TWI850195B - Cured film formation composition, orientation material and retardation material - Google Patents

Abstract

The present invention relates to a cured film forming composition which is used as an alignment material and, when a layer of polymerizable liquid crystal is arranged on it, forms a cured film exhibiting excellent liquid crystal alignment and light transmittance. The present invention relates to a cured film forming composition containing (A) a polymer having a photodimerization site and a self-crosslinking site, an alignment material characterized by the use of the composition, and a phase difference material characterized by the use of the composition.

Description

Cured film forming composition, alignment material and phase difference material

The present invention relates to a cured film forming composition of a liquid crystal alignment agent for light alignment by aligning liquid crystal molecules, an alignment material and a phase difference material obtained from the cured film forming composition. In particular, the present invention relates to a cured film forming composition of a liquid crystal alignment agent for light alignment, an alignment material and a phase difference material obtained from the cured film forming composition, which is used for a patterned phase difference material for a 3D display in a circularly polarized glasses method, or a phase difference material used in a circularly polarized plate used as an anti-reflection film for an organic EL display.

When a 3D display is performed by circularly polarized glasses, a phase difference material is usually arranged on a display element such as a liquid crystal panel that forms an image. The phase difference material is a phase difference material that is patterned, in which two types of phase difference regions with different phase difference characteristics are arranged in multiple numbers and regularly. In addition, in the following description, the patterned phase difference material that is to be arranged with multiple phase difference regions with different phase difference characteristics is referred to as a patterned phase difference material.

The patterned phase difference material is, for example, as disclosed in Patent Document 1, a phase difference material formed by polymerizable liquid crystal can be produced by optical mapping. The optical mapping of the phase difference material formed by polymerizable liquid crystal can utilize the known photo-alignment technology in the formation of alignment materials for liquid crystal panels. That is, a coating film formed by a photo-alignment material is set on a substrate, and two types of polarized light with different polarization directions are irradiated thereon. A photo-alignment film is obtained as an alignment material for forming two types of liquid crystal alignment regions with different alignment control directions for forming liquid crystal. A solution-like phase difference material containing polymerizable liquid crystal is applied on the photo-alignment film to achieve the alignment of the polymerizable liquid crystal. Thereafter, the aligned polymerizable liquid crystal is hardened to form a patterned phase difference material.

The anti-reflection film of the organic EL display is composed of a linear polarizer and a 1/4 wavelength phase difference plate. The linear polarizer converts the external light facing the image display panel into linear polarization, and then converts it into circular polarization by the 1/4 wavelength phase difference plate. Among them, the external light of the circular polarization is reflected on the surface of the image display panel, but the rotation direction of the polarization plane is reversed during the reflection. As a result, the reflected light is opposite to the incoming light, and after being converted into linear polarization in the direction blocked by the linear polarizer by the 1/4 wavelength phase difference plate, it is further blocked by the linear polarizer, and the emission to the outside is significantly suppressed.

Regarding the 1/4 wavelength phase difference plate, as described in Patent Document 2, when the 1/4 wavelength phase difference plate is formed by combining a 1/2 wavelength plate and a 1/4 wavelength plate, the optical film is formed by reverse dispersion characteristics. In the case of this method, for a wider wavelength band provided for the display of color images, a liquid crystal material with positive dispersion characteristics can be used to form an optical film with reverse dispersion characteristics.

In recent years, some people have proposed liquid crystal materials with reverse dispersion characteristics as liquid crystal materials applicable to the phase difference layer (Patent Documents 3, 4). Based on such liquid crystal materials with reverse dispersion characteristics, a 1/2 wavelength plate and a 1/4 wavelength plate are combined to form a 1/4 wavelength phase difference plate with two phase difference layers. Instead, the phase difference layer can be composed of a single layer to ensure reverse dispersion characteristics, thereby ensuring that the desired phase difference in a wider wavelength band can be achieved by simply constructing an optical film.

To align the liquid crystal, an alignment layer is used. As methods for forming the alignment layer, for example, a friction method or a photo-alignment method is known. The photo-alignment method is useful from the perspective that there is no static electricity or dust generation, which is a problem of the friction method, and that a quantitative alignment process can be controlled.

In the formation of alignment materials using the photoalignment method, acrylic resins or polyimide resins having photodimerization sites such as cinnamyl groups and chalcone groups on the side chains are known as available photoalignment materials. It has been reported that these resins can show the ability to control the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment) by irradiating them with polarized UV light (see Patent Documents 5 to 7).

In addition to the liquid crystal alignment ability, the alignment layer is also required to have solvent resistance. For example, the alignment layer is exposed to heat or solvents during the manufacturing process of the phase difference material. When the alignment layer is exposed to the solvent, there is a concern that the liquid crystal alignment ability may be significantly reduced.

Among them, for example, Patent Document 8 states that in order to obtain a stable liquid crystal alignment, a liquid crystal alignment agent containing a polymer component having a structure that can be crosslinked by light and a structure that can be crosslinked by heat, and a liquid crystal alignment agent containing a polymer component having a structure that can be crosslinked by light and a compound having a structure that can be crosslinked by heat are proposed.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Patent Publication No. 2005-49865

[Patent Document 2] Patent Publication No. 10-68816

[Patent Document 3] U.S. Patent No. 8119026 Specification

[Patent Document 4] Patent Publication No. 2009-179563

[Patent Document 5] Patent Gazette No. 3611342

[Patent Document 6] Patent Publication No. 2009-058584

[Patent Document 7] Patent Publication No. 2001-517719

[Patent Document 8] Patent Publication No. 4207430

As shown above, the phase difference material is composed of a layer of hardened polymerized liquid crystal laminated on the optical alignment film of the alignment material. Therefore, it is necessary to develop an alignment material with both excellent liquid crystal alignment and solvent resistance.

However, according to the inventor's review, it is known that acrylic resins having photodimerization sites such as cinnamyl or chalcone groups on the side chains cannot obtain sufficient characteristics when used to form phase difference materials. In particular, when these resins are irradiated with polarized UV to form alignment materials, a large amount of polarized UV exposure is required when the alignment materials are used to make phase difference materials composed of polymerizable liquid crystals. The polarized UV exposure must be more than the sufficient polarized UV exposure (for example, about 30 mJ/ ^cm2 ) for aligning liquid crystals used in general liquid crystal panels.

As the reason for the increase in polarized UV exposure, when the phase difference material is formed, unlike the liquid crystal used in the liquid crystal panel, the polymerizable liquid crystal is used in a solution state and is applied on the alignment material.

When forming alignment materials using acrylic resins with photodimerization sites such as cinnamyl groups on the side chains, photocrosslinking is performed on the acrylic resins by photodimerization reaction when polymerizable liquid crystals are to be aligned. Before the resistance to polymerizable liquid crystal solutions is shown, more exposure to polarized light is required. To align the liquid crystals of a liquid crystal panel, usually only the surface of the photoalignment alignment material is dimerized. However, when using the above-mentioned acrylic resins and other past materials, when solvent resistance is to be shown on the alignment material, the reaction must be carried out inside the alignment material, and more exposure is required. As a result, there is a problem that the alignment sensitivity of the past materials becomes very small.

