JPWO2018181350A1 - Cured film forming composition, alignment material and retardation material - Google Patents

Abstract

[Problem] To provide a cured film forming composition which is used as an alignment material and forms a cured film exhibiting excellent liquid crystal alignment and light transmittance when a layer of polymerizable liquid crystal is disposed thereon. To provide. The polymer contains (A) a polymer obtained by using a monomer which is a reaction product of a monomer having an epoxy group and a cinnamic acid derivative represented by the following formula (1), and (B) a crosslinking agent. A cured film forming composition, an alignment material obtained by using the composition, and a retardation material obtained by using the composition. (In the formula (1), A1 and A2 represent a hydrogen atom or a methyl group, R1 represents a hydrogen atom, a halogen atom, or the like, and R2 represents a divalent aromatic group or a divalent alicyclic group. A divalent heterocyclic group or a divalent condensed cyclic group, R3 is a single bond, an oxygen atom, or the like; R4 to R7 are each independently a hydrogen atom, a halogen atom, or the like; It is an integer of 3.) [Selection diagram] None

Description

  The present invention relates to a cured film forming composition, an alignment material, and a retardation material that can be used as a liquid crystal alignment agent for photo alignment for aligning liquid crystal molecules. In particular, the present invention is useful for producing a phase difference material used for a circularly polarized glasses type 3D display or a phase difference material used for a circularly polarizing plate used as an antireflection film of an organic EL display. The present invention relates to a cured film forming composition, an alignment material, and a retardation material that can be used as a liquid crystal alignment agent for optical alignment.

  In the case of a circularly polarized glasses type 3D display, a retardation material is usually arranged on a display element such as a liquid crystal panel on which an image is formed. In this phase difference material, a plurality of two types of phase difference regions having different phase difference characteristics are regularly arranged, respectively, to form a patterned phase difference material. Hereinafter, in the present specification, a retardation material patterned to arrange a plurality of retardation regions having different retardation characteristics is referred to as a patterned retardation material.

  As disclosed in Patent Document 1, for example, a patterned retardation material can be produced by optically patterning a retardation material composed of a polymerizable liquid crystal. Optical patterning of a retardation material composed of a polymerizable liquid crystal utilizes an optical alignment technique known for forming an alignment material of a liquid crystal panel. That is, a coating film made of a photo-alignable material is provided on a substrate, and two types of polarized lights having different polarization directions are irradiated on the coating film. Then, an optical alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed. A solution type retardation material containing a polymerizable liquid crystal is applied on the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Thereafter, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.

  The antireflection film of the organic EL display is composed of a linear polarizing plate and a quarter-wave retardation plate, and converts the external light traveling toward the panel surface of the image display panel into linearly polarized light by the linear polarizing plate. The light is converted into circularly polarized light by a phase difference plate. Here, the external light due to the circularly polarized light is reflected on the surface of the image display panel or the like, but the direction of rotation of the polarization plane is reversed at the time of the reflection. As a result, the reflected light is converted from the １ ／ wavelength phase difference plate into linearly polarized light in a direction in which the reflected light is shielded by the linear polarizer, and then shielded by the subsequent linear polarizer. As a result, emission to the outside is significantly suppressed.

  Regarding this quarter-wave retardation plate, Patent Document 2 discloses that a quarter-wave retardation plate is formed by combining a half-wave plate and a quarter-wave plate, thereby making the optical film have an inverse dispersion characteristic. Has been proposed. In the case of this method, in a wide wavelength band used for displaying a color image, an optical film can be formed by using a liquid crystal material having a positive dispersion characteristic and by using a reverse dispersion characteristic.

  In recent years, as a liquid crystal material applicable to the retardation layer, a material having an inverse dispersion characteristic has been proposed (Patent Documents 3 and 4). According to the liquid crystal material having such an inverse dispersion characteristic, instead of combining a half-wave plate and a quarter-wave plate to form a quarter-wave retardation plate with two retardation layers, a retardation layer is formed. Is composed of a single layer to secure the inverse dispersion characteristic, whereby an optical film capable of securing a desired phase difference in a wide wavelength band can be realized with a simple configuration.

  An alignment layer is used to align the liquid crystal. As a method of forming an alignment layer, for example, a rubbing method or a photo-alignment method is known, and the photo-alignment method does not generate static electricity or dust, which is a problem of the rubbing method, and can quantitatively control an alignment process. Useful in

  In forming an alignment material using a photo-alignment method, an acrylic resin, a polyimide resin, or the like having a photodimerization site such as a cinnamoyl group and a chalcone group in a side chain is known as a usable photo-alignment material. It has been reported that these resins exhibit a performance of controlling the orientation of liquid crystal (hereinafter, also referred to as liquid crystal orientation) by irradiation with polarized UV (see Patent Documents 5 to 7).

  The alignment layer is required to have solvent resistance in addition to liquid crystal alignment ability. For example, the alignment layer may be exposed to heat or a solvent during the production process of the retardation material. When the alignment layer is exposed to a solvent, the liquid crystal alignment ability may be significantly reduced.

  Therefore, for example, Patent Document 8 discloses that in order to obtain a stable liquid crystal alignment ability, a liquid crystal alignment agent containing a polymer component having a structure capable of performing a crosslinking reaction by light and a structure capable of being crosslinked by heat, and Liquid crystal aligning agents containing a polymer component having a structure capable of undergoing a crosslinking reaction and a compound having a structure capable of being crosslinked by heat have been proposed.

JP 2005-49865 A JP-A-10-68816 US Patent No. 8119026 JP 2009-179563 A Japanese Patent No. 3611342 JP 2009-058584 A JP 2001-517719 A Japanese Patent No. 4207430

  As described above, the retardation material is configured by laminating a cured polymerizable liquid crystal layer on the photo-alignment film as an alignment material. Therefore, there is a need to develop an alignment material that can achieve both excellent liquid crystal alignment and solvent resistance.

  However, studies by the present inventors have shown that acrylic resins having a photodimerization site such as a cinnamoyl group and a chalcone group in the side chain cannot obtain sufficient properties when applied to the formation of a retardation material. Was issued. In particular, in order to irradiate these resins with polarized UV to form an alignment material and to use the alignment material to produce a retardation material composed of a polymerizable liquid crystal, a large amount of polarized UV exposure is required. The amount of polarized UV light exposure is much larger than the amount of polarized UV light exposure (for example, about 30 mJ / cm 2) which is sufficient for aligning liquid crystals for a normal liquid crystal panel.

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

  When an alignment material is formed by using an acrylic resin or the like having a photodimerization site such as a cinnamoyl group in a side chain and the polymerizable liquid crystal is to be aligned, photocrosslinking is performed by a photodimerization reaction in the acrylic resin or the like. . Then, it is necessary to perform polarized light irradiation with a large amount of exposure until the resistance to the polymerizable liquid crystal solution is developed. In order to align the liquid crystal of the liquid crystal panel, usually, only the surface of the photo-alignment alignment material needs to undergo a dimerization reaction. However, if a conventional material such as the above-mentioned acrylic resin or the like is used to cause the alignment material to exhibit solvent resistance, it is necessary to cause the reaction to reach the inside of the alignment material, and a larger exposure amount is required. As a result, there has been a problem that the alignment sensitivity of the conventional material is extremely reduced.

  In addition, a technique of adding a cross-linking agent to make the above-described conventional resin exhibit such solvent resistance is known. However, after the thermosetting reaction with the cross-linking agent is performed, there is a problem that a three-dimensional structure is formed inside the coating film to be formed, and the photoreactivity decreases. That is, the alignment sensitivity is greatly reduced, and the desired effect has not been obtained even if a conventional material is used by adding a crosslinking agent.

  From the above, a photo-alignment technique capable of improving the alignment sensitivity of an alignment material and reducing the amount of polarized UV exposure, and a cured film forming composition that can be used as a liquid crystal alignment agent for photo-alignment used for forming the alignment material are required. Have been. There is a need for a technology that can provide a retardation material with high efficiency.

  The object of the present invention has been made based on the above findings and examination results. That is, an object of the present invention is to form a cured film that can be used as a liquid crystal alignment agent for photoalignment to provide an alignment material having excellent solvent resistance and capable of aligning a polymerizable liquid crystal with high sensitivity. It is to provide a composition.

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

  The present inventors have conducted intensive studies to achieve the above object, and as a result, (A) a reaction product of a monomer having an epoxy group and a specific cinnamic acid derivative, (B) a cured film based on a crosslinking agent The present inventors have found that by selecting a forming composition, it is possible to form a cured film (alignment material) having excellent solvent resistance and capable of aligning a polymerizable liquid crystal with high sensitivity, and completed the present invention.

