Cured film-forming composition, orientation material, and phase difference material

Abstract

The present invention provides a composition for forming a cured film, which can form a cured film used as an orientation material under relatively low temperature and short time conditions, and when a layer of polymerizable liquid crystal is arranged thereon, the cured film exhibits excellent liquid crystal orientation, light transmittance and solvent resistance. The present invention is a composition for forming a cured film, which contains a compound having a Michael addition donor site as component (A), and 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 orientation group. The present invention also provides a cured film and an orientation material obtained using the composition, and a phase difference material formed using the orientation material.

Description

Technical Field

[0001] The present invention relates to a cured film-forming composition, an orientation material, and a phase difference material that can form a cured film that orients liquid crystal molecules. The present invention particularly relates to a cured film-forming composition, an orientation material, and a phase difference material that are useful for producing a patterned phase difference material that can be used for a 3D display of a circularly polarized light glasses system and a phase difference material used for a circularly polarized light plate used as an antireflection film for an organic EL display. Background Art

[0002] In the case of a 3D display of circularly polarized glasses, a phase difference material is usually arranged on a display element such as a liquid crystal panel that forms an image. Regarding the phase difference material, two phase difference regions with different phase difference characteristics are regularly arranged in plurality, forming a patterned phase difference material. It should be noted that, hereinafter, in this specification, a phase difference material patterned in a manner of arranging a plurality of phase difference regions with different phase difference characteristics is referred to as a patterned phase difference material.

[0003] Patterned phase difference material, for example, as disclosed in patent document 1, can be produced by optically patterning a phase difference material formed by a polymerizable liquid crystal. The optical pattern formation of the phase difference material formed by the polymerizable liquid crystal utilizes the known photo-orientation technology in the formation of the orientation material of the liquid crystal panel. That is, a coating film formed by a photo-orientation material is provided on the substrate, and two polarized lights with different polarization directions are irradiated thereto. Thus, an orientation material having two liquid crystal orientation regions with different orientation control directions of the liquid crystal is formed, and a photo-orientation film is obtained. A solution-like phase difference material containing a polymerizable liquid crystal is applied to the photo-orientation film to achieve the orientation of the polymerizable liquid crystal. Then, the oriented polymerizable liquid crystal is cured to form a patterned phase difference material.

[0004] The anti-reflection film of the organic EL display is composed of a linear polarizing plate and a 1 / 4 wavelength phase difference plate. The external light toward the panel surface of the image display panel is converted into linear polarized light by the linear polarizing plate, and then converted into circular polarized light by the 1 / 4 wavelength phase difference plate. Although the external light based on the circular polarized light is reflected on the surface of the image display panel, the rotation direction of the polarization plane is reversed during the reflection. As a result, the reflected light is opposite to the arrival, and is converted into linear polarized light in the direction blocked by the linear polarizing plate through the 1 / 4 wavelength phase difference plate, and then blocked by the linear polarizing plate. As a result, the emission to the outside is significantly suppressed.

[0005] Regarding the 1 / 4 wavelength phase difference plate, a method of forming the 1 / 4 wavelength phase difference plate by combining a 1 / 2 wavelength plate and a 1 / 4 wavelength plate, thereby forming the optical film by reverse dispersion characteristics, is proposed in Patent Document 2. In the case of this method, an optical film can be formed by reverse dispersion characteristics using a liquid crystal material based on positive dispersion characteristics in a wide wavelength band for color image display.

[0006] In addition, in recent years, as a liquid crystal material that can be applied to the phase difference layer, a material having a reverse dispersion characteristic has been proposed (Patent Documents 3 and 4). According to such a liquid crystal material having a reverse dispersion characteristic, instead of combining a 1 / 2 wavelength plate and a 1 / 4 wavelength plate to form a 1 / 4 wavelength phase difference plate by two phase difference layers, the reverse dispersion characteristic can be ensured by forming a phase difference layer by a single layer, thereby realizing an optical film that can ensure a desired phase difference in a wide wavelength band by a simple structure.

[0007] An alignment layer is used to align liquid crystals. As methods for forming an alignment layer, for example, a rubbing method and a photo-alignment method are known. The photo-alignment method is free from static electricity and dust generation, which are problems of the rubbing method, and is useful in that a quantitative alignment process can be controlled.

[0008] For the formation of orientation materials using the photo-orientation method, as the photo-orientation materials that can be used, acrylic resins and polyimide resins having photo-dimerization sites such as cinnamoyl and chalcone groups in the side chains are known. It is reported that these resins show the performance of controlling the orientation of liquid crystals by irradiating them with polarized UV light (hereinafter also referred to as liquid crystal orientation). (See Patent Documents 5 to 7.)

[0009] In addition, the orientation layer is required to have solvent resistance in addition to liquid crystal orientation ability. For example, the orientation layer is sometimes exposed to heat and solvents during the manufacturing process of the phase difference material. If the orientation layer with low solvent resistance is exposed to a solvent, the liquid crystal orientation ability may be significantly reduced.

[0010] Therefore, for example, Patent Document 8 proposes a liquid crystal alignment agent containing a polymer component having a structure capable of undergoing a cross-linking reaction by light and a structure capable of undergoing a cross-linking reaction by heat, and a liquid crystal alignment agent containing a polymer component having a structure capable of undergoing a cross-linking reaction by light and a compound having a structure capable of undergoing a cross-linking reaction by heat in order to obtain a stable liquid crystal alignment ability.

[0011] On the other hand, in order to reduce the thermal stress on the film substrate, the manufacturing process of the phase difference material is studied to reduce the temperature. As one of the processes that requires the highest temperature in the manufacturing of the phase difference material, there is a process of forming a liquid crystal alignment film, and the film forming process of the liquid crystal alignment film is required to reduce the temperature.

[0012] As a method for forming a liquid crystal alignment film at a low temperature, a thermal crosslinking system has been proposed in which an acrylic resin is used and crosslinking is performed at a relatively low temperature (around 100° C.) using an acid generated from a thermal acid generator as a catalyst (Patent Document 9).

[0013] Prior art literature

[0014] Patent Literature

[0015] Patent Document 1: Japanese Patent Application Publication No. 2005-49865

[0016] Patent Document 2: Japanese Patent Application Laid-Open No. 10-68816

[0017] Patent Document 3: U.S. Patent No. 8119026

[0018] Patent Document 4: Japanese Patent Application Publication No. 2009-179563

[0019] Patent Document 5: Japanese Patent No. 3611342

[0020] Patent Document 6: Japanese Patent Application Publication No. 2009-058584

[0021] Patent Document 7: Japanese Patent Application No. 2001-517719

[0022] Patent Document 8: Japanese Patent No. 4207430

[0023] Patent Document 9: International Publication No. 2010 / 150748 Summary of the invention

[0024] Problems to be solved by the invention

[0025] The present invention has been accomplished 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 that can form an alignment film having excellent solvent resistance and aligning polymerizable liquid crystals with high sensitivity under conditions of relatively low temperature and in a short time.

[0026] Other objects and advantages of the present invention are described below.

[0027] Means of solving problems

[0028] The present inventors have repeatedly conducted intensive studies to achieve the above-mentioned purpose and have concluded that by selecting a curing film forming material based on a curing film forming composition containing a component having a Michael add donor site and a component having a Michael add acceptor site, a curing film having excellent solvent resistance can be formed under conditions of relatively low temperature and short time, and the curing film can orient polymerizable liquid crystals with high sensitivity, thereby completing the present invention.

[0029] That is, aspect 1 of the present invention relates to a cured film-forming composition comprising a compound having a Michael add donor site as component (A) and a compound having a Michael add acceptor site as component (B),

[0030] (A) At least one of the component and the component (B) contains a liquid crystal orientation group.

[0031] Aspect 2 is related with the cured film-forming composition 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 alignment group.

[0032] Aspect 3 relates to the cured film-forming composition according to aspect 1 or 2, wherein the component (A) is at least one selected from a low molecular weight compound (A1) having a liquid crystal orientation group and one Michael addition donor site, and a compound (A2) having two or more Michael addition donor sites and having or not having a liquid crystal orientation group,

[0033] The component (B) is at least one selected from a low molecular weight compound (B1) having a liquid crystal orientation group and one Michael addition acceptor site, and a compound (B2) having two or more Michael addition acceptor sites and having or not having a liquid crystal orientation group,

[0034] The components (A2) and (B2) are low molecular weight compounds or high molecular weight compounds.

[0035] Aspect 4 relates to the cured film-forming composition 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.

[0036] Aspect 5 is the cured film-forming composition according to any one of Aspects 1 to 4, further comprising (C) a Michael addition reaction catalyst.

[0037] Aspect 6 relates to the cured film-forming composition according to any one of aspects 1 to 5, wherein the Michael addition acceptor site is an acryloyl group.

[0038] Aspect 7 is the cured film-forming composition according to any one of Aspects 1 to 6, comprising 1 to 2000 parts by mass of the component (B) based on 100 parts by mass of the component (A).

[0039] Aspect 8 is the cured film-forming composition according to any one of aspects 5 to 7, comprising 0.01 to 20 parts by mass of the component (C) based on 100 parts by mass of the total amount of the component (A) and the component (B).

[0040] Aspect 9 relates to a cured film obtained by using the cured film-forming composition according to any one of aspects 1 to 8.

[0041] Aspect 10 relates to an orientation material obtained by using the cured film-forming composition according to any one of aspects 1 to 8.

[0042] Aspect 11 relates to a phase difference material formed using the orientation material described in Aspect 10.

[0043] Effects of the Invention

[0044] The present invention can provide a cured film having excellent solvent resistance and capable of aligning a polymerizable liquid crystal with high sensitivity, and a composition suitable for forming the cured film and capable of forming the cured film at a relatively low temperature and in a short time.

[0045] According to the present invention, it is possible to provide an orientation material having excellent liquid crystal orientation and light transmittance, and a phase difference material capable of optical patterning with high precision. DETAILED DESCRIPTION

[0046] <Cured film-forming composition>

[0047] The cured film-forming composition of the present invention contains components having one or more structures selected from the group consisting of a Michael add donor site, a Michael add acceptor site, and a liquid crystal alignment group, and necessarily contains the three structures as all components.

