TW202146566A - Cured film-forming composition, alignment material, and phase difference material - Google Patents

Abstract

To provide a cured film-forming composition that forms a cured film that exhibits an excellent adhesiveness for glass substrates and that exhibits excellent liquid crystal alignment properties and optical transparency when used as an alignment material and a layer of polymerizable liquid crystal is disposed thereon. A cured film-forming composition comprising (A) a polymer having a photoalignment group and a thermally crosslinkable group, (B) a crosslinking agent having a methylol group or alkoxymethyl group, and (C) an alkoxysilane having a thermally crosslinkable group different from the alkoxysilyl moiety. An alignment material characteristically obtained using the composition, and a phase difference material characteristically obtained using the composition.

Description

Cured film forming composition, alignment material and retardation material

The present invention relates to a liquid crystal alignment agent for photo-alignment, an alignment material and a retardation material for aligning liquid crystal molecules. In particular, the present invention relates to a patterned phase difference material for making a 3D display used in circularly polarized glasses, or a phase difference material used for a circularly polarizing plate used as an antireflection film of an organic EL display. Liquid crystal alignment agent for photo-alignment, alignment material and retardation material.

In the case of a 3D display of the circularly polarized glasses type, a retardation material is usually arranged on a display element that forms an image of a liquid crystal panel or the like. In this retardation material, two types of retardation regions with different retardation characteristics are arranged in a complex number and regularly, and a patterned retardation material is formed. Hereinafter, in this specification, a patterned phase difference material is referred to as a patterned phase difference material so as to arrange a plurality of phase difference regions having different phase difference characteristics.

A patterned retardation material, as disclosed in, for example, Patent Document 1, can be produced by optically patterning a retardation material composed of a polymerizable liquid crystal. The optical patterning of the retardation material composed of polymerizable liquid crystal is a known photo-alignment technique using the alignment material used in the liquid crystal panel. That is, a coating film made of a photo-alignment material is provided on the substrate, and two types of polarized light having different polarization directions are irradiated thereon. Furthermore, a photo-alignment film was obtained as an alignment material for forming two types of liquid crystal alignment regions in which the alignment control directions of the liquid crystal were different. A solution-like retardation material containing polymerizable liquid crystal is coated on the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Then, the aligned polymerizable liquid crystal is cured to form a patterned retardation material.

The anti-reflection film of the organic EL display is composed of a linear polarizer and a 1/4 wavelength retardation plate, and the light from the outside of the panel surface facing the image display panel is converted into linear polarized light by the linear polarizer. The 1/4 wavelength retardation plate is converted into circularly polarized light. Here, although the external light is reflected on the surface of the image display panel or the like by the circularly polarized light, the rotation direction of the polarized plane is reversed during the reflection. As a result, the reflected light is converted into linearly polarized light in the direction blocked by the linear polarizer by the 1/4 wavelength retardation plate, opposite to when it arrived, and then blocked by the linear polarizer. , significantly inhibits the emission to the outside.

Regarding this 1/4 wavelength retardation plate, Patent Document 2 proposes that a 1/4 wavelength retardation plate is formed by combining a 1/2 wavelength plate and a 1/4 wavelength plate, and this optical film is constituted by reverse dispersion characteristics method. In this method, an optical thin film can be formed by using a liquid crystal material with positive dispersion properties in a wide wavelength band for display of color images and with reverse dispersion properties.

In addition, in recent years, as a liquid crystal material applicable to this retardation layer, those having reverse dispersion properties have been proposed (Patent Documents 3 and 4). According to the liquid crystal material with such reverse dispersion characteristics, instead of combining the 1/2 wavelength plate and the 1/4 wavelength plate, a 1/4 wavelength retardation plate is formed by two retardation layers, and the retardation layer is formed by a single The layer structure can ensure the reverse dispersion characteristics, and thereby, an optical film that can ensure a desired retardation in a wide wavelength band can be realized with a simple structure.

An alignment layer is used to align the liquid crystal. As a method for forming an alignment layer, for example, a rubbing method and a photo-alignment method are known. The photo-alignment method does not have the problem of the rubbing method, ie, the generation of static electricity and dust, and is useful in that a quantitative alignment treatment can be controlled.

In the formation of an alignment material using a photo-alignment method, acrylic resins or polyimide resins having photodimerization sites such as cinnamyl groups and chalcone groups in their side chains are known as materials with photo-alignment properties that can be used. Wait. It is reported that these resins exhibit the performance of controlling the alignment of liquid crystal by irradiating polarized light UV (hereinafter, also referred to as liquid crystal alignment) (refer to Patent Documents 5 to 7).

Moreover, in addition to the liquid crystal alignment energy, solvent resistance is also required in the alignment layer. For example, the alignment layer may be exposed to heat or solvent during the manufacturing process of the retardation material. When the alignment layer is exposed to a solvent, the alignment energy of the liquid crystal may be significantly reduced.

Therefore, for example, in Patent Document 8, in order to obtain stabilized liquid crystal alignment energy, a liquid crystal alignment agent containing a polymer component having a structure capable of photocrosslinking reaction and a structure capable of being crosslinked by heat is proposed, and a liquid crystal alignment agent containing A liquid crystal aligning agent having a polymer component having a structure capable of photocrosslinking and a compound having a structure capable of being crosslinked by heat. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2005-49865 [Patent Document 2] Japanese Patent Application Laid-Open No. 10-68816 [Patent Document 3] Specification of US Patent No. 8119026 [Patent Document 4] Japanese Patent Laid-Open No. 2009-179563 [Patent Document 5] Japanese Patent No. 3611342 [Patent Document 6] Japanese Patent Laid-Open No. 2009-058584 [Patent Document 7] Japanese Patent Publication No. 2001-517719 [Patent Document 8] Japanese Patent No. 4207430

[The problem to be solved by the invention]

As described above, the retardation material is formed by laminating a layer of a cured polymerizable liquid crystal on the photo-alignment film of the alignment material. Therefore, it is necessary to develop an alignment material that can have both excellent liquid crystal alignment and solvent resistance.

However, according to the research of the present inventors, it was found that the acrylic resin having a photodimerization site such as a cinnamyl group or a chalcone group in its side chain does not have sufficient properties when applied to the formation of a retardation material. In particular, these resins are irradiated with polarized UV light to form an alignment material, and in order to produce a retardation material composed of a polymerizable liquid crystal by using the alignment material, a large amount of polarized light UV exposure is required. In order to align the liquid crystal for a normal liquid crystal panel, the amount of polarized UV exposure is more than a sufficient amount of polarized UV exposure (for example, about 30 mJ/cm ² ).

As a reason for increasing the amount of polarized UV exposure, when forming a retardation material, unlike liquid crystals for liquid crystal panels, polymerizable liquid crystals are used in a solution state and coated on an alignment material.

An acrylic resin or the like having a photodimerization site such as a cinnamyl group in its side chain is used to form an alignment material, and when a polymerizable liquid crystal is to be aligned, the acrylic resin or the like is subjected to photocrosslinking by a photodimerization reaction. Furthermore, it is necessary to perform polarized light irradiation with a large exposure amount until the resistance to the polymerizable liquid crystal solution is expressed. In order to align the liquid crystal of the liquid crystal panel, usually only the surface of the alignment material with photo-alignment properties is dimerized. However, in order to use conventional materials such as the above-mentioned acrylic resins, when showing solvent resistance to the alignment material, it is necessary to react to the inside of the alignment material, and more exposure is required. As a result, there is a problem that the alignment sensitivity of the conventional material is reduced to a very small level.

Moreover, in order to express such solvent resistance to the resin of the above-mentioned conventional material, the technique of adding a crosslinking agent is known. However, after the thermosetting reaction by the crosslinking agent was carried out, it was found that a 3-dimensional structure was formed in the inside of the formed coating film, and the photoreactivity was reduced. That is, the alignment sensitivity is greatly lowered, and even if a crosslinking agent is added to a conventional material, the desired effect cannot be obtained.