（式（１）中、Ａ^１とＡ^２はそれぞれ独立に、水素原子またはメチル基を表し、Ｒ^１は水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のハロアルキル基、炭素原子数１〜６のアルコキシ基、炭素原子数１〜６のハロアルコキシ基、炭素原子数３〜８のシクロアルキル基、炭素原子数３〜８のハロシクロアルキル基炭素、炭素原子数２〜６のアルケニル基、炭素原子数２〜６のハロアルケニル基、炭素原子数３〜８のシクロアルケニル基、炭素原子数３〜８のハロシクロアルケニル基、炭素原子数２〜６のアルキニル基、炭素原子数２〜６のハロアルキニル基、炭素原子数１〜６のアルコキシ基、炭素原子数１〜６のハロアルコキシ基、（炭素原子数１〜６のアルキル）カルボニル基、（炭素原子数１〜６のハロアルキル）カルボニル基、（炭素原子数１〜６のアルコキシ）カルボニル基、（炭素原子数１〜６のハロアルコキシ）カルボニル基、（炭素原子数１〜６のアルキルアミノ）カルボニル基、（炭素原子数１〜６のハロアルキル）アミノカルボニル基、ジ(炭素原子数１〜６のアルキル)アミノカルボニル基、シアノ基およびニトロ基からなる群から選ばれる置換基を表し、Ｒ^２は２価の芳香族基、２価の脂環族基、２価の複素環式基または２価の縮合環式基を表し、Ｒ^３は単結合、酸素原子、−ＣＯＯ−または−ＯＣＯ−を表し、Ｒ^４〜Ｒ^７はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のハロアルキル基、炭素原子数１〜６のアルコキシ基、炭素原子数１〜６のハロアルコキシ基、シアノ基、およびニトロ基からなる群から選ばれる置換基を表し、nは０〜３の整数である。）
（Ｂ）架橋剤
を含有する硬化膜形成組成物。
第２観点として、（Ｂ）成分の架橋剤がメチロール基またはアルコキシメチル基を有する架橋剤である、第１観点に記載の硬化膜形成組成物に関する。
第３観点として、（Ｃ）ヒドロキシ基、カルボキシル基、アミド基、アミノ基、およびアルコキシシリル基からなる群から選ばれる少なくとも１つの基を有するポリマーをさらに含有する第１観点または第２観点に記載の硬化膜形成組成物に関する。
第４観点として、（Ｄ）架橋触媒をさらに含有する第１観点乃至第３観点のうち何れか一項に記載の硬化膜形成組成物に関する。
第５観点として、（Ｅ）１つ以上の重合性基と、ヒドロキシ基、カルボキシル基、アミド基、アミノ基、およびアルコキシシリル基からなる群から選ばれる少なくとも１つの基Ａまたは該基Ａと反応する少なくとも１つの基とを有する化合物を含有する第１観点乃至第４観点のうち何れか一項に記載の硬化膜形成組成物に関する。
第６観点として、（Ａ）成分１００質量部に基づいて、１質量部〜５００質量部の（Ｂ）成分を含有する第１観点乃至第５観点のうち何れか一項に記載の硬化膜形成組成物に関する。
第７観点として、（Ａ）成分および（Ｂ）成分の架橋剤の合計量の１００質量部に対して１質量部〜４００質量部の（Ｃ）成分を含有する第３観点乃至第６観点のいずれか一項に記載の硬化膜形成組成物に関する。
第８観点として、（Ａ）成分および（Ｂ）成分の架橋剤の合計量の１００質量部に対して０．０１質量部〜２０質量部の（Ｄ）成分を含有する第４観点乃至第７観点のいずれか一項に記載の硬化膜形成組成物に関する。
第９観点として、（Ａ）成分および（Ｂ）成分の架橋剤の合計量の１００質量部に対して１質量部〜１００質量部の（Ｅ）成分を含有する第４観点乃至第８観点のいずれか一項に記載の硬化膜形成組成物に関する。
第１０観点として、第１観点乃至第９観点のうち何れか一項に記載の硬化膜形成組成物を硬化させて得られることを特徴とする硬化膜に関する。
第１１観点として、第１観点乃至第９観点のうち何れか一項に記載の硬化膜形成組成物を硬化させて得られることを特徴とする配向材に関する。
第１２観点として、第１観点乃至第９観点のうち何れか一項に記載の硬化膜形成組成物から得られる硬化膜を使用して形成されることを特徴とする位相差材に関する。That is, the present invention, as a first aspect,
(A) a polymer obtained using a monomer which is a reaction product of a monomer having an epoxy group and a cinnamic acid derivative represented by the following formula (1):

(In the formula (1), A ¹ and A ² each independently represent a hydrogen atom or a methyl group, and R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. A haloalkyl group, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a halocycloalkyl group having 3 to 8 carbon atoms, carbon, carbon An alkenyl group having 2 to 6 atoms, a haloalkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, a halocycloalkenyl group having 3 to 8 carbon atoms, Alkynyl group, haloalkynyl group having 2 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, haloalkoxy group having 1 to 6 carbon atoms, (alkyl having 1 to 6 carbon atoms) carbonyl group, (carbon C having 1 to 6 atoms (Alkyl) carbonyl group, (alkoxy having 1 to 6 carbon atoms) carbonyl group, (haloalkoxy having 1 to 6 carbon atoms) carbonyl group, (alkylamino having 1 to 6 carbon atoms) carbonyl group, (carbon number of 1 to 6 carbon atoms) 1 to 6 haloalkyl) aminocarbonyl group, di (alkyl having 1 to 6 carbon atoms) aminocarbonyl group, a substituent selected from the group consisting of a cyano group and a nitro group, and R ² is a divalent aromatic group A divalent alicyclic group, a divalent heterocyclic group or a divalent fused cyclic group, R ³ represents a single bond, an oxygen atom, —COO— or —OCO—, and R ^{4 to} R ^{4 And 7} independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a haloalkoxy having 1 to 6 carbon atoms. Group, cyano , And it represents a substituent selected from the group consisting of nitro group, n is an integer of 0-3.)
(B) A cured film-forming composition containing a crosslinking agent.
As a second aspect, the present invention relates to the cured film-forming composition according to the first aspect, wherein the crosslinking agent of the component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group.
As a third aspect, (C) the first aspect or the second aspect further comprising a polymer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group. And a cured film-forming composition.
As a fourth aspect, the present invention relates to the cured film-forming composition according to any one of the first to third aspects, further comprising (D) a crosslinking catalyst.
As a fifth aspect, (E) one or more polymerizable groups react with at least one group A selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, or a reaction with the group A The present invention relates to the cured film forming composition according to any one of the first to fourth aspects, which contains a compound having at least one group.
As a sixth aspect, based on 100 parts by mass of the component (A), the cured film according to any one of the first to fifth aspects, which contains 1 to 500 parts by mass of the component (B). Composition.
As a seventh aspect, the third to sixth aspects include 1 to 400 parts by mass of the component (C) based on 100 parts by mass of the total amount of the crosslinking agents of the components (A) and (B). A cured film-forming composition according to any one of the preceding claims.
As an eighth aspect, the fourth to seventh aspects contain 0.01 to 20 parts by mass of the component (D) based on 100 parts by mass of the total amount of the crosslinking agents of the components (A) and (B). A cured film-forming composition according to any one of aspects.
As a ninth aspect, the fourth to eighth aspects each include 1 to 100 parts by mass of the component (E) based on 100 parts by mass of the total amount of the crosslinking agents of the components (A) and (B). A cured film-forming composition according to any one of the preceding claims.
As a tenth aspect, the present invention relates to a cured film obtained by curing the cured film forming composition according to any one of the first to ninth aspects.
As an eleventh aspect, the present invention relates to an alignment material obtained by curing the cured film forming composition according to any one of the first to ninth aspects.
As a twelfth aspect, the present invention relates to a retardation material formed using a cured film obtained from the cured film forming composition according to any one of the first to ninth aspects.

According to the present invention, it is possible to provide a cured film having excellent solvent resistance, capable of aligning a polymerizable liquid crystal with high sensitivity, and a cured film forming composition suitable for forming the cured film.
According to the present invention, it is possible to provide an alignment material having excellent liquid crystal alignment and light transmittance and a retardation material capable of performing high-precision optical patterning.

<Curing film forming composition>
The cured film forming composition of the present invention comprises (A) a polymer obtained by using a monomer which is a reaction product of a monomer having an epoxy group and a cinnamic acid derivative represented by the above formula (1), and (B) ) It contains a crosslinking agent. The cured film-forming composition of the present invention further comprises, as a component (C), a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group in addition to the components (A) and (B). And a polymer having at least one group selected from the following. Further, a crosslinking catalyst may be contained as the component (D). Further, as the component (E), at least one polymerizable group and at least one group A selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, or at least one that reacts with the group A Compounds having one group can be contained. Further, other additives can be contained as long as the effects of the present invention are not impaired.
Hereinafter, details of each component will be described.

<(A) component>
The component (A) contained in the cured film forming composition of the present invention is a polymer obtained by using a monomer which is a reaction product of a monomer having an epoxy group and a cinnamic acid derivative represented by the above formula (1). It is united.

<Monomer having epoxy group>
Specific examples of the polymerizable unsaturated compound having an epoxy group (monomer) used for reacting with the cinnamic acid derivative represented by the above formula (1) in the present invention include, for example, glycidyl acrylate, glycidyl methacrylate, α- Glycidyl ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-acrylate Epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. Can be.

<Cinnamic acid derivative having a carboxyl group>
Examples of the cinnamic acid derivative having a carboxyl group include a compound represented by the above formula (1).

  Examples of the halogen atom in the above formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Incidentally, the notation “halo” in the present specification also represents these halogen atoms.

  The notation of an alkyl group having a carbon number of ab in the above formula (1) represents a linear or branched hydrocarbon group having a carbon number of ab, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 1,1 -Dimethylbutyl group and 1,3-dimethylbutyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like are specific examples, and are selected within the range of each specified number of carbon atoms. It is.

  The expression of the haloalkyl group having a carbon number of ab in the above formula (1) means that a hydrogen atom bonded to a carbon atom is arbitrarily substituted by a halogen atom, and that the straight-chain alkyl group has a carbon number of ab. Alternatively, it represents a branched hydrocarbon group, and when it is substituted with two or more halogen atoms, these halogen atoms may be the same or different from each other. For example, fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, chlorofluoromethyl, dichloromethyl, bromofluoromethyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trichloromethyl Group, bromodifluoromethyl group, bromochlorofluoromethyl group, dibromofluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2-chloro-2-fluoroethyl Group, 2,2-dichloroethyl group, 2-bromo-2-fluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2,2-difluoroethyl group, 2,2-dichloro-2 -Fluoroethyl group, 2,2,2-trichloroethyl group, 2 Bromo-2,2-difluoroethyl group, 2-bromo-2-chloro-2-fluoroethyl group, 2-bromo-2,2-dichloroethyl group, 1,1,2,2-tetrafluoroethyl group, penta Fluoroethyl group, 1-chloro-1,2,2,2-tetrafluoroethyl group, 2-chloro-1,1,2,2-tetrafluoroethyl group, 1,2-dichloro-1,2,2- Trifluoroethyl group, 2-bromo-1,1,2,2-tetrafluoroethyl group, 2-fluoropropyl group, 2-chloropropyl group, 2-bromopropyl group, 2-chloro-2-fluoropropyl group, 2,3-dichloropropyl group, 2-bromo-3-fluoropropyl group, 3-bromo-2-chloropropyl group, 2,3-dibromopropyl group, 3,3,3-trifluoropropyl group, 3-bu Mo-3,3-difluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2-chloro-3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoro Propyl group, 1,1,2,3,3,3-hexafluoropropyl group, heptafluoropropyl group, 2,3-dichloro-1,1,2,3,3-pentafluoropropyl group, 2-fluoro- 1-methylethyl group, 2-chloro-1-methylethyl group, 2-bromo-1-methylethyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, 1,2,2 2,2-tetrafluoro-1- (trifluoromethyl) ethyl group, 2,2,3,3,4,4-hexafluorobutyl group, 2,2,3,4,4,4-hexafluorobutyl group, 2,2,3,3,4,4,4-hepp Tafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, nonafluorobutyl group, 4-chloro-1,1,2,2,3,3,4,4 -Octafluorobutyl group, 2-fluoro-2-methylpropyl group, 2-chloro-1,1-dimethylethyl group, 2-bromo-1,1-dimethylethyl group, 5-chloro-2,2,3, Specific examples include a 4,4,5,5-heptafluoropentyl group, a tridecafluorohexyl group, and the like, which are selected within the range of each specified number of carbon atoms.