[0048] Specifically, it is a composition for forming a cured film, which contains a compound having a Michael add donor site as component (A) and a compound having a Michael add acceptor site as component (B), and at least one of the components (A) and (B) contains a liquid crystal orientation group. The components (A) and (B) may be the same compound containing a Michael add donor site, a Michael add acceptor site, and a liquid crystal orientation group.

[0049] The composition for forming a cured film of the present invention contains, as the above-mentioned (A) component, at least one selected from a low molecular weight compound (A1) having a liquid crystal orientation group and one Michael addition donor site, and a compound (A2) containing no liquid crystal orientation group or containing a liquid crystal orientation group and having two or more Michael addition donor sites, and as the above-mentioned (B) component, it contains at least one selected from a low molecular weight compound (B1) having a liquid crystal orientation group and one Michael addition acceptor site, and a compound (B2) containing no liquid crystal orientation group or containing a liquid crystal orientation group and having two or more Michael addition acceptor sites. In this case, the (A2) component and the (B2) component may be a low molecular weight compound or a high molecular weight compound.

[0050] Furthermore, other additives may be contained within a limit not impairing the effects of the present invention.

[0051] In addition, the "low molecular compound" mentioned above refers to a compound other than a "high molecular compound (polymer)", and includes compounds other than a compound having a repeating unit (formed by polymerization) in the compound.

[0052] Hereinafter, each component will be described in detail.

[0053] <Michael addition donor site>

[0054] 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.

[0055] An active methylene group refers to a methylene group that has a carbonyl group adjacent to a methylene group (-CH2-) and is reactive toward nucleophiles. In addition, the active methine group in the present invention refers to a group in the active methylene group that has a structure in which one hydrogen atom of the methylene group (-CH2-) is replaced by an alkyl group and is reactive toward nucleophiles.

[0056] As the active methylene group and the active methine group, a group represented by the following formula (a1) is more preferred.

[0057]

[0058] (In formula (a1), R represents an alkyl group, an alkoxy group or a phenyl group, and the dot-dash line represents a connecting bond.)

[0059] In the above formula (a1), examples of the alkyl group represented by R include alkyl groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 5 carbon atoms are preferred.

[0060] Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

[0061] Among them, methyl, ethyl, n-propyl and the like are preferred.

[0062] Examples of the alkoxy group represented by R in the above formula (a1) include alkoxy groups having 1 to 20 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are preferred.

[0063] 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.

[0064] Among them, methoxy, ethoxy, n-propoxy and the like are preferred.

[0065] Examples of the group represented by the formula (a1) include the following structures. In addition, the dot-dash line in the structural formula represents a connecting bond.

[0066]

[0067] <Method for introducing the group represented by formula (a1) (Michael addition donor site)>

[0068] As a method for introducing the group represented by formula (a1) into each component, for example, a method of reacting a low molecular weight compound or polymer having a hydroxyl group with an acylmeldrum acid obtained by reacting Meldrum acid with an acyl chloride can be cited. This method is well known. Here, as R, a methyl group is preferably used in consideration of availability and orientation.

[0069]

[0070] As another method, a method of reacting a low molecular weight compound or polymer having a hydroxyl group with tert-butyl acylacetate can be cited. This method is well known. Here, R is preferably a methyl group in consideration of availability and orientation.

[0071]

[0072] Furthermore, by copolymerizing a monomer having a Michael addition donor site, a compound having two or more Michael addition donor sites (component (A2) described later) can be obtained as a polymer.

[0073] 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.

[0074] <Michael Addition Receptor Site>

[0075] Examples of the Michael addition acceptor site in component (B) include (meth)acryloyl and maleimide groups, i.e., CH2=CH-C(=O)-, CH2=C(CH3)-C(=O)-, and maleimide groups. In this specification, "(meth)acryloyl" and the like represent both acryloyl and methacryloyl groups.

[0076] <Method for introducing (meth)acryloyl group>

[0077] 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 cited. In addition, 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 can be cited.

[0078] <Method for introducing maleimide group>

[0079] As a method for introducing a maleimide group into each component, 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 can be cited. In addition, a method in which N-(4-hydroxyphenyl)maleimide and a component having an isocyanate group are reacted by a known method can be cited.

[0080] <Liquid crystal orientation group>

[0081] As the liquid crystal alignment group used in the present invention contained in at least one of the (A) component and the (B) component, a vertical alignment group and a photo alignment group can be mentioned.

[0082] <Photo-aligning group>

[0083] The photo-alignment group in the present invention means a functional group capable of photodimerization or photoisomerization (also referred to as a photodimerization site or a photoisomerization site).

[0084] The photodimerization site is a site that can form a dimer by light irradiation, and specific examples thereof include cinnamoyl, chalcone, coumarin, anthracene, etc. Among them, cinnamoyl is preferred because of its high transparency in the visible light region and photodimerization reactivity.

[0085] The photoisomerization site refers to a site that undergoes a change between a cis-isomer and a trans-isomer by light irradiation, and specific examples thereof include an azobenzene structure, a stilbene structure, etc. Among them, the azobenzene structure is preferred because of its high reactivity.

[0086] As the photodimerization site, the following formula [1] or [2] shows an example structure of a further preferred cinnamoyl group.

[0087]

[0088] In the above formula [1], X 11 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. In this case, the phenyl group and the biphenyl group may be substituted by any of a halogen atom, an alkyl group, an alkoxy group and a cyano group.

[0089] In the above formula [2], X 12 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. In this case, the alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group may be bonded to the benzene ring via a single bond, an ether bond, an ester bond, an amide bond, or a urea bond.

[0090] <Method for introducing photo-alignment groups>

[0091] In order to introduce these photo-alignment groups into the various components of the present invention, examples include: a method of introducing a Michael addition donor site into a compound having a photo-alignment group and a hydroxyl group by the method described in the <Method for introducing the group represented by formula (a1) (Michael addition donor site)>, a method of directly using an acrylic monomer having a photo-alignment group or copolymerizing it, 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), etc.

[0092] The compound having a photo-alignment group and a hydroxyl group can be represented by any one of the following formulas [A1] to [A5].

[0093]

[0094] In the formula, A 1 and A 2 Each independently represents a hydrogen atom or a methyl group, X 1 It indicates a structure formed by bonding to one to three divalent groups selected from an alkylene group having 1 to 18 carbon atoms, a phenylene group, a biphenylene group, or a combination thereof via one or more bonds or groups selected from a single bond, an ether bond, an ester bond, an amide bond, a carbamate bond, an amino group, or a combination thereof.

[0095] X 2 represents 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 or 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.

[0096] X 3 It represents 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 biphenylylamino group, a phenyl group or a biphenylyl group.

[0097] X 4 Each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group. The alkylene group having 1 to 20 carbon atoms may be branched or linear.

[0098] X represents a single bond, an oxygen atom or a sulfur atom.

[0099] Furthermore, the hydrogen atoms on the phenyl group, biphenyl group, phenylene group and biphenylene group in these groups may be replaced by one or more substituents which are the same or different and are selected from 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.

[0100] In the above formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each 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.

[0101] Specific examples of the compound having a photo-aligning group and a hydroxyl group include 4-(8-hydroxyoctyloxy)cinnamic acid methyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid methyl ester, 4-(4-hydroxybutoxy)cinnamic acid methyl ester, 4-(3-hydroxypropoxy)cinnamic acid methyl ester, 4-(2-hydroxyethoxy)cinnamic acid methyl ester, 4-hydroxymethoxycinnamic acid methyl ester, 4-hydroxycinnamic acid methyl ester, 4-(8-hydroxyoctyloxy)cinnamic acid ethyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid ethyl ester, 4-(4-hydroxybutoxy)cinnamic acid ethyl ester, 4-(3-hydroxypropoxy)cinnamic acid ethyl ester, 4-(2-hydroxyethoxy)cinnamic acid ethyl ester, 4-hydroxymethoxycinnamic acid ethyl ester, 4 4-(8-hydroxyoctyloxy) cinnamic acid phenyl ester, 4-(6-hydroxyhexyloxy) cinnamic acid phenyl ester, 4-(4-hydroxybutoxy) cinnamic acid phenyl ester, 4-(3-hydroxypropoxy) cinnamic acid phenyl ester, 4-(2-hydroxyethoxy) cinnamic acid phenyl ester, 4-hydroxymethoxycinnamic acid phenyl ester, 4-hydroxycinnamic acid phenyl ester, 4-(8-hydroxyoctyloxy) cinnamic acid biphenyl ester, 4-(6-hydroxyhexyloxy) cinnamic acid biphenyl ester, 4-(4-hydroxybutoxy) cinnamic acid biphenyl ester, 4-(3-hydroxypropoxy) cinnamic acid biphenyl ester, 4-(2-hydroxyethoxy) cinnamic acid biphenyl ester, 4-hydroxymethoxycinnamic acid biphenyl ester, 4-hydroxycinnamic acid biphenyl ester, cinnamic acid 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, 4-(6-hydroxyhexyloxy)chalcone, 4-(4-hydroxybutoxy)chalcone, 4-(3-hydroxypropoxy)chalcone, 4-(2-hydroxyethoxy)chalcone, 4-hydroxymethoxychalcone, 4-hydroxychalcone chalcone, 4'-(8-hydroxyoctyloxy) chalcone, 4'-(6-hydroxyhexyloxy) chalcone, 4'-(4-hydroxybutoxy) chalcone, 4'-(3-hydroxypropoxy) chalcone, 4'-(2-hydroxyethoxy) chalcone, 4'-hydroxymethoxy chalcone, 4'-hydroxy chalcone, 7-(8-hydroxyoctyloxy) coumarin, 7-(6-hydroxyhexyloxy) coumarin, 7-(4-hydroxybutoxy) coumarin, 7-(3-hydroxypropoxy) coumarin, 7-(2-hydroxyethoxy) coumarin, 7-hydroxymethoxy coumarin, 7-hydroxycoumarin, 6-hydroxyoctyloxy coumarin, 6-hydroxyhexyloxy coumarin, 6-(4-hydroxybutoxy) coumarin, 6-(3-hydroxypropoxy) coumarin,6-(2-Hydroxyethoxy)coumarin, 6-hydroxymethoxycoumarin, 6-hydroxycoumarin.

[0102] In addition, the compound having a photo-alignment group and a carboxyl group is represented by the following formula.

[0103]

[0104] In formula (1), A 11 and A 12 Each independently represents a hydrogen atom or a methyl group.

