophenone, 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, 4-nitrostilbene, 4-nitrobenzophenone. , 5-nitroindole and the like. In particular, N, N-diethylaminobenzophenone which is a derivative of benzophenone is preferable.

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

  The use ratio of the sensitizer in the cured film forming composition of the present embodiment is 0.1 to 20 parts by mass with respect to 100 parts by mass of the total mass of the component (A) and the component (B). It is preferably 0.2 to 10 parts by mass. If this ratio is too small, the effect as a sensitizer may not be sufficiently obtained. If it is too large, the transmittance may be lowered and the coating film may be roughened.

<Preparation of cured film forming composition>
The cured film forming composition of the present embodiment is a (A) component low molecular photo-alignment component, and (B) component (A) a polymer that is more hydrophilic than the photo-alignment component; It contains a compound having two or more trialkoxysilyl groups as component (C) and a crosslinking catalyst as component (D). And as long as the effect of this invention is not impaired, another additive can be contained.

  The mixing ratio of the component (A) and the component (B) is preferably 5:95 to 65:35 in terms of mass ratio. When the content of the component (B) is excessive, the liquid crystal orientation is liable to be lowered, and when it is too small, the solvent resistance is lowered and the orientation is liable to be lowered.

Preferred examples of the cured film forming composition of the present embodiment are as follows.
[1]: The mixing ratio of the component (A) and the component (B) is 5:95 to 65:35 by mass ratio, and is based on 100 parts by mass of the total amount of the components (A) and (B). A cured film forming composition containing 10 parts by mass to 100 parts by mass of component (C) and 0.5 to 20 parts by mass of component (D).

  [2]: The mixing ratio of the component (A) and the component (B) is 5:95 to 65:35 by mass ratio, and is based on 100 parts by mass of the total amount of the components (A) and (B). A cured film forming composition containing 10 parts by mass to 100 parts by mass of component (C), 0.5 to 20 parts by mass of component (D), and a solvent.

The blending ratio, preparation method, and the like when the cured film forming composition of the present embodiment is used as a solution will be described in detail below.
The ratio of the solid content in the cured film forming composition of the present embodiment is not particularly limited as long as each component is uniformly dissolved in the solvent, but is preferably 1% by mass to 80% by mass, preferably Is 3% by mass to 60% by mass, more preferably 5% by mass to 40% by mass. Here, solid content means what remove | excluded the solvent from all the components of the cured film formation composition.

  The preparation method of the cured film forming composition of this Embodiment is not specifically limited. As a preparation method, for example, a method of mixing (A) component, (C) component and (D) component in a predetermined ratio to a solution of component (B) dissolved in a solvent to obtain a uniform solution, or this In an appropriate stage of the preparation method, there may be mentioned a method in which other additives are further added and mixed as necessary.

  In the preparation of the cured film forming 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, and at least one of a monomer having a carboxyl group and a monomer having a phenolic hydroxy group In the same manner as above, the (A) component, the (C) component, and the (D) component are put into a solution of the component (B) obtained by copolymerizing the above to obtain a uniform solution. At this time, a solvent may be further added for the purpose of adjusting the concentration. At this time, the solvent used in the production process of the component (B) and the solvent used for adjusting the concentration of the cured film forming composition may be the same or different.

  The prepared cured film-forming composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

<Hardened film, alignment material and retardation material>
The solution of the cured film forming composition according to the present embodiment is a substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, or a quartz substrate. , ITO substrate, etc.) and films (for example, triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, resin film such as acrylic film), etc., bar coating, spin coating, flow coating, roll coating A cured film can be formed by coating by slit coating, spin coating following the slit, inkjet coating, printing, or the like to form a coating film, followed by heat drying with a hot plate or oven.

  The heating and drying conditions may be such that the cross-linking reaction with the cross-linking agent proceeds to such an extent that the components of the alignment material formed from the cured film do not elute into the polymerizable liquid crystal solution applied thereon. A heating temperature and a heating time appropriately selected from the range of 0 to 200 ° C. and a time of 0.4 to 60 minutes are employed. The heating temperature and heating time are preferably 70 ° C. to 160 ° C., 0.5 minutes to 10 minutes.

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

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

  As the irradiation method of polarized UV, ultraviolet light or visible light having a wavelength of 150 nm to 450 nm is usually used, and it is performed by irradiating linearly polarized light from a vertical or oblique direction at room temperature or in a heated state.

  Since the alignment material formed from the cured film composition of the present embodiment has solvent resistance and heat resistance, after applying a retardation material composed of a polymerizable liquid crystal solution on the alignment material, By heating to the phase transition temperature, the phase difference material is brought into a liquid crystal state and is aligned on the alignment material. Then, the retardation material in an oriented state can be cured as it is to form a retardation material as a layer having optical anisotropy.