From the above, the photo-alignment technology that can improve the alignment sensitivity of the alignment material and reduce the UV exposure of polarized light, and the liquid crystal alignment agent for photo-alignment used in the formation of the alignment material are being sought. Furthermore, a technology that can provide a phase difference material with high efficiency is being sought.

In addition, although the conventional retardation material is produced by laminating an alignment material or liquid crystal on a thin film, by forming a direct alignment film on the glass substrate of the display element, a film is excluded from the retardation material, and an attempt is being made to reduce the cost. and thinning. In such a case, since sufficient adhesion to the glass surface is required in the alignment material, a technology that can achieve both high liquid crystal alignment and adhesion to a glass substrate is being sought.

The object of the present invention is accomplished based on the above findings or research results. That is, the object of the present invention is to provide a liquid crystal aligning agent for photo-alignment which has excellent solvent resistance, can align polymerizable liquid crystals with high sensitivity, and provides an alignment material excellent in adhesion to a glass substrate.

Other objects and advantages of the present invention will be apparent from the description below. [means to solve the problem]

The present inventors, as a result of repeated efforts to achieve the above object, found that by selecting (A) a reaction product of a polymer having an epoxy group and a specific cinnamic acid derivative, (B) having a hydroxymethyl group or The crosslinking agent of alkoxymethyl group, and (C) alkoxysilane having a crosslinking group different from the alkoxysilyl group part as the hard film forming material of the base, can be formed with excellent solvent resistance, In addition, the present invention can be completed as a cured film capable of aligning polymerizable liquid crystals with high sensitivity.

That is, the present invention relates to a cured film-forming composition containing: (A) a polymer having a photoalignment group and a thermally crosslinkable group, (B) a crosslinking agent having a methylol or alkoxymethyl group, and (C) The alkoxysilane which has a thermally crosslinkable group different from an alkoxysilyl group part. As a 2nd viewpoint, it is about the cured film formation composition as described in a 1st viewpoint which further contains (D) a crosslinking catalyst. As a 3rd viewpoint, it is about the cured film formation composition as described in a 1st viewpoint or a 2nd viewpoint which contains (E) has one or more radical polymerizable groups, and has a hydroxyl group and an N-alkoxy group selected from A compound containing the radical in the methyl group. As a 4th viewpoint, it is about the cured film forming composition described in any one of the 1st viewpoint to the 3rd viewpoint, which contains 1 mass part - 500 mass parts of (B) based on 100 mass parts of (A) components )Element. As a 5th viewpoint, it is about 100 of the total amount of the crosslinking agent with respect to (A) component and (B) component about the cured film forming composition as described in any one of the 1st viewpoint to the 4th viewpoint Part by mass, 0.001 parts by mass to 20 parts by mass of (C) component are contained. As a 6th viewpoint, it is about 100 of the total amount of the crosslinking agent with respect to (A) component and (B) component about the cured film forming composition as described in any one of the 2nd viewpoint to the 5th viewpoint Part by mass, 0.01 part by mass to 20 parts by mass of (D) component is contained. As a 7th viewpoint, it is about 100 of the total amount of the crosslinking agent with respect to (A) component and (B) component about the cured film forming composition as described in any one of the 3rd viewpoint to the 6th viewpoint Part by mass, 1 to 100 parts by mass of (E) component is contained. As a 8th viewpoint, it is about the cured film obtained by hardening the cured film-forming composition as described in any one of the 1st viewpoint to the 7th viewpoint. As a ninth viewpoint, it is about an alignment material obtained by hardening the cured film-forming composition described in any one of the first viewpoint to the seventh viewpoint. As a 10th viewpoint, it is about the retardation material characterized by using the cured film obtained from the cured film formation composition as described in any one of the 1st viewpoint to the 7th viewpoint, and it is formed. [Inventive effect]

According to the present invention, it is possible to provide a cured film which has excellent solvent resistance, can align polymerizable liquid crystals with high sensitivity, and is excellent in adhesion to a glass substrate, and a cured film-forming composition suitable for the formation thereon. According to the present invention, an alignment material excellent in liquid crystal alignment and light transmittance, and a retardation material capable of high-precision optical patterning can be provided.

<Curing film forming composition>

The cured film-forming composition of the present invention contains (A) a polymer having a photoalignment group and a thermal crosslinking group, (B) a crosslinking agent having a methylol or alkoxymethyl group, and (C) ) An alkoxysilane having a thermally crosslinkable group different from the alkoxysilyl moiety. In addition to the said (A) component, (B) component, and (C) component, the cured film formation composition of this invention may further contain a crosslinking catalyst as (D) component. Furthermore, as (E) component, the compound which has one or more radically polymerizable groups and has a group selected from a hydroxyl group and an N-alkoxymethyl group can be contained. Furthermore, other additives may be contained without impairing the effect of the present invention. Hereinafter, the details of each component will be described.

<(A) Ingredient> The component (A) in the cured film forming composition of the present invention is a polymer having a photoalignment group and a thermally crosslinkable group. That is, (A) component is a component which provides photo-alignment property to the cured film obtained from the cured-film formation composition of this invention, and (A) component is also called a photo-alignment component in this specification.

Component (A) contained in the cured film-forming composition of the present invention is a polymer having a photoalignment group, that is, as a photoalignment group, preferably, a structure having photodimerization or photoisomerization The polymer of the functional group of the site, especially the acrylic copolymer having at least a photodimerization site. Furthermore, in addition to the photodimerization site, it is desirable to have one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group (hereinafter, a group including these is also referred to as acrylic copolymers that are thermally cross-linked sites).

In the present invention, the term "acrylic copolymer" refers to a copolymer obtained by polymerizing monomers having unsaturated double bonds such as acrylate, methacrylate, and styrene.

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

As a photodimerization site|part, a cinnamyl group, a chalcone group, a coumarin group, an anthracenyl group, etc. are mentioned, for example. Among these, a cinnamonyl group is preferable from the viewpoint of the high transparency in the visible light region and the high photodimerization reactivity. As a more preferable cinnamyl group and a substituent containing a structure of a cinnamyl group, the structure represented by the following formula [1] or formula [2] can be mentioned. Furthermore, in this specification, even if the benzene ring of the cinnamyl group is a naphthalene ring, it is also included in the "cinnamyl group" and the "substituent containing a cinnamyl group structure".

In the above formula [1], X ¹ 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 with any one of a halogen atom and a cyano group.

In the above formula [2], X ² 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. At this time, the alkyl group, phenyl group, biphenyl group, and cyclohexyl group having 1 to 18 carbon atoms can pass through a bond selected from the group consisting of covalent bond, ether bond, ester bond, amide bond, urea bond, urethane bond, The amine bond, the carbonyl group, or a combination of one or two or more of these bonds are used to bond a plurality of types.

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

In the above formula [A1], formula [A2], formula [A3], formula [A4], formula [A5] and formula [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 thermal crosslinking site is a site bonded to the crosslinking agent of the component (B) by heating, and specific examples thereof include a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group.

The acrylic copolymer of the component (A) preferably has a weight average molecular weight of 3,000 to 200,000. If the weight-average molecular weight exceeds 200,000 and is too large, the solubility to the solvent may decrease and the handleability may be lowered. On the other hand, if the weight-average molecular weight is less than 3,000, if the weight-average molecular weight is too small, the curing is insufficient during thermal curing, and the decrease Solvent resistance or reduced heat resistance.

The method for synthesizing the acrylic copolymer having a photodimerization site and a thermal crosslinking site of the component (A) is a simple method of copolymerizing a monomer having a photodimerization site and a monomer having a thermal crosslinking site.

