阅读说明：本技术 固化膜形成用组合物、取向材和相位差材 (Composition for forming cured film, alignment material, and phase difference material ) 是由 伊藤润 汤川升志郎 于 2018-12-18 设计创作，主要内容包括：本发明提供固化膜形成用组合物,其能够以比较低温和短时间的条件形成作为取向材使用、并在其上配置聚合性液晶的层时显示出优异的液晶取向性、光透过性和耐溶剂性的固化膜。本发明是一种固化膜形成用组合物,含有作为(A)成分的具有麦克尔加成供体部位的化合物、和作为(B)成分的具有麦克尔加成受体部位的化合物,(A)成分和(B)成分中的至少一者含有液晶取向性基。本发明还是使用该组合物得到的固化膜和取向材、使用该取向材形成的相位差材。(The invention provides a composition for forming a cured film, which can form a cured film which is used as an alignment material and shows excellent liquid crystal alignment property, light transmission property and solvent resistance when a layer of polymerizable liquid crystal is arranged on the cured film under relatively mild conditions and short time. The present invention is a composition for forming a cured film, comprising a compound having a Michael addition donor site as a component (A) and a compound having a Michael addition acceptor site as a component (B), wherein at least one of the components (A) and (B) contains a liquid crystal aligning group. The present invention also relates to a cured film and an alignment material obtained using the composition, and a retardation material formed using the alignment material.)

1. A composition for forming a cured film, comprising a compound having a Michael addition donor site as a component (A) and a compound having a Michael addition acceptor site as a component (B),

(A) at least one of the component (A) and the component (B) contains a liquid crystal aligning group.

2. The composition for forming a cured film according to claim 1, wherein the component (A) and the component (B) are the same compound having a Michael addition donor site, a Michael addition acceptor site and a liquid crystal aligning group.

3. The composition for forming a cured film according to claim 1 or 2, wherein the component (A) is at least one member selected from the group consisting of a low-molecular compound (A1) having a liquid crystal alignment group and 1 Michael addition donor site, and a compound (A2) having 2 or more Michael addition donor sites and having no or a liquid crystal alignment group,

(B) the component (A) is at least one selected from a low molecular weight compound (B1) having a liquid crystal alignment group and 1 Michael addition acceptor site, and a compound (B2) having 2 or more Michael addition acceptor sites and having no or a liquid crystal alignment group,

(A2) the component (B2) is a low-molecular compound or a high-molecular compound.

4. The cured film-forming composition according to any one of claims 1 to 3, wherein the Michael addition donor site of component (A) is an active methylene group or an active methine group.

5. The cured film-forming composition according to any one of claims 1 to 4, further comprising (C) a Michael addition reaction catalyst.

6. The composition for forming a cured film according to any one of claims 1 to 5, wherein the Michael addition acceptor site is an acryloyl group.

7. The cured film forming composition according to any one of claims 1 to 6, which comprises the component (B) in an amount of 1 to 2000 parts by mass based on 100 parts by mass of the component (A).

8. The cured film forming composition according to any one of claims 5 to 7, which comprises 0.01 to 20 parts by mass of the component (C) per 100 parts by mass of the total amount of the components (A) and (B).

9. A cured film obtained by using the composition for forming a cured film according to any one of claims 1 to 8.

10. An alignment material obtained by using the cured film-forming composition according to any one of claims 1 to 8.

11. A phase difference material formed by using the alignment material according to claim 10.

Technical Field

The present invention relates to a composition for forming a cured film, an alignment material, and a retardation material, which are capable of forming a cured film in which liquid crystal molecules are aligned. The present invention particularly relates to a cured film-forming composition, an alignment material, and a retardation material which are useful for producing a patterned retardation material which can be used for a circularly polarized light glasses type 3D display and a retardation material used for a circularly polarized light plate which is used as an antireflection film for an organic EL display.

Background

In the case of a circularly polarized glasses type 3D display, a phase difference material is generally disposed on a display element such as a liquid crystal panel on which an image is formed. In this phase difference material, a plurality of 2 phase difference regions having different phase difference characteristics are regularly arranged, and a patterned phase difference material is configured. In the present specification, a retardation material patterned to have a plurality of retardation regions having different retardation characteristics is hereinafter referred to as a patterned retardation material.

The patterned retardation material can be produced by optically patterning a retardation material formed of polymerizable liquid crystal, for example, as disclosed in patent document 1. Optical patterning of a phase difference material formed of polymerizable liquid crystal utilizes a known photo-alignment technique for forming an alignment material of a liquid crystal panel. That is, a coating film made of a photo-alignment material is provided on a substrate, and 2 kinds of polarized light having different polarization directions are irradiated thereto. Then, an alignment material in which 2 liquid crystal alignment regions having different liquid crystal alignment control directions were formed was prepared, and a photo alignment film was obtained. A phase difference material in a solution state containing a polymerizable liquid crystal is applied to the photo-alignment film to align the polymerizable liquid crystal. Then, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.

An antireflection film of an organic EL display is composed of a linear polarizer and an 1/4 wavelength phase difference plate, and external light directed toward a panel surface of an image display panel is converted into linearly polarized light by the linear polarizer and then converted into circularly polarized light by the 1/4 wavelength phase difference plate. Here, although the external light based on the circularly polarized light is reflected on the surface of the image display panel, the rotation direction of the polarizing surface is reversed at the time of the reflection. As a result, the reflected light is converted into linearly polarized light in a direction shielded by the linearly polarizing plate by the 1/4 wavelength phase difference plate, contrary to the arrival time, and then is shielded by the linearly polarizing plate, and as a result, the emission to the outside is remarkably suppressed.

Regarding the 1/4 wavelength retardation plate, patent document 2 proposes a method of forming the optical film by inverse dispersion characteristics by forming a 1/4 wavelength retardation plate by combining a 1/2 wavelength plate and a 1/4 wavelength plate. In the case of this method, the optical film can be configured by the inverse dispersion characteristic using the liquid crystal material based on the positive dispersion characteristic in a wide wavelength band for color image display.

In recent years, materials having inverse dispersion characteristics have been proposed as liquid crystal materials that can be applied to the retardation layer (patent documents 3 and 4). According to such a liquid crystal material having inverse dispersion characteristics, instead of constituting a 1/4 wavelength retardation plate by 2 retardation layers by combining an 1/2 wavelength plate and a 1/4 wavelength plate, an optical film capable of securing a desired retardation in a wide wavelength band can be realized by a simple configuration by constituting a retardation layer by a single layer to secure inverse dispersion characteristics.

An alignment layer is used to align the liquid crystal. As a method for forming an alignment layer, for example, a rubbing method and a photo-alignment method are known, and the photo-alignment method is useful in that it is free from generation of static electricity and dust which are problems of the rubbing method and can control a quantitative alignment treatment.

As a material having photo-alignment properties that can be used for formation of an alignment material using a photo-alignment method, an acrylic resin, a polyimide resin, or the like having a photo-dimerization site such as a cinnamoyl group or a chalcone group in a side chain is known. These resins have been reported to exhibit a property of controlling the alignment of liquid crystals (hereinafter, also referred to as liquid crystal alignment properties) by polarized UV irradiation (see patent documents 5 to 7).

In addition, 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 of the retardation material. If the alignment layer having low solvent resistance is exposed to a solvent, the liquid crystal aligning ability may be significantly reduced.

For example, patent document 8 proposes a liquid crystal aligning agent containing a polymer component having a structure capable of undergoing a crosslinking reaction by light and a structure capable of undergoing crosslinking by heat, and a liquid crystal aligning agent containing a polymer component having a structure capable of undergoing a crosslinking reaction by light and a compound having a structure capable of undergoing crosslinking by heat, in order to obtain a stable liquid crystal aligning capability.

On the other hand, in order to reduce the thermal stress applied to the film substrate, the reduction in temperature of the process for producing the retardation material has been studied. One of the processes that requires the highest temperature for producing the retardation material is to form a liquid crystal alignment film, and the process for forming the liquid crystal alignment film is required to be at a lower temperature.

As a method for forming a liquid crystal alignment film at a low temperature, a thermal crosslinking system has been proposed which uses an acrylic resin and crosslinks the acrylic resin at a relatively low temperature (around 100 ℃) using an acid generated from a thermal acid generator as a catalyst (patent document 9).

Disclosure of Invention

Problems to be solved by the invention

The present invention has been completed based on the above findings and research results. That is, an object of the present invention is to provide a liquid crystal aligning agent for photo-alignment capable of forming an alignment film having excellent solvent resistance and aligning a polymerizable liquid crystal with high sensitivity under relatively low temperature and short time conditions.

Another object and advantage of the present invention is as follows.

Means for solving the problems

The present inventors have made extensive studies in order to achieve the above object, and as a result, have found that a cured film having excellent solvent resistance can be formed under relatively low temperature and short time conditions by selecting a cured film-forming material based on a cured film-forming composition containing a component having a michael addition donor site and a component having a michael addition acceptor site, and that the cured film can align polymerizable liquid crystals with high sensitivity, thereby completing the present invention.