[0105] R 11 represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkyl group, a C3-C8 halocycloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 cycloalkenyl group, a C3-C8 halocycloalkenyl group, a C2-C6 alkynyl group, a C2-C6 haloalkynyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a (C1-C6 alkyl)carbonyl group, a (C1-C6 haloalkyl)carbonyl group, a (C1-C6 alkoxy)carbonyl group, a (C1-C6 haloalkoxy)carbonyl group, a (C1-C6 alkylamino)carbonyl group, a (C1-C6 haloalkyl)aminocarbonyl group, a di(C1-C6 alkyl)aminocarbonyl group, a cyano group, a nitro group, and a group selected from the following formula (c-2),

[0106]

[0107] (In formula (c-2), the dot-dash line represents a connecting bond, R 101 is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms in the alkylene group may be replaced by a fluorine atom or an organic group. 101 The -CH2CH2- in the M may be replaced by -CH=CH-, and further replaced by a group selected from the group consisting of -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO- listed below, as long as these groups are not adjacent to each other. 1 is a hydrogen atom or a methyl group. )

[0108] R 12 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group,

[0109] R 13 is a single bond, an oxygen atom, -COO- or -OCO-,

[0110] R 14 ~R 17Each 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.

[0111] Preferred examples of the compound represented by the above formula (1) include compounds represented by the following formulae (1-1) to (1-5).

[0112]

[0113] (In the above formula, R 11 Respectively with R in the above formula (1) 11 Same meaning.)

[0114] In the compound represented by the above formula (1), R 11 Preferred examples of the compound in the case of a group represented by formula (c-2) include, for example, the following formulae M1-1 to M1-5.

[0115]

[0116] (Where M 1 is a hydrogen atom or a methyl group, and s1 represents the number of methylene groups, which is a natural number from 2 to 9.

[0117] The compound represented by the above formula (1) can be synthesized by appropriately combining conventional methods of organic chemistry.

[0118] Examples of the monomer having a photodimerization site include monomers having a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, etc. Among them, a monomer having a cinnamoyl group having good transparency and photodimerization reactivity in the visible light region is particularly preferred.

[0119] In particular, a monomer having a cinnamoyl group represented by the above formula [1] or [2] is more preferred. Specific examples of such a monomer are represented by the following formula [3] or [4].

[0120]

[0121] In the formula [3], X 11 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. In this case, the phenyl group and the biphenyl group may have any of a halogen atom, an alkyl group, an alkoxy group and a cyano group as a substituent.

[0122] In the above formula [4], X 12represents 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 or 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.

[0123] In the above formula [3] or formula [4], X 13 and X 15 Each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group. The alkylene group having 1 to 20 carbon atoms may be branched or linear, may have a hydroxyl substituent, or may be interrupted by at least one bond selected from an ether bond, an ester bond, an amide bond, a urea bond, and a urethane bond. 14 and X 16 represents 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.

[0124] The compound having a photo-alignment group and a hydroxyl group and the monomer having a photo-alignment group are well known and can be produced according to the methods described in Japanese Patent Application Laid-Open No. 62-284350, US Patent No. 4,696,990, Japanese Patent Application Laid-Open No. 9-118717, US Patent No. 6,107,427, and the like.

[0125] Furthermore, as the monomer having a photodimerization site, a compound obtained by reacting the cinnamic acid derivatives represented by the above formulae (1-1) to (1-5) with a (meth)acrylic monomer having an epoxy group can also be preferably used.

[0126] <Vertical alignment group>

[0127] The vertical alignment group is not particularly limited, but is preferably a group containing a hydrocarbon group having about 6 to 20 carbon atoms, and specifically, a group represented by formula (2) is preferred.

[0128]

[0129] In formula (2), Y 1 represents a single bond, or a bonding group selected from -O-, -CH2O-, -COO-, -OCO-, -NHCO-, -NH-CO-O- and -NH-CO-NH-, Y 2 represents a single bond, an alkylene group having 1 to 15 carbon atoms, or a -CH2-CH(OH)-CH2- group, or represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, and any hydrogen atom on the cyclic group may be replaced by Z, and Y 3represents a single bond or an alkylene group having 1 to 15 carbon atoms, Y 4 represents a single bond, or a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, a heterocyclic ring, or a divalent organic group having a steroid skeleton and having 17 to 30 carbon atoms, and any hydrogen atom on the cyclic group may be substituted by Z, and Y 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring, any hydrogen atom on these cyclic groups may be replaced by Z, m represents an integer of 0 to 4, and when m is 2 or more, Y 5 can be the same or different from each other, Y 6 represents 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 the alkylene group, the alkyl group, the fluorinated alkyl group, the alkoxy group, and the fluorinated alkoxy group may have 1 to 3 of the above-mentioned bonding groups as long as the bonding groups are not adjacent to each other, and Y 2 ~Y 6 In the above, alkylene, -CH2-CH(OH)-CH2- group, divalent cyclic group, divalent organic group having a steroid skeleton, alkyl group and fluorinated alkyl group may be bonded to their adjacent groups via the above-mentioned bonding groups. 2 ~Y 6 The total number of carbon atoms of the substituents represented is 6 to 30.

[0130] Examples of the alkylene group having 1 to 15 carbon atoms include divalent groups obtained by removing one hydrogen atom from an alkyl group having 1 to 15 carbon atoms in the alkyl group having 1 to 18 carbon atoms described later, and specific examples thereof include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene.

[0131] Specific examples of the heterocyclic ring include a pyrrole ring, an imidazole ring, azole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, The rings include oxadiazole ring, acridine ring, etc., among which pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring and benzimidazole ring are preferred.

[0132] Examples of the alkyl group having 1 to 18 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2- Methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3 -dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-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 1,3-dimethyl-n-pentyl, 2,2-dimethyl-n-pentyl, 2,3-dimethyl-n-pentyl, 3,3-dimethyl-n-pentyl, 1-ethyl-n-pentyl, 2-ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1-ethyl-n-butyl, 1-methyl-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n-butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1,1-dimethyl-n-hexyl, 1,2-dimethyl-n-hexyl, 1,3-dimethyl-n-hexyl, 2,2-dimethyl-n-hexyl, 2,3-dimethyl-n-hexyl, 3,3-dimethyl-n-hexyl, 1-ethyl-n-hexyl, 2-ethyl-n-hexyl, 3-ethyl-n-hexyl, 1-methyl-1-ethyl-n-pentyl, 1-methyl-2-ethyl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2-ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl, 3-methyl-3-ethyl-n-pentyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, etc.

[0133] Examples of the alkoxy group having 1 to 18 carbon atoms include groups in which the above-mentioned alkyl group having 1 to 18 carbon atoms is bonded to an oxygen atom (—O—).

[0134] Examples of the fluorinated alkyl group having 1 to 18 carbon atoms include groups in which at least one hydrogen atom in the above-mentioned alkyl group having 1 to 18 carbon atoms is replaced by 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 and 3,3,4,4,5,5,6,6,6-nonafluorohexyl.

[0135] Specific examples of fluorinated alkoxy groups having 1 to 18 carbon atoms include groups formed by combining the above-mentioned fluorinated alkyl groups having 1 to 18 carbon atoms with an oxygen atom (-O-), and specific examples thereof include fluoromethoxy, difluoromethoxy, trifluoromethoxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, heptafluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, 2,2,3,3-tetrafluoropropoxy, 2,2,2-trifluoro-1-(trifluoromethyl)ethoxy, 4,4,5,5,6,6-undecafluorohexyloxy, 2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy, 3,3,4,4,5,5,6,6,6-nonafluorohexyloxy and the like.

[0136] Furthermore, examples of the alkyl group having 1 to 3 carbon atoms in the above-mentioned Z include the alkyl group having 1 to 3 carbon atoms in the groups exemplified above with respect to carbon atoms 1 to 18, examples of the alkoxy group having 1 to 3 carbon atoms include the alkoxy group having 1 to 3 carbon atoms in the groups exemplified above with respect to carbon atoms 1 to 18 (a group in which the alkyl group having 1 to 3 carbon atoms in the groups exemplified above with respect to carbon atoms 1 to 18 and an oxygen atom (—O—) are bonded), examples of the fluorinated alkyl group having 1 to 3 carbon atoms include the fluorinated alkyl group having 1 to 3 carbon atoms in the groups exemplified above with respect to carbon atoms 1 to 18, and examples of the fluorinated alkoxy group having 1 to 3 carbon atoms include the groups exemplified above with respect to carbon atoms 1 to 3 carbon atoms.

[0137] In addition, Y 2 ~Y 6 The total number of carbon atoms of each substituent is 6 to 30, preferably 6 to 20.

[0138] 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 and coating property of the obtained liquid crystal polymer.

[0139] Specific vertical alignment groups include, for example, hydrocarbon groups having about 6 to 20 carbon atoms. Examples of the hydrocarbon group having 6 to 20 carbon atoms include hydrocarbon groups having 6 to 20 carbon atoms including linear, branched or cyclic alkyl groups having 6 to 20 carbon atoms or aromatic groups.

[0140] Therefore, the above formula (2) preferably has the above Y 1 , Y 2 and Y 4 is a single bond, Y 3 is 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, Y 6 is an alkyl group having 1 to 18 carbon atoms, Y 3 and Y 6 The alkyl group (a-1) having a total carbon number of 6 to 20 is preferably an alkyl group having a total carbon number of 7 to 18, and more preferably an alkyl group having a total carbon number of 8 to 15.

[0141] Specific examples of such vertical alignment groups (a-1) include n-nonadecyl and n-eicosyl groups in addition to the alkyl groups having 6 to 18 carbon atoms exemplified above as the alkyl groups having 1 to 18 carbon atoms.

[0142] In addition to the vertical alignment group (a-1), for example, the Y 1 ~Y 4 is a single bond, m is 2 or 3, Y5 is a benzene ring or a cyclohexyl ring, Y 6 The vertical alignment group (a-2) which is an alkyl group having 1 to 18 carbon atoms can also be preferably used.

[0143] Specific examples of such vertical alignment groups (a-2) include groups shown in the following (a-2-1) to (a-2-6), but are not limited to these.

[0144]

[0145] (In the formula, Y 6 With Y in the above formula (2) 6 Same meaning.)