As a monomer which has a photodimerization site|part, the monomer which has a cinnamyl group, a chalcone group, a coumarin group, an anthracene group, etc. is mentioned, for example. Among these, a monomer having a cinnamyl group is particularly preferred from the viewpoint of high transparency in the visible light region and high photodimerization reactivity.

Among them, more preferred are a cinnamyl group having a structure represented by the above formula [1] or formula [2] and a monomer containing a substituent having a cinnamyl group structure. When a specific example of such a monomer is given, it is a monomer represented by following formula [3] or formula [4].

In the above formula [3], X ¹ 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 with any one of a halogen atom and 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], X ² 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, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, and a cyclohexyl group can 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], X ³ and X ⁵ each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring, and a divalent aliphatic ring. The alkylene group having 1 to 20 carbon atoms may be branched or linear.

In the above formula [3] and formula [4], X ⁴ represents a polymerizable group. As a specific example of this polymerizable group, an acrylyl group, a methacrylamide group, a styryl group, a maleimide group, an acrylamide group, a methacrylamido group, etc. are mentioned, for example.

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

Examples of the monomer having a thermally crosslinked site include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxypropyl methacrylate, -Hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol Alcohol 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, 5-methyl Acryloyloxy-6-hydroxynorbornene-2-carboxylic acid group (Carboxylic)-6-lactone and other monomers with hydroxyl groups; acrylic acid, methacrylic acid, crotonic acid, mono-(2-(propylene) Acrylooxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide Amine, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide and other monomers with carboxyl groups; hydroxystyrene, N-(hydroxyphenyl)methacrylamide, Monomers with phenolic hydroxyl groups such as N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)maleimide, N-(hydroxyphenyl)maleimide, etc.; acrylamide, Monomers with amide groups such as methacrylamido; methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, acryloyloxypropyl Monomers with alkoxysilyl groups such as acrylotrimethoxysilane, acryloxypropyltriethoxysilane, etc.

The amount of the monomer having a photodimerization site and the monomer having a thermal crosslinking site used to obtain the specific copolymer is based on the total amount of all monomers used to obtain the specific copolymer. The content of the monomer of the chemical moiety is 40% by mass to 95% by mass, and the content of the monomer having a thermal crosslinking site is preferably 5% by mass to 60% by mass. By setting the content of the monomer having a photodimerization site to 40% by mass or more, high sensitivity and favorable liquid crystal alignment can be imparted. On the other hand, by setting it as 95 mass % or less, sufficient thermosetting property can be provided, and high sensitivity and favorable liquid crystal orientation can be maintained.

Moreover, when a specific copolymer is obtained from the cured film-forming composition of the present invention, a monomer having a photodimerization site and a thermal crosslinking site (hereinafter, these are also referred to as specific functional groups) can be used together with a copolymerizable monomer. (hereinafter also referred to as monomers with non-reactive functional groups).

Specific examples of such monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like. Hereinafter, although specific examples of the above-mentioned monomers are given, the present invention is not limited to these.

Examples of the above-mentioned acrylate compound include methacrylate, ethacrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracenyl acrylate, anthracenyl methacrylate, phenyl Acrylates, 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, etc.

Examples of the above-mentioned methacrylate compound include methmethacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracenyl methacrylate, anthracenyl 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 ester, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, gamma-butyrolactone methacrylate, 2-propyl -2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, etc.

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

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

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

Although the method of obtaining the specific copolymer used in the cured film forming composition of the present invention is not particularly limited, for example, a monomer having a specific functional group (a monomer having a photodimerization site and a monomer having a thermal crosslinking site) is obtained. Monomer), a monomer having a non-reactive functional group as desired, and a solvent in which a polymerization initiator and the like coexist, and are obtained by carrying out a polymerization reaction at a temperature of 50°C to 110°C. At this time, the solvent to be used is not particularly limited as long as it dissolves a monomer having a specific functional group, a monomer having a non-reactive functional group, a polymerization initiator, and the like are used as desired. As a specific example, the solvent described in the solvent mentioned later is mentioned.

The specific copolymer obtained in this way is usually in the state of being dissolved in a solution of a solvent, and can be used directly as a solution of the component (A) in the present invention.

In addition, the solution of the specific copolymer obtained as described above is poured into diethyl ether, water, etc. with stirring to reprecipitate, and after filtering and washing the generated precipitate, the solution is placed under normal pressure or reduced pressure. It can be dried at room temperature or by heating to obtain a powder of a specific copolymer. By such an operation, the polymerization initiator or unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. When sufficient purification cannot be performed in one operation, the obtained powder may be redissolved in a solvent, and the above operation may be repeated.

In the cured film formation composition of this invention, the powder of the said specific copolymer can be used as it is as (A) component, or this powder can be redissolved in the solvent mentioned later, for example, and can be used as the state of a solution.

Moreover, as (A) component, the polymer obtained by making a cinnamic-acid derivative react in the polymer which has an epoxy group in a side chain can also be used.

The polymer having an epoxy group in a side chain may be, for example, a polymer of a polymerizable unsaturated compound having an epoxy group, or a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound.

Specific examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-Butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, methacrylate Ethyl acrylate-6,7-epoxyheptyl, α-ethylacrylate-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether , p-vinylbenzyl glycidyl ether, etc.

Examples of other polymerizable unsaturated compounds include alkyl (meth)acrylate, cyclic alkyl (meth)acrylate, aryl methacrylate, aryl acrylate, unsaturated dicarboxylic acid diester, Bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, and others Polymerizable unsaturated compound.

As specific examples of these, the alkyl methacrylates include, for example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxyl methacrylate. Butyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloyloxyethyl glycoside, 4-hydroxyphenyl methacrylate, methmethacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl Methacrylate, tridecyl methacrylate, n-stearyl methacrylate, etc.; as alkyl acrylate, for example, methacrylate, isopropyl acrylate, etc.; as methacrylic acid Cyclic alkyl esters include, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate, tricyclic [5.2.1.0 ^2,6 ] Decan-8-yloxyethyl methacrylate, isobornyl methacrylate, cholestanyl methacrylate, etc.; as acrylic cyclic alkyl Examples of esters include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate, tricyclo[5.2.1.0 ^2,6 ]decane -8-yloxyethyl acrylate, isocamphenyl acrylate, cholestanyl acrylate, etc.; aryl methacrylate, phenyl methacrylate, benzyl methacrylate, etc. acrylic acid aryl ester, for example, phenyl acrylate, benzyl acrylate, etc.; unsaturated dicarboxylic acid diester, for example, diethyl maleate, diethyl fumarate, Diethylconate, etc.;

Examples of bicyclic unsaturated compounds include bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, and 5-ethylbicyclo[2.2. 1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dimethyl Oxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2 .1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene , 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5- Hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, etc.; as maleimide compounds such as phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N- -Succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide iminopropionate, N-(9-acridinyl)maleimide, etc.; as unsaturated aromatic compounds, for example, styrene, α-methylstyrene, m-methylstyrene, p -Methylstyrene, vinyltoluene, p-methoxystyrene, etc.; as conjugated diene compounds, 1,3-butadiene, isoprene, 2,3-dimethyl- 1,3-butadiene, etc.; as unsaturated monocarboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid, etc.; as unsaturated dicarboxylic acid, maleic acid, fumaric acid, citraconic acid, Mesaconic acid, itaconic acid, etc.; Examples of unsaturated dicarboxylic acid anhydrides include the anhydrides of the above-mentioned unsaturated dicarboxylic acids; Examples of polymerizable unsaturated compounds other than the above include acrylonitrile, methacrylonitrile, chlorine Ethylene, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, etc.

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

The synthesis of the polymer having an epoxy group can preferably be carried out by a known radical polymerization method in a solvent in the presence of a suitable polymerization initiator.