Furthermore, when it is desired to show such solvent resistance on the resin of the above-mentioned conventional materials, it is known that there is a technology of adding a crosslinking agent. However, it is known that after the heat curing reaction by the crosslinking agent, a three-dimensional structure is formed inside the formed coating film, which will cause a decrease in light reactivity. In other words, the orientation sensitivity will be greatly reduced. Even if the crosslinking agent is added to the conventional material and used, the desired effect cannot be obtained.

From the above, it can be seen that the photo-alignment technology that can improve the alignment sensitivity of the alignment material and reduce the polarized UV exposure and the cured film forming composition of the photo-alignment liquid crystal alignment agent used to form the alignment material are expected. And the technology that can efficiently provide phase difference materials is expected.

The purpose of the present invention is based on the above insights or review results. That is, the purpose of the present invention is to provide an alignment material with excellent solvent resistance and capable of aligning polymerizable liquid crystals at high sensitivity, and further to provide a cured film forming composition that becomes a liquid crystal alignment agent for photo-alignment.

Other purposes and advantages of this invention can be seen from the following description.

The inventors of the present invention have conducted repeated detailed studies to achieve the above-mentioned purpose and have found that by selecting a cured film-forming material based on a cured film-forming composition containing (A) a polymer having a photodimerization site and a self-crosslinking site, a cured film having excellent solvent resistance and capable of aligning polymerizable liquid crystals at high sensitivity can be formed, thereby completing the present invention.

That is, as the first aspect of the present invention, it is about a cured film forming composition containing (A) a polymer having a photodimerization site and a self-crosslinking site.

As a second aspect, it is a cured film forming composition described in the first aspect that the self-crosslinking site of the component (A) is a hydroxymethyl group or an alkoxymethyl group.

As a third aspect, it is a cured film forming composition described in the first aspect or the second aspect, further containing (B) a monomer or polymer having at least one group selected from the group consisting of hydroxymethyl, alkoxymethyl, hydroxyl, carboxyl, amide, amino and alkoxysilyl groups.

As a fourth aspect, it is a cured film forming composition described in any one of the first to third aspects further containing (C) a crosslinking catalyst.

As a fifth aspect, it is a cured film forming composition described in any one of the first to fourth aspects, containing (D) a compound having one or more polymerizable groups and at least one group A selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, or at least one group that reacts with the group A.

As a sixth aspect, it is a cured film forming composition described in any one of the third to fifth aspects, containing 1 to 400 parts by mass of the component (B) relative to 100 parts by mass of the component (A).

As a seventh aspect, it is a cured film forming composition described in any one of aspects 4 to 6, containing 0.01 to 20 parts by mass of component (C) relative to 100 parts by mass of component (A).

As an eighth aspect, it is a cured film forming composition described in any one of aspects 5 to 7, containing 1 to 100 parts by mass of component (D) relative to 100 parts by mass of component (A).

As a ninth aspect, it is a cured film characterized by being obtained by curing the cured film forming composition described in any one of the first to eighth aspects.

As the tenth aspect, it is an alignment material characterized by being obtained by curing a cured film forming composition described in any one of the first to eighth aspects.

As the 11th aspect, it is about a phase difference material characterized by being formed by using a cured film obtained by using a cured film forming composition described in any one of the 1st to 8th aspects.

According to the present invention, a cured film having excellent solvent resistance and capable of aligning polymerizable liquid crystals at high sensitivity, and a cured film forming composition suitable for the formation can be provided.

According to the present invention, an alignment material with excellent liquid crystal alignment and light transmittance, and a phase difference material capable of achieving high-precision optical mapping can be provided.

<Hard film forming composition>

The cured film forming composition of the present invention is a polymer containing (A) a photodimerization site and a self-crosslinking site. In addition to the above-mentioned (A) component, the cured film forming composition of the present invention may further contain as a component (B) a monomer or polymer having two or more groups selected from the group consisting of hydroxymethyl, alkoxymethyl, hydroxyl, carboxyl, amide, amino and alkoxysilyl groups. It may also further contain a crosslinking catalyst as a component (C). It may further contain as a component (D) a compound having one or more polymerizable groups and at least one group A selected from the group consisting of hydroxyl, carboxyl, amide, amino and alkoxysilyl groups, or at least one group that reacts with the group A. Other additives may be contained without damaging the effects of the present invention.

The following is a detailed description of each ingredient.

<(A) Ingredients>

Component (A) is an acrylic copolymer having a photodimerization site and a self-crosslinking site.

In the present invention, as the acrylic copolymer, a copolymer obtained by polymerizing monomers having unsaturated double bonds such as acrylate, methacrylate, and styrene can be used.

The acrylic copolymer having a photodimerization site and a self-crosslinking site (hereinafter also referred to as a specific copolymer) of the component (A) may be an acrylic copolymer having such a structure, and the types of the main chain skeleton and side chains of the polymer constituting the acrylic copolymer are not particularly limited.

The so-called photodimerization site is a site that forms a dimer by light irradiation. Specific examples thereof include cinnamyl, chalcone, coumarin, anthracene, etc. Among these, cinnamyl is preferred because it has high transparency and photodimerization reactivity in the visible light region. The structure of a preferred cinnamyl is shown in the following formula [1] or formula [2].

In the above formula, ^X1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a biphenyl group. In this case, the phenyl group and the biphenyl group may be substituted by any one of a halogen atom, an alkyl group, an alkoxy group, and a cyano group. ^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, a phenyl group, a biphenyl group, and a cyclohexyl group may be bonded to the benzene ring via a single bond, an ether bond, an ester bond, an amide bond, or a urea bond.

The so-called self-crosslinking site is the site that bonds with each other to form a crosslinking structure, and examples thereof include alkoxymethylamide, hydroxymethylamide, alkoxysilyl, and blocked isocyanate groups.

The weight average molecular weight of the acrylic copolymer of component (A) is preferably 3,000 to 200,000, more preferably 4,000 to 150,000, and even more preferably 5,000 to 100,000. If the weight average molecular weight is too large, exceeding 200,000, the solubility in solvents and the handling properties will be reduced. If the weight average molecular weight is too small, less than 3,000, the curing during thermal curing will become insufficient, and the solvent resistance and heat resistance will be reduced.

As described above, the method for synthesizing the acrylic copolymer having a photodimerization site and a self-crosslinking site in the side chain as component (A) is simple to copolymerize a monomer having a photodimerization site and a monomer having a self-crosslinking group.

As monomers having a photodimerization site, for example, monomers having a cinnamoyl group, a chalcone group, a coumarin group, or an anthracene group can be cited. Among these, monomers having a cinnamoyl group that has good transparency and photodimerization reactivity in the visible light region are particularly preferred.

In particular, a monomer having a cinnamyl group having a structure represented by the above formula [1] or formula [2] is preferred. Specific examples of such a monomer are represented by the following formula [3] or formula [4].