[0146] <Method for introducing vertical alignment groups>

[0147] In order to introduce the vertical alignment group described above into the various components of the present invention, the following methods can be listed: a method of introducing a Michael addition donor site into a compound having a vertical alignment group and a hydroxyl group using the method described in the <Method for introducing the group represented by formula (a1) (Michael addition donor site)>, a method of directly using an acrylic monomer having a vertical alignment group or copolymerizing it, a method of reacting a component having an epoxy group with a compound having a carboxyl group bonded to the vertical alignment group, etc.

[0148] Examples of the monomer having a vertical alignment group include alkyl (meth)acrylates, alkyl vinyl ethers, 2-alkylstyrenes, 3-alkylstyrenes, 4-alkylstyrenes, and N-alkylmaleimides, wherein the alkyl group in these compounds has 6 to 20 carbon atoms.

[0149] These monomers can be produced by known methods or can be obtained as commercial products.

[0150] When a vertical alignment group is introduced into a polymer using a (meth)acrylic monomer having a vertical alignment group represented by the above formula (2), the vertical alignment side chain is represented by the following formula (2′).

[0151]

[0152] (In the formula, Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 and m have the same meanings as those of the groups in formula (2). )<(A1) Low molecular weight compound having a liquid crystal alignment group and one Michael addition donor site>

[0153] As low molecular weight compounds (A1) having a liquid crystal orientation group and one Michael addition donor site, there can be listed: compounds obtained by introducing the Michael addition donor site into the compound having a photo-orientation group and a hydroxyl group according to the method described in the <Method for introducing the group (Michael addition donor site) represented by formula (a1)>, compounds obtained by introducing the Michael addition donor site into the compound having a vertical orientation group and a hydroxyl group according to the method described in the <Method for introducing the group (Michael addition donor site) represented by formula (a1)>, etc.

[0154] <(A2) Compounds having two or more Michael addition donor sites (low molecular weight compounds)>

[0155] When the compound (A2) having two or more Michael addition donor sites is a low molecular weight compound, examples of the low molecular weight compound (A2) include: compounds obtained by introducing a Michael addition donor site into a low molecular weight compound having two or more hydroxyl groups according to the method described in the <Method for introducing a group (Michael addition donor site) represented by formula (a1)>, polyfunctional thiols, diamines, etc.

[0156] <Low molecular weight compounds having two or more hydroxyl groups>

[0157] Specific examples of the divalent alcohol having two alcoholic hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, pentanediol, hexanediol, heptanediol, nonanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 2-(5-ethyl-5-hydroxymethyl-1,3-dioxane-2-yl)-2-methylpropane-1-ol (DOG), N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-tert-butyldiethanolamine, N-lauryldiethanolamine, stearyldiethanolamine, N-phenyldiethanolamine, m-tolyldiethanolamine, and p-tolyldiethanolamine.

[0158] Specific examples of the trivalent alcohol having three alcoholic hydroxyl groups include trimethylolethane, trimethylolpropane, glycerol, tris(2-hydroxyethyl)isocyanurate, hexanetriol, octantriol, decantriol, triethanolamine, triisopropanolamine, and the like.

[0159] Specific examples of the tetravalent alcohol having four alcoholic hydroxyl groups include di(trimethylol)ethane, di(trimethylol)propane, diglycerol, pentaerythritol, and the like.

[0160] In the present invention, these polyols may be used alone or in any combination of two or more.

[0161] <Multifunctional thiol compounds>

[0162] The polyfunctional thiol compound can be obtained in the form of an addition reaction product of a polyol and a monofunctional and / or polyfunctional thiol compound. Specific compounds include trifunctional thiol compounds such as 1,3,5-tris(3-mercaptopropionyloxyethyl)-isocyanurate, 1,3,5-tris(3-mercaptobutyryloxyethyl)-isocyanurate (manufactured by Showa Denko K.K., Calence MT (registered trademark) NR1), and trimethylolpropane tris(3-mercaptopropionate); tetrafunctional thiol compounds such as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko K.K., Calence MT (registered trademark) PEI); and hexafunctional thiol compounds such as dipentaerythritol hexa(3-propionate).

[0163] <Diamine>

[0164] The diamine component used is not particularly limited, but specific examples thereof are as follows.

[0165] Examples of the alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, and isophoronediamine.

[0166] 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-diamino-p-xylene, and 1,3-diamino-4-chlorobenzene.

[0167] Examples of the aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminophenethylamine, 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, 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.

[0168] 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, and 1,9-diamino-5-methylheptane.

[0169] <(A2) Compound (polymer) having two or more Michael addition donor sites>

[0170] In the case where the compound (A2) having two or more Michael addition donor sites is a polymer (high molecular weight compound), examples of the polymer (A2) include: polymers obtained by introducing Michael addition donor sites into precursors of the polymers (A2) and polymers (B2) described later according to the method described in the <Method for introducing the group (Michael addition donor site) represented by formula (a1)>, etc.

[0171] Furthermore, in the case of introducing a liquid crystal orientation group into a polymer (A2) having two or more Michael addition donor sites, the liquid crystal orientation group can be introduced into the precursors of the polymer (A2) and polymer (B2) described later by the above method, or the monomers having the above-mentioned liquid crystal orientation group can be copolymerized when manufacturing the precursors of the polymer (A2) and polymer (B2), and then the Michael addition donor sites can be introduced by the above method.

[0172] <(B1) Low molecular weight compound having a liquid crystal orientation group and one Michael addition acceptor site> As the low molecular weight compound (B1) having a liquid crystal orientation group and one Michael addition acceptor site, there can be listed esters obtained using the compound having the photo-orientation group and the hydroxyl group and (meth)acryloyl chloride, esters obtained using the compound having the vertical orientation group and the hydroxyl group and (meth)acryloyl chloride, etc.

[0173] <(B2) Compounds having two or more Michael addition acceptor sites (low molecular weight compounds)>

[0174] When the compound (B2) having two or more Michael addition acceptor sites is a low molecular weight compound, examples of the low molecular weight compound (B2) include polyfunctional (meth)acrylates and bismaleimide.

[0175] [Polyfunctional urethane (meth)acrylate compound having three or more (meth)acryloyl groups]

[0176] (1) Trifunctional (having three (meth)acryloyl groups) urethane (meth)acrylate

[0177] Specific examples of commercially available products of the polyfunctional urethane (meth)acrylate compound having three (meth)acryloyl groups include NK Oligo UA-7100 [manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 204, EBECRYL 205, EBECRYL 264, EBECRYL 265, EBECRYL 294 / 25HD, EBECRYL 1259, EBECRYL 4820, EBECRYL 8311, EBECRYL 8465, EBECRYL 8701, EBECRYL 9260, KRM (registered trademark) 8296, KRM 8667 [all of the above are manufactured by Daicel Olex Co., Ltd.]; Ziguang (registered trademark) UV-7550B, Ziguang 7000B, Ziguang 7510B, Ziguang 7461TE, Ziguang 2750B [all of the above are manufactured by Nippon Synthetic Chemical Industry Co., Ltd.], etc.

[0178] (2) Tetrafunctional (having four (meth)acryloyl groups) urethane (meth)acrylate

[0179] Specific examples of commercially available products of the polyfunctional urethane (meth)acrylate compound having four (meth)acryloyl groups include EBECRYL (registered trademark) 8210, EBECRYL 8405, and KRM (registered trademark) 8528 [all manufactured by Daicell Olex Co., Ltd.]; and UV-7650B (registered trademark) [manufactured by Nippon Synthetic Chemical Industry Co., Ltd.].

[0180] (3) Pentafunctional or higher-functional (having 5 or more (meth)acryloyl groups) urethane (meth)acrylate

[0181] Examples of the polyfunctional urethane (meth)acrylate compound having five or more (meth)acryloyl groups (urethane (meth)acrylate having five or more functional groups) include a urethane compound of pentaerythritol tri(meth)acrylate and hexamethylene diisocyanate, a urethane compound of pentaerythritol tri(meth)acrylate and toluene diisocyanate, a urethane compound of pentaerythritol tri(meth)acrylate and isophorone diisocyanate, and a urethane compound of dipentaerythritol penta(meth)acrylate and hexamethylene diisocyanate.

[0182] As the pentafunctional or higher-functional urethane (meth)acrylate, commercially available products can be preferably used, and examples thereof include UA-306H, UA-306T, UA-306I, and UA-510H [all of which are manufactured by Kyoeisha Chemical Co., Ltd.]; NKorigo U-6LPA, NKorigo U-10HA, NKorigo U-10PA, NKorigo U-1100H, NKorigo U-15HA, NKorigo UA-53H, and UA-33H [all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 220, EBECRYL 1290, EBECRYL 5129, EBECRYL 8254, EBECRYL 8301R, KRM (registered trademark) 8200, and KRM 8200AE, KRM8904, KRM 8452 [all of the above are manufactured by Daicel Olex Co., Ltd.]; Purple Light (registered trademark) UV-1700B, Purple Light 6300B, Purple Light 7600B, Purple Light 7605B, Purple Light 7610B, Purple Light 7620EA, Purple Light 7630B, Purple Light 7640B, Purple Light 7650B [all of the above are manufactured by Nippon Synthetic Chemical Industry Co., Ltd.], etc.

[0183] (1) Trifunctional compounds (having three (meth)acryloyl groups)

[0184] Examples of the compound having three (meth)acryloyl groups include 1,1,1-trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, di(trimethylolpropane) tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and glycerol tri(meth)acrylate.

[0185] The compound having three (meth)acryloyl groups may be a commercially available product, for example, Buscode #295, Buscode #300 [all manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Light Acrylite TMP-A, Light Acrylite PE-3A, Light Ester TMP [all manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester A-9300, NK Ester A- 9300-1CL, NK A-TMM-3, NK A-TMM-3L, NK A-TMM-3LM-N, NK A-TMPT, NK A-TMPT [all manufactured by Shin-Nakamura Chemical Co., Ltd.]; PETIA, PETRA, TMPTA, EBECRYL (registered trademark) 180 [all manufactured by Daicel Olunex Co., Ltd.], etc.

[0186] (2) Tetrafunctional compounds (having four (meth)acryloyl groups)

[0187] Examples of the compound having four (meth)acryloyl groups include di(trimethylolpropane)tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate.

[0188] The above-mentioned compound having four (meth)acryloyl groups may be preferably a commercially available product, for example, BUSCOAT #300 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; LITE ACRYLET PE-4A [manufactured by Kyoeisha Chemical Co., Ltd.]; NKESTEL AD-TMP, NKESTEL A-TMMT [all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 140, EBECRYL 1142, EBECRYL 180 [all manufactured by Dicel Olunex Co., Ltd.], etc.