  As the retardation material, for example, a liquid crystal monomer having a polymerizable group and a composition containing the same are used. And when the board | substrate which forms an orientation material is a film, the film which has the phase difference material of this Embodiment is useful as a phase difference film. The phase difference material that forms such a phase difference material is in a liquid crystal state and has an alignment state such as horizontal alignment, cholesteric alignment, vertical alignment, hybrid alignment, etc. on the alignment material. It can be used properly according to the phase difference.

  Moreover, when manufacturing the patterned phase difference material used for 3D display, it is predetermined | prescribed via the mask of a line and space pattern to the cured film formed by the above-mentioned method from the cured film composition of this embodiment. For example, polarized UV exposure is performed in a +45 degree direction from the reference, and then the polarized UV light is exposed in a -45 degree direction after removing the mask, and two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed. To obtain an alignment material. Thereafter, after applying a retardation material made of a polymerizable liquid crystal solution, the retardation material is brought into a liquid crystal state by being heated to the phase transition temperature of the liquid crystal, and is aligned on the alignment material. Then, the retardation material in an oriented state is cured as it is, and a patterned retardation material in which a plurality of two types of retardation regions having different retardation characteristics are regularly arranged can be obtained.

Further, after using the two substrates having the alignment material of the present embodiment formed as described above, the alignment materials on both the substrates are bonded to each other through a spacer, and then the substrates A liquid crystal display element in which the liquid crystal is aligned can also be obtained by injecting liquid crystal therebetween.
Therefore, the cured film forming composition of this Embodiment can be used suitably for manufacture of various retardation materials (retardation film), a liquid crystal display element, etc.

  Hereinafter, although an Example is given and this Embodiment is demonstrated in more detail, this Embodiment is not limited to these Examples.

[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<Compound having photoalignable group and hydroxy group>
CIN1: 4- (6-hydroxyhexyloxy) cinnamic acid methyl ester CIN2: 3-methoxy-4- (6-droxyhexyloxy) cinnamic acid methyl ester

<Specific polymer raw material>
MAA: methacrylic acid MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate AIBN: α, α′-azobisisobutyronitrile HPCEL: hydroxypropyl cellulose AADEG: polyester (adipic acid / diethylene glycol)

<Alkoxysilane compound>
TTMSI: Tris (3-trimethoxysilylpropyl) isocyanurate BTMSE: Bis (trimethoxysilyl) ethane

<Crosslinking catalyst>
PTSA: p-toluenesulfonic acid monohydrate PPTS: p-toluenesulfonic acid pyridine salt

<Solvent>
PM: Propylene glycol monomethyl ether

  The number average molecular weight and weight average molecular weight of the acrylic copolymer obtained in accordance with the following synthesis examples were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation, and the elution solvent tetrahydrofuran was flowed at 1 mL. It was measured under the condition that the column was eluted at a rate of 40 minutes per minute (column temperature: 40 ° C.). The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) were expressed in terms of polystyrene.

<Synthesis Example 1>
MAA 2.5 g, MMA 9.2 g, HEMA 5.0 g, 0.2 g of AIBN as a polymerization catalyst were dissolved in 50.7 g of PM, and reacted at 70 ° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration). 25% by mass) (P1) was obtained. Mn of the obtained acrylic copolymer was 19,600 and Mw was 45,200.

<Examples 1 to 5, Comparative Examples 1 and 2>
Each cured film forming composition of an Example and a comparative example was prepared with the composition shown in Table 1, and adhesiveness, orientation sensitivity, pattern formation property, and transmittance | permeability were evaluated about each.

[Evaluation of adhesion]
Each cured film forming composition of Examples and Comparative Examples was spin-coated on non-alkali glass at 2000 rpm for 30 seconds using a spin coater, and then heated and dried in a heat circulating oven at 130 ° C. for 120 seconds. Formed. This cured film was irradiated with 50 mJ / cm ² of 313 nm linearly polarized light vertically. The surface of the cured film formed on the exposed substrate is coated with a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Ltd. using a spin coater, and then pre-baked on a hot plate at 60 ° C. for 60 seconds. And a coating film having a thickness of 1.0 μm was formed. This coating film was exposed at 1000 mJ / cm ² to prepare a retardation material having a polymerizable liquid crystal layer on the cured film. A crosscut (1 mm × 1 mm × 100 squares) is put on the surface of the phase difference material on the obtained substrate using a cutter knife, and then an adhesive tape is applied, and then the adhesive tape is peeled off and then the position on the substrate is removed. The number of squares where the phase difference material (cured film and polymerizable liquid crystal layer) did not peel off was counted. A case where 90 or more squares remained without peeling off the retardation material was judged to have good adhesion.