  The notation of a cycloalkyl group having a carbon number of ab in the above formula (1) represents a cyclic hydrocarbon group having a carbon number of ab, and represents a monocyclic ring having 3 to 6-membered rings or A complex ring structure can be formed. Further, each ring may be arbitrarily substituted by an alkyl group within a specified number of carbon atoms. For example, cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, 2,2,3,3-tetramethylcyclopropyl group, cyclobutyl group, cyclopentyl group, 2- Specific examples include a methylcyclopentyl group, a 3-methylcyclopentyl group, a cyclohexyl group, a 2-methylcyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, and a bicyclo [2.2.1] heptane-2-yl group. And are selected within the range of each specified number of carbon atoms.

  The notation of a halocycloalkyl group having a carbon number of ab in the above formula (1) is a cyclic ring having a carbon number of ab in which a hydrogen atom bonded to a carbon atom is arbitrarily substituted by a halogen atom. Which can form a monocyclic or complex ring structure of three to six membered rings. Further, each ring may be arbitrarily substituted with an alkyl group in the range of the specified number of carbon atoms, and the substitution with a halogen atom may be a ring structure part, a side chain part, or Both may be used, and when substituted by two or more halogen atoms, those halogen atoms may be the same as each other or different from each other. For example, 2,2-difluorocyclopropyl, 2,2-dichlorocyclopropyl, 2,2-dibromocyclopropyl, 2,2-difluoro-1-methylcyclopropyl, 2,2-dichloro-1-methyl Cyclopropyl group, 2,2-dibromo-1-methylcyclopropyl group, 2,2,3,3-tetrafluorocyclobutyl group, 2- (trifluoromethyl) cyclohexyl group, 3- (trifluoromethyl) cyclohexyl group , 4- (trifluoromethyl) cyclohexyl group and the like are mentioned as specific examples, and each is selected within the range of the specified number of carbon atoms.

  The notation of an alkenyl group having a carbon number of ab in the above formula (1) is a straight or branched chain having a carbon number of ab and one or two or more carbon atoms in a molecule. Represents an unsaturated hydrocarbon group having a heavy bond, for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-methylethenyl group, a 2-butenyl group, a 1-methyl-2-propenyl group, a 2-methyl-2 -Propenyl group, 2-pentenyl group, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 2-ethyl-2-propenyl group, 1,1-dimethyl-2-propenyl group, 2-hexenyl Groups, 2-methyl-2-pentenyl group, 2,4-dimethyl-2,6-heptadienyl group, 3,7-dimethyl-2,6-octadienyl group and the like. Select in number range It is.

  The notation of a haloalkenyl group having a carbon number of ab in the above formula (1) means that a hydrogen atom bonded to a carbon atom is arbitrarily substituted by a halogen atom, and a straight chain composed of ab carbon atoms. Represents an unsaturated hydrocarbon group having a single or branched chain and having one or two or more double bonds in a molecule. At this time, when substituted by two or more halogen atoms, those halogen atoms may be the same or different from each other. For example, 2,2-dichlorovinyl group, 2-fluoro-2-propenyl group, 2-chloro-2-propenyl group, 3-chloro-2-propenyl group, 2-bromo-2-propenyl group, 3-bromo-2 -Propenyl group, 3,3-difluoro-2-propenyl group, 2,3-dichloro-2-propenyl group, 3,3-dichloro-2-propenyl group, 2,3-dibromo-2-propenyl group, 2, 3,3-trifluoro-2-propenyl group, 2,3,3-trichloro-2-propenyl group, 1- (trifluoromethyl) ethenyl group, 3-chloro-2-butenyl group, 3-bromo-2- Butenyl group, 4,4-difluoro-3-butenyl group, 3,4,4-trifluoro-3-butenyl group, 3-chloro-4,4,4-trifluoro-2-butenyl group, 3-bromo- 2-methyl- - propenyl group, etc. As a specific example, it may be selected from the range of the specified number of carbon atoms.

  The notation of a cycloalkenyl group having a carbon number of ab in the above formula (1) is a cyclic unsaturated hydrocarbon having a carbon number of ab and having one or two or more double bonds. Represents a group and can form a monocyclic or composite ring structure of three to six membered rings. Further, each ring may be optionally substituted by an alkyl group within the range of the specified number of carbon atoms, and the double bond may be either endo- or exo-. For example, 2-cyclopenten-1-yl group, 3-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, bicyclo [2.2.1] -5-heptene- A 2-yl group or the like is mentioned as a specific example, and is selected within the range of each specified number of carbon atoms.

  The notation of the halocycloalkenyl group having a carbon number of ab in the above formula (1) means that a hydrogen atom bonded to a carbon atom is arbitrarily substituted by a halogen atom, and the ring comprises ab carbon atoms. Represents an unsaturated hydrocarbon group having one or two or more double bonds, and can form a monocyclic or composite ring structure of three to six members. Further, each ring may be optionally substituted by an alkyl group within the range of the specified number of carbon atoms, and the double bond may be either endo- or exo-. The substitution with a halogen atom may be a ring structure portion, a side chain portion, or both of them. When substituted by two or more halogen atoms, those halogen atoms May be the same or different from each other. For example, a 2-chlorobicyclo [2.2.1] -5-hepten-2-yl group or the like is mentioned as a specific example, and is selected within the range of each specified number of carbon atoms.

  The expression of the alkynyl group having a carbon number of ab in the above formula (1) is a straight or branched chain having a carbon number of ab and one or two or more triplets in the molecule. Represents an unsaturated hydrocarbon group having a bond, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 1-methyl-2-propynyl group, 2-pentynyl group, 1-methyl-2- Specific examples include a butynyl group, a 1,1-dimethyl-2-propynyl group, and a 2-hexynyl group, which are selected within the range of the specified number of carbon atoms.

  The notation of the haloalkynyl group having a carbon number of ab in the above formula (1) means that a hydrogen atom bonded to a carbon atom is arbitrarily substituted by a halogen atom and a straight chain composed of ab carbon atoms. Represents an unsaturated hydrocarbon group having a single or branched chain and having one or more triple bonds in a molecule. At this time, when substituted by two or more halogen atoms, those halogen atoms may be the same or different from each other. For example, specific examples include a 2-chloroethynyl group, a 2-bromoethynyl group, a 2-iodoethynyl group, a 3-chloro-2-propynyl group, a 3-bromo-2-propynyl group, and a 3-iodo-2-propynyl group. And are selected within the range of each specified number of carbon atoms.

  The notation of an alkoxy group having a carbon number of ab in the above formula (1) represents an alkyl-O- group having the above-mentioned meaning having a carbon number of ab and is, for example, a methoxy group, an ethoxy group, or an n group. -Propyloxy group, i-propyloxy group, n-butyloxy group, i-butyloxy group, s-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group and the like, as specific examples, Each is selected within a specified range of carbon atoms.

  The notation of a haloalkoxy group having a carbon number of ab in the above formula (1) represents a haloalkyl-O- group having the above meaning having a carbon number of ab, and is, for example, a difluoromethoxy group, a trifluoro group. Methoxy group, chlorodifluoromethoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, 2-chloro-1,1,2-trifluoroethoxy group, 2-bromo-1,1,2-trifluoroethoxy group, pentafluoroethoxy group, 2,2-dichloro-1,1,2-trifluoroethoxy group Group, 2,2,2-trichloro-1,1-difluoroethoxy group, 2-bromo-1,1,2,2-tetrafluoroethoxy group, 2,2,3 A tetrafluoropropyloxy group, a 1,1,2,3,3,3-hexafluoropropyloxy group, a 2,2,2-trifluoro-1- (trifluoromethyl) ethoxy group, a heptafluoropropyloxy group, A 2-bromo-1,1,2,3,3,3-hexafluoropropyloxy group and the like are mentioned as specific examples, and are selected within the range of each specified number of carbon atoms.

  The notation of the (alkyl having a carbon number of ab) carbonyl group in the above formula (1) represents the above-mentioned alkyl-C (O)-group having a carbon number of ab and is, for example, acetyl. Group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, 2-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanoyl group, and the like. Selected.

  The notation of the (haloalkyl having a carbon number of ab) carbonyl group in the above formula (1) represents a haloalkyl-C (O)-group having the above-mentioned meaning having a carbon number of ab, and is, for example, fluoro. Acetyl, chloroacetyl, difluoroacetyl, dichloroacetyl, trifluoroacetyl, chlorodifluoroacetyl, bromodifluoroacetyl, trichloroacetyl, pentafluoropropionyl, heptafluorobutanoyl, 3-chloro-2 , 2-dimethylpropanoyl group and the like are mentioned as specific examples, and each is selected within the range of the specified number of carbon atoms.

  The notation of the (alkoxy having a carbon number of ab) carbonyl group in the above formula (1) represents an alkyl-OC (O)-group having the above-mentioned meaning having a carbon number of ab, For example, methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, i-propyloxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group and the like are specific examples. Selected within the specified number of carbon atoms.

  The notation of (haloalkoxy having a carbon number of ab) carbonyl group in the above formula (1) represents a haloalkyl-OC (O)-group having the above-mentioned meaning having a carbon number of ab. For example, a 2-chloroethoxycarbonyl group, a 2,2-difluoroethoxycarbonyl group, a 2,2,2-trifluoroethoxycarbonyl group, a 2,2,2-trichloroethoxycarbonyl group, etc. are mentioned as specific examples. Selected within the specified number of carbon atoms.