In the above formula, ^X1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. In this case, the phenyl group and the biphenyl group may be substituted by any one of a halogen atom, an alkyl group, an alkoxy group and a cyano group. ^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, a phenyl group, a biphenyl group and a cyclohexyl group may be bonded to the benzene ring via a single bond, an ether bond, an ester bond, an amide bond or a urea bond. ^X3 and ^X5 each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, an aromatic cyclic group or an aliphatic cyclic group. The alkylene group having 1 to 20 carbon atoms may be branched or linear, may be substituted by a hydroxyl group, or may be interrupted by at least one bond selected from an ether bond, an ester bond, an amide bond, a urea bond, and a carbamate bond. ^X4 and ^X6 represent polymerizable groups. Specific examples of the polymerizable group include acryl, methacryl, styryl, maleimide, acrylamide, and methacrylamide.

Examples of monomers having a self-crosslinking site include (meth)acrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, and N-butoxymethyl (meth)acrylamide; monomers having an alkoxysilyl group, such as 3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropyl acrylate, 3-trimethoxysilylpropyl methacrylate, and 3-triethoxysilylpropyl methacrylate; and monomers having a blocked isocyanate group, such as methacrylate 2-(0-(1'-methylpropyleneamino)carboxylamino)ethyl, methacrylate 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl, and the like. The so-called (meth)acrylamide refers to both acrylamide and methacrylamide.

Furthermore, in the present invention, when a specific copolymer is to be obtained, in addition to the monomer having a photodimerization site and a self-crosslinking site (hereinafter also referred to as a specific functional group), the monomer and a copolymerizable monomer can be used in combination.

Specific examples of such monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

The following are specific examples of the aforementioned monomers, but are not limited to these.

Examples of the acrylate compound include methacrylate, ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, diethylene glycol monoacrylate, 2-(acryloyloxy)ethyl caprolactone, poly(ethylene glycol)ethyl ether acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, acrylic acid, mono-(2-(acryloyloxy)ethyl)phthalate, glycidyl acrylate, isopropyl acrylate, benzyl acrylate, and naphthalene acrylate. , anthracene acrylate, anthracene methacrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate and 8-ethyl-8-tricyclodecyl acrylate, etc.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, 2-(methacryloxy)ethyl caprolactone, 5-methacryloxy-6-hydroxynorbornene-2-carboxy-6-lactone, glycidyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracenyl methacrylate, anthracenyl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate and 8-ethyl-8-tricyclodecyl methacrylate, etc.

Examples of the aforementioned acrylamide compound include acrylamide, methacrylamide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)acrylamide.

Examples of the aforementioned vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-vinyl-7-oxacyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monocyclic oxide.

Examples of the aforementioned styrene compounds include styrene, methylstyrene, chlorostyrene, bromostyrene, etc.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-(hydroxyphenyl)maleimide, N-(carboxyphenyl)maleimide, and N-cyclohexylmaleimide.

The amount of each monomer used to obtain a specific polymer is based on the total amount of all monomers, with 25 to 90 mol% of monomers having photodimerization sites, 10 to 75 mol% of monomers having self-crosslinking sites, and preferably monomers without 0 to 65 mol% of specific functional groups. If the content of monomers having photodimerization sites is less than 25 mol%, it is difficult to give high sensitivity and good liquid crystal alignment. If the content of monomers having self-crosslinking sites is less than 10 mol%, it is difficult to give sufficient thermosetting properties and it is difficult to maintain high sensitivity and good liquid crystal alignment.

The method for obtaining the specific copolymer used in the present invention is not particularly limited, for example, it can be obtained by polymerization reaction at a temperature of 50 to 110°C in a solvent in which a monomer having a specific functional group and a monomer not having a specific functional group as required and a polymerization initiator coexist. At this time, the solvent used is any solvent that can dissolve the monomer having a specific functional group, the monomer not having a specific functional group as required, and the polymerization initiator, etc., and is not particularly limited. Specific examples are described in <Solvent> described later.

The specific copolymer obtained by the above method is usually in the form of a solution dissolved in a solvent.

Furthermore, the solution of the specific copolymer obtained by the above method is put into diethyl ether or water under stirring to reprecipitate, and the resulting precipitate is filtered. After washing, it is dried at room temperature or heated under normal pressure or reduced pressure to form a powder of the specific copolymer. Through the above operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer is obtained. If the purification cannot be fully achieved in one operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated.

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

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

<(B) Ingredients>

The cured film forming composition of the present invention may contain, as component (B), a monomer or polymer having at least one group selected from the group consisting of hydroxymethyl, alkoxymethyl, hydroxyl, carboxyl, amide, amino and alkoxysilyl.

Examples of monomers or polymers having two or more hydroxymethyl groups or alkoxymethyl groups include hydroxymethyl compounds such as alkoxymethylated ethylene glycol urea, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

Specific examples of alkoxymethylated glycol urea include 1,3,4,6-tetrakis(methoxymethyl)glycol urea, 1,3,4,6-tetrakis(butoxymethyl)glycol urea, 1,3,4,6-tetrakis(hydroxymethyl)glycol urea, 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-imidazolidinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone. As commercially available products, there are compounds such as ethylene glycol urea compounds (trade names: Cymel (registered trademark) 1170, Powder link (registered trademark) 1174) manufactured by Japan Cytec Industries (formerly Mitsui Cytec), methylated urea resins (trade names: UFR (registered trademark) 65), butylated urea resins (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea/formaldehyde resins (highly condensed type, trade names: Beccamine (registered trademark) J-300S, same as P-955, same as N) manufactured by DIC (formerly Dainippon Ink & Chemicals Co., Ltd.).

Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. Commercially available products include products manufactured by Japan Cytec Industries (Former Mitsui Cytec) (trade name: Cymel (registered trademark) 1123), and products manufactured by Sanwa Chemical (trade name: Nicarac (registered trademark) BX-4000, BX-37, BL-60, BX-55H).

Specific examples of alkoxymethylated melamine include hexamethoxymethyl melamine. As commercially available products, there are Methoxymethyl melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Japan Cytec Industries (Former Mitsui Cytec (Co., Ltd.), butoxymethyl melamine compounds (trade names: My coat (registered trademark) 506, 508), methoxymethyl melamine compounds (trade names: Nicarac (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, MX-035) manufactured by Sanwa Chemical (Co., Ltd.), butoxymethyl melamine compounds (trade names: Nicarac (registered trademark) MX-45, MX-410, MX-302), etc.

In addition, it may be a compound obtained by condensing a melamine compound, a urea compound, an ethylene glycol urea compound, and a benzoguanamine compound in which the hydrogen atom of such an amino group is replaced by a hydroxymethyl 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. Patent No. 6323310 may be cited. As a commercial product of the aforementioned melamine compound, a product name: Cymel (registered trademark) 303 may be cited, and as a commercial product of the aforementioned benzoguanamine compound, a product name: Cymel (registered trademark) 1123 (the above are manufactured by Japan Cytec Industries (Co., Ltd.) (Former Mitsui Cytec (Co., Ltd.)) may be cited, etc.

