JP7492196B2 - Cured film-forming composition, alignment material and retardation material - Google Patents

Description

The present invention relates to a cured film-forming composition that forms a cured film that aligns liquid crystal molecules, a cured film, an optical film, an alignment material, and a retardation material. In particular, the present invention relates to a patterned retardation material used in a 3D display using circularly polarized glasses, and a retardation material used in a circular polarizing plate used as an anti-reflection film for an organic EL display, as well as a cured film-forming composition, a cured film, an optical film, and an alignment material that are useful for producing the retardation material.

In the case of circularly polarized glasses type 3D displays, a retardation material is usually placed on a display element that forms an image, such as a liquid crystal panel. This retardation material has two types of retardation regions with different retardation characteristics that are regularly arranged in multiples, constituting a patterned retardation material. In the rest of this specification, such a retardation material that is patterned so that multiple retardation regions with different retardation characteristics are arranged is referred to as a patterned retardation material.

For example, as disclosed in Patent Document 1, the patterned retardation material can be produced by optically patterning a retardation material made of polymerizable liquid crystal. The optical patterning of the retardation material made of polymerizable liquid crystal utilizes a photo-alignment technique known for forming alignment materials for liquid crystal panels. That is, a coating film made of a photo-alignable material is provided on a substrate, and two types of polarized light with different polarization directions are irradiated onto the coating film. Then, a photo-alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions with different liquid crystal alignment control directions are formed. A solution-like retardation material containing polymerizable liquid crystal is applied onto the photo-alignment film to realize the alignment of the polymerizable liquid crystal. The aligned polymerizable liquid crystal is then cured to form a patterned retardation material.

An anti-reflection film for an organic EL display is composed of a linear polarizer and a quarter-wave retardation plate, and external light heading toward the panel surface of the image display panel is converted into linearly polarized light by the linear polarizer, and then converted into circularly polarized light by the subsequent quarter-wave retardation plate. Here, this circularly polarized external light is reflected by the surface of the image display panel, etc., but the direction of rotation of the polarization plane is reversed during this reflection. As a result, this reflected light is converted by the quarter-wave retardation plate into linearly polarized light in a direction that is blocked by the linear polarizer, in the opposite direction to when it arrived, and is then blocked by the subsequent linear polarizer, resulting in significant suppression of emission to the outside.

Regarding this quarter-wave retardation plate, Patent Document 2 proposes a method of constructing this optical film with reverse dispersion characteristics by combining a half-wave plate and a quarter-wave plate to construct a quarter-wave retardation plate. With this method, an optical film with reverse dispersion characteristics can be constructed using a liquid crystal material with positive dispersion characteristics in a wide wavelength band used to display color images.

In recent years, liquid crystal materials with reverse dispersion characteristics have been proposed as liquid crystal materials that can be used for this retardation layer (Patent Documents 3 and 4). With such liquid crystal materials with reverse dispersion characteristics, instead of combining a half-wave plate and a quarter-wave plate to form a quarter-wave retardation plate with two retardation layers, it is possible to ensure reverse dispersion characteristics by forming the retardation layer from a single layer, and thus to realize an optical film capable of ensuring a desired retardation in a wide wavelength band with a simple configuration.

An alignment layer is used to align liquid crystals. Methods for forming an alignment layer include, for example, the rubbing method and the photoalignment method. The photoalignment method is useful in that it does not generate static electricity or dust, which are problems with the rubbing method, and it allows quantitative control of the alignment process.

When forming alignment materials using the photoalignment method, acrylic resins and polyimide resins that have photodimerization sites such as cinnamoyl groups and chalcone groups in the side chains are known as photoalignment materials that can be used. It has been reported that these resins exhibit the ability to control the alignment of liquid crystals (hereinafter referred to as liquid crystal alignment) when irradiated with polarized UV light (see Patent Documents 5 to 7).

In addition to being able to align liquid crystals, the alignment layer is also required to be solvent resistant. For example, the alignment layer may be exposed to heat or solvents during the manufacturing process of the retardation material. If the alignment layer is exposed to a solvent, its ability to align liquid crystals may be significantly reduced.

Therefore, for example, Patent Document 8 proposes a liquid crystal alignment agent that contains a polymer component having a structure capable of undergoing a crosslinking reaction by light and a structure that crosslinks by heat, in order to obtain stable liquid crystal alignment ability, and a liquid crystal alignment agent that contains a polymer component having a structure capable of undergoing a crosslinking reaction by light and a compound having a structure that crosslinks by heat.

In addition, the alignment layer must have good adhesion to the liquid crystal layer. If the adhesion between the alignment layer and the liquid crystal layer formed on it is insufficient, the liquid crystal layer may peel off, for example, during the winding process in the manufacture of the retardation film.

JP 2005-49865 A Japanese Patent Application Laid-Open No. 10-68816 U.S. Pat. No. 8,119,026 JP 2009-179563 A Patent No. 3611342 JP 2009-058584 A JP 2001-517719 A Japanese Patent No. 4207430

The present invention has been made based on the above findings and study results. That is, an object of the present invention is to provide a cured film-forming composition for forming a cured film used to form an alignment material having excellent solvent resistance, capable of aligning a polymerizable liquid crystal with high sensitivity, and excellent adhesion to a liquid crystal layer.
Another object of the present invention is to provide an optical film having the above-mentioned cured film, and an alignment material and a retardation material formed by using the cured film or the optical film.

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

The first aspect of the present invention is a method for producing a cellular membrane comprising the steps of:
(A) a polymer having a photoalignable group, a hydroxy group, and a polymerizable group containing a C═C double bond;
The present invention relates to a cured film-forming composition comprising: (B) a crosslinking agent; and (C) a crosslinking catalyst.
In the first aspect of the present invention, the photoalignable group of the component (A) is preferably 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 or a group having an azobenzene structure.
In the first aspect of the present invention, it is preferable to further contain (D) a polymer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group.
In the first aspect of the present invention, it is preferred that the polymer of component (A) contains a structural unit having a hydroxy group and a structural unit having a polymerizable group containing a C═C double bond, and that the abundance ratio of the structural unit having the hydroxy group is 20 mol % or more relative to 100 mol % of all structural units of the polymer, and that the abundance ratio of the structural unit having the polymerizable group containing a C═C double bond is 5 mol % or more relative to 100 mol % of all structural units of the polymer.
In the first aspect of the present invention, the cured film-forming composition preferably contains 5 parts by mass to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A).
In the first aspect of the present invention, the cured film-forming composition preferably contains 0.01 to 20 parts by mass of the component (C) based on 100 parts by mass of the component (A).

The second aspect of the present invention relates to a cured film obtained from the cured film-forming composition of the first aspect of the present invention.

The third aspect of the present invention relates to an optical film having a cured film obtained from the cured film-forming composition of the first aspect of the present invention.

The fourth aspect of the present invention relates to an alignment material characterized in that it is formed using the cured film of the second aspect of the present invention.

The fifth aspect of the present invention relates to a phase difference material characterized by being formed using the cured film of the second aspect of the present invention.

According to the present invention, it is possible to provide a cured film which has excellent solvent resistance, is capable of aligning a polymerizable liquid crystal with high sensitivity, and has excellent adhesion to a liquid crystal layer, and a cured film-forming composition suitable for forming the same.
Furthermore, according to the present invention, it is possible to provide an optical film having the above-mentioned cured film, and an alignment material and a retardation material formed using the cured film or the optical film.

As described above, there is a demand for a cured film (alignment material) that has excellent solvent resistance, can align polymerizable liquid crystals with high sensitivity, and has excellent adhesion to the liquid crystal layer. There is also a demand for a cured film-forming composition that is suitable for forming a cured film (alignment material) with such performance.