That is, aspect 1 of the present invention relates to a composition for forming a cured film, containing a compound having a Michael addition donor site as component (A) and a compound having a Michael addition acceptor site as component (B),

(A) at least one of the component (A) and the component (B) contains a liquid crystal aligning group.

Aspect 2 relates to the composition for forming a cured film according to aspect 1, wherein the component (a) and the component (B) are the same compound having a michael addition donor site, a michael addition acceptor site, and a liquid crystal aligning group.

Viewpoint 3 relates to the composition for forming a cured film according to viewpoint 1 or 2, wherein the component (a) is at least one selected from the group consisting of a low-molecular compound (a1) having a liquid crystal alignment group and 1 michael addition donor site, and a compound (a2) having 2 or more michael addition donor sites and having no or a liquid crystal alignment group,

(B) the component (A) is at least one selected from a low molecular weight compound (B1) having a liquid crystal alignment group and 1 Michael addition acceptor site, and a compound (B2) having 2 or more Michael addition acceptor sites and having no or a liquid crystal alignment group,

(A2) the component (B2) is a low-molecular compound or a high-molecular compound.

Aspect 4 relates to the composition for forming a cured film according to any one of aspects 1 to 3, wherein the Michael addition donor site of the component (A) is an active methylene group or an active methine group.

Embodiment 5 relates to the composition for forming a cured film according to any one of embodiments 1 to 4, further comprising (C) a Michael addition reaction catalyst.

Embodiment 6 relates to the composition for forming a cured film according to any one of embodiments 1 to 5, wherein the Michael addition acceptor site is an acryloyl group.

The aspect 7 relates to the composition for forming a cured film according to any one of aspects 1 to 6, wherein the component (B) is contained in an amount of 1 to 2000 parts by mass based on 100 parts by mass of the component (A).

The aspect 8 relates to the composition for forming a cured film according to any one of aspects 5 to 7, wherein the component (C) is contained in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

Viewpoint 9 relates to a cured film obtained by using the composition for forming a cured film according to any one of viewpoints 1 to 8.

Viewpoint 10 relates to an alignment material obtained by using the composition for forming a cured film according to any one of viewpoints 1 to 8.

View 11 relates to a phase difference material formed using the alignment material described in view 10.

Effects of the invention

The present invention provides a cured film having excellent solvent resistance and capable of aligning polymerizable liquid crystal with high sensitivity, and a composition suitable for forming the cured film and capable of forming the cured film under relatively low temperature and short time conditions.

The present invention can provide an alignment material having excellent liquid crystal alignment properties and light transmittance properties, and a retardation material that can be optically patterned with high precision.

Detailed Description

< composition for Forming cured film >

The composition for forming a cured film of the present invention contains a component having one or two or more structures selected from the group consisting of a Michael addition donor site, a Michael addition acceptor site, and a liquid crystal alignment group, and the three structures are required to be contained as all the components.

Specifically, the composition for forming a cured film contains a compound having a Michael addition donor site as component (A), a compound having a Michael addition acceptor site as component (B), and at least one of the components (A) and (B) contains a liquid crystal alignment group. The component (a) and the component (B) may be the same compound containing a michael addition donor site, a michael addition acceptor site, and a liquid crystal alignment group at the same time.

The composition for forming a cured film of the present invention contains at least one selected from the group consisting of a low-molecular compound (a1) having a liquid crystal aligning group and 1 michael addition donor site and a compound (a2) having no or no liquid crystal aligning group and 2 or more michael addition donor sites as the component (a), and contains at least one selected from the group consisting of a low-molecular compound (B1) having a liquid crystal aligning group and 1 michael addition acceptor site and a compound (B2) having no or no liquid crystal aligning group and 2 or more michael addition acceptor sites as the component (B), and in this case, the component (a2) and the component (B2) may be low-molecular compounds or high-molecular compounds.

Further, other additives may be contained within a range not to impair the effects of the present invention.

The term "low-molecular-weight compound" as used herein means a compound other than "high-molecular-weight compound (polymer)", and includes compounds other than compounds having a repeating unit (formed by polymerization) in the compound.

Hereinafter, each component will be specifically described.

< Michael addition donor site >

Examples of the Michael addition donor site in the component (A) include a mercapto group, an amino group, an active methylene group and an active methine group.

Active methylene is methylene (-CH)₂-) has a carbonyl group adjacent to it, a methylene group reactive with nucleophiles. In the present invention, the active methylene group means a methylene group (-CH) in the active methylene group₂-) wherein 1 hydrogen atom is substituted with an alkyl group and which is reactive with a nucleophile.

The active methylene group and the active methine group are more preferably represented by the following formula (a 1).

(in the formula (a1), R represents an alkyl group, an alkoxy group or a phenyl group, and the chain line represents a connecting bond.)

In the formula (a1), examples of the alkyl group represented by R include alkyl groups having 1 to 20 carbon atoms, and preferably alkyl groups having 1 to 5 carbon atoms.

Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

Among them, methyl, ethyl, n-propyl and the like are preferable.

Examples of the alkoxy group represented by R in the formula (a1) include an alkoxy group having 1 to 20 carbon atoms, and preferably an alkoxy group having 1 to 5 carbon atoms.

Examples of such an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

Among them, preferred are methoxy group, ethoxy group, n-propoxy group and the like.

Examples of the group represented by the formula (a1) include the following structures. In the structural formula, a chain line indicates a connecting bond.

Method for introducing group (Michael addition donor site) represented by the formula (a1)

As a method for introducing the group represented by the formula (a1) into each component, for example, a method in which a low-molecular compound or polymer having a hydroxyl group is reacted with acyl meldrum's acid obtained by reacting meldrum's acid with an acid chloride is mentioned. This method is well known. Here, R is preferably a methyl group in view of availability, orientation, and the like.

As another method, a method of reacting a low-molecular compound or polymer having a hydroxyl group with t-butyl acetoacetate can be cited. This method is well known. In view of availability, orientation, and the like, R herein is preferably a methyl group.

Further, by copolymerizing a monomer having a michael addition donor site, a compound having 2 or more michael addition donor sites (component (a2) described later) can be obtained as a polymer.

Examples of the monomer having a Michael addition donor site include 2-acetoacetoxyethyl acrylate (ethylene glycol monoacetoacetate monoacrylate), 2-acetoacetoxyethyl methacrylate (ethylene glycol monoacetoacetate monomethacrylate), and the like.

< Michael addition acceptor site >

Examples of the Michael addition acceptor site in the component (B) include a (meth) acryloyl group and a maleimide group, that is, CH₂CH-C (═ O) -radical, CH₂＝C(CH₃) -C (═ O) -yl, and maleimido. In the present specification, the expression "(meth) acryloyl group" or the like indicates both an acryloyl group and a methacryloyl group.

Method for introducing (meth) acryloyl group

As a method for introducing a (meth) acryloyl group into each component, a method of reacting a component having an epoxy group with (meth) acrylic acid by a known method can be exemplified. Further, a method of reacting a copolymer obtained from a monomer having a hydroxyalkyl group such as hydroxyethyl (meth) acrylate with a compound component having a (meth) acryloyl group and an isocyanate group by a known method is exemplified.

< method for introducing Maleimido group >

Examples of the method for introducing a maleimide group into each component include a method in which N- (4-carboxyphenyl) maleimide, N- (4-hydroxyphenyl) maleimide and a component having an epoxy group are reacted by a known method. Further, a method of reacting N- (4-hydroxyphenyl) maleimide with a component having an isocyanate group by a known method can be exemplified.

< liquid Crystal alignment group >

Examples of the liquid crystal alignment group used in the present invention, which is contained in at least one of the component (a) and the component (B), include a vertical alignment group and a photo-alignment group.

< photo-alignment group >

The photo-alignment group in the present invention represents a functional group (also referred to as a photo-dimerization site or a photo-isomerization site) capable of photodimerization or photoisomerization.

The photodimerization site is a site capable of forming a dimer by light irradiation, and specific examples thereof include cinnamoyl group, chalcone group, coumarin group, anthracene group, and the like. Among them, cinnamoyl group having high transparency in the visible light region and photodimerization reactivity is preferable.

The photoisomerization site is a site where a cis-isomer and a trans-isomer change upon irradiation with light, and specific examples thereof include an azobenzene structure, a stilbene structure, and the like. Among them, the azobenzene structure is preferable in view of high reactivity.

The photodimerization site is represented by the following formula [1] or formula [2], which is a further preferred example of the structure of cinnamoyl group.

The above formula [1]In, X¹¹Represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. At this time, the phenyl group and the biphenyl group may be substituted with any one of a halogen atom, an alkyl group, an alkoxy group, and a cyano group.

The above formula [2]In, X¹²Represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group. In this case, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded to the benzene ring via a single bond, an ether bond, an ester bond, an amide bond, or a urea bond.