Furthermore, the carbinol group as component (B) and the polymer having two or more alkoxymethyl groups are polymers produced using acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl (i.e., hydroxymethyl) or alkoxymethyl groups such as N-hydroxymethacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylmethacrylamide, and N-butoxymethylmethacrylamide.

As such polymers, for example, poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzylmethacrylate, and copolymers of N-butoxymethylacrylamide, benzylmethacrylate and 2-hydroxypropylmethacrylate, etc. can be cited.

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

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

There is no particular limitation on the method for obtaining the above-mentioned polymer. To give an example, an acrylic polymer having a specific functional group is generated in advance by a polymerization method such as free radical polymerization. Then, the specific functional group reacts with a compound having an unsaturated bond at the end (hereinafter referred to as a specific compound), and a polymerizable group containing a C=C double bond can be introduced into the polymer of component (B).

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

For the above reaction, the preferred combination of the specific functional group and the functional group of the specific compound and the group related to the reaction is carboxyl and epoxy, hydroxyl and isocyanate, phenolic hydroxyl and epoxy, carboxyl and isocyanate, amine and isocyanate, or hydroxyl and acid chloride. A more preferred combination is carboxyl and glycidyl methacrylate, or hydroxyl and isocyanate ethyl methacrylate.

The weight average molecular weight (polystyrene conversion value) of such a polymer is 1,000~500,000, preferably 2,000~200,000, more preferably 3,000~150,000, and even more preferably 3,000~50,000.

In addition, as component (B), monomers or polymers having at least one group selected from the group consisting of hydroxyl, carboxyl, amide, amino, and alkoxysilyl groups, for example, acrylic polymers, polyamides, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylates, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polyalkylene imines, polyallylamines, celluloses (cellulose or its derivatives), phenol novolac resins, melamine formaldehyde resins, etc., polymers having a linear or branched structure, cyclic polymers such as cyclodextrins, etc. can be cited.

Preferred examples include acrylic polymers, hydroxyalkyl cyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols.

An acrylic polymer is a preferred example of a polymer as component (B), which is a polymer obtained by polymerizing monomers having unsaturated double bonds such as acrylic acid, methacrylic acid, styrene, and vinyl compounds. It can be a polymer obtained by polymerizing monomers containing monomers having specific functional groups or a mixture thereof. The main chain skeleton and side chain types constituting the acrylic polymer are not particularly limited.

Examples of monomers having specific functional groups include monomers having polyethylene glycol ester groups, monomers having hydroxyalkyl ester groups having 2 to 5 carbon atoms, monomers having phenolic hydroxyl groups, monomers having carboxyl groups, monomers having amino groups, and monomers having alkoxysilyl groups and acetoacetyl groups.

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

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

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

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

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

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

In addition, in the present embodiment, when synthesizing the acrylic polymer of the example of component (B), a monomer that does not have any of the groups represented by hydroxyl, carboxyl, amide, amino and alkoxysilyl groups may be used in combination without damaging the effects of the present invention.

Specific examples of the monomer include acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

Examples of the acrylate compound include methacrylate, ethylacrylate, isopropylacrylate, benzylacrylate, naphthaleneacrylate, anthracenylacrylate, anthracenylmethacrylate, phenylacrylate, 2,2,2-trifluoroethylacrylate, tert-butylacrylate, cyclohexylacrylate, isobornylacrylate, 2-methoxyethylacrylate, methoxytriethyleneglycolacrylate, 2-ethoxyethylacrylate, tetrahydrofurfurylacrylate, 3-methoxybutylacrylate, 2-methyl-2-adamantylacrylate, 2-propyl-2-adamantylacrylate, 8-methyl-8-tricyclodecylacrylate, and 8-ethyl-8-tricyclodecylacrylate.

Examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthalene methacrylate, anthracene methacrylate, anthracene methyl methacrylate, phenyl 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, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

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

Examples of styrene compounds include styrene, methylstyrene, chlorostyrene, bromostyrene, etc.

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

The amount of the monomer with a specific functional group used to obtain the acrylic polymer of component (B) is preferably 2 mol% or more based on the total amount of all monomers used to obtain the acrylic polymer of component (B). If the amount of the monomer with a specific functional group is too small, the solvent resistance of the resulting cured film is likely to become insufficient.

The method for obtaining the acrylic polymer of the example of component (B) is not particularly limited, and it can be obtained by, for example, subjecting a monomer containing a monomer having a specific functional group, a monomer not having a specific functional group as required, and a polymerization initiator to polymerization reaction at a temperature of 50°C to 110°C in a solvent in which the monomer containing the monomer having a specific functional group, a monomer not having a specific functional group as required, and a polymerization initiator are coexistent. The solvent used at this time is not particularly limited as long as it can dissolve the monomer having a specific functional group, the monomer not having a specific functional group as required, and the polymerization initiator. As a specific example, it is described in the item [Solvent] described later.

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

Furthermore, the solution of the acrylic polymer of the example of component (B) obtained by the above method is put into diethyl ether or water under stirring to reprecipitate, and the resulting precipitate is filtered and washed, and then dried at room temperature or heated under normal pressure or reduced pressure to obtain a powder of the acrylic polymer of the example of component (B). By the above operation, the polymerization initiator and unreacted monomer coexisting with the acrylic polymer of the example of component (B) can be removed, and as a result, a purified powder of the acrylic polymer of the example of component (B) can be obtained. If it is not possible to purify sufficiently in one operation, the obtained powder can be dissolved in a solvent again, and the above operation can be repeated.

The weight average molecular weight of the acrylic polymer of the preferred example of component (B) is preferably 3000-200000, preferably 4000-150000, and more preferably 5000-100000. If the weight average molecular weight is too large, exceeding 200000, the solubility in the solvent is reduced, resulting in a decrease in handling properties. If the weight average molecular weight is less than 3000, it becomes insufficiently cured during thermal curing, resulting in a decrease in solvent resistance. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample. The same applies to the following descriptions in this manual.

Next, polyether polyols which are preferably used as component (B) include polyethylene glycol, polypropylene glycol, propylene glycol, or polyols such as bisphenol A, triethylene glycol, and sorbitol to which propylene oxide or polyethylene glycol, polypropylene glycol, etc. are added. Specific examples of polyether polyols include Adeka polyether P series, G series, EDP series, BPX series, FC series, CM series manufactured by ADEKA, UNIOX (registered trademark) HC-40, HC-60, ST-30E, ST-40E, G-450, G-750 manufactured by NOF, UNIOL (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, non-ionic (registered trademark) LT-221, ST-221, OT-221, etc.

As a preferred example of the polyester polyol of the component (B), there can be cited a product obtained by reacting a polycarboxylic acid such as adipic acid, sebacic acid, and isophthalic acid with a diol such as ethylene glycol, propylene glycol, butanediol, polyethylene glycol, and polypropylene glycol. As specific examples of the polyester polyol, there can be cited 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-355, OD-X-355, OD-X-400, OD-X-401, OD-X-402, OD-X-403, OD-X-404, OD-X-405, OD-X-406, OD-X-407, OD-X-408, OD-X-409, OD-X-410, OD-X-411, OD-X-413, OD-X-414, OD-X-415 -X-2523, OD-X-2555, OD-X-2560, Kuraray polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, etc.