As a result of extensive research conducted by the inventors in order to meet the above-mentioned requirements, it was discovered that a cured film obtained from a cured film-forming composition having a specific composition has excellent solvent resistance, is capable of aligning polymerizable liquid crystals with high sensitivity, and can be used as an alignment material with excellent adhesion to a liquid crystal layer.

The cured film-forming composition of the present invention will be described in detail below, with specific examples of components, etc. Then, the cured film and alignment material of the present invention using the cured film-forming composition of the present invention, as well as the retardation material and liquid crystal display element formed using the alignment material, etc. will be described.

<Cured Film-Forming Composition>
The cured film-forming composition of the present invention contains a polymer having a photoalignment group, a hydroxyl group, and a polymerizable group containing a C=C double bond, which is a component (A), a crosslinking agent, which is a component (B), and a crosslinking catalyst, which is a component (C). It can also contain a polymer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, which is a component (D). Furthermore, it can contain other additives as long as they do not impair the effects of the present invention. It can also contain a solvent.
Each component will be described in detail below.

[Component (A)]
The component (A) in the cured film-forming composition of the present invention is a polymer having a photoalignable group, a hydroxyl group, and a polymerizable group containing a C=C double bond. That is, the component (A) is a component that imparts photoalignment to the cured film obtained from the cured film-forming composition of the present invention, and in this specification, the component (A) is also referred to as a photoalignment component.

It is preferable that the component (A) contained in the cured film-forming composition of the present invention is an acrylic copolymer having a photoalignable group, a hydroxy group, and a polymerizable group containing a C=C double bond.

In the present invention, an acrylic copolymer refers to a copolymer obtained by polymerizing monomers having unsaturated double bonds, such as acrylic acid esters, methacrylic acid esters, and styrene.

The acrylic copolymer (hereinafter also referred to as the specific copolymer) having a photoalignable group, a hydroxyl group, and a polymerizable group containing a C=C double bond, which is the component (A), may be any acrylic copolymer having such a structure, and there are no particular limitations on the type of main chain skeleton and side chain of the polymer constituting the acrylic copolymer.

Examples of photo-alignable groups include cinnamoyl groups, chalcone groups, coumarin groups, and anthracene groups. Of these, cinnamoyl groups are preferred due to their high transparency in the visible light region and high photodimerization reactivity. More preferred cinnamoyl groups and substituents containing a cinnamoyl structure include structures represented by the following formula [1] or formula [2]. In this specification, groups in which the benzene ring in a cinnamoyl group is a naphthalene ring are also included in the "cinnamoyl group" and "substituents containing a cinnamoyl structure".

In the above formula [1], ^X1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a biphenyl group, in which case the phenyl group and the biphenyl group may be substituted with either a halogen atom or a cyano group.

In the above formula [2], ^X2 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. In this case, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded to each other via one or more bonds selected from a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, a carbonyl bond, or a combination thereof.

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

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

The hydroxy group is a site that bonds with the crosslinking agent, which is the component (B), upon heating. The polymer of the present invention may also have a thermally crosslinkable site other than the hydroxy group, such as a carboxyl group, an amide group, an amino group, or an alkoxysilyl group.
In the polymer of component (A), the ratio of structural units having a hydroxyl group is preferably 20 mol % or more relative to 100 mol % of all structural units in the polymer. By making it 20 mol % or more, the cured film obtained from the cured film-forming composition of the present invention can improve the efficiency of the photoreaction for photoalignment, and can have excellent alignment sensitivity.
Here, when the polymer of component (A) contains structural units having two or more hydroxy groups, the proportion of structural units having hydroxy groups represents (the number of moles of structural units having hydroxy groups) x (the number of hydroxy groups contained in the structural units) per 100 moles of all structural units of the polymer.

The acrylic copolymer of component (A) preferably has a weight-average molecular weight of 3,000 to 200,000. If the weight-average molecular weight is too large, exceeding 200,000, the solubility in solvents may decrease, leading to poor handling properties. On the other hand, if the weight-average molecular weight is too small, less than 3,000, the product may not be cured sufficiently during heat curing, resulting in poor solvent resistance or poor heat resistance.

Examples of methods for producing an acrylic copolymer having a photoalignable group (A), a hydroxy group, and a polymerizable group containing a C=C double bond include the following methods.

Manufacturing method 1 of component (A) involves copolymerizing a monomer having a photodimerization site with a monomer having an epoxy group, and then reacting the epoxy group of the resulting copolymer with a compound having a carboxyl group and a polymerizable group including a C=C double bond.

Manufacturing method 2 of component (A) is a method in which a monomer having a photodimerization site is copolymerized with a monomer having a carboxyl group, and then the carboxyl group of the resulting copolymer is reacted with a compound having an epoxy group and a polymerizable group including a C=C double bond.

Examples of monomers having a photodimerization site include monomers having a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, etc. Among these, monomers having a cinnamoyl group are particularly preferred due to their high transparency in the visible light region and high photodimerization reactivity.

Among them, monomers having a cinnamoyl group of the structure represented by the above formula [1] or formula [2] and a substituent containing a cinnamoyl structure are more preferred. Specific examples of such monomers include monomers represented by the following formula [3] or formula [4].

In the above formula [3], ^X1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a biphenyl group, in which case the phenyl group and the biphenyl group may be substituted with either a halogen atom or a cyano group.
L ¹ and L ² each independently represent a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond or a urethane bond.

In the above formula [4], ^X2 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. In this case, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.

In the above formulas [3] and [4], ^X3 and ^X5 each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring, or a divalent aliphatic ring. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear.

In the above formulas [3] and [4], ^X4 represents a polymerizable group. Specific examples of the polymerizable group include an acryloyl group, a methacryloyl group, a styrene group, a maleimide group, an acrylamide group, and a methacrylamide group.

In the above formulas [3] and [4], A represents any one of formulas [A1], [A2], [A3], [A4], [A5] and [A6] as described above.

Examples of monomers having a polymerizable group containing a C=C double bond and a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, mono-(2-(acryloyloxy)ethyl)hexahydrophthalate, mono-(2-(methacryloyloxy)ethyl)hexahydrophthalate, mono-(2-(acryloyloxy)ethyl)succinate, mono-(2-(methacryloyloxy)ethyl)succinate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, and ω-carboxy-polycaprolactone mono(meth)acrylate. As these monomers, for example, those commercially available as "Light Ester HO-MS", "Light Acrylate HOA-MS (N)", "Light Acrylate HOA-HH (N)" and "Light Acrylate HOA-MPL (N)" (all of which are product names manufactured by Kyoeisha Chemical Co., Ltd.), Aronix M-5300 and Aronix M-5400 (all of which are product names manufactured by Toa Gosei Co., Ltd.), A-SA and SA (all of which are product names manufactured by Shin-Nakamura Chemical Co., Ltd.) can be used.

Examples of monomers having a polymerizable group containing a C=C double bond and an epoxy group include glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl methacrylate glycidyl ether, allyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

Here, in the production of the polymer (A), it is preferable to select at least one of the raw materials, a monomer having an epoxy group and a monomer having a carboxyl group, that has a spacer between the polymerizable group and the group selected from the epoxy group and the carboxyl group. By selecting such a raw material, the resulting cured film of the present invention has better adhesion to the liquid crystal layer.

式中、Ｘ^４は重合性基を表し、この重合性基の具体例としては、例えば、アクリロイル基、メタクリロイル基、スチレン基、マレイミド基、アクリルアミド基、メタクリルアミド基等が挙げられる。Ｌ^１は共有結合、エーテル結合、エステル結合、アミド結合、尿素結合又はウレタン結合を表す。Ｑ^１およびＱ^３はそれぞれ独立に炭素原子数２乃至１０のアルキレン基を表し、Ｑ^２はジカルボン酸無水物由来の構造を有する二価の基を表す。ｎは１～１０の自然数を表す。 A preferred structure of the monomer having a spacer and a carboxyl group is either of the following (SC-1) or (SC-2).