[0189] (3) Compounds having five or more functional groups (having five or more (meth)acryloyl groups)

[0190] Examples of the compound having five or more (meth)acryloyl groups include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tripentaerythritol octa(meth)acrylate.

[0191] The above-mentioned compound having 5 or more (meth)acryloyl groups may be preferably a commercially available product, for example, Bison #802 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Light Acrylite DPE-6A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester A-9550, NK Ester A-DPH [all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; DPHA [manufactured by Dicel Olunex Co., Ltd.], etc.

[0192] <Bismaleimide>

[0193] The bismaleimide compound used as the component (B2) in the present invention is represented by the following formula (3).

[0194]

[0195] In the formula, R 33 It is an organic group selected from aliphatic groups, aliphatic groups containing a cyclic structure and aromatic groups, or an organic group composed of a combination of multiple organic groups selected from this group. 33 The polyol may contain ester bonds, ether bonds, amide bonds, carbamate bonds and the like.

[0196] Examples of such bismaleimide compounds include N,N'-3,3-diphenylmethane bismaleimide, N,N'-(3,3-diethyl-5,5-dimethyl)-4,4-diphenyl-methane bismaleimide, N,N'-4,4-diphenylmethane bismaleimide, 3,3-diphenylsulfone bismaleimide, 4,4-diphenylsulfone bismaleimide, N,N'-benzophenone bismaleimide, N,N'-diphenylethane bismaleimide, N,N'-diphenyl ether bismaleimide, N,N'-(methylenebis-tetrahydrophenyl)bismaleimide, N,N'-(3-ethyl)-4,4-diphenylmethane bismaleimide, N,N'-(3,3- bismaleimide, N,N'-(3,3-diethyl)-4,4-diphenylmethane bismaleimide, N,N'-(3,3-dichloro)-4,4-diphenylmethane bismaleimide, N,N'-isophorone bismaleimide, N,N'-tolidine bismaleimide, N,N'-diphenylpropane bismaleimide, N,N'-naphthalene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-5-methoxy-1,3-phenylene bismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-chloro-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis( 3-bromo-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-ethyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-propyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-isopropyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-butyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-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 -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,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-dodecamethylene bismaleimide, N,N'-m-xylene bismaleimide, N,N'-p-xylene bismaleimide, N,N'-1,3-bis(methylenecyclohexane) bismaleimide, N,N'-2,4-toluene bismaleimide, N,N'-2,6-toluene bismaleimide, etc. These bismaleimide compounds are not particularly limited to the above. One of them can be used alone or two or more components can be used in combination. ,

[0197] <(B2) Compound (polymer) having two or more Michael addition acceptor sites>

[0198] When the compound having two or more Michael addition acceptor sites is a polymer (high molecular weight compound), examples of the polymer (B2) include high molecular weight compounds having one or more side chains having a polymerizable unsaturated group at the end in the molecule.

[0199] As such a polymer compound having a side chain having a polymerizable unsaturated bond at the end, preferably, a polymer compound having a (meth)acryloyl group at two or more side chains in the molecule is used.

[0200] Examples of the polymer compound include polymer compounds having a (meth)acryloyl group such as urethane acrylate, epoxy acrylate, and various (meth)acrylate polymer compounds, and particularly polyfunctional polymer compounds having three or more of the (meth)acryloyl groups.

[0201] As the above-mentioned preferred example of the polymer compound having a (meth)acryloyl group, commercially available products can be preferably used, for example, Acleto 8KX-077, Acleto 8KX-078, Acleto 8KX-089, Acleto 8KX-127, Acleto 8KX-128, Acleto 8KX-012C, Acleto 8KX-014C, Acleto 8KX-016C, Acleto 8KX-017C, Acleto 8KX-018C, Acleto 8KX-020C, Acleto 8KX-021C, Acleto 8KX-023C, Acleto 8KX-024C, Acleto 8KX-025C, Acleto 8KX-026C, Acleto 8KX-027D, Acleto 8KX-028D, Acleto 8KX-029C, Acleto 8KX-030C, Acleto 8KX-031C, Acleto 8KX-032C, Acleto 8KX-033C, Acleto 8KX-034C, Acleto 8KX-035C, Acleto 8KX-036C, Acleto 8KX-037C, Acleto 8KX-038C, Acleto 8KX-039C, Acleto 8KX-140C, Acleto 8KX-141C, Acleto 8KX-142C, Acleto 8KX-143C, Acleto 8KX-144C, Acleto 8KX-145C, Acleto 8KX-127, Acleto 8KX-128 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, アクリット8UH-1012 [The above are all manufactured by Daisei Chemical Co., Ltd.]; SMP-220A, SMP-250A, SMP-360A, SMP-550A [the above are all manufactured by Kyoeisha Chemical Co., Ltd.], etc.

[0202] In addition, as a polymer (B2) having two or more Michael addition acceptor sites, there can be listed: a polymer obtained by introducing Michael addition acceptor sites into the precursors of the polymer (A2) and the polymer (B2) described later using the aforementioned method for introducing a (meth)acryloyl group or the method for introducing a maleimide group.

[0203] Furthermore, in the case of introducing a liquid crystal orientation group into a polymer (B2) having two or more Michael addition acceptor sites, the liquid crystal orientation group can be introduced into the precursors of the polymer (A2) and polymer (B2) described later by the above method, or when preparing the precursors of the polymer (A2) and polymer (B2), the monomer having the above-mentioned liquid crystal orientation group can be copolymerized with the monomer, and then the Michael addition acceptor site can be introduced by the above method.

[0204] <Precursors of polymers (A2) and (B2)>

[0205] In the case of introducing the side chain (specific side chain) with liquid crystal orientation group or Michael addition reaction site etc. to polymer, it is possible to react them by configuring the specific functional groups (or relative to specific compounds) that react easily to each other, thereby generating specific side chains. In the reaction of generating specific side chains, the combination of preferred specific functional groups and the combination of specific functional groups and specific compounds are: the combination of carboxyl and epoxy group, hydroxyl and isocyanate group, phenolic hydroxyl and epoxy group, carboxyl and isocyanate group, amino and isocyanate group, hydroxyl and acyl chlorides etc. As more specific preferred example, carboxyl and (methyl) acrylic acid glycidyl ester and hydroxyl and (methyl) acrylic acid isocyanate ethyl ester can be listed.

[0206] 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. At this time, the monomer having a specific functional group may be used alone, or in combination of multiple monomers if they do not react with the specific functional group during polymerization.

[0207] Specific examples of the monomer having a specific functional group are listed below, but the monomer is not limited to these.

[0208] 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.

[0209] Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleimide.

[0210] Examples of monomers having a hydroxyl group other than a 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, and diethylene glycol monomethacrylate.

[0211] Examples of the monomer having an amino group with active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

[0212] Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, allyl glycidyl ether, 3-vinyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

[0213] Examples of the monomer having an isocyanate group include acryloylethyl isocyanate, methacryloylethyl isocyanate, and m-tetramethylxylene isocyanate.

[0214] Furthermore, in the present invention, when obtaining a specific copolymer, in addition to using a monomer having a specific functional group, other monomers copolymerizable with the monomer may be used in combination.

[0215] Specific examples of such other monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

[0216] Specific examples of the other monomers are listed below, but the other monomers are not limited to these.

[0217] 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, 2-(acryloyloxy)ethyl caprolactone, poly(ethylene glycol)ethyl ether acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, acrylic acid, mono-(2-(acryloyloxy)ethyl)phthalate, glycidyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, acrylate, anthracenyl acrylate, anthracenyl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, etc.

[0218] Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, 2-(methacryloyloxy)ethyl caprolactone, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, glycidyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracenyl methacrylate, anthracenyl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2, 2-trifluoroethyl (methacrylate), tert-butyl (methacrylate), cyclohexyl (methacrylate), isobornyl (methacrylate), 2-methoxyethyl (methacrylate), methoxytriethylene glycol (methacrylate), 2-ethoxyethyl (methacrylate), 2-aminomethyl (methacrylate), tetrahydrofurfuryl (methacrylate), 3-methoxybutyl (methacrylate), 2-methyl-2-adamantyl (methacrylate), γ-butyrolactone (methacrylate), 2-propyl-2-adamantyl (methacrylate), 8-methyl-8-tricyclodecanyl (methacrylate), and 8-ethyl-8-tricyclodecanyl (methacrylate), etc.

[0219] Examples of the acrylamide compound include acrylamide, methacrylamide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)acrylamide, N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide. (Meth)acrylamide refers to both acrylamide and methacrylamide.

[0220] 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.

[0221] Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

[0222] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-(hydroxyphenyl)maleimide, N-(hydroxyphenyl)maleimide, N-(carboxyphenyl)maleimide, and N-cyclohexylmaleimide.

[0223] In the case of introducing a liquid crystal orientation group into the component (A2) or the component (B2) (polymer), the amount of each monomer used to obtain a specific copolymer is preferably 25 to 90 mol% of a monomer having a liquid crystal orientation group or a monomer for introducing these groups, 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 these groups, and 0 to 65 mol% of other monomers without a specific functional group, relative to the total amount of the monomers. Alternatively, it is preferably 25 to 100 mol% of a monomer having a liquid crystal orientation group and a Michael addition reaction site, and 0 to 75 mol% of a monomer without a specific functional group.

[0224] In the case where a liquid crystal orientation group is not introduced into component (A2) or component (B2) (polymer), the amount of each monomer used to obtain a specific copolymer is preferably 5 to 100 mol % of a monomer having a Michael addition reaction site or a monomer for introducing these groups, and 0 to 95 mol % of other monomers without specific functional groups, based on the total amount of all monomers.

[0225] There is no particular limitation on the method for obtaining the specific copolymer used in the present invention. For example, the copolymer can be obtained by performing a polymerization reaction at a temperature of 50 to 110° C. in a solvent in which a monomer having a specific functional group and other monomers not having a specific functional group added as desired and a polymerization initiator are coexistent. At this time, the solvent used is not particularly limited as long as it can dissolve the monomer having a specific functional group, the monomer not having a specific functional group used as desired and the polymerization initiator. Specific examples include those described in <Solvent> described later.