As a polymer which has an epoxy group in a side chain, a commercial item can be used. Examples of such commercially available products include EHPE3150, EHPE3150CE (the above are manufactured by Daicel Chemical Industry Co., Ltd.), UG-4010, UG-4035, UG-4040, and UG-4070 (the above are ALUFON series manufactured by Toagosei Co., Ltd.) ), ECN-1299 (manufactured by Asahi Kasei Co., Ltd.), DEN431, DEN438 (manufactured by The Dow Chemical Co., Ltd.), jER-152 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-660, N-665, N -670, N-673, N-695, N-740, N-770, N-775 (the above are manufactured by Dainippon Ink Chemical Industry Co., Ltd.), EOCN-1020, EOCN-102S, EOCN-104S (the above are Nippon Kayaku Co., Ltd.), etc.

(式中，R¹ 係表示氫原子、鹵素原子、C₁ ~C₆ 烷基、C₁ ~C₆ 烷氧基等)之任一者表示之化合物等。 又，作為具有羧基之肉桂酸衍生物，在上述之式[3]表示之單體，亦適合使用X¹ 為氫原子之化合物。Examples of the cinnamic acid derivatives having a carboxyl group include the following formulae (1-1) to (1-5)

(In the formula, R ¹ represents a compound represented by any one of a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C _{6 alkoxy group, and the like).} In addition, as the cinnamic acid derivative having a carboxyl group, a ^{compound in which X 1} is a hydrogen atom is also suitably used as the monomer represented by the above formula [3].

The compound represented by the above formula (1) can be synthesized by appropriate combination of methods of organic chemistry.

The reaction product of the above-mentioned polymer having an epoxy group in the side chain and a specific cinnamic acid derivative can be obtained by combining the above-mentioned polymer with an epoxy group and a specific cinnamic acid derivative, preferably in contact with each other. In the presence of a solvent, it is more preferable to perform a reaction in an appropriate organic solvent to synthesize. The use ratio of the cinnamic acid derivative used in the reaction is preferably 0.01-1.5 mol, more preferably 0.05-1.3 mol, relative to 1 mol of epoxy groups contained in the polymer having epoxy groups , and more preferably 0.1~1.1 mol. As an organic catalyst which can be used here, a well-known compound can be used as a so-called hardening accelerator which accelerates the reaction of an organic base or an epoxy compound and an acid anhydride.

As the above-mentioned organic bases, for example, ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, pyrrole's 1st to 2nd order organic amines; such as triethylamine, tri-n-propylamine, Tri-n-butylamine, pyridine, 4-dimethylaminopyridine, 3rd grade organic amine of diazabicycloundecene; such as 4th grade organic amine of tetramethylammonium hydroxide, etc. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine are preferred; The 4th grade organic amine of methyl ammonium hydroxide.

As the above-mentioned hardening accelerators, for example, tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, and triethanolamine can be listed; 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 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-bis(hydroxymethyl)imidazole, 1-(2-cyano) ethyl)-2-phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecyl Imidazolium trimellitate, 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methyl Imidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2,4-diamino-6 -(2'-n-Undecylimidazolyl)ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1' )] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6-[2 '-Methylimidazolyl-(1')] ethyl-s-triazine is an imidazole compound of isocyanuric acid adduct; such as diphenylphosphine, triphenylphosphine, organophosphorus of triphenylphosphite compound;

Such as benzyl triphenyl phosphonium chloride, tetra-n-butyl phosphonium bromide, methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, n-butyl triphenyl phosphonium bromide, tetra Phenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o,o-diethylthiodiphosphonate (Phosphorodithionate), tetra- 4th order phosphonium salt of n-butylphosphonium benzotriazole salt, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate ; Such as 1,8-diazabicyclo[5.4.0]undecene-7 or the diazabicycloalkene of its organic acid salt; such as zinc octoate, tin octoate, aluminum acetylacetone complex Organometallic compounds; such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride quaternary ammonium salt; such as boron trifluoride , boron compounds of triphenyl borate; metal halogen compounds such as zinc chloride and tin chloride; amine addition accelerators such as dicyandiamide or adducts of amines and epoxy resins, etc. High melting point dispersion potential Hardening accelerator; Microcapsule type latent hardening accelerator in which the surface of hardening accelerator such as the aforementioned imidazole compound, organophosphorus compound or quaternary phosphonium salt is coated with polymer; Amine salt type latent hardening agent accelerator; Lewis acid Salts, Bronsted acid salts, etc., high temperature dissociation type, thermal cationic polymerization type latent hardening accelerators, etc. latent hardening accelerators, etc.

Among these, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride are preferred.

The usage ratio of the catalyst is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and even more preferably 0.1 to 20 parts by weight, relative to 100 parts by weight of the polymer having an epoxy group.

As said organic solvent, a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, an alcohol compound etc. are mentioned, for example. Among these, ether compounds, ester compounds, ketone compounds, and alcohol compounds are preferred from the viewpoints of solubility of raw materials and products, and ease of purification of products. The solid content concentration of the solvent (the weight of the components other than the solvent in the reaction solution is the ratio of the total weight of the solution) is preferably used in an amount of 0.1% by weight or more, more preferably 5 to 50% by weight.

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.

In this way, a solution containing a reaction product of a polymer having an epoxy group and a specific cinnamic acid derivative is obtained. This solution can be directly used for the preparation of liquid crystal alignment agent, in addition to the polymer contained in the isolated solution, and can be used for the preparation of liquid crystal alignment agent, or in addition to purifying the isolated polymer, and can be used for liquid crystal alignment preparation of the agent.

Moreover, in this embodiment, the acrylic copolymer of (A) component may be a mixture of a plurality of specific copolymers.

As described above, in the present invention, a high molecular weight specific copolymer can be used as the component (A). Moreover, (A) component may be a mixture of 1 or more types of specific copolymers.

<(B) component> The (B) component of the cured film formation composition of this invention is a crosslinking agent which has a methylol group or an alkoxymethyl group. As a crosslinking agent of (B) component, the crosslinking agent which has, for example, two or more methylol groups or an alkoxymethyl group is preferable. Examples of compounds having such groups include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

Specific examples of the alkoxymethylated glycoluril include, for example, 1,3,4,6-tetra(methoxymethyl)glycoluril, 1,3,4,6-tetra(butoxymethyl) ) glycoluril, 1,3,4,6-tetra(hydroxymethyl) glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetra(butoxymethyl)urea , 1,1,3,3-tetra(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-tetrahydroimidazolone and 1,3-bis( Methoxymethyl)-4,5-dimethoxy-2-tetrahydroimidazolone, etc. Commercially available products include compounds such as glycoluril compounds (trade names: CYMEL (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Nippon Cytec・Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.), methyl Urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC (stock) (formerly Urea/formaldehyde resin (high condensation type, trade name: BECKAMINE (registered trademark) J-300S, same as P-955, same as N), manufactured by Dainippon Ink Chemical Industry Co., Ltd.

Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. Commercially available products include Cytec・Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) (trade name: CYMEL (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: NIKALACK (registered trademark) ) BX-4000, same as BX-37, same as BL-60, same as BX-55H) etc.

As a specific example of alkoxymethylated melamine, hexamethoxymethyl melamine etc. are mentioned, for example. Examples of commercially available products include methoxymethyl-type melamine compounds (trade name: CYMEL (registered trademark) 300, same 301, same 303, and same 350 manufactured by Nippon Cytec・Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.)) ), butoxymethyl-type melamine compound (trade name: MYCOAT (registered trademark) 506, Tong 508), methoxymethyl-type melamine compound (trade name: NIKALACK (registered trademark) MW) manufactured by Sanwa Chemical Co., Ltd. -30, same as MW-22, same as MW-11, same as MS-001, same as MX-002, same as MX-730, same as MX-750, same as MX-035), butoxymethyl melamine compound (trade name : NIKALACK (registered trademark) MX-45, same as MX-410, same as MX-302) etc.