In the formula, ^X4 represents a polymerizable group, and specific examples of the polymerizable group include an acryloyl group, a methacryloyl group, a styrene group, a maleimide group, an acrylamide group, and a methacrylamide group. ^L1 represents a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond, or a urethane bond. ^Q1 and ^Q3 each independently represent an alkylene group having 2 to 10 carbon atoms, and ^Q2 represents a divalent group having a structure derived from a dicarboxylic acid anhydride. n represents a natural number from 1 to 10.

Preferred examples of such a monomer having a spacer and a carboxyl group include mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, mono-(2-(acryloyloxy)ethyl)hexahydrophthalate, mono-(2-(methacryloyloxy)ethyl)hexahydrophthalate, mono-(2-(acryloyloxy)ethyl)succinate, mono-(2-(methacryloyloxy)ethyl)succinate, and ω-carboxy-polycaprolactone mono(meth)acrylate. Polyfunctional acrylates having a carboxyl group are also preferred. As commercially available products, for example, those commercially available as "Light Ester HO-MS", "Light Acrylate HOA-MS (N)", "Light Acrylate HOA-HH (N)" and "Light Acrylate HOA-MPL (N)" (all of which are product names manufactured by Kyoeisha Chemical Co., Ltd.), Aronix M-5300 and Aronix M-5400 (all of which are product names manufactured by Toagosei Co., Ltd.) can be used.

式中、Ｘ^４は重合性基を表し、この重合性基の具体例としては、例えば、アクリロイル基、メタクリロイル基、スチレン基、マレイミド基、アクリルアミド基、メタクリルアミド基等が挙げられる。Ｌ^１は共有結合、エーテル結合、エステル結合、アミド結合、尿素結合又はウレタン結合を表す。Ｑ^１は炭素原子数２乃至１０のアルキレン基を表す。 A preferred structure of the monomer having a spacer and an epoxy group is represented by the following (SE-1).

In the formula, ^X4 represents a polymerizable group, and specific examples of the polymerizable group include an acryloyl group, a methacryloyl group, a styrene group, a maleimide group, an acrylamide group, and a methacrylamide group. ^L1 represents a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond, or a urethane bond. ^Q1 represents an alkylene group having 2 to 10 carbon atoms.

Examples of monomers having such a spacer and epoxy group include 4-hydroxybutyl methacrylate glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

式中、Ｘ^４は重合性基を表し、この重合性基の具体例としては、例えば、アクリロイル基、メタクリロイル基、スチレン基、マレイミド基、アクリルアミド基、メタクリルアミド基等が挙げられる。Ｌ^１は共有結合、エーテル結合、エステル結合、アミド結合、尿素結合又はウレタン結合を表す。Ｑ^４は（ｍ＋１）価の有機基を表し、ｍは２～１０の自然数を表す。 As a monomer having a carboxyl group and a polymerizable group containing a C═C double bond for grafting to an epoxy group of a polymer, a polyfunctional acrylate having a carboxyl group represented by the following (SC-3) is also preferred.

In the formula, ^X4 represents a polymerizable group, and specific examples of the polymerizable group include an acryloyl group, a methacryloyl group, a styrene group, a maleimide group, an acrylamide group, and a methacrylamide group. ^L1 represents a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond, or a urethane bond. ^Q4 represents an organic group having a valence of (m+1), and m represents a natural number from 2 to 10.

Such compounds can be commercially available as Aronix M-510 and M-520 (both trade names manufactured by Toa Gosei Co., Ltd.).

The amounts of the monomer having a photodimerization site and the monomer having an epoxy group used to obtain the specific copolymer according to Production Method 1 are preferably 40% by mass to 95% by mass of the monomer having a photodimerization site and 5% by mass to 60% by mass of the monomer having an epoxy group, based on the total amount of all monomers used to obtain the specific copolymer. By making the content of the monomer having a photodimerization site 40% by mass or more, high sensitivity and good liquid crystal alignment properties can be imparted. On the other hand, by making it 95% by mass or less, sufficient thermosetting properties can be imparted and high sensitivity and good liquid crystal alignment properties can be maintained.

The amounts of the monomer having a photodimerization site and the monomer having a carboxyl group used to obtain a specific copolymer according to manufacturing method 2 correspond to the amounts of the monomer having an epoxy group used in the amounts of the monomer having a photodimerization site and the monomer having an epoxy group used above.

In addition, in the cured film-forming composition of the present invention, when obtaining a polymer that is a precursor of a specific copolymer, a monomer having any one of a photodimerization site, an epoxy group, and a carboxyl group (hereinafter, these are also referred to as specific functional groups) can be used in combination with a monomer that is copolymerizable with the monomer (hereinafter, also referred to as a monomer having a non-reactive functional group).

Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.
Specific examples of the above monomers are given below, but the present invention is not limited to these.

Examples of the acrylic acid ester compounds mentioned above include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compounds mentioned above include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

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

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

Examples of the maleimide compounds mentioned above include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The method for obtaining the polymer that serves as the precursor of the specific copolymer used in the cured film-forming composition of the present invention is not particularly limited, but for example, it can be obtained by carrying out a polymerization reaction at a temperature of 50°C to 110°C in a solvent in which a monomer having a specific functional group selected from a photodimerization site, an epoxy group, and a carboxyl group, a monomer having a non-reactive functional group if desired, and a polymerization initiator are coexisting. The solvent used in this case is not particularly limited as long as it dissolves the monomer having the specific functional group, the monomer having a non-reactive functional group if desired, and the polymerization initiator. Specific examples include the solvents described below in the section on solvents.

The reaction product of a polymer having an epoxy group in a side chain and a compound having a specific carboxyl group and a polymerizable group containing a C=C double bond can be synthesized by reacting the above-mentioned polymer having an epoxy group with a compound having a specific carboxyl group and a polymerizable group containing a C=C double bond, preferably in the presence of a catalyst, preferably in a suitable organic solvent.
The proportion of the compound having a carboxyl group and a polymerizable group containing a C═C double bond used in the reaction is preferably 0.01 to 0.9 mol, more preferably 0.05 to 0.8 mol, and even more preferably 0.1 to 0.7 mol, relative to 1 mol of epoxy groups contained in the polymer having epoxy groups.

The reaction product of a polymer having a carboxyl group in a side chain and a compound having a specific epoxy group and a polymerizable group containing a C=C double bond can be synthesized by reacting the above-mentioned polymer having a carboxyl group with a compound having a specific epoxy group and a polymerizable group containing a C=C double bond, preferably in the presence of a catalyst, preferably in a suitable organic solvent.
The proportion of the compound having an epoxy group and a polymerizable group containing a C═C double bond used in the reaction is preferably 0.01 to 0.9 mol, more preferably 0.05 to 0.8 mol, and even more preferably 0.1 to 0.7 mol, relative to 1 mol of carboxyl group contained in the polymer having a carboxyl group.

The organic catalyst that can be used here may be an organic base or a compound known as a curing accelerator that promotes the reaction between an epoxy compound and a carboxyl group.