< method for introducing photo-alignment group >

In order to introduce these photo-alignment groups into the components of the present invention, there may be mentioned: a method of introducing a michael addition donor site to a compound having a photo-alignment group and a hydroxyl group by the method described in the above-mentioned < method of introducing a group (michael addition donor site) represented by formula (a1) > a method of directly using an acrylic monomer having a photo-alignment group or copolymerizing the acrylic monomer, a method of reacting a component having an epoxy group with a cinnamic acid derivative having a carboxyl group (a compound having a photo-alignment group (cinnamoyl group) and a carboxyl group), and the like.

The compound having a photo-alignment group and a hydroxyl group can be represented by any one of the following formulae [ A1] to [ A5 ].

In the formula, A¹And A²Each independently represents a hydrogen atom or a methyl group, X¹Show the mediaA structure in which 1 or 2 or more bonds or groups selected from a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, an amino group, or a combination thereof are bonded to 1 to 3 2-valent groups selected from an alkylene group having 1 to 18 carbon atoms, a phenylene group, a biphenylene group, or a combination thereof.

X²Represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group. In this case, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded to the benzene ring via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.

X³Represents a hydroxyl group, a mercapto group, an amino group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, a phenoxy group, a phenylthio group, a phenylamino group, a biphenylamino group, a phenyl group or a biphenyl group.

X⁴Each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, a 2-valent aromatic ring group, or a 2-valent aliphatic ring group. Wherein the alkylene group having 1 to 20 carbon atoms may be branched or linear.

X represents a single bond, an oxygen atom or a sulfur atom.

Further, the hydrogen atoms on the phenyl group, the biphenyl group, the phenylene group and the biphenylene group in these groups may be substituted by 1 or more substituents which may be the same or different, selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group and a cyano group.

In the above formula, R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group or a cyano group.

Specific examples of the compound having a photo-alignment group and a hydroxyl group include methyl 4- (8-hydroxyoctyloxy) cinnamate, methyl 4- (6-hydroxyhexyloxy) cinnamate, methyl 4- (4-hydroxybutoxy) cinnamate, methyl 4- (3-hydroxypropoxy) cinnamate, methyl 4- (2-hydroxyethoxy) cinnamate, methyl 4-hydroxymethoxycinnamate, methyl 4-hydroxycinnamate, ethyl 4- (8-hydroxyoctyloxy) cinnamate, ethyl 4- (6-hydroxyhexyloxy) cinnamate, ethyl 4- (4-hydroxybutoxy) cinnamate, ethyl 4- (3-hydroxypropoxy) cinnamate, ethyl 4- (2-hydroxyethoxy) cinnamate, ethyl 4-hydroxyethoxy) cinnamate, ethyl 2-hydroxy-propoxy-ethyl cinnamate, ethyl 4- (2-hydroxyethoxy) cinnamate, and the like, Ethyl 4-hydroxymethoxycinnamate, ethyl 4-hydroxycinnamate, phenyl 4- (8-hydroxyoctyloxy) cinnamate, phenyl 4- (6-hydroxyhexyloxy) cinnamate, phenyl 4- (4-hydroxybutoxy) cinnamate, phenyl 4- (3-hydroxypropoxy) cinnamate, phenyl 4- (2-hydroxyethoxy) cinnamate, phenyl 4-hydroxymethoxycinnamate, phenyl 4-hydroxycinnamate, biphenyl 4- (8-hydroxyoctyloxy) cinnamate, biphenyl 4- (6-hydroxyhexyloxy) cinnamate, biphenyl 4- (4-hydroxybutoxy) cinnamate, biphenyl 4- (3-hydroxypropoxy) cinnamate, biphenyl 4- (3-hydroxyhexyloxy) cinnamate, biphenyl derivatives of the above compounds, and mixtures thereof, Biphenyl 4- (2-hydroxyethoxy) cinnamate, biphenyl 4-hydroxymethoxycinnamate, biphenyl 4-hydroxycinnamate, 8-hydroxyoctyl cinnamate, 6-hydroxyhexyl cinnamate, 4-hydroxybutyl cinnamate, 3-hydroxypropyl cinnamate, 2-hydroxyethyl cinnamate, hydroxymethyl cinnamate, 4- (8-hydroxyoctyloxy) azobenzene, 4- (6-hydroxyhexyloxy) azobenzene, 4- (4-hydroxybutoxy) azobenzene, 4- (3-hydroxypropoxy) azobenzene, 4- (2-hydroxyethoxy) azobenzene, 4-hydroxymethoxyazobenzene, 4-hydroxyazobenzene, 4- (8-hydroxyoctyloxy) chalcone, phenol, 4- (6-hydroxyhexyloxy) chalcone, 4- (4-hydroxybutoxy) chalcone, 4- (3-hydroxypropoxy) chalcone, 4- (2-hydroxyethoxy) chalcone, 4-hydroxymethoxychalcone, 4-hydroxychalcone, 4 ' - (8-hydroxyoctyloxy) chalcone, 4 ' - (6-hydroxyhexyloxy) chalcone, 4 ' - (4-hydroxybutoxy) chalcone, 4 ' - (3-hydroxypropoxy) chalcone, 4 ' - (2-hydroxyethoxy) chalcone, 4 ' -hydroxymethoxychalcone, 4 ' -hydroxychalcone, 7- (8-hydroxyoctyloxy) coumarin, 7- (6-hydroxyhexyloxy) coumarin, and mixtures thereof, 7- (4-hydroxybutoxy) coumarin, 7- (3-hydroxypropoxy) coumarin, 7- (2-hydroxyethoxy) coumarin, 7-hydroxymethoxycoumarin, 7-hydroxycoumarin, 6-hydroxyoctyloxycoumarin, 6-hydroxyhexyloxycoumarin, 6- (4-hydroxybutoxy) coumarin, 6- (3-hydroxypropoxy) coumarin, 6- (2-hydroxyethoxy) coumarin, 6-hydroxymethoxycoumarin, 6-hydroxycoumarin.

The compound having a photo-alignment group and a carboxyl group is represented by the following formula.

In the formula (1), A¹¹And A¹²Each independently represents a hydrogen atom or a methyl group.

R¹¹Represents a hydrogen atom, a halogen atom, C₁～C₆Alkyl radical, C₁～C₆Haloalkyl, C₁～C₆Alkoxy radical, C₁～C₆Haloalkoxy, C₃～C₈Cycloalkyl radical, C₃～C₈Halogenocycloalkyl, C₂～C₆Alkenyl radical, C₂～C₆Haloalkenyl, C₃～C₈Cycloalkenyl radical, C₃～C₈Halogenocycloalkenyl, C₂～C₆Alkynyl, C₂～C₆Halogenated alkynyl, C₁～C₆Alkoxy radical, C₁～C₆Haloalkoxy, (C)₁～C₆Alkyl) carbonyl (C)₁～C₆Haloalkyl) carbonyl, (C)₁～C₆Alkoxy) carbonyl (C)₁～C₆Haloalkoxy) carbonyl, (C)₁～C₆Alkylamino) carbonyl group, (C)₁～C₆Haloalkyl) aminocarbonyl, di (C)₁～C₆Alkyl) aminocarbonyl group, cyano group, nitro group and a group in the following formula (c-2),

(in the formula (c-2), the chain-dotted line represents a connecting bond, R¹⁰¹Is an alkylene group having 1 to 30 carbon atoms, wherein 1 or more hydrogen atoms in the alkylene group may be replaced with a fluorine atom or an organic group. This is achieved byOuter, R¹⁰¹In (C-CH)₂CH₂-may be replaced with-CH ═ CH-, and further may be replaced with a group selected from-O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, and-CO-listed below, provided that these groups are not adjacent to each other, and M¹Is a hydrogen atom or a methyl group. )

R¹²Is a 2-valent aromatic group, a 2-valent alicyclic group, a 2-valent heterocyclic group or a 2-valent condensed cyclic group,

R¹³is a single bond, an oxygen atom, -COO-or-OCO-,

R¹⁴～R¹⁷each independently represents a group selected from 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, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and a nitro group, and n is an integer of 0 to 3. )

Preferable examples of the compound represented by the formula (1) include compounds represented by the following formulae (1-1) to (1-5).

(in the above formula, R¹¹Are respectively related to R in the formula (1)¹¹The meaning is the same. )

In the compound represented by the above formula (1), R is¹¹Preferable examples of the compound represented by the formula (c-2) include, for example, the following formulae M1-1 to M1-5.

(in the formula, M¹Is a hydrogen atom or a methyl group, and s1 represents the number of methylene groups and is a natural number of 2 to 9. )

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

Examples of the monomer having a photodimerized moiety include monomers having a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, and the like. Among them, a monomer having a cinnamoyl group which is excellent in transparency in the visible light region and in photodimerization reactivity is particularly preferable.

Particularly, a cinnamoyl group-containing monomer having a structure represented by the above formula [1] or formula [2] is more preferable. Specific examples of such monomers are represented by the following formula [3] or formula [4 ].