  In the above formula (1), the notation of (alkylamino having a carbon number of ab) carbonyl group means carbamoyl in which one of the hydrogen atoms is substituted by an alkyl group having the above-mentioned meaning and having a carbon number of ab. And represents, for example, a methylcarbamoyl group, an ethylcarbamoyl group, an n-propylcarbamoyl group, an i-propylcarbamoyl group, an n-butylcarbamoyl group, an i-butylcarbamoyl group, an s-butylcarbamoyl group, a t-butylcarbamoyl group, and the like. Specific examples are given, and each is selected within the range of the specified number of carbon atoms.

  In the above formula (1), the notation of the (haloalkylamino having a carbon number of ab) carbonyl group is a carbamoyl group in which one of the hydrogen atoms is substituted by the above-mentioned haloalkyl group having a carbon number of ab. And specific examples include a 2-fluoroethylcarbamoyl group, a 2-chloroethylcarbamoyl group, a 2,2-difluoroethylcarbamoyl group, and a 2,2,2-trifluoroethylcarbamoyl group. It is selected in the range of the number of carbon atoms.

  The notation of a di (alkyl having a carbon number of ab) aminocarbonyl group in the above formula (1) means that both hydrogen atoms may be the same or different from each other. Represents a carbamoyl group substituted by an alkyl group having the above-mentioned meaning, for example, N, N-dimethylcarbamoyl group, N-ethyl-N-methylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-di- Specific examples include an n-propylcarbamoyl group and an N, N-di-n-butylcarbamoyl group, which are selected within the range of the specified number of carbon atoms.

Among the substituents R ¹ , R ⁴ , R ⁵ , R ⁶ and R ⁷ of the cinnamic acid derivative represented by the formula (1), among others, each independently represents a hydrogen atom, a halogen atom, an alkyl having 1 to 6 carbon atoms. A substituent selected from the group consisting of a group, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and a nitro group. preferable.

In addition, the substituent R ¹ is preferably a substituent other than a hydrogen atom in the above definition from the viewpoint of alignment sensitivity, and is preferably a halogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. And a substituent selected from the group consisting of a haloalkyl group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and a nitro group.

Examples of the divalent aromatic group of the substituents ^{R 2,} for example, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5, 6-tetrafluoro-1,4-phenylene group and the like; Examples of the divalent alicyclic group of R ² include 1,2-cyclopropylene group, 1,3-cyclobutylene group, and 1,4-cyclohexylene Examples of the divalent heterocyclic group of R ² include a 1,4-pyridylene group, a 2,5-pyridylene group, and a 1,4-furanylene group; and a divalent fused cyclic group of R ² Examples of the group include a 2,6-naphthylene group and the like. R ² is preferably a 1,4-phenylene group.

（上式中、Ｒ^１は、それぞれ、上記式（１）におけるＲ^１と同義である。）のそれぞれで表される桂皮酸誘導体等を挙げることができる。Preferred examples of the compound represented by the above formula (1) include, for example, the following formulas (1-1) to (1-5)

(In the above formulas, R ¹ are each the same meaning as R ¹ in the formula (1).) Of can be mentioned cinnamic acid derivatives represented by each.

  The cinnamic acid derivative represented by the above formula (1) can be synthesized by appropriately combining conventional methods of organic chemistry.

<Reaction of monomer having epoxy group with specific cinnamic acid derivative>
The reaction product (monomer) between the monomer having an epoxy group and the specific cinnamic acid derivative used for preparing the polymer which is the component (A) of the present invention is the monomer having the epoxy group and the specific cinnamic acid as described above. It can be synthesized by reacting with an acid derivative, preferably in the presence of a catalyst, preferably in a suitable organic solvent.
The ratio of the cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 mol, more preferably 0.05 to 1 mol, per 1 mol of the epoxy group contained in the monomer having an epoxy group. 0.3 mol, more preferably 0.1 to 1.1 mol.
As the organic catalyst that can be used here, a compound known as a so-called curing accelerator that promotes a reaction between an organic base or an epoxy compound and an acid anhydride can be used.

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

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

  Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide , Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra -N-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate Quaternary phosphonium salts such as dithiophene; diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; zinc octylate, tin octylate, and aluminum acetylacetone complex; Organic metal compounds; quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride; boron compounds such as boron trifluoride and triphenyl borate; zinc chloride , Stannic chloride, etc .; high melting point dispersion type latent curing accelerators such as amine addition type accelerators such as dicyandiamide or adducts of amines and epoxy resins; the above-mentioned imidazole compounds, organic phosphorus compounds and quaternary Surface of hardening accelerator such as phosphonium salt Polymer-coated microcapsule-type latent curing accelerator; amine salt-type latent curing accelerator; high-temperature dissociation-type thermal cationic polymerization-type latent curing accelerator such as Lewis acid salt and Bronsted acid salt A curing accelerator can be used.

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

  The use ratio of the catalyst is preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, and still more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the monomer having an epoxy group. is there.

Examples of the organic solvent include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, alcohol compounds and the like. Among them, ether compounds, ester compounds, ketone compounds, and alcohol compounds are preferable from the viewpoints of solubility of raw materials and products and easiness of purification of products. The solvent is used in such an amount that the solid content concentration (the ratio of the mass of components other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1% by mass or more, more preferably 5 to 50% by mass. Is done.
The reaction temperature is preferably from 0 to 200 ° C, more preferably from 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

  Thus, a solution containing a monomer which is a reaction product of the monomer having an epoxy group and the cinnamic acid derivative represented by the formula (1) is obtained. This solution may be directly used for the preparation of the polymer as the component (A), the monomer contained in the solution may be isolated and then used for the preparation of the polymer as the component (A), or The separated monomer may be purified and then used for preparing a polymer as the component (A).

<Polymer of component (A)>
The polymer as the component (A) used in the present invention is a polymer obtained by polymerizing a monomer which is a reaction product of the above-mentioned monomer having an epoxy group and the cinnamic acid derivative represented by the above formula (1). . The polymer of the component (A) is a copolymer of a monomer which is a reaction product of the above-mentioned monomer having an epoxy group with the cinnamic acid derivative represented by the above formula (1) and other polymerizable unsaturated compounds. There can be.

  Other polymerizable unsaturated compounds include (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compound, maleimide Examples thereof include compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, and other polymerizable unsaturated compounds.

Specific examples thereof include, as alkyl methacrylates, for example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, Methacryloxyethyl glycoside, 4-hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate Etc .; as alkyl acrylates, for example, methyl Over DOO, isopropyl acrylate and the like; as methacrylic acid cyclic alkyl esters such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl methacrylate, tricyclo [5.2. 1.0 ^2,6 ] decane-8-yloxyethyl methacrylate, isobornyl methacrylate, cholestanyl methacrylate and the like; as the cyclic alkyl acrylate, for example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1] 0.0 ^2,6 ] decane-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl acrylate, isobornyl acrylate, cholestanyl acrylate, etc .; meta Aryl acrylates such as phenyl methacrylate and benzyl methacrylate; aryl acrylates such as phenyl acrylate and benzyl acrylate; unsaturated dicarboxylic diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

  As the bicyclo unsaturated compounds, for example, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 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-dimethoxybicyclo [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-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di ( 2'-Hydroxyethyl) bicyclo [2.2.1] hept-2- 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 and the like; maleimide compounds such as phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like; unsaturated aromatic compounds such as styrene, α-methylstyrene, m- Methylstyrene, p-methylstyrene, vinyltoluene, p Methoxystyrene and the like; conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; and unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; As unsaturated dicarboxylic acids, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .; as unsaturated dicarboxylic anhydrides, each anhydride of the above unsaturated dicarboxylic acids; as a polymerizable unsaturated compound other than the above, For example, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate and the like can be mentioned.

  The copolymerization ratio of the monomer which is the reaction product of the monomer having an epoxy group and the cinnamic acid derivative represented by the above formula (1) in the polymer as the component (A) is preferably at least 30 mol%. , More preferably at least 50 mol%. From the viewpoint of the alignment sensitivity, it is more preferably at least 70 mol%.

  The synthesis of the polymer as the component (A) can be carried out by a known radical polymerization method, preferably in a solvent in the presence of a suitable polymerization initiator.

  Thus, a solution containing the polymer as the component (A) is obtained. This solution may be directly used for the preparation of the liquid crystal aligning agent, the polymer contained in the solution may be isolated and then used for the preparation of the liquid crystal aligning agent, or the isolated polymer may be purified. It may be used for preparing a liquid crystal aligning agent.

<(B) component>
The component (B) in the cured film forming composition of the present invention is a crosslinking agent.
As the crosslinking agent as the component (B), a compound having two or more groups capable of forming a crosslink with the thermally crosslinkable functional group of the component (A) is preferable, for example, a crosslink having two or more methylol groups or alkoxymethyl groups. It is preferably an agent. Examples of compounds having these 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-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 1,6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercially available products, compounds such as glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powder Link (registered trademark) 1174) manufactured by Nippon Cytec Industries (formerly Mitsui Cytec), methylated urea resin (Trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Corporation (former Dainippon Ink and Chemicals, Inc.) Urea / formaldehyde resin manufactured by Kogyo Co., Ltd. (high-condensation type, trade name: Becamine (registered trademark) J-300S, P-955, N).

  Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. Commercially available products are manufactured by Nippon Cytec Industries (formerly Mitsui Cytec) (trade name: Cymel (registered trademark) 1123), manufactured by Sanwa Chemical Co., Ltd. (trade name: Nicaraq (registered trademark) BX-). 4000, BX-37, BL-60, and BX-55H).

  Specific examples of the alkoxymethylated melamine include, for example, hexamethoxymethyl melamine. Commercially available products include methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, and 350) manufactured by Nippon Cytec Industries (formerly Mitsui Cytec), butoxymethyl type melamine Compounds (trade names: Mycoat (registered trademark) 506, 508), methoxymethyl type melamine compounds manufactured by Sanwa Chemical Co., Ltd. (trade names: Nicalac (registered trademark) MW-30, MW-22, MW-) 11, the same MS-001, the same MX-002, the same MX-730, the same MX-750, the same MX-035), the butoxymethyl-type melamine compound (trade name: Nicalac (registered trademark) MX-45, the same MX-410) And MX-302).