Moreover, the compound obtained by condensing such a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amine group is substituted with a methylol group or an alkoxymethyl group may be used. For example, high molecular weight compounds produced from melamine compounds and benzoguanamine compounds described in US Pat. No. 6,323,310 can be mentioned. As a commercial item of the said melamine compound, a trade name: CYMEL (registered trademark) 303 etc. are mentioned, as a commercial item of the said benzoguanamine compound, a trade name: CYMEL (registered trademark) 1123 (above, Japan Cytec ･Industries (Co., Ltd.) (former Mitsui Cytec Co., Ltd.), etc.

Furthermore, as a crosslinking agent of the (B) component, N-hydroxymethyl acrylamide, N-methoxymethylmethacrylamide, N-ethoxymethyl acrylamide can also be used. , N-butoxymethyl methacrylamide and other hydroxymethyl (ie methylol) or alkoxymethyl substituted acrylamide compounds or methacrylamide compounds produced polymers.

Examples of such polymers include poly(N-butoxymethacrylamide), copolymers of N-butoxymethacrylamide and styrene, and N-hydroxymethylmethacrylamide. Copolymers of amines and methmethacrylates, copolymers of N-ethoxymethylmethacrylamides and benzyl methacrylates, and N-butoxymethacrylamides and benzylmethyl Copolymer of acrylic acid ester and 2-hydroxypropyl methacrylate, etc.

The weight average molecular weight (in terms of polystyrene) of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, still 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 the component (B) in the cured film forming composition of the present invention is preferably 1 part by mass to 500 parts by mass, more preferably 5 parts by mass, based on 100 parts by mass of the polymer of the component (A) ~400 parts by mass.

式(5)中，R⁹ 係表示甲基或乙基。X係表示水解性基。Y係表示熱交聯性基。m為0~3之整數。n為0~3之整數。<(C)component> The composition of this invention contains the alkoxysilane which has a thermally crosslinkable group different from an alkoxysilyl group part. As said alkoxysilane, the silane compound represented by following formula (5) is preferable.

In formula (5), R ⁹ represents a methyl group or an ethyl group. X represents a hydrolyzable group. Y represents a thermally crosslinkable group. m is an integer from 0 to 3. n is an integer from 0 to 3.

Examples of the hydrolyzable group represented by X include a halogen atom, an alkoxy group having 1 to 3 carbon atoms, and an alkoxyalkoxy group having 2 to 4 carbon atoms. As said halogen atom, a chlorine atom, a bromine atom, etc. are mentioned. The alkoxy group having 1 to 3 carbon atoms is preferably linear or branched, and specifically, is a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. In addition, as the alkoxyalkoxy group having 2 to 4 carbon atoms, specifically, methoxymethoxy, 2-methoxyethoxy, ethoxymethoxy, and 2-ethoxyethyl Oxygen.

Examples of thermally crosslinkable groups different from the alkoxysilyl moiety represented by Y include a hydroxyl group, a mercapto group, a urea group, an isocyanate group, a group having an epoxy structure, a group having a propylene oxide (Oxetane) structure, and an amine. group and acryloxy group (CH ₂ =CHCOO) and the like. Among them, groups having a urea group, an isocyanate group, and an epoxy group are preferable in that they exhibit adhesion with a small amount added.

Specific examples of the alkoxysilane having a crosslinkable group of the component (C) include 3-hydroxypropyltrichlorosilane, 3-hydroxypropyltrimethoxysilane, and 3-hydroxypropyltriethoxy Silane, 3-hydroxypropylmethyldimethoxysilane, 3-hydroxypropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3 -Isocyanatopropyltrimethoxysilane, 3-Isocyanatopropyltriethoxysilane, 3-Isocyanatopropylmethyldimethoxysilane, 3-Isocyanatopropyl Methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane , 3-(3-ethyl oxide propane (Oxetane)-3-ylmethyloxy) propyl trimethoxysilane, 3-(3-ethyl oxide propane (Oxetane)-3-yl methyloxy propyl) propyl triethoxy silane, 3-(3-ethyl propylene oxide (Oxetane)-3-ylmethyloxy) propyl methyl dimethoxy silane, 3-(3-ethyl ring Oxetane-3-ylmethyloxy)propylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-(aminopropyltriethoxysilane, 3- Aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane Ethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane, etc.

Among them, particularly preferred are 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethyl Oxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethyl Oxysilane, 3-Isocyanatopropylmethyldimethoxysilane, 3-Isocyanatopropylmethyldiethoxysilane, 3-Glycidyloxypropyltrimethoxysilane, 3 - Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. As an alkoxysilane which has the crosslinkable group of the said (C)component, a commercial item can be used.

The content of the alkoxysilane having a crosslinkable group in the (C) component of the composition of the present invention is preferably 0.001 to 20 parts by mass, more preferably 0.001 to 20 parts by mass relative to 100 parts by mass of the polymer of the (A) component 0.01 to 8 parts by mass, more preferably 0.05 to 4 parts by mass.

＜(D)component＞ The cured film formation composition of this invention may contain a crosslinking catalyst as (D)component in addition to said (A) component, (B) component, and (C)component.

As a crosslinking catalyst of (D)component, for example, an acid or a thermal acid generator can be used suitably. This (D)component is effective in promoting the thermosetting reaction of the cured film-forming composition of this invention.

(D) Component specifically, as said acid, the compound containing a sulfonic acid group, hydrochloric acid, or its salt are mentioned. In addition, as the thermal acid generator, if it is a compound that thermally decomposes during heat treatment to generate an acid, that is, a compound that thermally decomposes at a temperature of 80°C to 250°C to generate an acid, it is not particularly limited. Qualifier.

Specific examples of the acid include hydrochloric acid or its salt; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, and p-toluene Sulfonic 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-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane- A sulfonic acid group-containing compound such as 1-sulfonic acid and dodecylbenzenesulfonic acid, or a hydrate or salt thereof.

Further, examples of compounds that generate an acid by heat include bis(p-toluenesulfonyl (Tosyl)oxy)ethane, bis(p-toluenesulfonyl (Tosyl)oxy)propane, bis(p-toluenesulfonyl) Acetyl (Tosyl) oxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylene (methylsulfonate) , p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morpholinium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonate Isobutyl sulfonate, methyl p-toluenesulfonate, phenethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluene Sulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-p-toluenesulfonamide, and further compounds represented by the following formula:

等。

Wait.

The content of the component (D) in the cured film-forming composition of the present invention is preferably 0.01 part by mass to 100 parts by mass of the total amount of the polymer of the component (A) and the crosslinking agent of the component (B) 20 parts by mass, more preferably 0.1 parts by mass to 15 parts by mass, still more preferably 0.5 parts by mass to 10 parts by mass. By making content of (D)component 0.01 mass part or more, sufficient thermosetting property and solvent resistance can be provided. However, when it is more than 20 parts by mass, the storage stability of the composition may be lowered.

<(E) Ingredient> The present invention may contain, as the component (E), a compound having one or more radically polymerizable groups and having a group selected from a hydroxyl group and an N-alkoxymethyl group. (E) A component is used as a component (henceforth, it is also called an adhesion improvement component) which improves the adhesiveness of the formed cured film and a liquid crystal layer.

When the cured film formed from the cured film forming composition of the present embodiment containing the component (E) is used as an alignment material, if the adhesion between the alignment material and the layer of the polymerizable liquid crystal is improved, the polymerizable liquid crystal can be polymerized The functional group and the cross-linking reaction site of the alignment material are linked by covalent bonds. As a result, the retardation material of the present embodiment, which is formed by laminating the hardened polymerizable liquid crystal on the alignment material of the present embodiment, can maintain strong adhesion even under high temperature and high-quality conditions, and can exhibit resistance to peeling. Equally high durability.