Said formula [3]In, X¹¹Represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. At this time, the phenyl group and the biphenyl group may have any one of a halogen atom, an alkyl group, an alkoxy group, and a cyano group as a substituent.

The above formula [4]In, X¹²Represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group. In this case, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded to the benzene ring via a single bond, an ether bond, an ester bond, an amide bond, or a urea bond.

The above formula [3]Or formula [4]In, X¹³And X¹⁵Each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, a 2-valent aromatic ring group, or a 2-valent aliphatic ring group. The alkylene group having 1 to 20 carbon atoms may be branched or linear, may have a hydroxyl group substituent, or may be interrupted with at least one bond selected from an ether bond, an ester bond, an amide bond, a urea bond and a urethane bond interposed therebetween. X¹⁴And X¹⁶Represents a polymerizable group. Specific examples of the polymerizable group include an acryloyl group, a methacryloyl group, a styryl group, a maleimide group, an acrylamide group, and a methacrylamide group.

Further, the compound having the photo-alignment group and the hydroxyl group and the monomer having the photo-alignment group are known. Can be produced by the methods described in Japanese patent laid-open publication No. 62-284350, U.S. Pat. No. 4,696,990, Japanese patent laid-open publication No. 9-118717, U.S. Pat. No. 6,107,427, and the like.

Further, as the monomer having a photodimerization site, a compound obtained by reacting the cinnamic acid derivative represented by the above formulas (1-1) to (1-5) with a (meth) acrylic monomer having an epoxy group can be preferably used.

< vertical orientation radical >

The vertical alignment group is not particularly limited, and is preferably a group containing a hydrocarbon group having about 6 to 20 carbon atoms, and more preferably a group represented by formula (2).

In the formula (2), Y¹Represents a single bond or is selected from-O-, -CH₂A binding group of O-, -COO-, -OCO-, -NHCO-, -NH-CO-O-and-NH-CO-NH-, Y²Represents a single bond, an alkylene group having 1 to 15 carbon atoms or-CH₂-CH(OH)-CH₂-radical, or represents a 2-valent cyclic radical chosen from a phenyl ring, a cyclohexyl ring or a heterocycle, any hydrogen atom of which may be replaced by Z, Y³Represents a single bond or an alkylene group having 1 to 15 carbon atoms, Y⁴Represents a single bond, or a 2-valent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocycle, or a 2-valent organic group having a steroid skeleton and having 17 to 30 carbon atoms, wherein any hydrogen atom in the cyclic group may be replaced by Z, and Y is⁵Represents a 2-valent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring, any hydrogen atom on the cyclic groups can be replaced by Z, m represents an integer of 0-4, Y is more than 2⁵May be the same or different from each other, Y⁶Represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorinated alkoxy group having 1 to 18 carbon atoms, Z represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and may have 1 to 3 of the above-mentioned binding groups, Y and Z are not adjacent to each other, provided that the binding groups are not adjacent to each other²～Y⁶Middle alkyleneradical-CH₂-CH(OH)-CH₂A group-a 2-valent cyclic group, a 2-valent organic group having a steroid skeleton, an alkyl group and a fluorinated alkyl group, and may be bonded to the adjacent groups via the above-mentioned bonding group. But Y is²～Y⁶The total number of carbon atoms of the substituent is 6-30.

Examples of the alkylene group having 1 to 15 carbon atoms include a 2-valent group obtained by removing 1 hydrogen atom from an alkyl group having 1 to 15 carbon atoms among alkyl groups having 1 to 18 carbon atoms described later, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group.

Specific examples of the heterocyclic ring include a pyrrole ring, an imidazole ring, and,An azole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, a purine ring, a thiadiazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a cinnoline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, a phenanthroline ring, a quinoline ring, a carbazole ring, a purine ring, a pyrimidine ring, a pyrazole ring, a pyrazoline ring,

and a diazole ring, an acridine ring, etc., among which a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyrazoline ring, a carbazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, and a benzimidazole ring are preferable.

Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a1, 1-dimethyl-n-propyl group, a1, 2-dimethyl-n-propyl group, a2, 2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a cyclopentyl group, a 1-methylcyclobutyl group, a 2-methylcyclobutyl group, a 3-methylcyclobutyl group, a1, 2-dimethylcyclopropyl group, a2, 3-dimethylcyclopropyl group, a 1-ethylcyclopropyl group, a 2-ethylcyclopropyl group, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1-dimethyl-n-butyl, 1, 2-dimethyl-n-butyl, 1, 3-dimethyl-n-butyl, 2, 2-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, 3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 1,2, 2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1, 2-dimethylcyclobutyl, 1, 2-dimethylcyclopentyl, 1,1, 3-dimethylcyclobutyl, 2, 2-dimethylcyclobutyl, 2, 3-dimethylcyclobutyl, 2, 4-dimethylcyclobutyl, 3-dimethylcyclobutyl, 1-propylcyclopropyl, 2-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2, 2-trimethylcyclopropyl, 1,2, 3-trimethylcyclopropyl, 2,2, 3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl, 3-methyl-n-hexyl, 1, 1-dimethyl-n-pentyl, 1, 2-dimethyl-n-pentyl, 1, 3-dimethyl-n-pentyl, 2-dimethyl-n-pentyl, 2, 3-dimethyl-n-pentyl, 3-dimethyl-n-pentyl, 1-ethyl-n-pentyl, 2-ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1-ethyl-n-butyl, 1-methyl-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n-butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1-dimethyl-n-hexyl, 1, 2-dimethyl-n-hexyl, 1, 3-methyl-n, 1, 3-dimethyl-n-hexyl group, 2-dimethyl-n-hexyl group, 2, 3-dimethyl-n-hexyl group, 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-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, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group and the like.

Examples of the alkoxy group having 1 to 18 carbon atoms include groups in which the alkyl group having 1 to 18 carbon atoms is bonded to an oxygen atom (-O-).

Examples of the fluorinated alkyl group having 1 to 18 carbon atoms include those wherein at least 1 hydrogen atom in the alkyl group having 1 to 18 carbon atoms is replaced with a fluorine atom. Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, heptafluoropropyl, 2,2,3,3, 3-pentafluoropropyl, 2,2,3, 3-tetrafluoropropyl, 2,2, 2-trifluoro-1- (trifluoromethyl) ethyl, nonafluorobutyl, 4,4, 4-trifluorobutyl, undecafluoropentyl, 2,2,3,3,4,4,5,5, 5-nonafluoropentyl, 2,2,3,3,4,4,5, 5-octafluoropentyl, tridecafluorohexyl, 2,2,3,3,4,4,5,5,6,6, 6-undecafluorohexyl, 2,2,3,3,4,4,5,5,6, 6-decafluorohexyl, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl and the like.

Specific examples of the fluorinated alkoxy group having 1 to 18 carbon atoms include a group in which the fluorinated alkyl group having 1 to 18 carbon atoms is bonded to an oxygen atom (-O-), and specific examples thereof include a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a pentafluoroethoxy group, a2, 2, 2-trifluoroethoxy group, a heptafluoropropoxy group, a2, 2,3,3, 3-pentafluoropropoxy group, a2, 2,3, 3-tetrafluoropropoxy group, a2, 2, 2-trifluoro-1- (trifluoromethyl) ethoxy group, a nonafluorobutoxy group, a 4,4, 4-trifluorobutoxy group, an undecafluoropentyloxy group, a2, 2,3,3,4,4,5,5, 5-nonafluoropentyloxy group, a2, 2,3,3,4,4,5, 5-octafluoropentyloxy group, a tridecafluorohexyloxy group, 2,2,3,3,4,4,5,5,6,6, 6-undecafluorohexanyloxy, 2,3,3,4,4,5,5,6, 6-decafluorohexyloxy, 3,3,4,4,5,5,6,6, 6-nonafluorohexyloxy and the like.

Examples of the alkyl group having 1 to 3 carbon atoms in Z include alkyl groups having 1 to 3 carbon atoms among the groups exemplified by the above-mentioned groups having 1 to 18 carbon atoms, alkoxy groups having 1 to 3 carbon atoms, examples of the fluorinated alkyl group having 1 to 3 carbon atoms include an alkoxy group having 1 to 3 carbon atoms (a group in which an alkyl group having 1 to 3 carbon atoms is bonded to an oxygen atom (-O-)) of the groups exemplified as the alkoxy group having 1 to 18 carbon atoms, examples of the fluorinated alkyl group having 1 to 3 carbon atoms among the groups exemplified as the fluorinated alkyl group having 1 to 18 carbon atoms include a fluorinated alkoxy group having 1 to 3 carbon atoms, examples thereof include those having 1 to 3 carbon atoms among the groups exemplified as the fluorinated alkoxy group having 1 to 18 carbon atoms.

Furthermore, Y²～Y⁶The total number of carbon atoms of the substituents represented by each is 6 to 30, preferably 6 to 20.

In particular, the vertical alignment group is preferably a group containing an alkyl group having 7 to 18 carbon atoms, particularly 8 to 15 carbon atoms, from the viewpoint of the vertical alignment property, coatability, and the like of the obtained liquid crystal polymer.