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and diazabicycloundecene; and quaternary organic amines such as tetramethylammonium hydroxide. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine; and quaternary organic amines such as tetramethylammonium hydroxide are preferred.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, and triethanolamine; 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 1,2-dimethylimidazole. azole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2-cyanoethyl)-2-n-undecylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di(hydroxymethyl)imidazole, 1-(2-cyanoethyl)-2-phenyl-4, 5-di[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazolium trimellitate, 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2,4-diamino-6-(2'-n-undecylimidazolyl)ethyl-s imidazole compounds such as 2-methylimidazole, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s-triazine, an isocyanuric acid adduct of 2-methylimidazole, an isocyanuric acid adduct of 2-phenylimidazole, and an isocyanuric acid adduct of 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine; organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenyl phosphite;

quaternary phosphonium salts such as benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o,o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, and tetraphenylphosphonium tetraphenylborate; diaza such as 1,8-diazabicyclo[5.4.0]undecene-7 and its organic acid salts; Examples of the latent curing accelerator include bicycloalkenes; zinc octylate, tin octylate, and organic metal compounds such as aluminum acetylacetone complexes; quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride; boron compounds such as boron trifluoride and triphenyl borate; metal halide compounds such as zinc chloride and stannic chloride; high melting point dispersion type latent curing accelerators such as amine addition type accelerators such as dicyandiamide and adducts of amines and epoxy resins; microcapsule type latent curing accelerators in which the surface of the curing accelerators such as the imidazole compounds, organic phosphorus compounds, and quaternary phosphonium salts is coated with a polymer; amine salt type latent curing accelerators; and high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.
Of these, preferred are quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

The proportion of catalyst used is preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, and even more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polymer having an epoxy group or the polymer having a carboxyl group.

Examples of the organic solvent include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, and alcohol compounds. Of these, ether compounds, ester compounds, ketone compounds, and alcohol compounds are preferred from the viewpoints of the solubility of the raw materials and the product and the ease of purifying the product. The solvent is used in an amount such that the solids concentration (the ratio of the mass of the components other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1% by mass or more, more preferably 5 to 50% by mass.

The reaction temperature is preferably 0 to 200°C, more preferably 50 to 150°C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

<Production method 3 of component (A)>
Production method 3 of component (A) is a method in which a polymer having an epoxy group in the side chain is reacted with a cinnamic acid derivative and the above-mentioned compound having a carboxyl group and a polymerizable group including a C═C double bond.

The polymer having an epoxy group in its side chain may be, for example, a polymer of a monomer having the above-mentioned epoxy group, or a copolymer of the above-mentioned monomer having the epoxy group and the above-mentioned monomer having a non-reactive functional group.

The copolymerization ratio of the polymerizable unsaturated compound having an epoxy group in the polymer having an epoxy group is preferably 30% by mass or more, and more preferably 50% by mass or more.

The synthesis of polymers having epoxy groups can be carried out by known radical polymerization methods, preferably in a solvent and in the presence of a suitable polymerization initiator.

Commercially available products may be used as polymers having epoxy groups in their side chains. Examples of such commercially available products include EHPE3150, EHPE3150CE (manufactured by Daicel Corporation), UG-4010, UG-4035, UG-4040, and UG-4070 (manufactured by Toagosei Co., Ltd., ARUFON series), ECN-1299 (manufactured by Asahi Kasei Corporation), DEN431 and DEN438 (manufactured by The Dow Chemical Company), jER-152 (manufactured by Mitsubishi Chemical Corporation), Epicron N-660, N-665, N-670, N-673, N-695, N-740, N-770, and N-775 (manufactured by DIC Corporation), and EOCN-1020, EOCN-102S, and EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.).

（式中、Ｒ^１は水素原子、ハロゲン原子、炭素原子数１乃至６のアルキル基、炭素原子数１乃至６のアルコキシ等を表す。）のいずれかで表される化合物等を挙げることができる。
また、カルボキシル基を有する桂皮酸誘導体として、上述の式［３］で表されるモノマーにおいて、Ｘ^１が水素原子である化合物も好適に用いられる。 Examples of cinnamic acid derivatives having a carboxyl group include those represented by the following formulas (1-1) to (1-5).

(wherein R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or the like).
As the cinnamic acid derivative having a carboxyl group, a compound in which X ¹ is a hydrogen atom in the monomer represented by the above formula [3] is also preferably used.

The above cinnamic acid derivatives can be synthesized by appropriately combining standard methods of organic chemistry.

Here, as for the compound (monomer) having a carboxyl group and a polymerizable group containing a C=C double bond, it is preferable to select one having a spacer between the group having a C=C double bond and the carboxyl group, as described above.

The method of reacting a polymer having an epoxy group in the side chain with a cinnamic acid derivative and a compound having a carboxyl group and a polymerizable group containing a C=C double bond described above is as described above. In this case, the polymer having an epoxy group in the side chain may be reacted with the cinnamic acid derivative and the compound having a carboxyl group and a polymerizable group containing a C=C double bond described above together or separately.

In the polymer of component (A), the ratio of structural units having a polymerizable group containing a C=C double bond is preferably 5 mol % or more, more preferably 10 mol % or more, per 100 mol of the total structural units of the polymer. If the total is less than 5 mol %, the adhesion to the liquid crystal layer may be insufficient.
Here, when the polymer of component (A) contains a structural unit having a polymerizable group containing two or more C═C double bonds, the abundance ratio of the structural unit having a polymerizable group containing a C═C double bond represents (the number of moles of structural units having a polymerizable group containing a C═C double bond) × (the number of polymerizable groups having a C═C double bond contained in the structural unit) per 100 moles of all structural units of the polymer.

In this way, a solution containing a polymer having a photoalignable group, a hydroxyl group, and a polymerizable group containing a C=C double bond, which is component (A), is obtained. This solution may be used as is to prepare a liquid crystal alignment agent, or the polymer contained in the solution may be isolated and then used to prepare a liquid crystal alignment agent, or the isolated polymer may be purified and then used to prepare a liquid crystal alignment agent.

The solution of the specific copolymer obtained as described above can be reprecipitated by adding it to diethyl ether, water, or the like under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal or reduced pressure to obtain a powder of the specific copolymer. By such an operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a powder of the purified specific copolymer can be obtained. If the specific copolymer cannot be sufficiently purified by a single operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated.

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

In addition, in this embodiment, the acrylic copolymer of component (A) may be a mixture of multiple specific copolymers.

As described above, in the present invention, a high molecular weight specific copolymer can be used as component (A). Component (A) may also be a mixture of one or more specific copolymers.

[Component (B)]
The cured film-forming composition of the present invention contains a crosslinking agent as component (B). More specifically, component (B) is a crosslinking agent that reacts with the above-mentioned components (A) and (C). Component (B) bonds with the thermally crosslinkable group (particularly the hydroxyl group) of the polymer that is component (A) and with the hydroxyl group contained in component (C). The cured film-forming composition of the present embodiment can form an alignment material with high photoreaction efficiency as a cured film.

The crosslinking agent of component (B) may be an epoxy compound, a methylol compound, an isocyanate compound, or the like, but is preferably a methylol compound. Among them, the crosslinking agent of component (B) is preferably a compound having two or more groups that form a crosslink with the thermally crosslinkable functional group of component (A), and is preferably a crosslinking agent having two or more methylol groups or alkoxymethyl groups. Examples of compounds having these groups include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

Specific examples of the above-mentioned methylol compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, alkoxymethylated melamine, tetra(alkoxymethyl)bisphenol, and tetra(hydroxymethyl)bisphenol.

Specific examples of alkoxymethylated glycoluril include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include glycoluril compounds manufactured by Mitsui Cytec Co., Ltd. (product names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174), methylated urea resins (product names: UFR (registered trademark) 65), butylated urea resins (product names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea/formaldehyde resins (high condensation type, product names: Beckamin (registered trademark) J-300S, P-955, and N) manufactured by DIC Corporation.

Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine, etc. Commercially available products include those manufactured by Mitsui Cytec Co., Ltd. (product name: Cymel (registered trademark) 1123) and those manufactured by Sanwa Chemical Co., Ltd. (product names: Nikalac (registered trademark) BX-4000, BX-37, BL-60, and BX-55H).

Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine. Commercially available products include methoxymethyl type melamine compounds manufactured by Mitsui Cytec Co., Ltd. (product names: Cymel (registered trademark) 300, 301, 303, and 350), butoxymethyl type melamine compounds (product names: Mycoat (registered trademark) 506 and 508), methoxymethyl type melamine compounds manufactured by Sanwa Chemical Co., Ltd. (product names: Nikalac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS-001, MX-002, MX-730, MX-750, and MX-035), and butoxymethyl type melamine compounds (product names: Nikalac (registered trademark) MX-45, MX-410, and MX-302).

Examples of tetra(alkoxymethyl)bisphenols and tetra(hydroxymethyl)bisphenols include tetra(alkoxymethyl)bisphenol A, tetra(hydroxymethyl)bisphenol A, etc.

The crosslinking agent (B) may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amino group is replaced with a methylol group or an alkoxymethyl group. For example, a high molecular weight compound produced from a melamine compound and a benzoguanamine compound described in U.S. Pat. No. 6,323,310 may be mentioned. Commercially available products of the melamine compound include Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available products of the benzoguanamine compound include Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).

In addition, polymers produced using acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl groups (i.e., methylol groups) or alkoxymethyl groups, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, and N-butoxymethylmethacrylamide, can also be used as the crosslinking agent for component (B).

Examples of such polymers include poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate.

As such a polymer, a polymer having an N-alkoxymethyl group and a polymerizable group containing a C=C double bond can also be used.

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

There is no particular limitation on the method for obtaining a polymer having a polymerizable group containing a C=C double bond. For example, an acrylic polymer having a specific functional group is produced in advance by a polymerization method such as radical polymerization. Then, this specific functional group is reacted with a compound having an unsaturated bond at the end (hereinafter referred to as a specific compound), thereby introducing a polymerizable group containing a C=C double bond into the polymer, which is the component (B).

Here, the specific functional group refers to a functional group such as a carboxyl group, a glycidyl group, a hydroxyl group, an amino group having active hydrogen, a phenolic hydroxyl group, or an isocyanate group, or a plurality of functional groups selected from these. By polymerizing a monomer having such a group, an acrylic polymer having the specific functional group can be obtained.

Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide.

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

Examples of monomers having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2-(acryloyloxy)ethyl ester, caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

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

Examples of monomers having a phenolic hydroxy group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleimide.

Examples of monomers having an isocyanate group include acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, and m-tetramethylxylene isocyanate.

In the above-mentioned reaction, preferred combinations of the specific functional group and the functional group of the specific compound that participates in the reaction are a carboxyl group and an epoxy group, a hydroxyl group and an isocyanate group, a phenolic hydroxyl group and an epoxy group, a carboxyl group and an isocyanate group, an amino group and an isocyanate group, or a hydroxyl group and an acid chloride. More preferred combinations are a carboxyl group and glycidyl methacrylate, or a hydroxyl group and an isocyanate ethyl methacrylate.

The weight average molecular weight (polystyrene equivalent) of such polymers is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

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

The content of the crosslinking agent of component (B) in the cured film-forming composition of the present invention is preferably 5 to 500 parts by mass, and more preferably 10 to 400 parts by mass, based on 100 parts by mass of the total amount of the polymer of component (A) and the crosslinking catalyst of component (C). If the content of the crosslinking agent is too small, the solvent resistance of the cured film obtained from the cured film-forming composition may decrease, and the liquid crystal alignment property may decrease. On the other hand, if the content is too large, the liquid crystal alignment property and storage stability may decrease.

[Component (C)]
The cured film-forming composition that forms a cured film on the surface of the optical film of the present invention may further contain a crosslinking catalyst as component (C) in addition to the above-mentioned components (A) and (B).
Examples of the crosslinking catalyst that is the component (C) include an acid or a thermal acid generator. The component (C) is effective in promoting a thermal curing reaction in the formation of a cured film using the cured film-forming composition that forms a cured film on the surface of the optical film of the present invention.

When an acid or a thermal acid generator is used as component (C), component (C) is not particularly limited as long as it is a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof, or a compound that undergoes thermal decomposition during pre-bake or post-bake to generate an acid, i.e., a compound that undergoes thermal decomposition at a temperature of 80°C to 250°C to generate an acid.

Examples of such compounds include sulfonic acids such as hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octane sulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic 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,2H-perfluorooctane sulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, and dodecylbenzenesulfonic acid, or their hydrates or salts.

Examples of compounds that generate acid when heated 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-hydroxybutyl p-tosylate, N-ethyl-4-toluenesulfonamide, and compounds represented by the following formulae [TAG-1] to [TAG-41].

The content of component (C) in the cured film-forming composition of an embodiment of the present invention is 0.01 to 20 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.05 to 8 parts by weight, and even more preferably 0.1 to 6 parts by weight, relative to 100 parts by weight of the polymer component (A). By making the content of component (C) 0.01 parts by weight or more, sufficient thermosetting properties and solvent resistance can be imparted, and high sensitivity to light exposure can also be imparted. In addition, by making the content 20 parts by weight or less, the storage stability of the cured film-forming composition can be improved.

[Component (D)]
The composition of the present invention may further contain, as component (D), a polymer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group.

Examples of the polymer that is component (D) include acrylic polymers, urethane-modified acrylic polymers, polyamic acids, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylic acids, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polyalkyleneimines, polyallylamine, celluloses (cellulose or derivatives thereof), polymers having a linear or branched structure such as phenol novolac resins, and cyclic polymers such as cyclodextrins.

Among these, the acrylic polymer may be a polymer obtained by polymerizing a monomer having an unsaturated double bond, such as an acrylic acid ester, a methacrylic acid ester, or styrene. A convenient synthesis method is to (co)polymerize a monomer having at least one group selected from the group consisting of a monomer having a hydroxyl group, a monomer having a carboxyl group, a monomer having an amide group, a monomer having an amino group, and a monomer having an alkoxysilyl group, as exemplified in the chapters on components (A) and (B) above, and, if desired, other monomers, by the method described in the chapters on components (A) and (B) above.

The acrylic polymer, an example of component (D), preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and even more preferably 5,000 to 100,000.

A preferred example of the polyether polyol (D) is polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, sorbitol, or other polyhydric alcohol to which propylene oxide, polyethylene glycol, polypropylene glycol, etc. have been added. Specific examples of polyether polyols include the Adeka Polyether P series, G series, EDP series, BPX series, FC series, and CM series manufactured by ADEKA CORPORATION, and Uniox (registered trademark) HC-40, HC-60, ST-30E, ST-40E, G-450, and G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, and DB-400, and Nonion (registered trademark) LT-221, ST-221, and OT-221, etc., manufactured by NOF Corporation.

A preferred example of the polyester polyol (D) is a polycarboxylic acid such as adipic acid, sebacic acid, or isophthalic acid, which is reacted with a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, or polypropylene glycol. Specific examples of polyester polyols include Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2547 ... -2523, OD-X-2555, OD-X-2560, and Kuraray Co., Ltd. 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, and PNNA-2016.

A preferred example of the polycaprolactone polyol of component (D) is one obtained by ring-opening polymerization of ε-caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of polycaprolactone polyols include Polylite (registered trademark) OD-X-2155, OD-X-640, and OD-X-2568 manufactured by DIC Corporation, and Plaxel (registered trademark) 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, and 320 manufactured by Daicel Chemical Industries, Ltd.