[0226] The specific copolymer obtained by the above method is usually in a solution state in which the copolymer is dissolved in a solvent.

[0227] In addition, the solution of the specific copolymer obtained by the above method is put into stirring ether or water, etc. for reprecipitation, and the generated precipitate is filtered and washed, and then dried at room temperature or heated under normal pressure or reduced pressure to obtain a powder of the specific copolymer. Through the above operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer is obtained. In the case where the purification cannot be fully performed by one operation, the obtained powder is dissolved in a solvent again, and the above operation is repeated.

[0228] In the present invention, the specific copolymer can be used in the form of a powder or in the form of a solution obtained by re-dissolving the purified powder in a solvent described below.

[0229] The acrylic copolymer used as the component (A2) or (B2) of the present invention may have a weight average molecular weight of, for example, 3,000 to 200,000, 4,000 to 150,000, or 5,000 to 100,000. When the weight average molecular weight of the copolymer is greater than 200,000, it is too large, solubility in solvents is reduced, and workability may be reduced. When the weight average molecular weight is less than 3,000, it is too small, so curing may be insufficient during thermal curing, and solvent resistance and heat resistance may be reduced.

[0230] Furthermore, as a precursor of the component (A2) or the component (B2), a polymer other than the above-mentioned polymers having a plurality of hydroxyl groups may be used.

[0231] Preferred examples of polyether polyols of polymers having a plurality of hydroxyl groups include polyether polyols obtained by adding propylene oxide, polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, sorbitol, and the like. Specific examples of the polyether polyol include Adeka Polyether P series, G series, EDP series, BPX series, FC series, and CM series manufactured by ADEKA, UNIOX (registered trademark) HC-40, HC-60, ST-30E, ST-40E, G-450, and G-750 manufactured by NOF Corporation, TU-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, and DB-400, and NONION (registered trademark) LT-221, ST-221, and OT-221.

[0232] As a preferred example of a polymer having a plurality of hydroxyl groups, polyester polyols are those obtained by reacting a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, and a polycarboxylic acid such as adipic acid, sebacic acid, or isophthalic acid. 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, Polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, etc. manufactured by Kuraray Co., Ltd.

[0233] As a preferred example of a polycaprolactone polyol having a plurality of hydroxyl groups, there can be mentioned polycaprolactone polyols obtained by ring-opening polymerization of ε-caprolactone using a polyol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of polycaprolactone polyols include OD-X-2155, OD-X-640, and OD-X-2568 manufactured by DIC Corporation, and Placcell (registered trademark) 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, and 410 manufactured by DIC Corporation.

[0234] As a preferred example of a polycarbonate polyol having a plurality of hydroxyl groups, there can be mentioned polycarbonate polyols obtained by reacting a polyol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc. Specific examples of polycarbonate polyols include Plaquecell (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel, and C-590, C-1050, C-2050, C-2090, C-3090 manufactured by Kuraray, etc.

[0235] As a preferred example of a polymer having multiple hydroxyl groups, cellulose includes 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, etc., preferably, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose.

[0236] As a preferred example of a polymer having a plurality of hydroxyl groups, 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-hydroxy Hydroxyalkyl cyclodextrins such as ethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2,3-dihydroxypropyl-β-cyclodextrin, and 2,3-dihydroxypropyl-γ-cyclodextrin.

[0237] As a preferred example of a urethane-modified acrylic polymer having a plurality of hydroxyl groups, commercially available products include Aclet (registered trademark) 8UA-017, 8UA-239, 8UA-239H, 8UA-140, 8UA-146, 8UA-585H, 8UA-301, 8UA-318, 8UA-347A, 8UA-347H, 8UA-366, etc., manufactured by Daisei Film Chemical Co., Ltd.

[0238] As a phenol novolac resin which is a preferred example of the polymer having a plurality of hydroxyl groups, for example, a phenol-formaldehyde polycondensate and the like can be cited.

[0239] When the above-mentioned (B) component is contained (when the (A2) component and the (B2) component described later are not the same compound), the content of the (B) component 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, relative to 100 parts by mass of the (A) component.

[0240] <When the component (A) and the component (B) are the same compound>

[0241] In this case, the above-mentioned introduction methods can be combined to introduce both the Michael addition donor site and the Michael addition acceptor site, and further introduce the liquid crystal orientation group as needed. As such a method, for example, 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 orientation group added as needed is reacted with (meth) acrylic acid.

[0242] <(C) Michael addition reaction catalyst>

[0243] The cured film-forming composition of the present invention may contain a Michael addition reaction catalyst for accelerating Michael addition reaction as the component (C), in addition to the component (A) and the component (B).

[0244] As the Michael addition reaction catalyst, the following basic compounds can be more specifically listed, but are not limited to these. As the basic compound, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal alkoxides such as sodium methoxide and potassium ethoxide; quaternary ammonium hydroxide salts such as tetrabutylammonium hydroxide salt and benzyltrimethylammonium hydroxide salt; quaternary ammonium carbonate salts such as tetrabutylammonium carbonate, benzyltrimethylammonium carbonate, triethylmonomethylammonium 2-ethylhexanoate, and tetrabutylammonium acetate; quaternary ammonium fluoride such as tetrabutylammonium fluoride and benzyltrimethylammonium fluoride; quaternary ammonium tetrahydroborane such as tetrabutylammonium borohydride and benzyltrimethylammonium borohydride; tertiary amines such as tetramethylguanidine, 1,8-diazabicyclo[5,4,0]undecene-7, and diazabicyclo[4,3,0]nonene-5; tertiary phosphines such as guanidine, pyridine, and triphenylphosphine, etc.

[0245] Furthermore, in order to improve the storage stability during storage, an acidic compound may be added together with the Michael addition reaction catalyst. In particular, when using a strong basic compound with high catalytic activity, 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.

[0246] As the component (C), a quaternary ammonium carbonate, a quaternary ammonium hydroxide, and a tertiary amine are further preferred from the viewpoint of reactivity and storage stability.

[0247] When the cured film-forming composition of the present invention contains component (C), the content of component (C) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the total amount of component (A) and component (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, when the content is more than 20 parts by mass, the storage stability of the composition may be reduced.

[0248] <Solvent>

[0249] The cured film-forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used in this case is not particularly limited in type and structure as long as it can dissolve component (A), component (B), component (C) as required, and other additives described below that are added as required.

[0250] 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, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl -2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxylate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, cyclopentyl methyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, etc.

[0251] When an orientation material is produced by forming a cured film on a resin film using the cured film-forming composition of the present invention, 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 preferred from the viewpoint of being a solvent with which the resin film exhibits resistance.

[0252] These solvents may be used alone or in combination of two or more.

[0253] <Other additives>

[0254] Furthermore, the cured film-forming composition of the present invention may contain an adhesion improver, a silane coupling agent, a surfactant, a rheology regulator, a pigment, a dye, a storage stabilizer, a defoaming agent, an antioxidant, inorganic oxide particles, etc. as necessary, unless the effects of the present invention are impaired.

[0255] <Preparation of Cured Film-Forming Composition>

[0256] The cured film-forming composition of the present invention contains a compound having a Michael addition donor site as component (A), a compound having a Michael addition acceptor site as component (B), and a Michael addition reaction catalyst as component (C), and may further contain other additives as long as the effects of the present invention are not impaired. In general, these are used in the form of a solution dissolved in a solvent.

[0257] Preferred examples of the cured film-forming composition of the present invention are as follows.

[0258] [1]: A composition for forming a cured film, comprising a compound having a Michael add donor site as component (A) and a compound having a Michael add acceptor site as component (B), and 0.01 to 20 parts by mass of a component (C) and a solvent, relative to 100 parts by mass of the total amount of components (A) and (B).

[0259] The blending ratio, preparation method, and the like when the cured film-forming composition of the present invention is used in the form of a solution will be described in detail below.

[0260] The ratio 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% to 60% by mass, preferably 2% to 50% by mass, and more preferably 2% to 20% by mass. Here, the so-called solid content refers to the components after removing the solvent from all the components of the cured film-forming composition.

[0261] The method for preparing the cured film-forming composition of the present invention is not particularly limited. Examples of the preparation method include a method in which a solution of component (A) dissolved in a solvent is prepared by mixing component (B) and component (C) at a predetermined ratio to prepare a uniform solution; or a method in which other additives are further added and mixed as needed at an appropriate stage of the preparation method.

[0262] In the modulation of the composition for forming a cured film of the present invention, a solution of a specific copolymer (polymer) obtained by a polymerization reaction in a solvent can be directly used. In this case, for example, component (A) or component (B) and component (C) are added to a polymer solution of component (A) or component (B) to prepare a uniform solution. At this time, a solvent can be further added for the purpose of concentration adjustment. At this time, the solvent used in the polymer generation process of component (A) or component (B) and the solvent used for concentration adjustment of the composition for forming a cured film can be the same or different.

[0263] Furthermore, the prepared solution of the cured film-forming composition is preferably filtered using a filter having a pore size of about 0.2 μm or the like before use.

[0264] <Cured film, orientation material and phase difference material>

[0265] A solution of the composition for forming a cured film of the present invention is applied to a substrate (e.g., 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, an ITO substrate, etc.), a film substrate (e.g., a resin film such as a triacetylcellulose (TAC) film, a polycarbonate (PC) film, a cycloolefin polymer (COP) film, a cycloolefin copolymer (COC) film, a polyethylene terephthalate (PET) film, an acrylic film, a polyethylene film, etc.) by bar coating, spin coating, flow coating, roll coating, slit coating, slit coating followed by spin coating, inkjet coating, printing, etc. to form a coating film, and then, the cured film is dried by heating on a hot plate or an oven, etc. The cured film can be used as an orientation material as it is.

[0266] As the conditions for heating and drying, as long as the components of the cured film (orientation material) are not dissolved in the polymerizable liquid crystal solution coated thereon, a crosslinking reaction based on a crosslinking agent can be carried out, for example, a heating temperature and a heating time appropriately selected from the range of 60°C to 200°C and a time of 0.4 minutes to 60 minutes can be used. The heating temperature and the heating time are preferably 70°C to 160°C and 0.5 minutes to 10 minutes.

[0267] The film thickness of the cured film (orientation 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 height difference, optical properties, and electrical properties of the substrate used.