As a preferred example of the component (B), polycaprolactone polyols include those obtained by ring-opening polymerization of ε-caprolactone using a polyol such as trihydroxymethylpropane or ethylene glycol as an initiator. Specific examples of polycaprolactone polyols include Polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568 manufactured by DIC, Plaxel (registered trademark) 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320 manufactured by Daicell Chemical, etc.

As a preferred example of component (B), polycarbonate polyols include those obtained by reacting a polyol such as trihydroxymethylpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc. Specific examples of polycarbonate polyols include Plaxel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicellul Chemical, and C-590, C-1050, C-2050, C-2090, C-3090 manufactured by Kuraray, etc.

As a preferred example of cellulose as component (B), there can be cited hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyalkylalkylcelluloses such as hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, and hydroxyethylethylcellulose, and cellulose, etc. For example, hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose are preferred.

Preferred examples of the cyclodextrin as the polymer of component (B) 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- Ethyl-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, 2,3-dihydroxypropyl-γ-cyclodextrin and other hydroxyalkylcyclodextrins, etc.

Melamine formaldehyde resin, which is a preferred example of component (B), is a resin obtained by polycondensing melamine and formaldehyde, and is shown in the following formula.

In the above formula, ^R21 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents a natural number of the number of repeating units.

From the perspective of storage stability, melamine formaldehyde resins that are alkylated with hydroxymethyl groups generated by the polycondensation of melamine and formaldehyde are preferred.

There is no particular limitation on the method of obtaining melamine formaldehyde resin. Generally, melamine and formaldehyde are mixed, and then heated at 60℃~100℃ using weak alkalinity such as sodium carbonate or ammonia to synthesize. The hydroxymethyl group can be further alkoxylated by reacting with alcohol.

The weight average molecular weight of melamine formaldehyde resin is preferably 250~5000, preferably 300~4000, and more preferably 350~3500. If the weight average molecular weight is too large, exceeding 5000, the solubility in solvents will be reduced and the handling property will be reduced. If the weight average molecular weight is too small, less than 250, the curing will be insufficient during thermal curing and the solvent resistance will not be fully improved.

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

As a preferred example of the phenol novolac resin of component (B), phenol-formaldehyde polycondensate can be cited.

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

In addition, for the cured film forming composition of this embodiment, the component (B) may be a mixture of a plurality of monomers and polymers exemplified as the component (B).

The content of the (B) component in the cured film forming composition of the present invention is preferably 400 parts by mass or less, more preferably 10 parts by mass to 380 parts by mass, and more preferably 40 parts by mass to 360 parts by mass, based on 100 parts by mass of the total amount of the polymer of the (A) component. When the content of the (B) component is too large, the liquid crystal orientation is easily reduced.

<(C) Ingredients>

The cured film forming composition of the present invention may further contain a crosslinking catalyst as component (C) in addition to the aforementioned component (A).

As a crosslinking catalyst of component (C), for example, an acid or a thermal acid generator may be used. Component (C) is effective in promoting the thermal curing reaction of the curable film forming composition of the present invention.

(C) component, as the above-mentioned acid, specifically, a compound containing a sulfonic acid group, hydrochloric acid or its salt can be cited. As for the above-mentioned thermal acid generator, as long as it is a compound that generates an acid after thermal decomposition during heat treatment, that is, a compound that generates an acid after thermal decomposition at a temperature of 80°C to 250°C, it can be used without special limitation.

Specific examples of the above-mentioned acid include hydrochloric acid or its salt; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, trimethylbenzenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid and other sulfonic acid group-containing compounds or their hydrates or salts.

Examples of compounds that generate an acid by heat include bis(toluenesulfonyloxy)ethane, bis(toluenesulfonyloxy)propane, bis(toluenesulfonyloxy)butane, p-nitrobenzyl toluenesulfonate, o-nitrobenzyl toluenesulfonate, 1,2,3-phenylene thiophene (methanesulfonate), p-toluenesulfonate pyridinium salt, p-toluenesulfonate molarium salt, p-toluenesulfonate, Sulfonic 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-toluenesulfonate, N-ethyl-p-toluenesulfonamide, and further compounds represented by the following formulas can be cited:

The content of the component (C) in the cured film forming composition of the present invention is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the polymer of the component (A). When the content of the component (C) is set to 0.01 parts by mass or more, sufficient heat curing and solvent resistance can be imparted. However, if it is more than 20 parts by mass, the storage stability of the composition will be reduced.

<(D) Ingredients>

In the present invention, as component (D), a compound having one or more polymerizable groups and at least one group A selected from the group consisting of hydroxyl group, carboxyl group, amide group, amino group and alkoxysilyl group, or at least one group that reacts with the group A may be contained. This component can improve the adhesion of the formed cured film (hereinafter also referred to as adhesion improving component).

When the cured film formed by the cured film forming composition of the present embodiment containing the component (D) is used as an alignment material, in order to improve the adhesion between the alignment material and the polymerizable liquid crystal layer, the polymerizable functional group of the polymerizable liquid crystal and the cross-linking reaction site of the alignment material can be connected by a covalent bond. As a result, the phase difference material of the present embodiment formed by laminating the cured polymerizable liquid crystal on the alignment material of the present embodiment can maintain strong adhesion even under high temperature and high humidity conditions, and can show high durability against peeling, etc.

As component (D), monomers and polymers having a group selected from a hydroxyl group and an N-alkoxymethyl group and a polymerizable group are preferred.

As such a component (D), there can be cited compounds having a hydroxyl group and a (meth) acrylic group, compounds having an N-alkoxymethyl group and a (meth) acrylic group, polymers having an N-alkoxymethyl group and a (meth) acrylic group, etc. The following are specific examples of each.

As an example of component (D), a multifunctional acrylate containing a hydroxyl group (hereinafter also referred to as a multifunctional acrylate containing a hydroxyl group) can be cited.

Examples of multifunctional acrylates containing hydroxyl groups as component (D) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

As an example of component (D), a compound having one acrylic group and one or more hydroxyl groups can also be cited. In this way, a preferred example of a compound having one acrylic group and one or more hydroxyl groups can be cited. In addition, the compound of component (D) is not limited to the following compound examples.

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

In addition, as the compound of component (D), there can be cited a compound having at least one polymerizable group containing a C=C double bond and at least one N-alkoxymethyl group in one molecule.

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

As N of the N-alkoxymethyl group, i.e., the nitrogen atom, there can be cited the nitrogen atom of amide, the nitrogen atom of thiamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of carbamate, the nitrogen atom bonded to the adjacent position of the nitrogen atom of the nitrogen-containing heterocyclic ring, etc. Therefore, as the N-alkoxymethyl group, there can be selected a structure in which the alkoxymethyl group is bonded to the nitrogen atom such as the nitrogen atom of amide, the nitrogen atom of thiamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of carbamate, the nitrogen atom bonded to the adjacent position of the nitrogen atom of the nitrogen-containing heterocyclic ring, etc.