As the component (E), a monomer and a polymer having a group selected from a hydroxyl group, an N-alkoxymethyl group, and a polymerizable group are preferable. As such (E) component, the compound which has a hydroxyl group and (meth)acryloyl group, the compound which has N-alkoxymethyl group and (meth)acryloyl group, the compound which has N-alkoxymethyl group, Polymers of (meth)acryloyl and (meth)acryloyl groups, etc. Specific examples are shown below.

As one example of the component (E), a hydroxyl group-containing polyfunctional acrylate (hereinafter also referred to as a hydroxyl group-containing polyfunctional acrylate) can be mentioned. As an example of (E) component, the polyfunctional acrylate containing a hydroxyl group is mentioned, for example, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. are mentioned.

As an example of (E) component, the compound which has one acrylyl group and one or more hydroxyl groups can also be mentioned. A preferable example of the compound which has such one acrylyl group and one or more hydroxyl groups is mentioned. Furthermore, the compound of the component (E) is not limited to the following compound examples.

(上述式中，R¹¹ 係表示氫原子或甲基，m係表示1~10之整數)。

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

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

As a polymerizable group containing a C=C double bond, an acryl group, a methacryl group, a vinyl group, an allyl group, a maleimide group, etc. are mentioned.

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

(式中，R³¹ 係表示氫原子或甲基，R³² 係表示氫原子，或是直鏈或分枝之碳原子數1至10之烷基)As (E) component, although what has the above-mentioned group may be sufficient, for example, the compound represented by following formula (X1) is mentioned preferably.

(In the formula, R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 10 carbon atoms)

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and 1-methyl. yl-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 yl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2-ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl, n-nonyl, n-decyl, etc.

Specific examples of the compound represented by the above formula (X1) include N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl Hydroxymethyl or alkoxymethyl substituted acrylamide compounds or methacrylamide compounds such as N-butoxymethyl (meth) acrylamide and N-butoxymethyl (meth) acrylamide. In addition, the so-called (meth)acrylamide means both methacrylamide and acrylamide.

式中，R⁵¹ 係表示氫原子或甲基。 R⁵² 係表示碳原子數2至20之烷基、碳原子數5至6之1價脂肪族環基，或是包含碳原子數5至6之脂肪族環之1價脂肪族基，可於構造中包含醚鍵。 R⁵³ 係表示直鏈或分枝鏈之碳原子數2至20之伸烷基、碳原子數5至6之2價脂肪族環基，或是包含碳原子數5至6之脂肪族環之2價脂肪族基，可於構造中包含醚鍵。 R⁵⁴ 係表示直鏈或分枝鏈之碳原子數1至20之2價至9價脂肪族基、碳原子數5至6之2價至9價脂肪族環基，或是包含碳原子數5至6之脂肪族環之2價至9價脂肪族基，此等之基的一個亞甲基或複數個彼此不相鄰之亞甲基可被醚鍵取代。 Z係表示＞NCOO-或-OCON＜(於此「-」係表示鍵結部為一個。又，「＞」「＜」係表示鍵結部為2個，且於任一個鍵結部鍵結烷氧基甲基(亦即-OR⁵² 基))。 r為2以上9以下之自然數。As another aspect of the polymerizable group containing the C=C double bond of the component (E) and the compound having an N-alkoxymethyl group, for example, a compound represented by the following formula (X2) is preferably used.

In the formula, R ⁵¹ represents a hydrogen atom or a methyl group. R ⁵² represents an alkyl group with 2 to 20 carbon atoms, a monovalent aliphatic ring group with 5 to 6 carbon atoms, or a monovalent aliphatic group containing an aliphatic ring with 5 to 6 carbon atoms. The construction contains ether bonds. R ⁵³ represents a straight-chain or branched chain alkylene group with 2 to 20 carbon atoms, a divalent aliphatic ring group with 5 to 6 carbon atoms, or an aliphatic ring containing 5 to 6 carbon atoms. A divalent aliphatic group may contain an ether bond in its structure. R ⁵⁴ represents a linear or branched bivalent to 9-valent aliphatic group with 1 to 20 carbon atoms, a 2- to 9-valent aliphatic cyclic group with 5 to 6 carbon atoms, or a group containing carbon atoms Divalent to 9-valent aliphatic groups of the aliphatic rings of 5 to 6, one methylene group or a plurality of methylene groups not adjacent to each other in these groups may be substituted with ether bonds. Z means >NCOO- or -OCON< (here, "-" means that there is one key part. Also, ">" and "<" means that there are two key parts, and they are connected to any key part. alkoxymethyl (ie -OR ⁵² group)). r is a natural number of 2 or more and 9 or less.

Specific examples of the alkylene group having 2 to 20 carbon atoms as defined in R ⁵³ include divalent groups obtained by removing one hydrogen atom from the alkyl group having 2 to 20 carbon atoms. In addition, as ^{a specific example of the aliphatic group having 1 to 20 carbon atoms and a 2- to 9-valent aliphatic group defined in R 54} , there can be mentioned an alkyl group having 1 to 20 carbon atoms and further 1 to 8 hydrogen atoms are removed. 2 price to 9 price basis.

The alkyl group having 1 carbon atoms is a methyl group, and as specific examples of the alkyl group having 2 to 20 carbon atoms, ethyl, n-propyl, i-propyl, n-butyl, i-butyl can be used. base, 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 yl-n-butyl, 1,1,2-trimethyl-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 group, n-eicosyl group, cyclopentyl group, cyclohexyl group, one or more of these groups bonded to the range up to 20 carbon atoms, a methylene group or a group of these groups A group in which a plurality of methylene groups that are not adjacent to each other are substituted by ether bonds, etc., are exemplified.

Among these, an alkylene group having 2 to 10 carbon atoms is preferable, ^R53 is an ethylidene group, and ^R54 is a hexylene group, and it is particularly preferable from the viewpoint of availability of raw materials and the like.

Specific examples of the alkyl group having 1 to 20 carbon atoms defined in R ⁵² include specific examples of the alkyl group having 2 to 20 carbon atoms defined ^{in R 53 and a methyl group.} Among these, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group or an n-butyl group is particularly preferable.

Although a natural number of 2 or more and 9 or less can be mentioned as r, among them, 2 to 6 are preferable.

The content of the component (E) in the cured film-forming composition of the embodiment of the present invention is preferably 1 with respect to 100 parts by mass of the total amount of the polymer of the component (A) and the crosslinking agent of the component (B). Parts by mass to 100 parts by mass, more preferably 5 parts by mass to 70 parts by mass.

Moreover, in the cured film formation composition of this embodiment, (E)component may be a mixture of plural types of the compound of (E)component.

＜Solvent＞ The cured film-forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent to be used at this time may dissolve the (A) component, (B) component, (C) component, and if necessary (D) component, (E) component and/or other additives described later. The structure and the like are not particularly limited.

Specific examples of the solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Ethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, Isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, gamma-butyrolactone, ethyl 2-hydroxypropionate ester, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate ester, butyl lactate, cyclopentyl methyl ether, N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc.

When using the cured film forming composition of the present invention to form a cured film on a resin film and manufacture 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., from The resin film is preferable in that it is a solvent exhibiting resistance.

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

＜Other additives＞ Furthermore, the cured film-forming composition of the present invention may contain a sensitizer, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, and an antioxidant, if necessary, as long as the effect of the present invention is not impaired. Wait.

<Preparation of cured film forming composition> The cured film-forming composition of the present invention contains the polymer of the component (A), the crosslinking agent of the component (B), and the alkoxysilane of the component (C), and may contain the crosslinking catalyst of the component (D) if desired. and the adhesion promoter of the component (E), and further, as long as the effect of the present invention is not impaired, a composition containing other additives may be included. In addition, these are usually used in the form of a solution dissolved in a solvent.