Specific examples of the vertical alignment group include hydrocarbon groups having about 6 to 20 carbon atoms. Examples of the hydrocarbon group having 6 to 20 carbon atoms include a hydrocarbon group having 6 to 20 carbon atoms which contains a linear, branched or cyclic alkyl group having 6 to 20 carbon atoms or an aromatic group.

Accordingly, the above formula (2) is preferably Y¹、Y²And Y⁴Is a single bond, Y³Is a single bond or an alkylene group having 1 to 15 carbon atoms (preferably an alkylene group having 1 to 15 carbon atoms), m is 0, Y⁶Is C1-18 alkyl, Y³And Y⁶The alkyl group (a-1) having 6 to 20 total carbon atoms, preferably an alkyl group having 7 to 18 total carbon atoms, more preferably an alkyl group having 8 to 15 total carbon atoms.

Specific examples of the vertically aligning group (a-1) include n-nonadecyl groups, n-eicosyl groups, and the like, in addition to the alkyl groups having 6 to 18 carbon atoms exemplified as the alkyl groups having 1 to 18 carbon atoms.

In addition to the vertically aligning group (a-1), for example, Y is¹～Y⁴Is a single bond, m is 2 or 3, Y⁵Is a benzene ring or a cyclohexane ring, Y⁶The vertically-oriented group (a-2) having 1 to 18 carbon atoms can be preferably used.

Specific examples of such a vertically-oriented group (a-2) include, but are not limited to, the groups shown in the following (a-2-1) to (a-2-6).

(in the formula, Y⁶And Y in the above formula (2)⁶The meaning is the same. )

< method for introducing vertical alignment group >

In order to introduce the above-described vertical alignment group into each component of the present invention, there may be mentioned: a method of introducing a Michael addition donor site to a compound having a vertically-aligning group and a hydroxyl group by the method described in the above < method of introducing a group (Michael addition donor site) represented by the formula (a1) > a method of directly using or copolymerizing an acrylic monomer having a vertically-aligning group, a method of reacting a component having an epoxy group with a compound having a carboxyl group bonded to a vertically-aligning group, and the like.

Examples of the monomer having a vertically-oriented group include compounds corresponding to alkyl esters of (meth) acrylic acid, alkyl vinyl ethers, 2-alkylstyrene, 3-alkylstyrene, 4-alkylstyrene, and N-alkylmaleimide, in which the number of carbon atoms in the alkyl group in these compounds is 6 to 20.

These monomers can be produced by a known method and can be obtained as a commercially available product.

When a (meth) acrylic monomer having a vertically-oriented group represented by the above formula (2) is used to introduce a vertically-oriented group into a polymer, the vertically-oriented side chain is represented by the following formula (2').

(in the formula, Y¹、Y²、Y³、Y⁴、Y⁵、Y⁶And m is the same as each group in the formula (2). ) < (A1) A Low-molecular Compound having a liquid Crystal alignment group and 1 Michael addition Donor site

Examples of the low-molecular compound (a1) having a liquid crystal aligning group and 1 michael addition donor site include: a compound obtained by introducing a Michael addition donor site to the compound having a photo-alignment group and a hydroxyl group according to the method described in the < method for introducing a group (Michael addition donor site) represented by the formula (a1) > and a compound obtained by introducing a Michael addition donor site to the compound having a vertically-aligned group and a hydroxyl group according to the method described in the < method for introducing a group (Michael addition donor site) represented by the formula (a1) > and the like.

< (A2) A Compound having 2 or more Michael addition Donor sites (Low molecular weight Compound) >

When the compound (a2) having 2 or more michael addition donor sites is a low-molecular compound, examples of the low-molecular compound (a2) include: a compound obtained by introducing a Michael addition donor site into a low-molecular-weight compound having 2 or more hydroxyl groups, a polyfunctional thiol, a diamine, or the like, according to the method described in < method for introducing a group (Michael addition donor site) represented by formula (a1) >.

< Low molecular weight Compound having 2 or more hydroxyl groups >

Specific examples of the 2-membered alcohol having 2 alcoholic hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, pentanediol, hexanediol, heptanediol, nonanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 2- (5-ethyl-5-hydroxymethyl-1, 3-dioxan-2-yl) -2-methylpropan-1-ol (DOG), N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-t-butyldiethanolamine, N-lauryldiethanolamine, stearyldiethanolamine, N-phenyldiethanolamine, and the like, M-tolyldiethanolamine, p-tolyldiethanolamine, and the like.

Specific examples of the 3-membered alcohol having 3 alcoholic hydroxyl groups include trimethylolethane, trimethylolpropane, glycerol, tris (2-hydroxyethyl) isocyanurate, hexanetriol, octanetriol, decanetriol, triethanolamine, triisopropanolamine, and the like.

Specific examples of the 4-membered alcohol having 4 alcoholic hydroxyl groups include ditrimethylolethane, diglycerol, pentaerythritol, and the like.

These polyols may be used singly or in any combination of two or more.

< polyfunctional thiol Compound >

The polyfunctional thiol compound may be obtained as an addition reaction product of a polyol and a monofunctional and/or polyfunctional thiol compound. Specific examples of the compound include 3-functional thiol compounds such as 1,3, 5-tris (3-mercaptopropionyloxyethyl) -isocyanurate and 1,3, 5-tris (3-mercaptobutyryloxyethyl) -isocyanurate (カレンズ MT (registered trademark) NR1 manufactured by SHOWA DENKO K.K.) and trimethylolpropane tris (3-mercaptopropionate); 4-functional thiol compounds such as pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by showa electrical corporation, カレンズ MT (registered trademark) PEI); and 6-functional thiol compounds such as dipentaerythritol hexa (3-propionate).

< diamine >

The diamine component to be used is not particularly limited. Specific examples thereof are as follows.

Examples of the alicyclic diamine include 1, 4-diaminocyclohexane, 1, 3-diaminocyclohexane, 4 ' -diaminodicyclohexylmethane, 4 ' -diamino-3, 3 ' -dimethyldicyclohexylamine, and isophoronediamine.

Examples of the aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2, 4-diaminotoluene, 2, 5-diaminotoluene, 3, 5-diaminotoluene, 1, 4-diamino-2-methoxybenzene, 2, 5-diaminop-xylene, and 1, 3-diamino-4-chlorobenzene.

Examples of the aromatic-aliphatic diamine include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenylethylamine, 4-aminophenylethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, and mixtures thereof, 4- (4-methylaminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopentyl) aniline, 3- (5-methylaminopentyl) aniline, 4- (5-methylaminopentyl) aniline, 2- (6-aminonaphthyl) methylamine, 3- (6-aminonaphthyl) methylamine, 2- (6-aminonaphthyl) ethylamine, 3- (6-aminonaphthyl) ethylamine and the like.

Examples of the aliphatic diamines include 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, 1, 3-diamino-2, 2-dimethylpropane, 1, 6-diamino-2, 5-dimethylhexane, 1, 7-diamino-2, 5-dimethylheptane, 1, 7-diamino-4, 4-dimethylheptane, 1, 7-diamino-3-methylheptane, 1, 9-diamino-5-methylheptane, and the like.

< (A2) Compound (Polymer) having 2 or more Michael addition Donor sites

When the compound (a2) having 2 or more michael addition donor sites is a polymer (high molecular weight compound), examples of the polymer (a2) include a polymer obtained by introducing a michael addition donor site into a precursor of the polymer (a2) and the polymer (B2) described later according to the method described in the above-mentioned < method for introducing a group (michael addition donor site) represented by formula (a1) >.

In the case where a liquid crystal aligning group is to be introduced into the polymer (a2) having 2 or more michael addition donor sites, the liquid crystal aligning group may be introduced into a precursor of the polymer (a2) and the polymer (B2) described later by the above-described method, or the monomer having the liquid crystal aligning group may be copolymerized in the production of the precursor of the polymer (a2) and the polymer (B2), and then the michael addition donor site may be introduced by the above-described method.

The low-molecular compound having a liquid crystal aligning group and 1 michael addition acceptor site (B1) includes esters obtained using the compound having a liquid crystal aligning group and a hydroxyl group and (meth) acryloyl chloride, esters obtained using the compound having a vertical aligning group and a hydroxyl group and (meth) acryloyl chloride, and the like.

< (B2) Compound having 2 or more Michael addition acceptor sites (Low molecular weight Compound) >

When the compound (B2) having 2 or more michael addition acceptor sites is a low-molecular compound, examples of the low-molecular compound (B2) include polyfunctional (meth) acrylates and bismaleimides.