[0268] Since the orientation material formed by 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 vertical orientation can be coated on the orientation material to orient it on the orientation material. Furthermore, by directly curing the phase difference material in an oriented state, a phase difference material can be formed as a layer having optical anisotropy. Furthermore, when the substrate forming the orientation material is a film, it can be used as a phase difference film.

[0269] Alternatively, two substrates having the orientation material of the present invention formed as described above may be used, and after bonding the orientation materials on the two substrates to face each other via an insulator, liquid crystal may be injected between the substrates to produce a liquid crystal display element having the liquid crystal oriented.

[0270] Thus, the cured film-forming composition of the present invention can be suitably used for production of various retardation materials (retardation films), liquid crystal display elements, and the like.

[0271] Example

[0272] Hereinafter, the present invention will be described in detail with reference to examples of the present invention, but the present invention is not limited to these examples.

[0273] [Abbreviations used in the examples]

[0274] The meanings of the abbreviations used in the following examples are as follows.

[0275] <Raw materials>

[0276] GMA: Glycidyl Methacrylate

[0277] M100: 3,4-Epoxycyclohexylmethyl methacrylate

[0278] EGAMA: Ethylene glycol monoacetoacetate monomethacrylate

[0279] LA: Lauryl acrylate

[0280] HA: Hexyl Acrylate

[0281] AIBN: α,α'-azobisisobutyronitrile

[0282] CIN1:

[0283]

[0284] CIN2:

[0285]

[0286] CIN3:

[0287]

[0288] CIN4:

[0289]

[0290] CIN5: (a mixture of the following isomers)

[0291]

[0292] CIN6: (a mixture of the following isomers)

[0293]

[0294] CIN7:

[0295]

[0296] CIN8:

[0297]

[0298] CIN9:

[0299]

[0300] <A2 ingredients>

[0301] TMPI: 1,3,5-Tris(3-mercaptopropionyloxyethyl)-isocyanurate

[0302]

[0303] TMBI: 1,3,5-Tris(3-mercaptobutyryloxyethyl)-isocyanurate

[0304]

[0305] <B2 ingredient>

[0306] DPHA: dipentaerythritol hexaacrylate [A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)]

[0307] UA: Urethane acrylate [UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.)]

[0308] SMP: Acryloyl-containing acrylic polymer [SMP-220A (manufactured by Kyoeisha Chemical Co., Ltd.)]

[0309] <Ingredient C>

[0310] UCAT: triethylmonomethylammonium 2-ethylhexanoate [U-CAT18X (manufactured by Sanapro Co., Ltd.)]

[0311] TBAAc: Tetrabutylammonium acetate

[0312] TBAH: Tetrabutylammonium hydroxide

[0313] DBU: 1,8-diazabicyclo[5.4.0]-7-undecene

[0314] <Other ingredients (ingredient D)>

[0315] PGM-AC: Organic silica sol [PGM-AC-2140Z (manufactured by Nissan Chemical Industries, Ltd.)]

[0316] <Solvent>

[0317] Each composition of the examples and comparative examples contained a solvent, and propylene glycol monomethyl ether (PM), propylene glycol monomethyl ether acetate (PMA), butyl acetate (BA), and ethyl acetate (EA) were used as the solvent.

[0318] <Measurement of molecular weight of polymer>

[0319] The molecular weight of the acrylic copolymer in the polymerization example was measured in the following manner using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Corporation and columns (KD-803, KD-805) manufactured by Shodex Corporation.

[0320] In addition, the number average molecular weight (hereinafter referred to as Mn) and the weight average molecular weight (hereinafter referred to as Mw) described below are values ​​in terms of polystyrene.

[0321] Column temperature: 40°C

[0322] Eluent: Tetrahydrofuran

[0323] Flow rate: 1.0mL / min

[0324] Standard samples for making standard wires: Standard polystyrene manufactured by Showa Denko K.K. (molecular weights of approximately 197,000, 55,100, 12,800, 3,950, 1,260, and 580).

[0325] <Synthesis of raw materials>

[0326] <Synthesis Example 1> Synthesis of CIN3

[0327] 8.3 g of GMA, 20.7 g of 4-methoxycinnamic acid, 0.2 g of dibutyl hydroxytoluene, and triphenylethyl bromide were added. 0.3g of 1.4-dioxane was mixed with 80mL of 1.4-dioxane and heated at 90°C for 3 days. After the reaction was completed, 1.4-dioxane was distilled off under reduced pressure, and then 150mL of ethyl acetate was added. Insoluble matter was filtered off, and then 100mL of sodium bicarbonate water was added for washing 3 times to remove excess methoxycinnamic acid. Ethyl acetate was distilled off under reduced pressure to obtain 16.5g of the target product CIN3.

[0328] <Synthesis Example 2> Synthesis of Acetyl Meldrum Acid

[0329] Meldrum acid 18.3g and pyridine 20.0g were dissolved in chloroform 150mL, then cooled to -20°C, and acetyl chloride 13.5g was added dropwise. The temperature was slowly raised to room temperature and reacted for 20 hours. 2N hydrochloric acid 40mL and water 150mL were added, extracted with a separatory funnel, and concentrated to obtain an orange solid. Chloroform 100mL was added, and the bottom was removed with a silica gel (neutral) short column (bottom cut), and the solvent was distilled off to obtain acetylmeldrum acid 20.5g shown below.

[0330]

[0331] <Synthesis Example 3> Synthesis of CIN4

[0332] 16.3 g of CIN3 and 9.5 g of acetylmeldrum acid obtained in Synthesis Example 2 were dissolved in 80 mL of 1.4-dioxane, and heated at 80° C. for 1 hour. 1.4-dioxane was distilled off under reduced pressure to obtain 20.4 g of CIN4.

[0333] <Synthesis Example 4> Synthesis of CIN5

[0334] M100 4.9g, 4-methoxycinnamic acid 8.9, dibutylhydroxytoluene 0.1g, triphenylethyl bromide 0.18 g of 1.4-dioxane 40 mL was heated at 90°C for 3 days. After the reaction was completed, 1.4-dioxane was distilled off under reduced pressure, and then 100 mL of ethyl acetate was added, and insoluble matter was filtered off, and then 100 mL of sodium bicarbonate water was added and washed three times. Ethyl acetate was distilled off under reduced pressure to obtain 6.3 g of the target CIN5.

[0335] <Synthesis Example 5> Synthesis of CIN6

[0336] 5.0 g of CIN5 and 2.4 g of acetylmeldrum acid obtained in Synthesis Example 2 were dissolved in 40 mL of 1.4-dioxane, and heated at 80° C. for 1 hour. 1.4-dioxane was distilled off under reduced pressure to obtain 7.1 g of CIN6.

[0337] <Synthesis of component A1>

[0338] <Synthesis Example 6> Synthesis of CIN8

[0339] 5.0 g of CIN7 and 3.3 g of acetylmeldrum acid obtained in Synthesis Example 2 were dissolved in 40 mL of 1.4-dioxane, and heated at 80° C. for 1 hour. 1.4-dioxane was distilled off under reduced pressure to obtain 8.0 g of CIN8.

[0340] <Synthesis of component A2>

[0341] <Synthesis Example 7>

[0342] 10.0 g of CIN1, 4.3 g of EGAMA, and 0.43 g of polymerization catalyst AIBN were dissolved in 132.4 g of PM and reacted at 90°C for 20 hours to obtain a solution containing 10% by mass of an acrylic copolymer (A2-1) having acetoacetyl groups in side chains. The obtained acrylic copolymer had Mn of 12,000 and Mw of 23,000.

[0343] <Synthesis example 8>

[0344] 10.0 g of CIN2, 2.5 g of EGAMA, and 0.38 g of polymerization catalyst AIBN were dissolved in 115.9 g of PM and reacted at 80° C. for 20 hours to obtain a solution containing 10% by mass of an acrylic copolymer (A2-2) having an acetoacetyl group in a side chain. The obtained acrylic copolymer had an Mn of 18,000 and an Mw of 35,000.

[0345] <Synthesis Example 9>

[0346] 15.0 g of CIN4 and 0.3 g of polymerization catalyst AIBN were dissolved in 61.2 g of PM and reacted at 80° C. for 20 hours to obtain a solution containing 20% ​​by mass of an acrylic copolymer (A2-3) having acetoacetyl groups in side chains. The obtained acrylic copolymer had Mn of 17,000 and Mw of 32,000.

[0347] <Synthesis Example 10>

[0348] 15.0 g of CIN6 and 0.3 g of polymerization catalyst AIBN were dissolved in 61.2 g of PM and reacted at 80° C. for 20 hours to obtain a solution containing 20% ​​by mass of an acrylic copolymer (A2-4) having acetoacetyl groups in side chains. The obtained acrylic copolymer had Mn of 23,000 and Mw of 40,000.

[0349] <Synthesis Example 11>

[0350] 10.0 g of Placcel 410 (polycaprolactone tetraol manufactured by Daicel Corporation) and 6.3 g of t-butyl acetoacetate were dissolved in 38.1 g of PMA, and the mixture was reacted at 130° C. for 10 hours to obtain a solution containing 30% by mass of the compound (A2-5) having an acetoacetyl group.

[0351] <Synthesis Example 12>

[0352] 8.0 g of EGAMA and 0.3 g of polymerization catalyst AIBN were dissolved in 33.2 g of PM and reacted at 80° C. for 20 hours to obtain a solution containing 20% ​​by mass of an acrylic copolymer (A2-6) having acetoacetyl groups in side chains. The obtained acrylic copolymer had Mn of 10,000 and Mw of 22,000.

[0353] <Synthesis Example 13>

[0354] 10.0 g of CIN3, 4.3 g of EGAMA, and 0.4 g of polymerization catalyst AIBN were dissolved in 58.9 g of PM and reacted at 80° C. for 20 hours to obtain a solution containing 20% ​​by mass of an acrylic copolymer (A2-7) having an acetoacetyl group in a side chain. The obtained acrylic copolymer had an Mn of 17,000 and an Mw of 32,000.

[0355] <Synthesis Example 14>

[0356] 10.0 g of CIN1, 3.3 g of EGAMA, 3.3 g of GMA, and 0.5 g of AIBN as a polymerization catalyst were reacted in 8.7 g of PM6 at 90° C. for 20 hours to obtain an acrylic copolymer solution having acetoacetyl groups in the side chains. Next, 2.0 g of acrylic acid and triphenylethyl bromide were added. 0.1 g of butylated hydroxytoluene and 0.2 g of dibutyl hydroxytoluene were reacted at 100°C for 18 hours to introduce acryloyl groups into the side chains of the acrylic copolymer. The acrylic copolymer (A2-8) having acetoacetyl groups and acryloyl groups in the side chains was obtained by reprecipitation in hexane. The Mn and Mw of the obtained acrylic copolymer were 23,000 and 42,000.