  Further, as the crosslinking agent, a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which a hydrogen atom of an amino 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 are mentioned. Commercial products of the melamine compound include Cymel (registered trademark) 303 and the like. Commercial products of the benzoguanamine compound include a commercial name of Cymel (registered trademark) 1123 (all of which are available from Nippon Cytec Industries, Inc.). ) (Formerly manufactured by Mitsui Cytec Co., Ltd.).

  Further, as a crosslinking agent of the component (B), a hydroxymethyl group (that is, a methylol group) or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, etc. A polymer produced by using an acrylamide compound or a methacrylamide compound substituted with, can also be used.

  Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, and N-ethoxymethyl. Copolymers of methacrylamide and benzyl methacrylate, and copolymers of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate, and the like can be mentioned.

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

  Examples of the polymerizable group containing a C = C double bond include an acryl group, a methacryl group, a vinyl group, an allyl group, and a maleimide group.

  The method for obtaining the above polymer is not particularly limited. For example, an acrylic polymer having a specific functional group is generated in advance by a polymerization method such as radical polymerization. Next, a specific functional group of the acrylic polymer is reacted with a compound having an unsaturated bond at a terminal (hereinafter, referred to as a specific compound), whereby a C ＝ C double bond is added to the polymer as the component (B). Can be introduced.

  Here, the specific functional group of the acrylic polymer is a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a functional group such as a phenolic hydroxy group or an isocyanate group, or a plurality of types selected from these. Refers to a functional group.

  In the above-mentioned reaction, a preferable combination of a specific functional group of the acrylic polymer and a functional group of the specific compound and a group involved in the reaction includes a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, and a phenolic hydroxy group. And an epoxy group, a carboxyl group and an isocyanate group, an amino group and an isocyanate group, or a hydroxy group and an acid chloride-group. Further, a more preferable combination is a carboxyl group and an epoxy group in glycidyl methacrylate, or a hydroxy group and an isocyanate group in isocyanate ethyl methacrylate.

  The weight average molecular weight (in terms of polystyrene) of such a polymer is from 1,000 to 500,000, preferably from 2,000 to 200,000, and more preferably from 3,000 to 150,000. And 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 from 1 to 500 parts by mass, more preferably from 100 parts by mass of the polymer as the component (A). 5 parts by mass to 400 parts by mass. If the content of the crosslinking agent is too small, the cured film obtained from the cured film-forming composition will have reduced solvent resistance and will have reduced liquid crystal alignment. On the other hand, if the content is too large, the liquid crystal alignment and storage stability may decrease.

<(C) component>
The cured film forming composition of the present invention may contain, as the component (C), a polymer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group. good.

  Examples of the polymer as the component (C) include acrylic polymers, polyamic acids, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylic acids, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polyalkylene imines, and polyalkylene imines. Examples thereof include polymers having a linear or branched structure such as allylamine, celluloses (cellulose or derivatives thereof), phenol novolak resins and melamine formaldehyde resins, and cyclic polymers such as cyclodextrins.

  Preferred examples of the polymer as the component (C) include acrylic polymers, hydroxyalkylcyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols.

  The acrylic polymer, which is a preferred example of the polymer of the component (C), is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, or a vinyl compound. Any polymer may be used as long as it is a polymer obtained by polymerizing a monomer containing a monomer having a functional group or a mixture thereof, and there is no particular limitation on the type of main chain skeleton and side chain of the polymer constituting the acrylic polymer.

（式中、Ｒ^６２は炭素原子数１〜１２のアルキル基、炭素原子数１〜１２のアルコキシ基又はフェニル基を表す。）で表される基を有するモノマーが挙げられる。Examples of the monomer having a specific functional group include a monomer having a polyethylene glycol ester group, a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms, a monomer having a phenolic hydroxy group, a monomer having a carboxyl group, and having an amino group. A monomer, a monomer having an alkoxysilyl group, and the following formula (2)

(Wherein, R ⁶² represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a phenyl group).

Examples of the monomer having a polyethylene glycol ester groups described above, _H- (OCH ₂ CH ₂₎ monoacrylate or monomethacrylate of n -OH and the like. The value of n is 2 to 50, preferably 2 to 10.

  Examples of the above-mentioned 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, and 4-hydroxybutyl acrylate. And 4-hydroxybutyl methacrylate.

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

  Examples of the above-mentioned monomer having a carboxyl group include acrylic acid, methacrylic acid, and vinylbenzoic acid.

  Examples of the monomer having an amino group described above include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate.

  Examples of the above-mentioned monomer having an alkoxysilyl group include, for example, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyl Examples include trimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane and the like.

In the above formula (2), as the alkyl group having 1 to 12 carbon atoms and the alkoxy group having 1 to 12 carbon atoms in R ⁶² , a group having the corresponding carbon atom among the above-exemplified alkyl groups or alkoxy groups Is mentioned.
Examples of the monomer having a group represented by the above formula (2) include a monomer having a group represented by the following formulas [2-1] to [2-5].

  In the present embodiment, when synthesizing an acrylic polymer as an example of the component (C), a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group are used as long as the effects of the present invention are not impaired. Monomers without any of the groups represented can be used in combination.

  Specific examples of such a monomer include an acrylate compound, a methacrylate compound, a maleimide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl compound.

  As the acrylate compound, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl 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, Beauty 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and 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 the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

  Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

  Examples of the vinyl compound 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 having a specific functional group used to obtain the acrylic polymer which is an example of the component (C) is based on the total amount of all the monomers used to obtain the acrylic polymer which is the component (C). It is preferably at least 2 mol%. If the amount of the monomer having the specific functional group is too small, the resulting cured film tends to have insufficient solvent resistance.

  The method for obtaining the acrylic polymer which is an example of the component (C) is not particularly limited. For example, a monomer containing a monomer having a specific functional group, a monomer having no specific functional group as desired, a polymerization initiator, etc. Is obtained by a polymerization reaction at a temperature of 50 ° C to 110 ° C in a solvent in which At this time, the solvent used is not particularly limited as long as it dissolves a monomer having a specific functional group, a monomer having no specific functional group, a polymerization initiator, and the like, which are optionally used. Specific examples are described in the section of [solvent] described below.

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

  Further, a solution of an acrylic polymer, which is an example of the component (C) obtained by the above method, is put into diethyl ether, water, or the like with stirring to reprecipitate, and the resulting precipitate is filtered and washed. Drying at room temperature or under heating under normal pressure or reduced pressure can give an acrylic polymer powder as an example of the component (C). By the above-mentioned operation, the polymerization initiator and the unreacted monomer which coexist with the acrylic polymer which is an example of the component (C) can be removed, and as a result, the acrylic polymer which is an example of the purified component (C) Powder is obtained. When the purification cannot be sufficiently performed by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

  The acrylic polymer as a preferred example of the component (C) preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and still more preferably 5,000 to 100,000. If the weight-average molecular weight is more than 200,000, the solubility in a solvent may be reduced and handling properties may be reduced. If the weight-average molecular weight is less than 3,000, the curing is insufficient during thermal curing. And the solvent resistance may decrease. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as standard data. Hereinafter, the same applies to this specification.

  Next, polyether polyols, which are preferable examples of the polymer of the component (C), include polyhydric alcohols such as polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, and sorbitol, as well as propylene oxide, polyethylene glycol, and polypropylene. Glycols and the like may be added. Specific examples of the polyether polyols include ADEKA polyether P series, G series, EDP series, BPX series, FC series, CM series, NOOX UNIOX (registered trademark) HC-40, HC-60, and ST- made by ADEKA. 30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400 , Nonion (registered trademark) LT-221, ST-221, OT-221 and the like.

  As a polyester polyol which is a preferable example of the polymer of the component (C), a polyhydric carboxylic acid such as adipic acid, sebacic acid, or isophthalic acid is reacted with a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, or polypropylene glycol. What was made is mentioned. Specific examples of polyester polyols include DIC Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD- X-2555, OD-X-2560, Kuraray 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 and the like.

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

  Examples of the polycarbonate polyol which is a preferable example of the polymer of the component (C) include those obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like. Specific examples of the polycarbonate polyol include Praxel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel, and C-590, C-1050, C-2050, C-2090, and C-3090 manufactured by Kuraray.

  Examples of cellulose which is a preferred example of the polymer of the component (C) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and cellulose. For example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.

  Preferred examples of the polymer of the component (C) include cyclodextrins such as cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, methyl-α-cyclodextrin, methyl-β-cyclodextrin and methyl-cyclodextrin. methylated cyclodextrin such as γ-cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxyethyl- β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl Ru-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2 And hydroxyalkyl cyclodextrins such as 2,3-dihydroxypropyl-β-cyclodextrin and 2,3-dihydroxypropyl-γ-cyclodextrin.

  The melamine formaldehyde resin, which is a preferred example of the polymer of the component (C), includes a resin obtained by polycondensing melamine and formaldehyde.

  In the melamine formaldehyde resin of the component (C), it is preferable that a methylol group generated during polycondensation of melamine and formaldehyde is alkylated from the viewpoint of storage stability. Examples of the melamine formaldehyde resin include a resin having a unit structure represented by the following formula.

上記式中、Ｒ^２１は水素原子または炭素原子数１〜４のアルキル基を表し、ｎは繰り返し単位の数を表す自然数である。

In the above formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is a natural number representing the number of repeating units.

  The method for obtaining the melamine formaldehyde resin as the component (C) is not particularly limited, but generally, melamine and formaldehyde are mixed, and the mixture is made weakly alkaline with sodium carbonate, ammonia, or the like, and then heated at 60 ° C to 100 ° C. Are synthesized. Further, a methylol group can be alkoxylated by reacting with an alcohol.

  The weight average molecular weight of the melamine formaldehyde resin of the component (C) is preferably from 250 to 5,000, more preferably from 300 to 4,000, even more preferably from 350 to 3,500. If the weight average molecular weight is more than 5,000 and is too large, the solubility in a solvent may be reduced and the handleability may be reduced. If the weight average molecular weight is less than 250 and too small, insufficient curing may occur during thermal curing. And the effect of improving solvent resistance may not be sufficiently exhibited.