A preferred example of the polycarbonate polyol (D) is a polycarbonate polyol obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc. Specific examples of polycarbonate polyols include Plaxel (registered trademark) CD205, CD205PL, CD210, and CD220 manufactured by Daicel Corporation, and C-590, C-1050, C-2050, C-2090, and C-3090 manufactured by Kuraray Co., Ltd.

Preferred examples of cellulose as component (D) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and cellulose, and the like. For example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferred.

Preferred examples of cyclodextrins as component (D) include cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, methylated cyclodextrins such as methyl-α-cyclodextrin, methyl-β-cyclodextrin, and methyl-γ-cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxyethyl-β-cyclodextrin, 2-hydroxyethyl- Examples of hydroxyalkyl cyclodextrins include γ-cyclodextrin, 2-hydroxypropyl-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, and 2,3-dihydroxypropyl-γ-cyclodextrin.

Preferred examples of urethane-modified acrylic polymers as component (D) include commercially available products such as Acrylate (registered trademark) 8UA-017, 8UA-239, 8UA-239H, 8UA-140, 8UA-146, 8UA-585H, 8UA-301, 8UA-318, 8UA-347A, 8UA-347H, and 8UA-366 manufactured by Taisei Fine Chemical Co., Ltd.

A preferred example of component (D) is a phenol novolac resin, such as a phenol-formaldehyde polycondensate.

In the composition of the present invention, the polymer of component (D) may be used in powder form or in solution form in which the purified powder is redissolved in the solvent described below.

In addition, in the composition of the present invention, component (D) may be a mixture of multiple types of polymers exemplified as component (D).

The content of component (D) in the cured film-forming composition of the present invention is 5 parts by mass to 500 parts by mass based on 100 parts by mass of component (A).

[Component (E)]
The composition of the present invention may further contain a low molecular weight photo-alignment component as component (E). By containing a low molecular weight photo-alignment component, the amount of photo-alignment groups present in the surface layer of the alignment film increases, and the alignment sensitivity is improved. Examples of such low molecular weight photo-alignment components include the monomer represented by formula [3] exemplified in the section on component (A) of this specification, the monomer represented by formula [4], the compound in which the group X ⁴ of the monomer represented by formula [3] is replaced with a hydrogen atom, the compound in which the group X ⁴ of the monomer represented by formula [4] is replaced with a hydrogen atom, and the cinnamic acid derivative having a carboxyl group represented by any of the above formulas (1-1) to (1-5).

In addition, in the composition of the present invention, component (E) may be a mixture of multiple types of the compounds exemplified as component (E).

When component (E) is contained in the cured film-forming composition of the present invention, the content is 5 parts by mass to 500 parts by mass based on 100 parts by mass of the polymer of component (A).

[Other additives]
The cured film-forming composition according to an embodiment of the present invention may contain other additives as long as the additives do not impair the effects of the present invention.
As other additives, for example, a sensitizer may be contained. The sensitizer is effective in promoting the photoreaction when forming a cured film on the surface of the optical film of the present invention.

Examples of sensitizers include derivatives of benzophenone, anthracene, anthraquinone, and thioxanthone, as well as nitrophenyl compounds. Of these, N,N-diethylaminobenzophenone, a derivative of benzophenone, and 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, 4-nitrostilbene, 4-nitrobenzophenone, and 5-nitroindole, which are nitrophenyl compounds, are particularly preferred.

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

In an embodiment of the present invention, the proportion of the sensitizer used is preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass, per 100 parts by mass of component (A). If this proportion is too small, the effect of the sensitizer may not be fully obtained, and if it is too large, the transmittance of the cured film formed may decrease or the coating film may become rough.

In addition, the cured film-forming composition of an embodiment of the present invention may contain other additives such as silane coupling agents, surfactants, rheology adjusters, pigments, dyes, storage stabilizers, defoamers, antioxidants, etc., as long as the effects of the present invention are not impaired.

[solvent]
The cured film-forming composition according to the embodiment of the present invention is often used in a state of solution in a solvent. The solvent used in this case dissolves the components (A), (B) and (C), and optionally the components (D) and (E) and/or other additives, and the type and structure of the solvent are not particularly limited as long as the solvent has such dissolving ability.

Specific examples of solvents include 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, propylene glycol propyl ether acetate, cyclopentyl methyl ether, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, and 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, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, n-propyl acetate, isopropyl acetate, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

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

<Preparation of Cured Film-Forming Composition>
The cured film forming composition of the present invention is a thermosetting cured film forming composition having photoalignment. As described above, the cured film forming composition of the present invention contains a polymer having a photoalignment group, a hydroxyl group, and a polymerizable group containing a C=C double bond, which is the component (A), a crosslinking agent which is the component (B), and a crosslinking catalyst which is the component (C). If necessary, it contains a polymer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, which is the component (D). And, other additives can be contained as long as they do not impair the effects of the present invention, and further, a solvent can be contained.

Preferred examples of the cured film-forming composition of the present embodiment are as follows.
[1]: A cured film-forming composition comprising: component (A) a polymer having a photoalignable group, a hydroxy group, and a polymerizable group containing a C═C double bond; component (B) a crosslinking agent in an amount of 1 part by mass to 500 parts by mass, preferably 5 parts by mass to 500 parts by mass, based on 100 parts by mass of the polymer (A); and component (C) a crosslinking catalyst in an amount of 0.01 parts by mass to 20 parts by mass, based on 100 parts by mass of the polymer (A).

[2]: A cured film-forming composition comprising: component (A) a polymer having a photoalignable group, a hydroxyl group, and a polymerizable group containing a C=C double bond; component (B) a crosslinking agent in an amount of 1 to 500 parts by mass, preferably 5 to 500 parts by mass, based on 100 parts by mass of the polymer (A); component (C) a crosslinking catalyst in an amount of 0.01 to 20 parts by mass, based on 100 parts by mass of the polymer (A); and component (D) a polymer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group; and a solvent.

The compounding ratios, preparation method, etc. when the cured film-forming composition of this embodiment is used as a solution are described in detail below.

The proportion of solids in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1% by mass to 80% by mass, preferably 2% by mass to 60% by mass, and more preferably 3% by mass to 40% by mass. Here, the solids refers to all the components of the cured film-forming composition excluding the solvent.

The method for preparing the cured film-forming composition of the present invention is not particularly limited. Examples of the preparation method include a method in which a solution of component (A) dissolved in a solvent is mixed with component (B), component (C), and further component (D), component (E), and/or other additives in a predetermined ratio to prepare a homogeneous solution, or a method in which other additives are further added and mixed as necessary at an appropriate stage of this preparation method.

In preparing the cured film-forming composition of the present invention, the solution of the specific copolymer obtained by the polymerization reaction in the solvent can be used as is. In this case, for example, the solution in which the polymer (acrylic polymer) of component (A) is prepared is added with components (B), (C), and further components (D), (E) and/or other additives to prepare a homogeneous solution. In this case, additional solvent may be added for the purpose of adjusting the concentration. In this case, the solvent used in the preparation process of component (A) and the solvent used to adjust the concentration of the cured film-forming composition may be the same or different.

It is also preferable to filter the prepared solution of the cured film-forming composition using a filter having a pore size of approximately 0.2 μm before use.

As described above, the cured film-forming composition of the present invention is composed of component (A) which is at least one selected from the group consisting of polymers having a photoalignable group, a hydroxy group, and a polymerizable group containing a C=C double bond, component (B) which is a crosslinking agent, and component (C) which is a crosslinking catalyst.