Preferable examples of the cured film-forming composition of the present invention are as follows. [1]: Cured film-forming composition containing (A) component, (B) component, and (C) component, containing 1 to 500 parts by mass of (B) component based on 100 parts by mass of (A) component , and based on 100 parts by mass of (A) component, 0.001 parts by mass to 20 parts by mass of (C) component are contained. [2]: The cured film-forming composition containing (A) component, (B) component, (C) component, and a solvent, in which 1 to 500 parts by mass of ( B) Component contains 0.001 to 20 parts by mass of (C) component based on 100 parts by mass of (A) component. [3]: The cured film-forming composition containing (A) component, (B) component, (C) component, (D) component, and a solvent, in which 1 to 500 parts by mass is contained based on 100 parts by mass of (A) component Component (B) in parts by mass, relative to 100 parts by mass of the polymer of component (A), contains 0.001 to 20 parts by mass of component (C) relative to the polymer of component (A) and component (B) 0.01 to 20 parts by mass of (D) component is contained in 100 parts by mass of the total amount of the crosslinking agent. [4]: Cured film-forming composition containing (A) component, (B) component, (C) component, (D) component, (E) component, and a solvent, wherein, based on 100 parts by mass of (A) component, Contains 1 to 500 parts by mass of component (B), relative to 100 parts by mass of the polymer of component (A), contains 0.001 to 20 parts by mass of component (C), relative to the polymerization of component (A) 100 parts by mass of the total amount of the crosslinking agent of the product and the component (B), containing 0.01 to 20 parts by mass of the component (D) relative to the polymer of the component (A) and the crosslinking agent of the component (B) The total amount of 100 parts by mass contains 1 to 100 parts by mass of the (E) component.

The mixing ratio, preparation method, etc. when the cured film forming composition of the present invention is used as a solution will be described in detail below. The ratio of the solid content of 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 to 60% by mass, preferably 2 to 50% by mass , more preferably 2% by mass to 20% by mass. Here, a solid content means what removed a solvent from all the components of a cured film formation composition.

The preparation method of the cured film formation composition of this invention is not specifically limited. The preparation method includes, for example, mixing (B) component and (C) component in a solution of (A) component dissolved in a solvent at a predetermined ratio, and further mixing (D) component and (E) component at a predetermined ratio, etc., A method of forming a homogeneous solution, or a method of adding and mixing other additives if necessary at an appropriate stage of the preparation method.

In the preparation of the cured film formation composition of this invention, the solution of the specific copolymer (polymer) obtained by the polymerization reaction in a solvent can be used as it is. In this case, for example, the solution of (A) component is put into (B) component, (C) component similarly to the above, and (D) component, (E) component etc. are further put into it, and it becomes a homogeneous solution. In this case, the solvent may be further added for the purpose of concentration adjustment. In this case, the solvent used in the production process of the component (A) and the solvent used for concentration adjustment of the cured film forming composition may be the same or different.

Moreover, it is preferable to filter and use the solution of the prepared cured film-forming composition using a filter or the like having a pore diameter exceeding about 0.2 μm.

<Curing film, alignment material and retardation material> By applying the solution of the cured film-forming composition of the present invention to substrates (such as silicon/silicon dioxide coated substrates, silicon nitride substrates, metal substrates such as aluminum, molybdenum, chromium coated substrates, glass substrates, quartz substrates, ITO substrates, etc.), by bar coating, rotary coating, flow coating, roll coating, slit coating, slit followed by rotary coating, inkjet coating, printing, etc., to form a coating film, Then, it can be heated and dried with a hot plate, an oven, or the like to form a cured film. The cured film can be directly used as an alignment material.

As a condition for heating and drying, the components of the cured film (alignment material) may be subjected to a crosslinking reaction by a crosslinking agent to such an extent that the polymerizable liquid crystal solution applied thereon does not dissolve. Appropriately select heating temperature and heating time in the range of ~200°C and time from 0.4 minutes to 60 minutes. The heating temperature and heating time are preferably 70° C. to 160° C. for 0.5 minutes to 10 minutes.

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

Since the alignment material formed from the cured film composition of the present invention has solvent resistance and heat resistance, the alignment material can be coated with a retardation material such as a polymerizable liquid crystal solution having vertical alignment on the alignment material. alignment on. Furthermore, the retardation material can be formed as a layer having optical anisotropy by directly curing the retardation material in the aligned state.

Furthermore, using two substrates having the alignment material of the present invention formed as described above, and pasting the alignment materials on the two substrates so as to face each other through a gap, injecting liquid crystal between the substrates, also It can become a liquid crystal display element with aligned liquid crystal. Thus, the cured film formation composition of this invention can be used suitably for manufacture of various retardation materials, a liquid crystal display element, etc.. [Example]

＜C成分＞ SC-1：1-[3-(三乙氧基矽烷基)丙基]脲(東麗道康寧(股)製) SC-2：1-[3-(三甲氧基矽烷基)丙基]脲(東京化成工業(股)製) SC-3：3-異氰酸酯丙基三甲氧基矽烷(Momentive Performance Materials Japan合同公司製) SC-4：2-(3、4-環氧基環己基乙基)三甲氧基矽烷(信越矽利光製) SC-5：3-巰基丙基三甲氧基矽烷(信越矽利光製) SC-6：3-丙烯醯氧基丙基三甲氧基矽烷(信越矽利光製) ＜D成分＞ PPTS：p-甲苯磺酸･吡啶鹽 PTSA：p-甲苯磺酸･一水合物 ＜E成分＞ E-1：具有以下述之構造式表示之N-烷氧基甲基及丙烯醯基之化合物

＜溶劑＞ 實施例及比較例之各樹脂組成物含有溶劑，並作為其溶劑，係使用將丙二醇單甲基醚與乳酸乙酯以1對4之比混合之溶媒(PM/EL)。Hereinafter, although the Example of this invention is given and this invention is demonstrated concretely, this invention is not limited to these and it is not interpreted. [Abbreviations used in the examples] The meanings of the abbreviations used in the following examples are as follows. <Raw material> GMA: Glycidyl methacrylate GLM: Glycerol monomethacrylate AIBN: α,α'-azobisisobutyronitrile HEMA: 2-hydroxyethyl methacrylate <Component B> TMGU: 1,3,4,6-4(methoxymethyl)glycoluril (manufactured by Tokyo Chemical Industry Co., Ltd.) HMM: a melamine crosslinking agent represented by the following structural formula [CYMEL (CYMEL) (registered trademark) 303 (Mitsui Cytec Corporation)]

<Component C> SC-1: 1-[3-(triethoxysilyl)propyl]urea (manufactured by Toray Dow Corning) SC-2: 1-[3-(trimethoxysilyl) Propyl]urea (manufactured by Tokyo Chemical Industry Co., Ltd.) SC-3: 3-isocyanatopropyltrimethoxysilane (manufactured by Momentive Performance Materials Japan Contract Co., Ltd.) SC-4: 2-(3,4-epoxy ring Hexylethyl)trimethoxysilane (manufactured by Shin-Etsu Silico) SC-5: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Silico) SC-6: 3-propenyloxypropyltrimethoxysilane ( Shin-Etsu Silicon Co., Ltd.) <Component D> PPTS: p-toluenesulfonic acid・pyridinium salt PTSA: p-toluenesulfonic acid・monohydrate <Component E> E-1: N-alkoxy represented by the following structural formula Compounds of methyl and acryloyl groups

<Solvent> Each resin composition of Examples and Comparative Examples contained a solvent, and as the solvent, a solvent (PM/EL) in which propylene glycol monomethyl ether and ethyl lactate were mixed in a ratio of 1 to 4 was used.