[ polyfunctional urethane (meth) acrylate compound having 3 or more (meth) acryloyl groups ]

(1) 3-functional (having 3 (meth) acryloyl groups) urethane (meth) acrylates

Specific examples of commercially available products of a polyfunctional urethane (meth) acrylate compound having 3 (meth) acryloyl groups include NK オリゴ UA-7100 (manufactured by NORMAL CORPORATION INDUSTRIAL CO., LTD.); EBECRYL (registered trademark) 204, EBECRYL 205, EBECRYL 264, EBECRYL 265, EBECRYL 294/25HD, EBECRYL 1259, EBECRYL4820, EBECRYL 8311, EBECRYL 8465, EBECRYL 8701, EBECRYL 9260, KRM (registered trademark) 8296, KRM 8667[ all of which are made from ダイセル · オルネクス (strain) ]; violet light (registered trademark) UV-7550B, violet light 7000B, violet light 7510B, violet light 7461TE, and violet light 2750B (all of the above are manufactured by japan synthetic chemical industry co.).

(2) 4-functional (having 4 (meth) acryloyl groups) urethane (meth) acrylates

Specific examples of commercially available products of the polyfunctional urethane (meth) acrylate compound having 4 (meth) acryloyl groups include EBECRYL (registered trademark) 8210, EBECRYL 8405, and KRM (registered trademark) 8528[ both of which are manufactured by ダイセル · オルネクス (ltd.); violet light (registered trademark) UV-7650B (manufactured by Nippon synthetic chemical industries, Ltd.), and the like.

(3) 5-or more functional (having 5 or more (meth) acryloyl groups) urethane (meth) acrylate

Examples of the polyfunctional urethane (meth) acrylate compound having 5 or more (meth) acryloyl groups (i.e., a urethane (meth) acrylate having 5 or more functional groups) include a urethane of pentaerythritol tri (meth) acrylate and hexamethylene diisocyanate, a urethane of pentaerythritol tri (meth) acrylate and toluene diisocyanate, a urethane of pentaerythritol tri (meth) acrylate and isophorone diisocyanate, and a urethane of dipentaerythritol penta (meth) acrylate and hexamethylene diisocyanate.

Commercially available urethane (meth) acrylates having 5 or more functional groups are preferably used, and examples thereof include UA-306H, UA-306T, UA-306I, UA-510H (all of the above are manufactured by Kyoeisha chemical Co., Ltd.); NK オリゴ U-6LPA, NK オリゴ U-10HA, NK オリゴ U-10PA, NK オリゴ U-1100H, NK オリゴ U-15HA, NK オリゴ UA-53H and same as UA-33H (all manufactured by Newzhongcun chemical industry Co., Ltd.); EBECRYL (registered trademark) 220, EBECRYL 1290, EBECRYL 5129, EBECRYL 8254, EBECRYL 8301R, KRM (registered trademark) 8200, KRM 8200AE, KRM8904, and KRM 8452 (all of which are manufactured by ダイセル and オルネクス (ltd.); violet light (registered trademark) UV-1700B, violet light 6300B, violet light 7600B, violet light 7605B, violet light 7610B, violet light 7620EA, violet light 7630B, violet light 7640B, and violet light 7650B (all manufactured by japan chemical industries, ltd.).

(1) 3-functional (having 3 (meth) acryloyl groups) compounds

Examples of the compound having 3 (meth) acryloyl groups include 1,1, 1-trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and glycerol tri (meth) acrylate.

The compound having 3 (meth) acryloyl groups can be suitably used as a commercially available compound, and examples thereof include ビスコート #295 and ビスコート #300[ both manufactured by osaka organic chemical industry (ltd.); ライトアクリレート TMP-A, ライトアクリレート PE-3A, and ライトエステル TMP [ all of which are manufactured by KyoeishｃA chemical Co., Ltd. ]; NK エステル A-9300, NK エステル A-9300-1CL, NK エステル A-TMM-3, NK エステル A-TMM-3L, NK エステル A-TMM-3LM-N, NK エステル A-TMPT and NK エステル TMPT [ all manufactured by Xinzhongcun chemical industry Co., Ltd ]; PETIA, PETRA, TMPTA, EBECRYL (registered trademark) 180[ all manufactured by ダイセル & オルネクス (strain) ], etc.

(2) 4-functional (having 4 (meth) acryloyl groups) compounds

Examples of the compound having 4 (meth) acryloyl groups include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like.

The compound having 4 (meth) acryloyl groups can be suitably used as a commercially available compound, and examples thereof include ビスコート #300 (manufactured by osaka organic chemical industry (ltd.); ライトアクリレート PE-4A (manufactured by Kyoeisha chemical Co., Ltd.); NK エステル AD-TMP and NK エステル A-TMMT (all of which are manufactured by Xinzhongcun chemical industry Co., Ltd.); EBECRYL (registered trademark) 140, EBECRYL 1142, EBECRYL 180[ all of which are manufactured by ダイセル & オルネクス (manufactured by KOKAI Co., Ltd.) ], and the like.

(3) 5-or more functional (having 5 or more (meth) acryloyl groups) compound

Examples of the compound having 5 or more (meth) acryloyl groups include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, and the like.

The compound having 5 or more (meth) acryloyl groups can be suitably used as a commercially available compound, and examples thereof include ビスコート #802 (manufactured by osaka organic chemical industry (ltd.); ライトアクリレート DPE-6A (manufactured by Kyoeisha chemical Co., Ltd.); NK エステル A-9550 and NK エステル A-DPH (all manufactured by Xinzhongcun chemical industry Co., Ltd.); DPHA (manufactured by DPHA, ダイセル & オルネクス, Inc.).

< bismaleimide >

The bismaleimide compound used as the component (B2) in the present invention is represented by the following formula (3).

In the formula, R³³Is an organic group selected from an aliphatic group, an aliphatic group having a cyclic structure and an aromatic group, or an organic group formed by combining a plurality of organic groups selected from the group. R³³The (B) may contain a bond such as an ester bond, an ether bond, an amide bond, or a urethane bond.

Examples of such bismaleimide compounds include N, N '-3, 3-diphenylmethane bismaleimide, N' - (3, 3-diethyl-5, 5-dimethyl) -4, 4-diphenyl-methane bismaleimide, N '-4, 4-diphenylmethane bismaleimide, 3-diphenylsulfone bismaleimide, 4-diphenylsulfone bismaleimide, N' -p-benzophenone bismaleimide, N '-diphenylethane bismaleimide, N' -diphenyl ether bismaleimide, N '- (methylenebis-tetrahydrophenyl) bismaleimide, N' - (3-ethyl) -4, 4-diphenylmethane bismaleimide, N ' - (3, 3-dimethyl) -4, 4-diphenylmethane bismaleimide, N ' - (3, 3-diethyl) -4, 4-diphenylmethane bismaleimide, N ' - (3, 3-dichloro) -4, 4-diphenylmethane bismaleimide, N ' -isophorone bismaleimide, N ' -ditoluidine bismaleimide, N ' -diphenylpropane bismaleimide, N ' -naphthalene bismaleimide, N ' -m-phenylene bismaleimide, N ' -5-methoxy-1, 3-phenylene bismaleimide, 2-bis (4- (4-maleimidophenoxy) phenyl) propane, 2, 2-bis (3-chloro-4- (4-maleimidophenoxy) phenyl) propane, 2-bis (3-bromo-4- (4-maleimidophenoxy) phenyl) propane, 2-bis (3-ethyl-4- (4-maleimidophenoxy) phenyl) propane, 2-bis (3-propyl-4- (4-maleimidophenoxy) phenyl) propane, 2-bis (3-isopropyl-4- (4-maleimidophenoxy) phenyl) propane, 2-bis (3-butyl-4- (4-maleimidophenoxy) phenyl) propane, 2-bis (3-methoxy-4- (4-maleimidophenoxy) phenyl) propane, 1, 1-bis (4- (4-maleimidophenoxy) phenyl) ethane, 1, 1-bis (3-methyl-4- (4-maleimidophenoxy) phenyl) ethane, 1, 1-bis (3-chloro-4- (4-maleimidophenoxy) phenyl) ethane, 1, 1-bis (3-bromo-4- (4-maleimidophenoxy) phenyl) ethane, 3, 3-bis (4- (4-maleimidophenoxy) phenyl) pentane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis (4- (4-maleimidophenoxy) phenyl) propane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis (3, 5-dimethyl-4- (4-maleimidophenoxy) phenyl) propane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis (3, 5-dibromo-4- (4-maleimidophenoxy) phenyl) propane, N ' -ethylenebismaleimide, N ' -hexamethylenebismaleimide, N ' -dodecamethylenebismaleimide, n, N ' -m-xylene bismaleimide, N ' -p-xylene bismaleimide, N ' -1, 3-dimethylene cyclohexane bismaleimide, N ' -2, 4-toluene bismaleimide, N ' -2, 6-toluene bismaleimide, and the like. These bismaleimide compounds are not particularly limited to the above. One of them may be used alone or 2 or more of them may be used in combination.

< (B2) Compound (Polymer) having 2 or more Michael addition acceptor sites

When the compound having 2 or more Michael addition acceptor sites is a polymer (polymer), examples of the polymer (B2) include a polymer having 1 or more side chains each having a polymerizable unsaturated group at the end in the molecule.