[0357] <Synthesis of component B2>

[0358] <Synthesis Example 15>

[0359] 8.0 g of CIN1, 3.4 g of GMA, and 0.3 g of polymerization catalyst AIBN were dissolved in 27.5 g of PM and reacted at 90° C. for 20 hours to obtain an acrylic copolymer solution. Next, 1.7 g of acrylic acid and triphenylethyl bromide were added. 0.1 g of butylated hydroxytoluene and 0.2 g of dibutylhydroxytoluene were reacted at 100°C for 18 hours to introduce acryloyl groups into the side chains of the acrylic copolymer. Then, reprecipitation was performed with hexane to obtain an acrylic copolymer (B2-1) having acryloyl groups in the side chains. The obtained acrylic copolymer had an Mn of 12,000 and an Mw of 32,000.

[0360] <Example 1>

[0361] A solution containing 10% by mass of the acrylic copolymer (A2-1) obtained in the above-mentioned Synthesis Example 7 as the component (A-1) is mixed in an amount equivalent to 100 parts by mass of the acrylic copolymer (A2-1) (solid content), 30 parts by mass of DPHA as the component (B), and 3 parts by mass of UCAT as the component (C), and PM and PMA are added thereto to prepare a composition (A-1) for forming an oriented material having a solvent composition of PM:PMA=80:20 (mass ratio) and a solid content concentration of 5.0% by mass.

[0362] <Examples 2 to 25 and Comparative Examples 1 to 4>

[0363] Orientation material forming compositions A-2 to A-29 (components (A) to (D) are all values ​​calculated on a solid basis) were prepared in the same manner as in Example 1 except that the types and amounts of the components were as described in Table 1.

[0364] Table 1

[0365]

[0366] <Example 26>

[0367] [Evaluation of Orientation]

[0368] The composition A-1 for forming an orientation material of Example 1 was applied to the TAC film with a wet film thickness of 4 μm using a bar coater. The composition was dried in a heat circulation oven at 110°C for 2 minutes to form a cured film on the TAC film. Each cured film was subjected to a 20 mJ / cm 2 The oriented material was irradiated with linear polarized light of 313 nm vertically with an exposure amount of 1.5 % to form an oriented material. On the oriented material on the TAC film, a polymerizable liquid crystal solution RMS03-013c (Melco Co., Ltd.) was coated with a wet film thickness of 6 μm using a rod coater. The coated film was heated and dried on a hot plate set at 60°C for 2 minutes, and then heated at 300 mJ / cm 2Exposure was performed to produce a phase difference material. The phase difference material on the produced substrate was sandwiched between a pair of polarizing plates, and the phase difference characteristics in the phase difference material were observed. The case where the phase difference was exhibited without defects was marked as ○, and the case where the phase difference was not exhibited was marked as × and recorded in the "Orientation" column of Table 2.

[0369] <Examples 27 to 50 and Comparative Examples 5 to 8>

[0370] A retardation material was prepared in the same manner as in Example 26 except that the composition for forming an orientation material, and the heating temperature and heating time in the heat circulation oven were respectively as described in Table 2. The evaluation results are collectively shown in Table 2 below.

[0371] Table 2

[0372]

[0373] In Examples 26 to 50, a phase difference material showing good orientation can be produced by firing at a low temperature and in a short time.

[0374] On the other hand, in Comparative Examples 5 to 8, it was not possible to produce a phase difference material showing good orientation by firing at a low temperature and for a short time.

[0375] [Fitness]

[0376] <Examples 51 to 53>

[0377] A 10×10 grid is cut with a cutter at intervals of 1 mm in length and width on the phase difference material on the film produced in Examples 48 to 50. A transparent tape peeling test is performed on the cut using Scotch (registered trademark) tape. The case where all 100 grids are left after the tape is peeled off and are not peeled off is evaluated as ○, and even if one grid is peeled off, it is evaluated as ×. The evaluation results are shown in the "Initial" column in Table 3 described later.

[0378] [Evaluation of durable adhesion]

[0379] The phase difference material produced by the same method as the above-mentioned evaluation of adhesion was placed in an oven set at a temperature of 80°C and a humidity of 90% for more than 200 hours. The phase difference material was then taken out and the adhesion was evaluated by the same method as the above-mentioned evaluation of adhesion. The evaluation results are shown in the "Durability" column in Table 3 described later.

[0380] Table 3

[0381]

[0382] The phase difference materials produced in Examples 51 to 53 also exhibited excellent durability and good adhesion.

[0383] <Synthesis of component (A)>

[0384] <Synthesis Example 16>

[0385] 14.1 g of LA, 7.2 g of EGAMA, and 0.68 g of polymerization catalyst AIBN were dissolved in 107.0 g of PM and reacted at 80° C. for 16 hours to obtain a solution containing 30% by mass of an acrylic copolymer (A2-9). The obtained acrylic copolymer had an Mn of 13,300 and an Mw of 27,800.

[0386] <Synthesis Example 17>

[0387] 14.1 g of HA, 7.2 g of EGAMA, and 0.68 g of polymerization catalyst AIBN were dissolved in 107.0 g of PM and reacted at 80° C. for 16 hours to obtain a solution containing 30% by mass of an acrylic copolymer (A2-10). The obtained acrylic copolymer had an Mn of 13,300 and an Mw of 27,800.

[0388] <Examples 54 to 57 and Comparative Examples 9 and 10>

[0389] Orientation material forming compositions A-30 to A-35 (components (A) to (D) are all values ​​calculated on a solid basis) were prepared in the same manner as in Example 1 except that the types and amounts of the components were as described in Table 4.

[0390] Table 4

[0391]

[0392] <Example 58>

[0393] [Evaluation of vertical orientation]

[0394] The composition A-30 for forming an oriented material obtained in Example 54 was coated on the TAC film with a wet film thickness of 4 μm using a rod coater. The oriented material was formed on the TAC film by heating and drying in a heat circulation oven at a temperature of 120°C for 2 minutes. A polymerizable liquid crystal solution RMS03-015 (manufactured by Melku Co., Ltd.) was coated on the oriented material on the TAC film with a wet film thickness of 6 μm using a rod coater. The coated film was heated and dried on a hot plate set at a temperature of 65°C for 2 minutes, and then heated at 300 mJ / cm 2Exposure to produce phase difference material. The produced phase difference material is measured for the incident angle dependence of the in-plane phase difference using the phase difference measuring device RETS100 manufactured by Otsuka Electronics Co., Ltd. Phase difference materials with an in-plane phase difference value of 0 at an incident angle of 0 degrees and an in-plane phase difference in the range of 38±5nm at an incident angle of ±50 degrees are evaluated as vertically oriented. The evaluation results are recorded in the column of "Vertical Orientation" in Table 5.

[0395] <Examples 59 to 61 and Comparative Examples 11 to 12>

[0396] A phase difference material was prepared and the vertical alignment property was evaluated in the same manner as in Example 58 except that the compositions for forming an alignment material were respectively as described in Table 5. The evaluation results are collectively shown in Table 5 below.

[0397] Table 5

[0398]

[0399] In Examples 58 to 61, a phase difference material showing good vertical alignment properties can be produced by firing at a low temperature and in a short time.

[0400] On the other hand, in Comparative Examples 11 and 12, it was not possible to produce a phase difference material showing good orientation by firing at a low temperature and for a short time.

[0401] Industrial Availability

[0402] The cured film-forming composition according to the present invention is very useful as a material for forming an orientation material for forming a liquid crystal orientation film of a liquid crystal display element or an optically anisotropic film provided inside or outside a liquid crystal display element. The cured film-forming composition according to the present invention is particularly suitable as a material for a phase difference material for a circularly polarizing plate used as an antireflection film for IPS-LCDs and organic EL displays.

Claims

1. A cured film-forming composition comprising a compound having a Michael add donor site as component (A) and a compound having a Michael add acceptor site as component (B), wherein at least one of component (A) and component (B) contains a liquid crystal orientation group, The Michael addition donor site is selected from a mercapto group and a group represented by formula (a1), the Michael addition acceptor site is selected from an acryloyl group and a methacryloyl group, and the liquid crystal alignment group is represented by the following formula [1] or formula [2]: In formula (a1), R represents an alkyl group, an alkoxy group or a phenyl group, and the dotted line represents a connecting bond. In the above formula [1], X 11 represents an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group, wherein The phenyl group and the biphenyl group may be substituted by any of a halogen atom, an alkyl group, an alkoxy group and a cyano group. In the above formula [2], X 12 It represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group, wherein the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group or 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. 2 . The cured film-forming composition 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 alignment group.

3. The cured film-forming composition according to claim 1, wherein the component (A) is at least one selected from a low molecular weight compound (A1) having a liquid crystal orientation group and one Michael addition donor site, and a compound (A2) having two or more Michael addition donor sites and having or not having a liquid crystal orientation group, The component (B) is at least one selected from a low molecular weight compound (B1) having a liquid crystal orientation group and one Michael addition acceptor site, and a compound (B2) having two or more Michael addition acceptor sites and having or not having a liquid crystal orientation group, The components (A2) and (B2) are low molecular weight compounds or high molecular weight compounds, in, The low molecular weight compound refers to a compound other than a high molecular weight compound, that is, a compound other than a compound having a repeating unit formed by polymerization. 4 . The cured film-forming composition according to claim 1 , further comprising (C) a Michael addition reaction catalyst. The cured film-forming composition according to claim 1 , wherein the Michael addition acceptor site is an acryloyl group. 6 . The cured film-forming composition according to claim 1 , comprising 1 to 2000 parts by mass of the component (B) based on 100 parts by mass of the component (A). 7 . The cured film-forming composition according to claim 4 , comprising 0.01 to 20 parts by mass of the component (C) based on 100 parts by mass of the total amount of the component (A) and the component (B). 8 . A cured film obtained by using the cured film-forming composition according to claim 1 . 9 . An orientation material obtained by using the cured film-forming composition according to claim 1 . 10 . A phase difference material formed by using the orientation material according to claim 9 .

Images