As the component (D), any compound having the above-mentioned group may be used, and for example, a compound represented by the following formula (X1) is preferred.

(wherein, R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms)

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

As specific examples of the compound represented by the above formula (X1), there can be cited hydroxymethyl or alkoxymethyl-substituted acrylamide compounds or methacrylamide compounds such as N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, and N-butoxymethyl (meth)acrylamide. The so-called (meth)acrylamide means both methacrylamide and acrylamide.

Another embodiment of the compound having a polymerizable group containing a C=C double bond and an N-alkoxymethyl group as component (D) is preferably a compound represented by the following formula (X2).

In the formula, R ⁵¹ represents a hydrogen atom or a methyl group.

R ⁵² represents an alkyl group having 2 to 20 carbon atoms, a monovalent aliphatic ring group having 5 to 6 carbon atoms, or a monovalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, and may contain an ether bond in the structure.

R ⁵³ represents a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent aliphatic ring group having 5 to 6 carbon atoms, or a divalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, and may contain an ether bond in the structure.

R ⁵⁴ represents a linear or branched divalent to 9valent aliphatic group having 1 to 20 carbon atoms, a divalent to 9valent aliphatic ring group having 5 to 6 carbon atoms, or a divalent to 9valent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, and one or more non-adjacent methyl groups of these groups may be substituted with an ether bond.

Z represents >NCOO- or -OCON< (wherein "-" represents one bond. Also, ">" and "<" represent two bonds, and an alkoxymethyl group (i.e., -OR ⁵² group) is bonded to any one of the bonds).

r is a natural number greater than 2 and less than 9.

Specific examples of the alkylene group having 2 to 20 carbon atoms in the definition of R ⁵³ include a divalent group obtained by further removing one hydrogen atom from an alkyl group having 2 to 20 carbon atoms.

Specific examples of the divalent to 9-valent aliphatic group having 1 to 20 carbon atoms in the definition of R ⁵⁴ include divalent to 9-valent groups obtained by further removing 1 to 8 hydrogen atoms from an alkyl group having 1 to 20 carbon atoms.

The alkyl group having 1 carbon atom is methyl. Specific examples of the alkyl group having 2 to 20 carbon atoms include ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl ...methyl-n-butyl, 1-methyl-n-butyl, 1-methyl-n-butyl, 1-methyl-n-butyl, 1-methyl-n-butyl, 1-methyl-n-butyl, 1-methyl-n-butyl, 1-methyl-n-butyl, 1 Methyl-n-propyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, cyclopentyl, cyclohexyl, groups in which one or more of these groups are bonded to carbon atoms ranging from 20, and groups in which the methyl group of one of these groups or multiple non-adjacent methyl groups can be replaced with ether bonds can be cited as examples.

Among them, an alkylene group having 2 to 10 carbon atoms is preferred, and R ⁵³ is an ethylene group and R ⁵⁴ is a hexylene group, which are particularly preferred from the viewpoint of being easily available from raw materials.

As specific examples of the alkyl group having 1 to 20 carbon atoms in the definition of R ⁵² , there can be cited the specific examples of the alkyl group having 2 to 20 carbon atoms in the definition of R ⁵³ and a methyl group. Among these, an alkyl group having 1 to 6 carbon atoms is preferred, and a methyl group, an ethyl group, an n-propyl group or an n-butyl group is particularly preferred.

As r, we can cite natural numbers from 2 to 9, among which 2 to 6 are the best.

The content of the (D) component in the cured film forming composition of the embodiment of the present invention is preferably 1 to 100 parts by mass, and more preferably 5 to 70 parts by mass, relative to 100 parts by mass of the polymer of the (A) component. When the content of the (D) component is 1 part by mass or more, the formed cured film can be given sufficient adhesion. However, if it is more than 100 parts by mass, the liquid crystal orientation is likely to decrease.

In addition, for the cured film forming composition of this embodiment, the (D) component may be a mixture of multiple types of compounds of the (D) component.

<Solvent>

The curable film forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used at this time can only dissolve the (A) component and the necessary (B) component, (C) component, (D) component and/or other additives described below, and there is no particular limitation on its type and structure.

Specific examples of the solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3- Methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxylate, 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, cyclopentyl methyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, etc.

When using the curing film forming composition of the present invention to form a curing film on a resin film and manufacturing an alignment material, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol, 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, etc. are preferably used as solvents that the resin film exhibits resistance to.

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

<Other additives>

The curing film forming composition of the present invention may contain adhesion promoter, silane coupling agent, surfactant, rheology modifier, pigment, dye, storage stabilizer, defoamer, antioxidant, etc. as necessary without damaging the effect of the present invention.

<Preparation of hardened film forming composition>

The curing film forming composition of the present invention is a polymer containing component (A), and may contain a polymer of component (B), a crosslinking catalyst of component (C), and an adhesion promoter of component (D) as necessary. It may also contain other additives without damaging the effect of the present invention. It is usually used in the form of a solution in which these are dissolved in a solvent.

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

[1]: A hardened film-forming composition containing component (A).

[2]: A curable film forming composition comprising component (A), 1 to 400 parts by mass of component (B) based on 100 parts by mass of component (A), and a solvent.

[3]: A curable film forming composition comprising component (A), 1 to 400 parts by mass of component (B) based on 100 parts by mass of component (A), 0.01 to 20 parts by mass of component (C) based on 100 parts by mass of the polymer of component (A), and a solvent.

[4]: A cured film forming composition comprising component (A), 1 to 400 parts by mass of component (B) based on 100 parts by mass of component (A), 0.01 to 20 parts by mass of component (C) based on 100 parts by mass of the polymer of component (A), 1 to 100 parts by mass of component (D) based on 100 parts by mass of the polymer of component (A), and a solvent.

The mixing ratio and preparation method when the curable film forming composition of the present invention is used as a solution are described in detail below.

The ratio of the solid components in the cured film forming composition of the present invention is not particularly limited as long as each component can be uniformly dissolved in the solvent, but is preferably 1% to 60% by mass, more preferably 2% to 50% by mass, and even more preferably 2% to 20% by mass. The so-called solid components refer to the total components of the cured film forming composition minus the solvent.

The preparation method of the curing film forming composition of the present invention is not particularly limited. As the preparation method, for example, a method of dissolving component (A) in a solvent, mixing component (B), component (C), component (D), etc. in a predetermined ratio as necessary to form a uniform solution, or a method of further adding other additives as necessary at an appropriate stage of the preparation method and mixing can be cited.

For the preparation of the curable film forming composition of the present invention, the solution of the specific copolymer (polymer) obtained by the polymerization reaction in the solvent can be used directly. At this time, for example, in the solution of the component (A), the components (B), (C), (D), etc. are added as necessary to form a uniform solution in the same manner as described above. At this time, the solvent can be added for the purpose of concentration adjustment. At this time, the solvent used in the generation process of the component (A) and the solvent used for concentration adjustment of the curable film forming composition can be the same or different.