The polymer compound having a side chain having a polymerizable unsaturated bond at the end is preferably a polymer compound having a (meth) acryloyl group in2 or more side chains in the molecule.

Examples of the polymer compound include polymer compounds having a (meth) acryloyl group such as urethane acrylic, epoxy acrylic, and various (meth) acrylate esters, and in particular, polyfunctional polymer compounds containing 3 or more (meth) acryloyl groups.

As the polymer compound having a (meth) acryloyl group of the above-mentioned preferred examples, commercially available products can be preferably used, and examples thereof include アクリット 8KX-077, アクリット 8KX-078, アクリット 8KX-089, アクリット 8KX-127, アクリット 8KX-128, アクリット 8KX-012C, アクリット 8KX-014C, アクリット 8KX-018C, アクリット 8KX-052C, アクリット 8KQ-2001, アクリット 8BR-600, アクリット 8UH-1006 and アクリット 8UH-1012[ all of which are available from Dacheng ファインケミカル (strain) ]; SMP-220A, SMP-250A, SMP-360A, SMP-550A (all of the above are made by Kyoeisha chemical Co., Ltd.), and the like.

Examples of the polymer (B2) having 2 or more Michael addition acceptor sites include polymers obtained by introducing Michael addition acceptor sites into the precursors of the polymer (A2) and the polymer (B2) described later by using the aforementioned method for introducing a (meth) acryloyl group or method for introducing a maleimide group.

When a liquid crystal aligning group is to be introduced into the polymer (B2) having 2 or more michael addition acceptor sites, the liquid crystal aligning group may be introduced into a precursor of the polymer (a2) and the polymer (B2) described later by the above-described method, or may be introduced into the michael addition acceptor site by the above-described method after copolymerizing a monomer having the liquid crystal aligning group in the production of the precursor of the polymer (a2) and the polymer (B2).

< precursors of Polymer (A2) and Polymer (B2) >)

When a side chain (specific side chain) having a liquid crystal alignment group, a michael addition reaction site, or the like is introduced into a polymer, a specific functional group (or a specific compound) which is easily reactive with each other is disposed and reacted with each other to form a specific side chain. In the reaction for forming a specific side chain, preferred combinations of specific functional groups and combinations of specific functional groups with specific compounds are: combinations of carboxyl and epoxy groups, hydroxyl and isocyanate groups, phenolic hydroxyl and epoxy groups, carboxyl and isocyanate groups, amino and isocyanate groups, hydroxyl and acid chloride groups, and the like. More specific preferable examples include carboxyl groups and glycidyl (meth) acrylate, and hydroxyl groups and isocyanatoethyl (meth) acrylate.

The polymer having a specific functional group (also referred to as a specific copolymer) is a copolymer obtained by copolymerizing a monomer having a functional group (specific functional group) capable of reacting with a specific compound as an essential component, and has a number average molecular weight of 2,000 to 25,000. In this case, the monomer having the specific functional group to be used may be used alone, or a plurality of monomers may be used in combination if they are not reacted with the specific functional group during polymerization.

Specific examples of the monomer having a specific functional group are listed below, but the monomer is not limited to these.

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

Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, and N- (hydroxyphenyl) maleimide.

Examples of the monomer having a hydroxyl group other than the phenolic hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2, 3-dihydroxypropyl acrylate, 2, 3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, and the like.

Examples of the monomer having an amino group having an active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, 3, 4-epoxycyclohexyl methacrylate, allyl glycidyl ether, 3-vinyl-7-oxabicyclo [4.1.0] heptane, 1, 2-epoxy-5-hexene, 1, 7-octadiene monoepoxide, and the like.

Examples of the monomer having an isocyanate group include acryloylethyl isocyanate, methacryloylethyl isocyanate, and m-tetramethylxylene isocyanate.

In the present invention, when a specific copolymer is to be obtained, other monomers copolymerizable with the specific functional group may be used in combination with the specific functional group.

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

Specific examples of the other monomers are shown below, but the monomers are not limited to these.

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

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

Examples of the acrylamide compound include acrylamide, methacrylamide, N- (carboxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) acrylamide, N- (hydroxymethyl) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide. The term (meth) acrylamide refers to both acrylamide and methacrylamide.

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

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

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

When a liquid crystal aligning group is introduced into the component (a2) or the component (polymer) (B2), it is preferable that the amount of each monomer used for obtaining the specific copolymer is 25 to 90 mol% of a monomer having a liquid crystal aligning group or a monomer for introducing such a group, 10 to 75 mol% of a monomer having a michael addition reaction site (michael addition donor site, michael addition acceptor site) or a monomer for introducing such a group, and 0 to 65 mol% of another monomer having no specific functional group, based on the total amount of the monomers. Or preferably 25 to 100 mol% of a monomer having a liquid crystal aligning group and a Michael addition reaction site, and 0 to 75 mol% of a monomer having no specific functional group.

When the liquid crystal aligning group is not introduced into the component (a2) or the component (polymer) (B2), the amount of each monomer used to obtain the specific copolymer is preferably 5 to 100 mol% of a monomer having a michael addition reaction site or a monomer for introducing such a group, and 0 to 95 mol% of another monomer having no specific functional group, based on the total amount of all monomers.

The method for obtaining the specific copolymer used in the present invention is not particularly limited, and the specific copolymer can be obtained by, for example, carrying out a polymerization reaction in a solvent in which a monomer having a specific functional group, another monomer having no specific functional group and a polymerization initiator, which are added as desired, coexist, and at a temperature of 50 to 110 ℃. In this case, the solvent to be used is not particularly limited as long as it can dissolve the monomer having the specific functional group, the monomer having no specific functional group to be used as desired, the polymerization initiator, and the like. Specific examples thereof include the following description of < solvent >.

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

The solution of the specific copolymer obtained by the above method is put into diethyl ether or water under stirring and reprecipitated, and the formed precipitate is filtered and washed, and then dried at normal temperature or under reduced pressure or dried by heating to obtain a powder of the specific copolymer. By the above operation, the polymerization initiator and the unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. In the case where the purification cannot be sufficiently performed by one operation, the obtained powder may be dissolved in the solvent again, and the above-mentioned operation may be repeated.

In the present invention, the specific copolymer may be used in the form of a powder or a solution obtained by redissolving a purified powder in a solvent described later.

The acrylic copolymer used as the component (A2) or the component (B2) in the present invention may have a weight average molecular weight of, for example, 3,000 to 200,000, or may have a weight average molecular weight of, for example, 4,000 to 150,000, or 5,000 to 100,000. When the weight average molecular weight of the copolymer is more than 200,000, it is too large, the solubility to a solvent is lowered, and the handling property is sometimes lowered, and when the weight average molecular weight is less than 3,000, it is too small, so that curing is sometimes insufficient at the time of heat curing, and the solvent resistance and heat resistance are lowered.

Further, as the precursor of the component (a2) or the component (B2), a polymer other than the above-mentioned one having a plurality of hydroxyl groups can be used.

Examples of polyether polyols which are preferable examples of the polymer having a plurality of hydroxyl groups include polyether polyols obtained by adding propylene oxide, polyethylene glycol, polypropylene glycol, and the like to a polyol such as polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol a, triethylene glycol, and sorbitol. Specific examples of polyether polyols include アデカポリ ether P series, G series, EDP series, BPX series, FC series, CM series, Japanese oil ユニオックス (registered trademark) HC-40, HC-60, ST-30E, ST-40E, G-450, G-750, ユニ alcohol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, ノニオン (registered trademark) LT-221, ST-221, and OT-221 manufactured by ADEKA.

As a preferable example of the polyester polyol as the polymer having a plurality of hydroxyl groups, there can be mentioned a polyester polyol obtained by reacting a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol or polypropylene glycol with a polycarboxylic acid such as adipic acid, sebacic acid or isophthalic acid. Specific examples of the polyester polyol include ポリライト (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, (strain) クラレポリオール P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F-2010, and the like, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, etc.

As a preferred example of the polycaprolactone polyol which is a polymer having a plurality of hydroxyl groups, there can be mentioned a polycaprolactone polyol obtained by ring-opening polymerization of caprolactone using a polyol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of polycaprolactone polyols include ポリライト (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, manufactured by DIC (trade name) and プラクセル (registered trademark) 205, manufactured by ダイセル, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, and 410.

As a polycarbonate polyol which is a preferable example of the polymer having a plurality of hydroxyl groups, there can be mentioned a polycarbonate polyol 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 プラクセル (registered trademark) CD205, CD205PL, CD210, CD220 (manufactured by LTD ダイセル), C-590, C-1050, C-2050, C-2090, and C-3090 (manufactured by LTD クラレ).

Preferable examples of the cellulose as the polymer having a plurality of hydroxyl groups include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and preferable examples thereof include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose.