Therefore, the cured film formed from the cured film-forming composition of the present invention is formed with its inside being hydrophilic due to the properties of the (A) component so that the film structure is stabilized. The photo-alignable group of the (A) component and the polymerizable group containing a C=C double bond in the cured film are unevenly distributed near the surface of the cured film. More specifically, the polymer of the (A) component is unevenly distributed near the surface of the cured film while adopting a structure in which the hydrophilic hydroxyl group faces the inside of the cured film and the hydrophobic photo-reactive part and the polymerizable group containing a C=C double bond face the surface side. As a result, the cured film of the present invention realizes a structure in which the ratio of the photo-reactive group of the (A) component and the polymerizable group containing a C=C double bond present near the surface is increased. And, when the cured film of the present invention is used as an alignment material, it can improve the efficiency of the photoreaction for photo-alignment and have excellent alignment sensitivity. Furthermore, it becomes an alignment material suitable for forming a patterned retardation material, and the patterned retardation material manufactured using this can have excellent pattern formability.

As described above, the cured film-forming composition of the present invention contains a crosslinking agent, which is the component (B). Therefore, inside the cured film obtained from the cured film-forming composition of the present invention, a crosslinking reaction due to a thermal reaction with the component (B) can occur before the photoreaction due to the photoalignable group of the polymer of the component (A). As a result, when used as an alignment material, it is possible to improve resistance to the polymerizable liquid crystal and its solvent that are applied thereon.

In addition, the polymerizable group containing a C=C double bond of the polymer, which is component (A), functions to strengthen the adhesion between the cured film obtained from the cured film-forming composition of the present invention and the layer of cured polymerizable liquid crystal formed thereon when the cured film is used as an alignment material.

<Cured Film, Alignment Material, and Retardation Material>
A solution of the cured film-forming composition of the present embodiment is applied onto a substrate (e.g., a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal, for example, aluminum, molybdenum, chromium, or the like, a glass substrate, a quartz substrate, an ITO substrate, or the like) or a film (e.g., a resin film such as a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, or an acrylic film) by bar coating, spin coating, flow coating, roll coating, slit coating, spin coating followed by slit coating, inkjet coating, printing, or the like to form a coating film, and then the coating is heated and dried on a hot plate or in an oven, or the like to form a cured film.

The conditions for heat drying should be such that the curing reaction proceeds to such an extent that the components of the alignment material formed from the cured film are not dissolved in the polymerizable liquid crystal solution applied on top of it, and for example, a heating temperature and heating time appropriately selected from within the ranges of 60°C to 200°C and 0.4 minutes to 60 minutes are used. The heating temperature and heating time are preferably 70°C to 160°C and 0.5 minutes to 10 minutes.

The thickness of the cured film formed using the curable composition of this embodiment is, for example, 0.05 μm to 5 μm, and can be selected appropriately taking into account the step height and optical and electrical properties of the substrate used.

The cured film formed in this manner can be made to function as an alignment material, i.e., a material that aligns compounds having liquid crystal properties, including polymerizable liquid crystals, by irradiating them with polarized UV light.

Polarized UV irradiation typically uses ultraviolet to visible light with a wavelength of 150 nm to 450 nm, and is performed by irradiating linearly polarized light from a vertical or oblique direction at room temperature or in a heated state.

The alignment material formed using the cured film formed from the cured film-forming composition of the present invention has solvent resistance and heat resistance, so that after a retardation material made of a polymerizable liquid crystal solution is applied onto this alignment material, the retardation material is put into a liquid crystal state by heating to the phase transition temperature of the liquid crystal, and aligned on the alignment material. The retardation material in the desired alignment state is then cured as is, to form a retardation material having a layer with optical anisotropy.

As the retardation material, for example, a liquid crystal monomer having a polymerizable group and a composition containing the same are used. When the substrate on which the alignment material is formed is a film, a film having the retardation material of this embodiment is useful as a retardation film. Retardation materials forming such retardation materials include those that are in a liquid crystal state and take on an alignment state such as horizontal alignment, cholesteric alignment, vertical alignment, and hybrid alignment on the alignment material, and can be used according to the retardation characteristics required.

In addition, when manufacturing a patterned retardation material for use in a 3D display, the cured film formed from the cured film-forming composition of the present invention by the above-mentioned method is exposed to polarized UV light through a line-and-space pattern mask at, for example, +45 degrees from a predetermined reference, and then exposed to polarized UV light at -45 degrees after removing the mask to form an alignment material in which two types of liquid crystal alignment regions with different liquid crystal alignment control directions are formed. Thereafter, a retardation material made of a polymerizable liquid crystal solution is applied, and the retardation material is put into a liquid crystal state by heating to the phase transition temperature of the liquid crystal. The polymerizable liquid crystal in the liquid crystal state is oriented on the alignment material in which the two types of liquid crystal alignment regions are formed, forming an alignment state corresponding to each liquid crystal alignment region. Then, the retardation material in which such an alignment state is realized is cured as it is, the above-mentioned alignment state is fixed, and a patterned retardation material in which two types of retardation regions with different retardation characteristics are regularly arranged in multiples can be obtained.

In addition, the alignment material formed by using the cured film formed from the cured film-forming composition of the present invention can also be used as a liquid crystal alignment film for a liquid crystal display element. For example, two substrates having the alignment material of the present invention formed as described above are used, and are bonded together via a spacer so that the alignment materials on both substrates face each other, and then liquid crystal is injected between the substrates to produce a liquid crystal display element in which the liquid crystal is aligned.
Therefore, the cured film-forming composition of the present embodiment can be suitably used in the production of various retardation materials (retardation films), liquid crystal display elements, and the like.

The present invention will be explained in detail below with reference to examples, but the present invention should not be construed as being limited to these.

ＣＩＮ２：

[Abbreviations used in the Examples]
The abbreviations used in the following examples have the following meanings.
<Ingredients>
GMA: glycidyl methacrylate AIBN: α,α'-azobisisobutyronitrile BMAA: N-butoxymethylacrylamide CIN1:

CIN2:

P-2: EHPE3150 (manufactured by Daicel Corporation, epoxy equivalent 180 g/eq)

A-1: Aronix M-5300 (manufactured by Toagosei Co., Ltd.)

A-2: Aronix M-5400 (manufactured by Toagosei Co., Ltd.)

A-3: 2-acryloyloxyethyl succinate

<Component B>
HMM: A melamine crosslinking agent represented by the following structural formula [CYMEL (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.)]

<Component C>
PTSA: p-toluenesulfonic acid monohydrate

（上記式中、Ｒは、アルキレン基を表す。） <Component D>
PEPO: Polyester polyol polymer (adipic acid/diethylene glycol copolymer having the following structural unit. Molecular weight: 4,800.)

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

<Solvent>
PM: Propylene glycol monomethyl ether EA: Ethyl acetate

<Measurement of molecular weight of polymer>
The molecular weight of the acrylic (co)polymer in the polymerization examples was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co., Ltd.
The number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.
Column temperature: 40°C
Eluent: tetrahydrofuran Flow rate: 1.0 mL/min Standard sample for preparing calibration curve: standard polystyrene (molecular weights: about 197,000, 55,100, 12,800, 3,950, 1,260, 580) manufactured by Showa Denko K.K.

<Synthesis of Component A>
<Synthesis Example 1>
15.0 g of GMA and 0.8 g of AIBN as a polymerization catalyst were dissolved in 63.0 g of tetrahydrofuran, and the mixture was reacted for 20 hours under heating and reflux to obtain an acrylic polymer solution. The acrylic polymer solution was gradually added dropwise to 500.0 g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain an acrylic polymer (P-1). The Mn of the obtained acrylic polymer was 6,500 and the Mw was 11,000.

<Synthesis Example 2>
10.0 g of the acrylic polymer (P-1) having epoxy groups obtained in Synthesis Example 1, 8.4 g of CIN1, 0.8 g of acrylic acid, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, and 0.4 g of dibutylhydroxytoluene as a polymerization inhibitor were dissolved in 46.1 g of PM and reacted at 80° C. for 20 hours to obtain a solution containing 30% by mass of acrylic polymer (PA-1). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy groups had disappeared.