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

<Hard film, orientation material and phase difference material>

The solution of the curable film forming composition of the present invention is applied to a substrate (e.g., a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a metal such as an aluminum, molybdenum, chromium, etc. coated substrate, a glass substrate, a quartz substrate, an ITO substrate, etc.) or a film substrate (e.g., a triacetyl cellulose (TAC) film, a polycarbonate (PC) film, a cycloolefin polymer (COP) film, a cycloolefin copolymer) Coating is performed on resin films such as carbon fiber (COC) film, polyethylene terephthalate (PET) film, acrylic film, polyethylene film, etc. by rod coating, rotary coating, flow coating, roller coating, slit coating, slit continuous rotary coating, inkjet coating, printing, etc. to form a coating film, and then heating and drying with a heating plate or oven to form a cured film. The cured film can be used directly as an alignment material.

As the conditions for heat drying, the components of the hardened film (alignment material) can be crosslinked by a crosslinking agent to the extent that they will not dissolve in the polymerizable liquid crystal solution after being applied thereon. For example, a heating temperature and heating time are appropriately selected within the range of 60°C to 200°C and 0.4 minutes to 60 minutes. The heating temperature and heating time are preferably 70°C to 160°C and 0.5 minutes to 10 minutes.

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

In order to make the alignment material formed by the cured film composition of the present invention solvent-resistant and heat-resistant, a phase difference material such as a polymerizable liquid crystal solution with vertical alignment is coated on the alignment material, and alignment can be performed on the alignment material. After the phase difference material in the alignment state is directly cured, a phase difference material as a layer with optical anisotropy can be formed. When the substrate forming the alignment material is a thin film, it can be used as a phase difference film.

Furthermore, by using two substrates with the alignment material of the present invention formed as described above, and by using a spacer to make the alignment materials on the two substrates face each other, liquid crystal is injected between these substrates, and the liquid crystal can also be used as an aligned liquid crystal display element.

Thus, the cured film forming composition of the present invention can be applied to the manufacture of various phase difference materials (phase difference films) or liquid crystal display elements.

[Implementation example]

The following are examples of the present invention to explain the present invention in detail, but the present invention is not limited to these examples.

[Abbreviations used in the examples]

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

<Raw materials>

CIN1

CIN2

CIN3

CIN4

GMA: Glycidyl Methacrylate

AIBN: α,α’-azobisisobutyronitrile

BMAA: N-Butoxymethylacrylamide

HEMA: 2-Hydroxyethyl methacrylate

MMA: Methyl methacrylate

<Ingredient B>

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

<Ingredient C>

PTSA: p-Toluenesulfonic acid, monohydrate

<Ingredient D>

D-1: A compound having a hydroxyl group and an acrylic group represented by the following structural formula

D-2: A compound having an N-alkoxymethyl group and an acrylic acid group as shown in the following structural formula

<Solvent>

Each resin composition of the embodiment and comparative example contains a solvent, and propylene glycol monomethyl ether (PM) and cyclohexanone (CH) are used as the solvent.

<Determination of molecular weight of polymer>

The molecular weight of the acrylic copolymer in the polymerization example was measured using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Corporation and columns (KD-803, KD-805) manufactured by Shodex Corporation as shown below.

In addition, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed as polystyrene conversion values.

Column temperature: 40℃

Solvent: Tetrahydrofuran

Flow rate: 1.0mL/min

Standard sample for preparing the standard curve: Standard polystyrene manufactured by Showa Denko K.K. (molecular weight: approximately 197,000, 55,100, 12,800, 3,950, 1,260, 580).

<Reference Example 1> Synthesis of CIN1

CIN1 was synthesized according to the synthesis method described in the Special Table No. 2013-514449.

<Reference Example 2> Synthesis of CIN2

Mix GMA 8.3g (58.4mmol), 4-methoxycinnamic acid 20.7g (116.2mmol), dibutylhydroxytoluene 0.2g, triphenylethylphosphonium bromide 0.3g, and dioxane 80mL, and heat at 90℃ for 3 days. After the reaction is completed, dioxane is distilled off under reduced pressure, 150mL of ethyl acetate is added, insoluble matter is filtered and separated, and then 100mL of sodium bicarbonate water is added to wash 3 times to remove excess methoxycinnamic acid. After distilling off ethyl acetate under reduced pressure, 16.5g of the target CIN2 (yield: 88%) is obtained.

<Reference Example 3> Synthesis of CIN3

CIN3 was synthesized according to the synthesis method described in the international publication WO2013/191251.

<Reference Example 4> Synthesis of CIN4

CIN4 was synthesized according to the synthesis method described in Macromolecules, 39, 9357-9364 (2006).

<Synthesis of component A> <Polymerization Example 1>

15.0g of CIN1, 1.7g of BMAA, and 0.4g of AIBN as a polymerization catalyst were dissolved in 123.4g of PM and 30.9g of CH. After reacting at 80°C for 20 hours, a solution containing 10% by weight of acrylic copolymer (PA-1) was obtained. The Mn of the obtained acrylic copolymer was 10,000 and the Mw was 29,000.

<Polymerization Example 2>

15.0g of CIN2, 1.7g of BMAA, and 0.5g of AIBN as a polymerization catalyst were dissolved in 155.9g of PM and reacted at 80°C for 20 hours to obtain a solution containing 10% by weight of acrylic copolymer (PA-2). The Mn of the obtained acrylic copolymer was 8,400 and the Mw was 18,000.

<Polymerization Example 3>

15.0g of CIN3, 1.4g of BMAA, and 0.4g of AIBN as a polymerization catalyst were dissolved in 120.3g of PM and 30.1g of CH. After reacting at 80°C for 20 hours, a solution containing 10% by weight of acrylic copolymer (PA-3) was obtained. The Mn of the obtained acrylic copolymer was 18,000 and the Mw was 55,000.

<Polymerization Example 4>

15.0g of CIN4, 1.8g of BMAA, and 0.9g of AIBN as a polymerization catalyst were dissolved in 111.5g of PM and 47.8g of CH, and reacted at 80°C for 20 hours. After that, a solution containing 10% by weight of acrylic copolymer (PA-4) was obtained. The Mn of the obtained acrylic copolymer was 9,000 and the Mw was 20,000.

<Polymerization Example 5>

10.0g of CIN3, 3.0g of BMAA, and 0.4g of AIBN as a polymerization catalyst were dissolved in 96.6g of PM and 24.2g of CH, and reacted at 80°C for 20 hours to obtain a solution containing 10% by weight of an acrylic copolymer (PA-5). The Mn of the obtained acrylic copolymer was 8,000 and the Mw was 20,000.

<Polymerization Example 6>

15.0g of CIN3, 0.9g of BMAA, 0.7g of HEMA, and 0.4g of AIBN as a polymerization catalyst were dissolved in 122.4g of PM and 30.6g of CH. After reacting at 80°C for 20 hours, a solution containing 10% by weight of acrylic copolymer (PA-6) was obtained. The Mn of the obtained acrylic copolymer was 11,000 and the Mw was 32,000.