Preferred examples of the cyclodextrin as a polymer having a plurality of hydroxyl groups include cyclodextrins such as α -cyclodextrin, β -cyclodextrin and γ -cyclodextrin, methylated cyclodextrins such as methyl- α -cyclodextrin, methyl- β -cyclodextrin and methyl- γ -cyclodextrin, hydroxymethyl- α -cyclodextrin, hydroxymethyl- β -cyclodextrin, hydroxymethyl- γ -cyclodextrin, 2-hydroxyethyl- α -cyclodextrin, 2-hydroxyethyl- β -cyclodextrin, 2-hydroxyethyl- γ -cyclodextrin, 2-hydroxypropyl- α -cyclodextrin, 2-hydroxypropyl- β -cyclodextrin, 2-hydroxypropyl- γ -cyclodextrin, 3-hydroxypropyl- α -cyclodextrin, and mixtures thereof, Hydroxyalkyl cyclodextrins such as 3-hydroxypropyl- β -cyclodextrin, 3-hydroxypropyl- γ -cyclodextrin, 2, 3-dihydroxypropyl- α -cyclodextrin, 2, 3-dihydroxypropyl- β -cyclodextrin, and 2, 3-dihydroxypropyl- γ -cyclodextrin, and the like.

As a preferred example of the urethane-modified acrylic polymer having a plurality of hydroxyl groups, commercially available products such as アクリット (registered trademark) 8UA-017, 8UA-239H, 8UA-140, 8 UA-146, 8UA-585H, 8UA-301, 8UA-318, 8UA-347A, 8UA-347H, and 8UA-366, manufactured by great strain ファインケミカル (incorporated herein by reference), are listed.

As a phenol novolac resin, which is a preferable example of a polymer having a plurality of hydroxyl groups, for example, a phenol-formaldehyde condensation polymer and the like can be cited.

When the component (B) is contained (when the component (a2) and the component (B2) are not the same compound, the content of the component (B) is 1 to 2000 parts by mass, for example, 5 to 2000 parts by mass, preferably 15 to 700 parts by mass, or 1 to 400 parts by mass, based on 100 parts by mass of the component (a).

<thecase where the component (A) and the component (B) are the same compound

In this case, the above introduction methods may be combined to introduce both a michael addition donor site and a michael addition acceptor site, and further to introduce a liquid crystal aligning group as necessary. Examples of such a method include a method in which a polymer obtained by copolymerizing a monomer having an active methylene group, a monomer having an epoxy group, and a monomer having a liquid crystal aligning group added as necessary is reacted with (meth) acrylic acid.

Catalyst for Michael addition reaction

The composition for forming a cured film of the present invention may further contain a Michael addition reaction catalyst for promoting a Michael addition reaction as the component (C) in addition to the components (A) and (B).

The catalyst for Michael addition reaction may be, but is not limited to, the following basic compounds. Examples of the basic compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal alkoxides such as sodium methoxide and potassium ethoxide; quaternary ammonium hydroxides such as tetrabutylammonium hydroxide salt and benzyltrimethylammonium hydroxide salt; quaternary ammonium carbonates such as tetrabutylammonium carbonate, benzyltrimethylammonium carbonate, triethylmonomethylammonium 2-ethylhexanoate, tetrabutylammonium acetate, and the like; quaternary ammonium fluorides such as tetrabutylammonium fluoride and benzyltrimethylammonium fluoride; quaternary ammonium tetrahydroboron such as tetrabutylammonium tetrahydroboron and benzyltrimethylammonium tetrahydroboron; tertiary amines such as tetramethylguanidine, 1, 8-diazabicyclo [5,4,0] undecene-7, diazabicyclo [4,3,0] nonene-5; tertiary phosphines such as guanidine, pyridine, and triphenylphosphine.

Further, in order to improve storage stability during storage, an acidic compound may be added together with a Michael addition reaction catalyst. In particular, when a strongly basic compound having high catalytic activity is used, the addition of an acidic compound is effective for improving the storage stability. Examples of the acidic compound include low-boiling carboxylic acids such as acetic acid, formic acid, and propionic acid, and high-boiling carboxylic acids such as monochloroacetic acid and octanoic acid.

The component (C) is preferably a quaternary ammonium carbonate, a quaternary ammonium hydroxide, or a tertiary amine from the viewpoint of reactivity and storage stability.

When component (C) is contained in the cured film-forming composition of the present invention, the content of component (C) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and still more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total amount of components (a) and (B). By setting the content of component (C) to 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, if the amount is more than 20 parts by mass, the storage stability of the composition may be lowered.

< solvent >

The composition for forming a cured film of the present invention is used mainly in the form of a solution dissolved in a solvent. The solvent used in this case is not particularly limited in kind, structure and the like as long as it can dissolve the component (a), the component (B), and if necessary, the component (C), and further if necessary, other additives described later.

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

When the alignment material is produced by forming a cured film on a resin film using the composition for forming a cured film of the present invention, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol, 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol monomethyl ether, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, and the like are preferable from the viewpoint of a solvent which exhibits resistance to the resin film.

These solvents may be used alone in1 kind or in a combination of 2 or more kinds.

< other additives >

Further, the composition for forming a cured film of the present invention may contain, if necessary, adhesion improving agents, silane coupling agents, surfactants, rheology control agents, pigments, dyes, storage stabilizers, antifoaming agents, antioxidants, inorganic oxide particles, and the like, as long as the effects of the present invention are not impaired.

< preparation of composition for Forming cured film >

The composition for forming a cured film of the present invention contains a compound having a Michael addition donor site as the component (A), a compound having a Michael addition acceptor site as the component (B), and a Michael addition reaction catalyst as the component (C), and may further contain other additives as long as the effects of the present invention are not impaired. In general, they are used in the form of a solution dissolved in a solvent.

Preferred examples of the composition for forming a cured film of the present invention are as follows.

A composition for forming a cured film, comprising a compound having a Michael addition donor site as a component (A) and a compound having a Michael addition acceptor site as a component (B), wherein the composition comprises a component (C) in an amount of 0.01 to 20 parts by mass, and a solvent, based on 100 parts by mass of the total amount of the components (A) and (B).

The mixing ratio, the preparation method, and the like in the case of using the cured film-forming composition of the present invention in the form of a solution will be described in detail below.

The proportion of the solid component 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 to 60 mass%, preferably 2 to 50 mass%, and more preferably 2 to 20 mass%. Here, the solid component refers to a component obtained by removing a 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. Examples of the preparation method include a method of mixing the component (B) and the component (C) in a solution of the component (A) dissolved in a solvent at a predetermined ratio to prepare a uniform solution; alternatively, other additives may be added and mixed as necessary at an appropriate stage of the preparation method.

In the preparation of the composition for forming a cured film of the present invention, a solution of a specific copolymer (polymer) obtained by polymerization reaction in a solvent may be used as it is. In this case, for example, the component (a) or the components (B) and (C) are added to a polymer solution of the component (a) or the component (B) to prepare a uniform solution. In this case, a solvent may be further additionally charged for the purpose of concentration adjustment. In this case, the solvent used in the process of producing the polymer of the component (A) or the component (B) may be the same as or different from the solvent used for adjusting the concentration of the cured film-forming composition.

The solution of the cured film-forming composition thus prepared is preferably filtered through a filter having a pore size of about 0.2 μm and then used.

< cured film, alignment material and retardation material >

A cured film can be formed by applying a solution of the composition for forming a cured film of the present invention on a substrate (e.g., a silicon/silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate), a film substrate (e.g., a resin film such as a triacetyl cellulose (TAC) film, a Polycarbonate (PC) film, a cycloolefin polymer (COP) film, a cycloolefin copolymer (COC) film, a polyethylene terephthalate (PET) film, an acrylic film, or a polyethylene film) by bar coating, spin coating, flow coating, roll coating, slit coating, spin coating followed by spin coating, inkjet coating, printing, or the like to form a coating film, and then heating and drying with an electric hot plate, an oven, or the like. The cured film can be directly applied as an alignment material.

The conditions for the heat drying may be such that the crosslinking reaction by the crosslinking agent is carried out to such an extent that the component of the cured film (alignment material) does not elute into the polymerizable liquid crystal solution applied thereon, and for example, a heating temperature and a heating time appropriately selected from the range of 60 ℃ to 200 ℃ and the time range of 0.4 to 60 minutes can be used. The heating temperature and the heating time are preferably 70 to 160 ℃ and 0.5 to 10 minutes.

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

Since the alignment material formed of the cured film composition of the present invention has solvent resistance and heat resistance, a retardation material such as a polymerizable liquid crystal solution having vertical alignment properties can be applied to the alignment material to align the alignment material. Further, by directly curing the retardation material in the aligned state, the retardation material can be formed as a layer having optical anisotropy. Further, when the substrate on which the alignment material is formed is a film, the film can be used as a retardation film.

Further, a liquid crystal display element in which liquid crystal is aligned can be also produced by using 2 substrates having the alignment material of the present invention formed as described above, bonding the alignment materials on the two substrates so as to face each other via a spacer, and then injecting liquid crystal between the substrates.

The composition for forming a cured film of the present invention can be suitably used for producing various retardation materials (retardation films), liquid crystal display devices, and the like.