[Evaluation of orientation sensitivity]
Each of the cured film forming compositions of Examples and Comparative Examples was spin-coated on a non-alkali glass at 2000 rpm for 30 seconds using a spin coater, and then heated and dried in a heat circulation oven at a temperature of 130 ° C. for 120 seconds. A film was formed. This cured film was irradiated vertically with 313 nm linearly polarized light to form an alignment material. On the surface of the alignment material on the substrate, a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, and then pre-baked on a hot plate at 60 ° C. for 60 seconds to obtain a film thickness of 1 A coating film of 0.0 μm was formed. This coating film was exposed at 1000 mJ / cm ² to prepare a retardation material having a polymerizable liquid crystal layer on the alignment material. The retardation material on the produced substrate was sandwiched between a pair of polarizing plates, the state of retardation characteristics in the retardation material was observed, and the exposure amount of polarized UV necessary for the alignment material to exhibit liquid crystal alignment was measured. . An alignment material having higher alignment sensitivity can exhibit alignment in the polymerizable liquid crystal layer on the alignment material with a lower exposure amount.

[Evaluation of pattern formability]
Each cured film forming composition of Examples and Comparative Examples was spin-coated on non-alkali glass at 2000 rpm for 30 seconds using a spin coater, and then heated and dried in a heat circulating oven at 130 ° C. for 120 seconds. Formed. This cured film was irradiated with 313 nm linearly polarized light vertically by 30 mJ / cm ² through a 100 μm line and space mask. After removing the mask and rotating the substrate by 90 degrees, 313 nm linearly polarized light is irradiated vertically by 15 mJ / cm ² to obtain an alignment material in which two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed by 90 degrees. It was. On the alignment material on the substrate, a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, and then prebaked on a hot plate at 60 ° C. for 60 seconds to form a film. A coating film having a thickness of 1.0 μm was formed. This coating film was exposed at 1000 mJ / cm ² to polymerize the polymerizable liquid crystal, and a patterned retardation material in which two types of regions having different retardation characteristics were regularly arranged was produced. The patterned phase difference material on the produced substrate was observed using a polarizing microscope, and evaluation was made with ◯ indicating that the phase difference pattern was formed without alignment defects, and × indicating that the alignment defects were observed.

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

[Evaluation results]
Table 2 shows the results of the above evaluation.

The alignment materials obtained by using the thermosetting film-forming compositions prepared in Examples 1 to 5 all exhibit liquid crystal alignment with an exposure amount less than 100 mJ / cm ² and have high alignment sensitivity. I can understand. Moreover, optical patterning could be performed. Furthermore, it showed high transparency.

  Comparative Examples 1 and 2 were difficult to align and could not be subjected to optical patterning.

  The cured film forming composition according to the present invention is very useful as an alignment material for forming a liquid crystal alignment film of a liquid crystal display element and an optically anisotropic film provided inside or outside the liquid crystal display element, It is suitable as a material for forming a patterned retardation material for a 3D display.

Claims (15)

(A) a compound having a photoalignment group and one or more substituents selected from a hydroxy group, a carboxyl group, a trialkoxysilyl group and an amino group,
(B) a hydrophilic polymer having one or more substituents selected from a hydroxy group, a carboxyl group and an amino group;
(C) A cured film-forming composition comprising a compound having two or more trialkoxysilyl groups, and (D) a crosslinking catalyst.   2. The cured film forming composition according to claim 1, wherein the photo-alignment group of the component (A) is a functional group having a structure that undergoes photodimerization or photoisomerization.   The cured film forming composition according to claim 1 or 2, wherein the photo-alignment group of the component (A) is a cinnamoyl group.   The cured film forming composition according to claim 1 or 2, wherein the photo-alignment group of the component (A) is a group having an azobenzene structure.   The cured film forming composition according to any one of claims 1 to 4, wherein the compound of the component (A) has two or more hydroxy groups.   The component (B) is at least one polymer selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols and polycaprolactone polyols. A cured film forming composition as described in the item.   The cured film forming composition according to any one of claims 1 to 5, wherein the component (B) is cellulose or a derivative thereof.   The component (B) is an acrylic polymer having at least one of 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 hydroxy group. The cured film forming composition according to any one of claims 1 to 5, wherein:   The cured film forming composition according to any one of claims 1 to 5, wherein the component (B) is cyclodextrin or a derivative thereof.   The said (D) component is an acid or a thermal acid generator, The cured film formation composition of any one of Claim 1 thru | or 9 characterized by the above-mentioned.   The ratio of the said (A) component and (B) component is 5:95 thru | or 65:35 by mass ratio, The cured film formation composition of any one of Claim 1 thru | or 10 characterized by the above-mentioned. object.   The component (C) is contained in an amount of 10 to 100 parts by mass based on 100 parts by mass of the total amount of the component (A) and the component (B). The cured film formation composition of any one of Claims 1.   The component (D) is contained in an amount of 0.5 to 20 parts by mass based on 100 parts by mass of the total amount of the component (A) and the component (B). The cured film formation composition of any one of Claims 1.   An alignment material made from the cured film-forming composition according to any one of claims 1 to 13.   A phase difference material formed using a cured film obtained from the cured film forming composition according to claim 1.