<Polymerization Example 7>

15.0g of CIN3, 1.2g of HEMA, and 0.4g of AIBN as a polymerization catalyst were dissolved in 118.4g of PM and 29.6g of CH, and reacted at 80°C for 20 hours to obtain a solution containing 10% by weight of acrylic copolymer (PA-7). The Mn of the obtained acrylic copolymer was 10,000 and the Mw was 35,000.

<Polymerization Example 8>

15.0g of CIN2, 1.5g of HEMA, and 0.5g of AIBN as a polymerization catalyst were dissolved in 122.4g of PM and 30.6g of CH, and reacted at 80°C for 20 hours to obtain a solution containing 10% by weight of an acrylic copolymer (PA-8). The Mn of the obtained acrylic copolymer was 8,700 and the Mw was 28,000.

<Synthesis of component B> <Polymerization Example 9>

100.0g of BMAA and 4.2g of AIBN as a polymerization catalyst were dissolved in 193.5g of PM and reacted at 90°C for 20 hours to obtain an acrylic polymer solution. The Mn of the obtained acrylic polymer was 2,700 and the Mw was 3,900. The acrylic polymer solution was slowly dripped into 2000.0g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PB-1).

<Polymerization Example 10>

30.0g of MMA, 3.0g of HEMA, and 0.3g of AIBN as a polymerization catalyst were dissolved in 146.0g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was slowly dripped into 1000.0g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PB-2). The Mn of the obtained acrylic copolymer was 18,000 and the Mw was 32,800.

<Preparation of polymerizable liquid crystal solution>

29.0 g of polymerizable liquid crystal LC242 (manufactured by BASF), 0.9 g of IRGACURE907 (manufactured by BASF) as a polymerization initiator, 0.2 g of BYK-361N (manufactured by BYK) as a leveling agent, and cyclopentanone as a solvent were added to obtain a polymerizable liquid crystal solution (RM-1) with a solid content concentration of 30% by mass.

<Implementation Example 1>

The solution containing the acrylic copolymer (PA-1) obtained in the above-mentioned polymerization example 1 is equivalent to 100 parts by mass of the acrylic copolymer (PA-1) and 5 parts by mass of p-toluenesulfonic acid monohydrate. PM and CH are added here, and the solvent composition is PM:CH=80:20 (mass ratio), and the solid content concentration is 5.0 mass %. After filtering the solution with a filter with a pore size of 1μm, the liquid crystal alignment agent composition A-1 is prepared.

<Examples 2 to 10 and Comparative Examples 1 to 3>

In addition to the acrylic copolymer of component A and the types and amounts of other components as shown in Table 1, the same steps as in Example 1 were carried out to prepare liquid crystal alignment agent compositions A-2 to A-13.

<Examples 11 to 20 and Comparative Examples 4 to 6> [Evaluation of Orientation]

Each alignment agent composition of Examples 1 to 10 and Comparative Examples 1 to 3 was applied to a TAC film using a rod coater to a wet film thickness of 4 μm. Each was heated and dried in a heat circulation oven at a temperature of 110°C for 120 seconds to form a cured film on the TAC film. A 313nm linear polarized light was irradiated in a vertical direction at an exposure amount of 20mJ/ ^cm2 on each cured film to form an alignment material. A polymerizable liquid crystal solution (RM-1) was applied to the alignment material on the TAC film using a rod coater to a wet film thickness of 6 μm. After the coating was dried on a heating plate at a temperature of 90°C for 60 seconds, it was exposed at 300mJ/ ^cm2 to produce a phase difference material. The phase difference material on the prepared substrate was sandwiched between a pair of polarizing plates, and the phase difference characteristics of the phase difference material were observed. The phase difference without defects was evaluated as ○, and the phase difference without defects was evaluated as ×, and recorded in the "Orientation" column. The evaluation results are summarized in Table 2 described below.

As shown in Table 2, the phase difference materials obtained in Examples 11 to 20 show good orientation. In contrast, the phase difference materials obtained in Comparative Examples 4 to 6 do not have good orientation.

[Industrial Availability]

The cured film-forming composition obtained by the present invention is very useful as a material for forming a liquid crystal alignment film for a liquid crystal display element, or as an alignment material when an optical anisotropic film is to be set inside or outside a liquid crystal display element, and is particularly suitable as a material mainly composed of a phase difference material for a circular polarizing plate used as an anti-reflection film for an IPS-LCD or organic EL display.

Claims (10)

A cured film forming composition comprising (A) a photodimerization site that forms a dimer upon light irradiation, and a polymer having a hydroxymethyl group or an alkoxymethyl group as a crosslinking site that bonds with each other to form a crosslinking structure, wherein the monomer that imparts the photodimerization site to the polymer is a monomer represented by the following formula [3] or [4],

In the formula, ^X1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group; in this case, the phenyl group and the biphenyl group may be substituted by any one of a halogen atom, an alkyl group, an alkoxy group and a cyano group; ^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, a phenyl group, a biphenyl group and a cyclohexyl group may be bonded to the benzene ring via a single bond, an ether bond, an ester bond, an amide bond or a urea bond; ^X3 and X4 represent a halogen atom, an alkyl group having 1 to 18 carbon atoms ... ⁵ each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, an aromatic cyclic group or an aliphatic cyclic group; wherein the alkylene group having 1 to 20 carbon atoms may be branched or linear, may be substituted by a hydroxyl group, or may be interrupted by at least one bond selected from an ether bond, an ester bond, an amide bond, a urea bond and a carbamate bond; ^X4 and ^X6 represent polymerizable groups. The curing film forming composition of claim 1 further contains (B) a monomer or polymer having at least one group selected from the group consisting of hydroxymethyl, alkoxymethyl, hydroxyl, carboxyl, amide, amino and alkoxysilyl. The hardened film forming composition of claim 1 further contains (C) a crosslinking catalyst. The curable film forming composition of claim 1 further contains (D) a compound having one or more polymerizable groups and at least one group A selected from the group consisting of hydroxyl group, carboxyl group, amide group, amino group and alkoxysilyl group, or at least one group that reacts with the group A. The hardened film forming composition of claim 2, wherein for 100 parts by mass of component (A), 1 part by mass to 400 parts by mass of component (B) are contained. The hardened film forming composition of claim 3, wherein the component (C) is contained in an amount of 0.01 to 20 parts by mass for 100 parts by mass of the component (A). The hardened film forming composition of claim 4, wherein the component (D) is contained in an amount of 1 to 100 parts by mass for 100 parts by mass of the component (A). A cured film, characterized in that it is obtained by curing a cured film forming composition as described in any one of claims 1 to 7. An alignment material characterized by being obtained by curing a cured film-forming composition as described in any one of claims 1 to 7. A phase difference material characterized by being formed using a cured film obtained from a cured film forming composition as described in any one of claims 1 to 7.