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

  The phenol novolak resin, which is a preferred example of the specific polymer as the component (C), includes, for example, a phenol-formaldehyde polycondensate.

  In the cured film forming composition of the present embodiment, the polymer as the component (C) may be used in the form of a powder or in the form of a solution in which a purified powder is redissolved in a solvent described below.

  In the cured film forming composition of the present embodiment, the component (C) may be a mixture of plural kinds of polymers exemplified as the component (C).

  The content of the component (C) in the cured film-forming composition of the present invention is preferably 400 parts by mass or less based on 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent as the component (B). And more preferably 10 parts by mass to 380 parts by mass, and still more preferably 40 parts by mass to 360 parts by mass. When the content of the component (C) is too large, the liquid crystal alignment tends to decrease.

<(D) component>
The cured film forming composition of the present invention can further contain a crosslinking catalyst as a component (D) in addition to the components (A) and (B).
As the crosslinking catalyst as the component (D), for example, an acid or a thermal acid generator can be suitably used. This component (D) is effective in accelerating the thermosetting reaction of the cured film forming composition of the present invention.
The component (D) specifically includes a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof as the acid. The thermal acid generator is not particularly limited as long as it is a compound that generates an acid by thermal decomposition during heat treatment, that is, a compound that generates an acid by thermal decomposition at a temperature of 80 ° C. to 250 ° C. .

  Specific examples of the acid include, for example, hydrochloric acid or a salt thereof; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphor Sulfonic 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, A sulfonic acid group-containing compound such as 1H, 2H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, or Its hydrates and salts And the like.

  Compounds that generate an acid by heat include, for example, bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3 -Phenylene squirt (methylsulfonate), pyridinium p-toluenesulfonate, morphonium p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, 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-hydroxy Butyl p- toluenesulfonate, N- ethyl -p- toluenesulfonamide, further represented by the following compound:

等が挙げられる。

And the like.

  The content of the component (D) in the cured film-forming composition of the present invention is preferably 0.01 part by mass relative to 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent as the component (B). Parts to 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 setting the content of the component (D) to 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, when the amount is more than 20 parts by mass, the storage stability of the composition may decrease.

<(E) component>
The present invention can also contain, as the component (E), a component for improving the adhesiveness of the formed cured film (hereinafter, also referred to as an adhesion improving component).

When a cured film formed from the cured film-forming composition of the present embodiment containing the component (E) is used as an alignment material, the polymerizable liquid crystal is formed so that the adhesion between the alignment material and the polymerizable liquid crystal layer is improved. The polymerizable functional group and the crosslinking reaction site of the alignment material can be linked by a covalent bond. As a result, the retardation material of the present embodiment obtained by laminating the cured polymerizable liquid crystal on the alignment material of the present embodiment can maintain strong adhesion even under conditions of high temperature and high humidity , and can be peeled off. Can exhibit high durability.

As the component (E), one or more polymerizable groups react with at least one group A selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, or react with the group A. Compounds having at least one group can be used.
As the component (E), monomers and polymers having a polymerizable group and a group selected from a hydroxy group and an N-alkoxymethyl group are preferable.
Examples of the component (E) include a compound having a hydroxy group and a (meth) acryl group, a compound having an N-alkoxymethyl group and a (meth) acryl group, and a compound having an N-alkoxymethyl group and a (meth) acryl group. And the like. Hereinafter, specific examples are shown.

As an example of the component (E), a polyfunctional acrylate containing a hydroxy group (hereinafter also referred to as a hydroxy group-containing polyfunctional acrylate) can be given.
Examples of the hydroxy group-containing polyfunctional acrylate as an example of the component (E) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

  An example of the component (E) is a compound having one (meth) acryl group and one or more hydroxy groups. Preferred examples of such a compound having one (meth) acryl group and one or more hydroxy groups will be given. The compound of the component (E) is not limited to the following compound examples.

（上記式中、Ｒ^１１は水素原子またはメチル基を表し、ｍは１〜１０の整数を表す。）

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

  Examples of the compound (E) include compounds having at least one polymerizable group containing a C ＝ C double bond and at least one N-alkoxymethyl group in one molecule.

  Examples of the polymerizable group containing a C = C double bond include an acryl group, a methacryl group, a vinyl group, an allyl group, and a maleimide group.

  The N in the N-alkoxymethyl group, that is, the nitrogen atom, is the nitrogen atom of an amide, the nitrogen atom of a thioamide, the nitrogen atom of a urea, the nitrogen atom of a thiourea, the nitrogen atom of a urethane, or the nitrogen atom of a nitrogen-containing heterocycle. And a nitrogen atom bonded to. Therefore, as the N-alkoxymethyl group, a nitrogen atom of an amide, a nitrogen atom of a thioamide, a nitrogen atom of a urea, a nitrogen atom of a thiourea, a nitrogen atom of a urethane, a nitrogen atom bonded to a nitrogen atom adjacent to a nitrogen atom of a nitrogen-containing heterocycle. And a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from atoms and the like.

（式中、Ｒ^３１は水素原子またはメチル基を表し、Ｒ^３２は水素原子、または直鎖若しくは分岐の炭素原子数１乃至１０のアルキル基を表す）The component (E) may have any of the above groups, but preferably includes, for example, a compound represented by the following formula (X1).

(In the formula, 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 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n -Butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl- n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl- n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2 , 3-dimethyl-n-butyl group, 3, -Dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl Group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1-methyl-n-hexyl group, 2-methyl-n-hexyl group , 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1,3-dimethyl-n-pentyl group, 2,2-dimethyl-n -Pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n- Pentyl group, 1-methyl-1-ethyl-n-butyl group, -Methyl-2-ethyl-n-butyl group, 1-ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group , N-octyl group, 1-methyl-n-heptyl group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl- n-hexyl group, 1,3-dimethyl-n-hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1 -Ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl Group, 1-methyl-3-ethyl-n-pentyl group, 2-methyl 2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group and the like. .

  Specific examples of the compound represented by the above formula (X1) include N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) An acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as acrylamide is exemplified. In addition, (meth) acrylamide means both methacrylamide and acrylamide.

式中、Ｒ^５１は水素原子またはメチル基を表す。
Ｒ^５２は炭素原子数２乃至２０のアルキル基、炭素原子数５乃至６の１価の脂肪族環基、若しくは炭素原子数５乃至６の脂肪族環を含む１価の脂肪族基を表し、構造中にエーテル結合を含んでいてもよい。
Ｒ^５３は直鎖または分枝鎖の炭素原子数２乃至２０のアルキレン基、炭素原子数５乃至６の２価の脂肪族環基、若しくは炭素原子数５乃至６の脂肪族環を含む２価の脂肪族基を表し、構造中にエーテル結合を含んでいてもよい。
Ｒ^５４は直鎖または分枝鎖の炭素原子数１乃至２０の２価乃至９価の脂肪族基、炭素原子数５乃至６の２価乃至９価の脂肪族環基、若しくは炭素原子数５乃至６の脂肪族環を含む２価乃至９価の脂肪族基を表し、これらの基の一つのメチレン基または隣り合わない複数のメチレン基がエーテル結合に置き換わっていてもよい。
Ｚは＞ＮＣＯＯ−、または−ＯＣＯＮ＜（ここで「−」は結合手が１つであることを示す。また、「＞」「＜」は結合手が２つであることを示し、かつ、どちらか１つの結合手にアルコキシメチル基（即ち−ＯＲ^５２基）が結合していることを示す。）を表す。
ｒは２以上９以下の自然数である。As another embodiment of the compound having a polymerizable group having a C ＝ C double bond and an N-alkoxymethyl group of the component (E), preferably, for example, a compound represented by the following formula (X2) is exemplified. .

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, The structure may contain an ether bond.
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 group containing an aliphatic ring having 5 to 6 carbon atoms. Which may contain an ether bond in the structure.
R ⁵⁴ is a straight-chain or branched-chain divalent to -9-valent aliphatic group having 1 to 20 carbon atoms, a divalent to 9-valent aliphatic ring group having 5 to 6 carbon atoms, or 5 Represents a divalent to ninth-valent aliphatic group containing 6 to 6 aliphatic rings, and one methylene group or a plurality of non-adjacent methylene groups of these groups may be replaced by an ether bond.
Z is> NCOO- or -OCON <(where "-" indicates that there is one bond; ">" and "<" indicate that there are two bonds; and Represents that an alkoxymethyl group (that is, -OR ⁵² group) is bonded to any one of the bonds.
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 in the definition of ^R53 include a divalent group obtained by removing one hydrogen atom from an alkyl group having 2 to 20 carbon atoms.
Further, as a specific example of the C 1 to C 20 divalent to C 9 -valent aliphatic group in the definition of R ⁵⁴ , 1 to 8 hydrogen atoms are further removed from the C 1 to C 20 alkyl group. Examples thereof include divalent to 9-valent groups.

  The alkyl group having 1 carbon atom is a methyl group, and specific examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl. Group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl- n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 1, 1,2-trimethyl-n-propyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group , N-pentadecyl group, n-hexadecyl group, n A heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-eicosyl group, a cyclopentyl group, a cyclohexyl group, a group in which one or more of them are bonded in a range of up to 20 carbon atoms, and one of these groups Examples include methylene or a group in which a plurality of non-adjacent methylene groups are replaced with ether bonds.

Of these, preferably an alkylene group having 2 to 10 carbon atoms, R ⁵³ is ethylene group, R ⁵⁴ is particularly preferred from the viewpoint of availability of raw materials that hexylene group.

Specific examples of the alkyl group having 1 to 20 carbon atoms in the definition of R ⁵² include 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 preferable, and a methyl group, an ethyl group, an n-propyl group or an n-butyl group is particularly preferable.

  r is a natural number of 2 or more and 9 or less, and among them, a natural number of 2 to 6 is preferable.

  The content of the component (E) in the cured film forming composition of the embodiment of the present invention is preferably 1 to 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent as the component (B). It is from 100 parts by mass to 100 parts by mass, and more preferably from 5 parts by mass to 70 parts by mass. By setting the content of the component (E) to 1 part by mass or more, it is possible to impart sufficient adhesiveness to the formed cured film. However, when the amount is more than 100 parts by mass, the liquid crystal alignment tends to decrease.

  Further, in the cured film forming composition of the present embodiment, the component (E) may be a mixture of a plurality of types of compounds of the component (E).