<Synthesis Examples 3 to 10>
Solutions containing 30% by mass of polymers (PA-2) to (PA-9) were obtained in the same manner as in Synthesis Example 2, except that the types and amounts of the polymer having an epoxy group (acrylic polymer), the compound giving a photoalignment group, and the compound giving a group containing a polymerizable double bond were as shown in Table 1 below. Note that blanks in Table 1 indicate that the corresponding component was not added.

<Synthesis of Component B>
<Synthesis Example 11>
100.0 g of BMAA and 4.2 g of AIBN as a polymerization catalyst were dissolved in 193.5 g of PM, and the mixture was reacted at 90° C. for 20 hours to obtain an acrylic polymer solution. The obtained acrylic polymer had an Mn of 2,700 and an Mw of 3,900. The acrylic polymer solution was gradually added dropwise to 2,000.0 g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain a polymer (PB-1).

<Preparation of polymerizable liquid crystal solution>
A polymerizable liquid crystal solution (RM-1) having a solid content of 30% by mass was obtained by mixing 29.0 g of polymerizable liquid crystal LC242 (manufactured by BASF Corporation), 0.9 g of Irgacure 907 (manufactured by BASF Corporation) as a polymerization initiator, 0.2 g of BYK-361N (manufactured by BYK Corporation) as a leveling agent, and methyl isobutyl ketone as a solvent.

< Example 1 >
As the component (A), an amount equivalent to 100 parts by mass of a solution containing 30% by mass of the acrylic polymer (PA-1) obtained in Synthesis Example 2 above, converted to acrylic polymer (PA-1), as the component (B), 30 parts by mass of HMM, and as the component (C), 3 parts by mass of PTSA were mixed, to which PM and EA were added to prepare a cured film (alignment material) forming composition (A-1) having a solvent composition of PM:EA=100:30 (mass ratio) and a solid content concentration of 5.0% by mass.

< Example 2, Examples 3 to 12, and Comparative Examples 1 and 2>
Cured film (alignment material) forming compositions A-2 to A-15 were prepared in the same manner as in Example 1 , except that the type and amount of each component was as shown in Table 2. Note that blanks in Table 2 indicate that the corresponding component was not blended.

< Examples 13 to 14, Examples 15 to 24, and Comparative Examples 3 to 4>
[Evaluation of Orientation]
Each of the cured film (alignment material) forming compositions of Examples 1-2, Examples 3-12, and Comparative Examples 1-2 was applied to a TAC film with a wet film thickness of 4 μm using a bar coater. Each was heated and dried in a heat circulation oven at a temperature of 110 ° C. for 60 seconds to form a cured film on the film. Each of these cured films was irradiated vertically with linearly polarized light of 313 nm at an exposure dose of 10 mJ/cm ² to form an alignment material. A polymerizable liquid crystal solution (RM-1) was applied to the alignment material on the film with a wet film thickness of 6 μm using a bar coater. This coating film was dried on a hot plate at a temperature of 90 ° C. for 60 seconds, and then exposed to light at 300 mJ/cm ² to prepare a retardation material. The retardation material on the film thus prepared was sandwiched between a pair of polarizing plates, and the expression state of the retardation characteristics in the retardation material was observed, and those in which the retardation was expressed without defects were marked with ○, and those in which the retardation was not expressed were marked with ×, and were recorded in the "alignment" column. The evaluation results are summarized in Table 3 below.

[Evaluation of Adhesion]
Each of the cured film (alignment material) forming compositions of Examples 1-2, Examples 3-12, and Comparative Examples 1-2 was applied to a TAC film with a wet film thickness of 4 μm using a bar coater. Each was heated and dried in a heat circulation oven at a temperature of 110° C. for 60 seconds to form a cured film on the film. Each of these cured films was irradiated vertically with linearly polarized light of 313 nm at an exposure dose of 10 mJ/cm ² to form an alignment material. A polymerizable liquid crystal solution (RM-1) was applied to the alignment material on the film with a wet film thickness of 6 μm using a bar coater. This coating film was dried on a hot plate at a temperature of 90° C. for 60 seconds, and then exposed to light at 300 mJ/cm ² to prepare a retardation material. This retardation material was cut with a cutter knife to form 5×5 squares at intervals of 1 mm vertically and horizontally. A cellophane tape peeling test was performed on the cuts using Scotch tape. The evaluation result was taken as "adhesion", and the number of squares that remained without peeling out of the 25 squares was recorded. For example, a score of 25/25 indicates that all the squares remain without peeling, and that the adhesion is high. The evaluation results are summarized in Table 3 below.

As shown in Table 3, the retardation materials obtained in Examples 15 to 24 exhibited good alignment and high adhesion.

In contrast, the retardation material obtained in Comparative Example 3 showed good alignment, but did not provide sufficient adhesion. The retardation material obtained in Comparative Example 4 was insufficient in both alignment and adhesion.

The cured film formed from the cured film-forming composition of the present invention is very useful as an alignment material for forming a liquid crystal alignment film of a liquid crystal display element or an optically anisotropic film provided inside or outside a liquid crystal display element. In particular, the cured film-forming composition of the present invention is suitable as a material for forming a cured film used in a patterned retardation material of a 3D display. Furthermore, the cured film-forming composition of the present invention is also suitable as a material for forming a cured film such as a protective film, a flat film, or an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element or an organic EL element, particularly as a material for forming an interlayer insulating film of a TFT type liquid crystal display element, a protective film of a color filter, or an insulating film of an organic EL element.

Claims (12)

(A) a polymer having a photoalignable group, a hydroxy group, and a polymerizable group containing a C═C double bond;
A cured film-forming composition comprising: (B) a crosslinking agent having two or more methylol groups or alkoxymethyl groups ; and (C) a crosslinking catalyst,
The compound which provides a polymerizable group containing a C═C double bond is either of the following (SC-1) and (SC-2):

(In the formula, ^X4 represents a polymerizable group containing a C=C double bond, ^L1 represents a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond or a urethane bond, ^Q1 and ^Q3 each independently represent an alkylene group having 2 to 10 carbon atoms, ^Q2 represents a divalent group having a structure derived from a dicarboxylic acid anhydride, and n represents a natural number from 1 to 10.) The cured film-forming composition according to claim 1, wherein the photoalignable group of 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 photoalignable group of component (A) is a cinnamoyl group. 3. The photoalignable group of the component (A) is a group having an azobenzene structure.
The cured film-forming composition according to claim 1. The cured film-forming composition according to any one of claims 1 to 4, further comprising (D) a polymer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group. The polymer of component (A) contains a structural unit having a hydroxyl group and a structural unit having a polymerizable group containing a C=C double bond, the proportion of the structural unit having the hydroxyl group is 20 mol% or more relative to 100 mol% of all structural units of the polymer, and the proportion of the structural unit having the polymerizable group containing the C=C double bond is 5 mol% or more relative to 100 mol% of all structural units of the polymer. The cured film-forming composition according to any one of claims 1 to 5. The cured film-forming composition according to any one of claims 1 to 6, which contains 5 to 500 parts by mass of a crosslinking agent (B) based on 100 parts by mass of the polymer (A). The cured film-forming composition according to any one of claims 1 to 7, which contains 0.01 to 20 parts by mass of a crosslinking catalyst (C) based on 100 parts by mass of the polymer (A). A cured film obtained from the cured film-forming composition according to any one of claims 1 to 8. An optical film having the cured film according to claim 9. An alignment material formed using the cured film according to claim 9. A phase difference material formed using the cured film according to claim 9.