<Measurement of molecular weight of polymer> In the molecular weight of the acrylic copolymer in the polymerization example, the room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co. The measurement is carried out as follows. Incidentally, the following 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℃ Eluent: tetrahydrofuran Flow rate: 1.0mL/min Standard sample for calibration curve preparation: Standard polystyrene manufactured by Showa Denko Co., Ltd. (molecular weight about 197,000, 55,100, 12,800, 3,950, 1,260, 580).

<Synthesis of Component A> <Polymerization example 1> An acrylic polymer solution was obtained by dissolving 15.0 g of GMA and 0.5 g of AIBN as a polymerization catalyst in 46.4 g of tetrahydrofuran, and making it react under heating under reflux for 20 hours. By slowly dropping the obtained acrylic copolymer solution into 500.0 g of hexane, the solid was precipitated, filtered and dried under reduced pressure to obtain an epoxy group-containing acrylic polymer (P1). The Mn of the obtained acrylic polymer was 9,800, and the Mw was 25,000.

<Polymerization example 2> An acrylic copolymer solution was obtained by dissolving 16.0 g of GMA, 8.0 g of GLM, and 0.5 g of AIBN as a polymerization catalyst in 80.0 g of tetrahydrofuran, and making it react under heating under reflux for 20 hours. The acrylic copolymer solution (P2) having an epoxy group and a hydroxyl group was obtained by slowly dropping the obtained acrylic copolymer solution into 500.0 g of hexane, precipitation of a solid, filtration and drying under reduced pressure. The Mn of the obtained acrylic polymer was 12,000, and the Mw was 29,000.

<Synthesis example 1> By dissolving 10.0 g of the acrylic polymer (P1) having an epoxy group obtained in Polymerization Example 1, 11.3 g of 4-methoxycinnamic acid, and 0.4 g of benzyltriethylammonium chloride as a reaction catalyst in 50.8 g of PM was reacted at 120°C for 20 hours. This solution was gradually dripped into 500 g of diethyl ether, the solid was precipitated, filtered and dried under reduced pressure to obtain a polymer (PA-1). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group disappeared.

<Synthesis example 2> 5.0 g of acrylic polymer (P2) having epoxy groups and hydroxyl groups obtained in Polymerization Example 2, 4.6 g of 4-methoxycinnamic acid, and 0.2 g of benzyltriethylammonium chloride as a reaction catalyst It was dissolved in 22.8 g of PM, and it was made to react at 120 degreeC for 20 hours. This solution was gradually dripped into 500 g of diethyl ether, a solid was deposited, filtered and dried under reduced pressure to obtain a polymer (PA-2). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group disappeared.

<Synthesis of C component> <Polymerization example 3> An acrylic copolymer solution ( PC-1). The Mn of the obtained acrylic polymer was 1,2100, and the Mw was 2,9000.

<Polymerization example 4> A high molecular weight copolymer (PC -2).

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

<Examples and comparative examples> In the composition shown in Table 1, each cured film formation composition of an Example and a comparative example was prepared. Next, a composition was formed using each retardation material, a cured film was formed, and the orientation of the obtained cured film was individually evaluated.

[Evaluation of Orientation] The cured film-forming compositions of Examples and Comparative Examples were coated on a glass substrate so that the film thickness after firing was 60 nm using a spin coater. The temperature was 100° C. for 10 minutes, respectively, and heat-drying was performed on a hot plate to form a cured film on the glass, respectively. Here, each cured film was vertically irradiated with a linearly polarized light of 313 nm at ^{an exposure amount of 100 mJ/cm 2} to form an alignment material. On the alignment material on the glass substrate, the polymerizable liquid crystal solution (RM-1) was applied using a spin coater so that the retardation value after film formation was about 140 nm at a wavelength of 550 nm. This coating film was exposed to light at 500 mJ/cm ² to produce a retardation material. Hold the phase difference material on the fabricated substrate with a pair of polarizers, and observe the performance of the phase difference characteristics on the phase difference material. The phase difference without defects is marked as ○, and the phase difference without phase difference is marked as × , recorded in the "Orientation" column. The evaluation results are collectively shown in Table 2 later.

[Evaluation of Adhesion with Substrate] Each cured film-forming composition of Examples and Comparative Examples was applied on a glass substrate so that the film thickness after firing was 60 nm using a spin coater. The temperature was 100° C. for 10 minutes, respectively, and heat-drying was performed on a hot plate to form a cured film on the glass, respectively. Here, each cured film was vertically irradiated with a linearly polarized light of 313 nm at ^{an exposure amount of 100 mJ/cm 2} to form an alignment material. Using a cutter for the alignment material, 11 notches with a width of 1 cm were placed vertically and horizontally, and grooves were formed in the alignment material in a lattice shape of 100 mass. Adhesion to the glass substrate possessed by the alignment material was evaluated with respect to the mass ratio of the alignment material remaining on the glass substrate when the substrate was peeled off at an angle of 45° from the sufficient adhesion of the adhesive tape. The case where almost all of the alignment material remained was designated as 0, and the case where almost all of the alignment material was peeled was designated as ×, and recorded in the column of "adhesion". The evaluation results are collectively shown in Table 2 later.

As shown in Table 2, the alignment materials to which the silane coupling agents having siloxane groups of Examples 1 to 12 were added showed good liquid crystal alignment and sufficient adhesion to the glass substrate.

In contrast, the composition to which the silane coupling agent of Counter Example 1 (Comparative Example 1) was not added did not exhibit sufficient adhesion to glass in addition to exhibiting favorable liquid crystal alignment. In addition, in Counter-Example 2 (Comparative Example 2), although the addition amount of the silane coupling agent showing adhesion in Example 12 was set to be the same amount as the other low-molecular-weight silane coupling agents in Examples 1 to 11, this composition The material did not show adhesion to glass. This is because it is a silane coupling agent with low reactivity with respect to other molecules in the composition, and it is necessary to increase the amount added in order to obtain sufficient adhesion with glass. [Industrial Availability]

The cured film forming composition of the present invention is very useful as a liquid crystal alignment film for a liquid crystal display element, or as a material for forming an alignment material for an optically anisotropic plate disposed inside or outside the liquid crystal display element, especially It is a phase difference material suitable for circular polarizers used as anti-reflection films for IPS-LCD or organic EL displays.

Claims (10)

A hardened film-forming composition comprising: (A) a polymer having a photoalignment group and a thermally crosslinkable group, (B) a crosslinking agent having a methylol or alkoxymethyl group, and (C) The alkoxysilane which has a thermally crosslinkable group different from an alkoxysilyl group part. The cured film-forming composition according to claim 1, which further contains (D) a crosslinking catalyst. The cured film-forming composition according to claim 1 or 2, comprising (E) having one or more polymerizable groups and a group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group A compound of at least one group A in the group, or at least one group reacted with the group A. The cured film forming composition according to any one of claims 1 to 3, which contains 1 to 500 parts by mass of component (B) based on 100 parts by mass of (A) component. The cured film forming composition according to any one of claims 1 to 4, which contains 0.001 parts by mass to 20 parts by mass of (C) component with respect to 100 parts by mass of (A) component. The cured film-forming composition according to any one of claims 2 to 5, containing 0.01 to 20 parts by mass relative to 100 parts by mass of the total amount of the crosslinking agent of the (A) component and (B) component The (D) component. The cured film-forming composition according to any one of claims 3 to 6, which contains 1 part by mass to 100 parts by mass relative to 100 parts by mass of the total amount of the crosslinking agent of (A) component and (B) component The (E) component. A cured film obtained by curing the cured film-forming composition as claimed in claims 1 to 7. An alignment agent formed by curing the cured film-forming composition according to claims 1 to 7. A retardation material having a cured film obtained by curing the cured film-forming composition of claims 1 to 7.