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

  Specific examples of the solvent include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve 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 Tyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate; Methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, cyclopentyl methyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. Is mentioned.

  When a cured film is formed on a resin film using the cured film-forming composition of the present invention to produce 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, and the like are preferable in that the resin film is a solvent showing resistance. .

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

<Other additives>
Furthermore, the cured film-forming composition of the present invention may contain, as necessary, an adhesion improver, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, and storage stability as long as the effects of the present invention are not impaired. Agents, defoamers, antioxidants and the like.

<Preparation of cured film forming composition>
The composition for forming a cured film of the present invention contains a polymer of the component (A) and a crosslinking agent of the component (B), and optionally a polymer of the component (C), a crosslinking catalyst of the component (D), and adhesion of the component (E). It is a composition which can contain an accelerator and other additives as long as the effects of the present invention are not impaired. And usually, they are used in the form of a solution in which they are dissolved in a solvent.

Preferred examples of the cured film forming composition of the present invention are as follows.
[1]: A cured film-forming composition containing 1 to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A) and the component (A).
[2]: 1 part by mass to 500 parts by mass of component (B), based on 100 parts by mass of component (A) and component (A), and a polymer as component (A) and a crosslinking agent of component (B) The cured film-forming composition contains 1 to 400 parts by mass of the component (C) based on 100 parts by mass of the total amount of the above.
[3]: A cured film-forming composition containing 1 to 500 parts by mass of the component (B) and a solvent based on 100 parts by mass of the component (A) and the component (A).
[4]: The total of 1 part by mass to 500 parts by mass of the component (B), the polymer as the component (A), and the crosslinking agent of the component (B) based on 100 parts by mass of the component (A) and the component (A). A cured film-forming composition containing 1 to 400 parts by mass of the component (C) and a solvent based on 100 parts by mass of the composition.
[5]: The total of 1 part by mass to 500 parts by mass of the component (B), the polymer as the component (A), and the crosslinking agent of the component (B) based on 100 parts by mass of the component (A) and the component (A). 1 to 400 parts by mass based on 100 parts by mass of the component (C), 0.01 parts by mass based on 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent of the component (B). A cured film-forming composition containing 20 parts by mass of the component (D) and a solvent.
[6]: The total of 1 part by mass to 500 parts by mass of the component (B), the polymer as the component (A), and the crosslinking agent of the component (B) based on 100 parts by mass of the component (A) and the component (A). 1 to 400 parts by mass based on 100 parts by mass of the component (C), 0.01 parts by mass based on 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent of the component (B). 20 parts by mass of component (D), 1 part by mass to 100 parts by mass based on 100 parts by mass of the total amount of the polymer as component (A) and the crosslinking agent as component (B), and a solvent A cured film-forming composition comprising:

The mixing ratio and the preparation method when the cured film forming composition of the present invention is used as a solution will be described in detail below.
The proportion of the solid content in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1% by mass to 60% by mass, preferably 2% by mass. It is from 50% by mass to 50% by mass, more preferably from 2% by mass to 20% by mass. Here, the solid content refers to a composition obtained by removing the solvent from all components of the cured film forming composition.

  The method for preparing the cured film-forming composition of the present invention is not particularly limited. As a preparation method, for example, a component (B), a component (C), a component (D), a component (E) and the like are mixed at a predetermined ratio in a solution of the component (A) dissolved in a solvent, and the mixture is uniformly mixed. A method of preparing a solution or a method of adding and mixing other additives as necessary at an appropriate stage of the preparation method may be mentioned.

  In the preparation of the cured film forming composition of the present invention, a solution of the specific copolymer (polymer) obtained by a polymerization reaction in a solvent can be used as it is. In this case, for example, the component (B), the component (C), the component (D), the component (E) and the like are added to the solution of the component (A) in the same manner as described above to form a uniform solution. At this time, a solvent may be additionally introduced for the purpose of adjusting the concentration. At this time, the solvent used in the process of producing the component (A) and the solvent used for adjusting the concentration of the cured film-forming composition may be the same or different.

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

<Curing film, alignment material and retardation material>
A solution of the composition for forming a cured film of the present invention is applied to a substrate (eg, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc.), a glass substrate, a quartz substrate, and ITO. Substrate) or a film substrate (eg, triacetyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET) film, acrylic film, polyethylene On a resin film such as a film, etc., a bar coat, a spin coat, a flow coat, a roll coat, a slit coat, a rotary coat following the slit, an ink jet coat, a print, and the like are applied to form a coat. Hot Dried by heating with a plate or an oven or the like, it is possible to form a cured film. The cured film can be directly used as an alignment material.

  The heating and drying conditions may be such that the crosslinking reaction by the crosslinking agent proceeds to such an extent that the components of the cured film (alignment material) do not elute into the polymerizable liquid crystal solution applied thereon. A heating temperature and a heating time appropriately selected from the range of 200 ° C. and the time of 0.4 to 60 minutes are employed. The heating temperature and the heating time are preferably 70 ° C to 160 ° C, for 0.5 minute 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 is appropriately determined in consideration of the step and optical and electrical properties of the substrate used. You can choose.

  Since the alignment material formed from the cured film composition of the present invention has solvent resistance and heat resistance, a phase difference material such as a polymerizable liquid crystal solution having a vertical alignment property is coated on the alignment material. Can be oriented on an orientation material. Then, by curing the aligned retardation material as it is, the retardation material can be formed as a layer having optical anisotropy. When the substrate on which the alignment material is formed is a film, it is useful as a retardation film.

Further, using the two substrates having the alignment material of the present invention formed as described above, and after bonding the alignment materials on both substrates so as to face each other via a spacer, between the substrates. By injecting liquid crystal, a liquid crystal display element in which liquid crystal is aligned can be obtained.
As described above, the cured film forming composition of the present invention can be suitably used for manufacturing various retardation materials (retardation films), liquid crystal display elements, and the like.

ＣＩＮ２（下記異性体の混合物）

ＣＩＮ３

ＣＩＮ４

＜Ｂ成分＞
ＨＭＭ：下記の構造式で表されるメラミン架橋剤［サイメル（ＣＹＭＥＬ）（登録商標）３０３（三井サイテック（株）製）］

＜Ｄ成分＞
ＰＴＳＡ：ｐ−トルエンスルホン酸・一水和物
＜Ｅ成分＞
Ｅ−１：下記の構造式で示されるヒドロキシ基およびアクリル基を有する化合物

Ｅ−２：下記の構造式で示されるＮ−アルコキシメチル基およびアクリル基を有する化合物

＜溶剤＞
溶剤として、プロピレングリコールモノメチルエーテル（ＰＭ）、シクロヘキサノン（ＣＨ）、シクロペンタノン（ＣＰ）、メチルイソブチルケトン（ＭＩＢＫ）を用いた。Hereinafter, the present invention will be described specifically with reference to examples of the present invention, but the present invention is not construed as being limited thereto.
[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<Raw materials>
GMA: glycidyl methacrylate M100: 3,4-epoxycyclohexylmethyl methacrylate 4MCA: 4-methoxycinnamic acid HEMA: 2-hydroxyethyl methacrylate MMA: methyl methacrylate AIBN: α, α'-azobisisobutyronitrile BMAA: N- Butoxymethylacrylamide CIN1

CIN2 (mixture of the following isomers)

CIN3

CIN4

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

<D component>
PTSA: p-toluenesulfonic acid monohydrate <E component>
E-1: a compound having a hydroxy group and an acrylic group represented by the following structural formula

E-2: Compound having an N-alkoxymethyl group and an acryl group represented by the following structural formula

<Solvent>
As the solvent, propylene glycol monomethyl ether (PM), cyclohexanone (CH), cyclopentanone (CP), and methyl isobutyl ketone (MIBK) were used.

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

Reference Example 1 Synthesis of CIN1 8.3 g (58.4 mmol) of GMA, 20.7 g (116.2 mmol) of 4-methoxycinnamic acid, 0.2 g of dibutylhydroxytoluene, 0.3 g of triphenylethylphosphonium bromide, 80 mL of dioxane And heated at 90 ° C. for 3 days. After completion of the reaction, dioxane was distilled off under reduced pressure, 150 mL of ethyl acetate was added, and the insoluble matter was separated by filtration. Then, 100 mL of aqueous sodium bicarbonate was added and washed three times to remove excess methoxycinnamic acid. Ethyl acetate was distilled off under reduced pressure to obtain 16.5 g of the target product, CIN1 (yield: 88%).

<Reference Example 2> Synthesis of CIN2 4.9 g (25.0 mmol) of M100, 8.9 (50.0 mmol) of 4-methoxycinnamic acid, 0.1 g of dibutylhydroxytoluene, 0.18 g of triphenylethylphosphonium bromide, 40 mL of dioxane Was heated at 90 ° C. for 3 days. After completion of the reaction, dioxane was distilled off under reduced pressure, 100 mL of ethyl acetate was added, and the insoluble material was separated by filtration. Then, 100 mL of aqueous sodium bicarbonate was added, followed by washing three times. Ethyl acetate was distilled off under reduced pressure to obtain 6.3 g of the desired product. (Yield: 74%).

<Reference Example 3> Synthesis of CIN3 CIN3 was synthesized according to the synthesis method described in Table 2013-514449.

Reference Example 4 Synthesis of CIN4 CIN4 was synthesized according to the synthesis method described in Polymer International 43 (1997) 317.

<Synthesis of component A>
<Polymerization Example 1>
15.0 g of CIN1, 1.5 g of HEMA, 0.5 g of AIBN as a polymerization catalyst were dissolved in 122.4 g of PM and 30.6 of CH, and reacted under heating and reflux for 20 hours to obtain an acrylic copolymer (PA-1). ) Was obtained at 10% by mass. Mn of the obtained acrylic copolymer was 12,000 and Mw was 32,000.

<Polymerization Example 2>
15.0 g of CIN1 and 0.4 g of AIBN as a polymerization catalyst were dissolved in 110.4 g of PM and 27.6 of CH, and reacted under heating and refluxing for 20 hours to obtain 10% by mass of an acrylic copolymer (PA-2). A solution containing was obtained. Mn of the obtained acrylic copolymer was 8,100 and Mw was 23,000.

<Polymerization Example 3>
15.0 g of CIN2, 1.3 g of HEMA and 0.4 g of AIBN as a polymerization catalyst were dissolved in 120.0 g of PM and 30.0 of CH, and reacted under heating and reflux for 20 hours to obtain an acrylic copolymer (PA-3). ) Was obtained at 10% by mass. Mn of the obtained acrylic copolymer was 12,000, and Mw was 41,000.

<Polymerization Example 4>
15.0 g of CIN1, 1.5 g of MMA and 0.5 g of AIBN as a polymerization catalyst were dissolved in 122.4 g of PM and 30.6 of CH, and reacted under heating and reflux for 20 hours to obtain an acrylic copolymer (PA-4). ) Was obtained at 10% by mass. Mn of the obtained acrylic copolymer was 11,000 and Mw was 38,000.

<Polymerization Example 5>
15.0 g of CIN3, 1.4 g of HEMA and 0.4 g of AIBN as a polymerization catalyst were dissolved in 121.6 g of PM and 30.4 of CH, and reacted under heating and reflux for 20 hours to obtain an acrylic copolymer (PA-5). ) Was obtained at 10% by mass. Mn of the obtained acrylic copolymer was 9,000 and Mw was 22,000.

<Polymerization Example 6>
15.0 g of CIN4, 1.7 g of HEMA, and 0.5 g of AIBN as a polymerization catalyst were dissolved in 124.0 g of PM and 31.0 of CH, and reacted under heating and reflux for 20 hours to obtain an acrylic copolymer (PA-6). ) Was obtained at 10% by mass. Mn of the obtained acrylic copolymer was 10,000 and Mw was 33,000.

<Polymerization Example 9>
10.0 g of CIN1 and 2.7 g of HEMA, 0.4 g of AIBN as a polymerization catalyst were dissolved in 118.2 g of PM, and the mixture was reacted under heating and reflux for 20 hours to obtain an acrylic copolymer (PA-7) of 10% by mass. A solution containing was obtained. Mn of the obtained acrylic copolymer was 22,000 and Mw was 41,000.

<Synthesis of component B>
<Polymerization Example 7>
Acrylic polymer solution was obtained by dissolving 100.0 g of BMAA and 4.2 g of AIBN as a polymerization catalyst in 193.5 g of PM and reacting at 90 ° C. for 20 hours. Mn of the obtained acrylic polymer was 2,700 and Mw was 3,900. The acrylic polymer solution was gradually dropped into 2000.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PB-1).

<Synthesis of C component>
<Polymerization Example 8>
30.0 g of MMA, 3.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 146.0 g of PM, and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually dropped into 1000.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PC-1). Mn of the obtained acrylic copolymer was 18,000 and Mw was 32,800.

<Preparation of polymerizable liquid crystal solution>
<Preparation Example 1>
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 MIBK as a solvent were added. A polymerizable liquid crystal solution (RM-1) having a solid content of 30% by mass was obtained.

<Preparation Example 2>
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 CP as a solvent were added. A polymerizable liquid crystal solution (RM-2) having a solid content of 30% by mass was obtained.

<Example 1>
(A) an amount equivalent to 100 parts by mass in terms of the acrylic copolymer (PA-1) in a solution containing 10% by mass of the acrylic copolymer (PA-1) obtained in Polymerization Example 1 as a component; 30 parts by mass of HMM as the component (B) and 3 parts by mass of PTSA as the component (D) were mixed, PM and CH were added thereto, the solvent composition was PM: CH = 80: 20 (mass ratio), and the solid content concentration was 5.0% by mass of the alignment material forming composition (A-1) was prepared.

<Examples 2 to 9 and Comparative Examples 1 to 3>
Except that the kind and amount of each component were as shown in Table 1, the same procedure as in Example 1 was carried out to prepare alignment material forming compositions A-2 to A-12, respectively.

<Examples 10 to 18 and Comparative Examples 4 to 6>
[Evaluation of orientation]
The alignment agent compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were applied on a TAC film using a bar coater at a wet film thickness of 4 μm. Heat drying was performed in a heat circulating oven at a temperature of 110 ° C. for 60 seconds, respectively, to form cured films on the TAC film. Each cured film was vertically irradiated with 313 nm linearly polarized light at an exposure of 20 mJ / cm ² to form an alignment material. On the alignment material on the TAC film, a polymerizable liquid crystal solution (RM-1) or (RM-2) was applied at a wet film thickness of 6 μm using a bar coater. This coating film was dried on a hot plate at a temperature of 90 ° C. for 60 seconds, and then exposed at 300 mJ / cm ² to prepare a retardation material. The phase difference material on the prepared substrate is sandwiched between a pair of polarizing plates, and the state of the phase difference characteristics of the phase difference material is observed. The results were described as "Poor" in the column of "Orientation". The evaluation results are summarized in Table 2 later.

  As shown in Table 2, in each of Examples 10 to 18, the obtained retardation material showed good orientation regardless of whether the polymerizable liquid crystal solution RM-1 or RM-2 was used.

  On the other hand, in Comparative Examples 4 and 5, the retardation material obtained using RM-1 showed good orientation, but the retardation material obtained using RM-2 had good orientation. Could not be obtained.

  Further, in Comparative Example 6, no good orientation was obtained in the retardation material using either RM-1 or RM-2.

<Example 19>
(A) an amount corresponding to 100 parts by mass in terms of the acrylic copolymer (PA-7) in a solution containing 10% by mass of the acrylic copolymer (PA-7) obtained in Polymerization Example 9 as the component; 30 parts by mass of HMM as the component (B) and 3 parts by mass of PTSA as the component (D) were mixed, PM and CH were added thereto, the solvent composition was PM: CH = 80: 20 (mass ratio), and the solid content concentration was 5.0% by mass of an alignment material forming composition (A-13) was prepared.

<Examples 20 to 22>
[Evaluation of orientation]
Each of the compositions for alignment agents of Examples 1 to 2 and 19 was applied on a TAC film using a bar coater at a wet film thickness of 4 μm. Each was dried by heating in a heat circulating oven at a temperature of 90 ° C. for 60 seconds to form a cured film on the TAC film. The linearly polarized light of 313nm in the cured film was irradiated perpendicularly with an exposure amount of 5 mJ / cm ² or 20 mJ / cm ^2, to form an alignment material. On the alignment material on the TAC film, a polymerizable liquid crystal solution (RM-1) was applied using a bar coater at a wet film thickness of 6 μm. This coating film was dried on a hot plate at a temperature of 90 ° C. for 60 seconds, and then exposed at 300 mJ / cm ² to prepare a retardation material. The phase difference material on the prepared substrate is sandwiched between a pair of polarizing plates, and the state of the phase difference characteristics of the phase difference material is observed. The results were described as "Poor" in the column of "Orientation". The evaluation results are summarized in Table 3 below.

  The cured film forming composition according to the present invention is very useful as a material for forming a liquid crystal alignment film of a liquid crystal display element or an alignment material for forming an optically anisotropic film provided inside or outside the liquid crystal display element. Particularly, it is suitable as a material for a retardation material of a circularly polarizing plate used as an antireflection film of an IPS-LCD or an organic EL display.

Claims (12)

(A) a polymer obtained using a monomer which is a reaction product of a monomer having an epoxy group and a cinnamic acid derivative represented by the following formula (1), and (B) a cured film-forming composition containing a crosslinking agent object.

(In the formula (1), A ¹ and A ² each independently represent a hydrogen atom or a methyl group, and R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. Haloalkyl group, cycloalkyl group having 3-8 carbon atoms, halocycloalkyl group having 3-8 carbon atoms, alkenyl group having 2-6 carbon atoms, haloalkenyl group having 2-6 carbon atoms, carbon atom Cycloalkenyl group having 3 to 8 carbon atoms, halocycloalkenyl group having 3 to 8 carbon atoms, alkynyl group having 2 to 6 carbon atoms, haloalkynyl group having 2 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms Group, haloalkoxy group having 1 to 6 carbon atoms, (alkyl having 1 to 6 carbon atoms) carbonyl group, (haloalkyl having 1 to 6 carbon atoms) carbonyl group, (alkoxy having 1 to 6 carbon atoms) carbonyl Group, A haloalkoxy) carbonyl group having 1 to 6 carbon atoms, a (alkylamino having 1 to 6 carbon atoms) carbonyl group, a (haloalkyl having 1 to 6 carbon atoms) aminocarbonyl group, a di (having 1 to 6 carbon atoms) Alkyl) aminocarbonyl group, cyano group and nitro group, and R ² represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent group. Wherein R ³ represents a single bond, an oxygen atom, —COO— or —OCO—, and R ^{4 to} R ⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl having 1 to 6 carbon atoms. A haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group, and a substituent selected from the group consisting of a nitro group; n is an integer from 0 to 3 .) The cured film-forming composition according to claim 1, wherein the crosslinking agent (B) is a crosslinking agent having a methylol group or an alkoxymethyl group. 3. The cured film forming composition according to claim 1, further comprising (C) a polymer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group. The cured film-forming composition according to any one of claims 1 to 3, further comprising (D) a crosslinking catalyst. (E) one or more polymerizable groups, at least one group A selected from the group consisting of a hydroxy 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 The cured film-forming composition according to any one of claims 1 to 4, further comprising a compound having the following formula: The cured film-forming composition according to any one of claims 1 to 4, comprising 1 to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A). The composition according to any one of claims 3 to 6, comprising 1 to 400 parts by mass of the component (C) based on 100 parts by mass of the total amount of the crosslinking agent of the component (A) and the component (B). A cured film forming composition. The composition according to any one of claims 4 to 7, comprising 0.01 to 20 parts by mass of the component (D) based on 100 parts by mass of the total amount of the crosslinking agent of the component (A) and the component (B). The composition for forming a cured film according to the above. The composition according to any one of claims 5 to 8, comprising 1 to 100 parts by mass of the component (E) based on 100 parts by mass of the total amount of the crosslinking agent of the component (A) and the component (B). A cured film forming composition. A cured film obtained by curing the cured film forming composition according to claim 1. An alignment material formed by curing the cured film forming composition according to claim 1. A retardation material having a cured film obtained by curing the cured film forming composition according to any one of claims 1 to 9.