Cured film-forming composition, alignment material and retardation material

Abstract

To provide a cured film-forming composition which is used as an alignment material and which, when a polymerizable liquid crystal layer is disposed thereon, forms a cured film exhibiting excellent liquid crystal alignment properties, light transmittance and solvent resistance under conditions of a relatively low temperature and a short time. [Solution] A cured film-forming composition for an alignment material, which comprises, as component (A), a compound containing a Michael donor moiety, and as component (B), a compound containing a Michael acceptor moiety, and at least one of component (A) and component (B) contains a liquid crystal alignment group; a cured film and alignment material obtained using the composition; and a retardation material formed using the alignment material.

Description

[Technical field]

[0001] The present invention relates to a cured film-forming composition, an alignment material, and a retardation material that form a cured film that aligns liquid crystal molecules. In particular, the present invention relates to a cured film-forming composition, an alignment material, and a retardation material that are useful for producing a patterned retardation material used in a 3D display using circularly polarized glasses, and a retardation material used in a circular polarizing plate used as an anti-reflection film for an organic EL display. The present invention also relates to a cured film-forming composition for an alignment material. [Background technology]

[0002] In the case of a circularly polarized glasses type 3D display, a retardation material is usually arranged on a display element that forms an image, such as a liquid crystal panel. This retardation material has two types of retardation regions with different retardation characteristics arranged regularly, forming a patterned retardation material. In the following, in this specification, such a patterned retardation material that arranges multiple retardation regions with different retardation characteristics is referred to as a patterned retardation material.

[0003] The patterned retardation material can be produced by optically patterning a retardation material made of polymerizable liquid crystal, as disclosed in Patent Document 1, for example. The optical patterning of the retardation material made of polymerizable liquid crystal utilizes a photo-alignment technique known for forming alignment materials for liquid crystal panels. That is, a coating film made of a photo-alignable material is provided on a substrate, and two types of polarized light with different polarization directions are irradiated onto the coating film. Then, a photo-alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions with different liquid crystal alignment control directions are formed. A solution-like retardation material containing polymerizable liquid crystal is applied onto the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Then, the aligned polymerizable liquid crystal is cured to form a patterned retardation material.

[0004] The anti-reflection film of an organic EL display is composed of a linear polarizer and a quarter-wave retardation plate, and converts external light toward the panel surface of the image display panel into linearly polarized light by the linear polarizer, and then into circularly polarized light by the subsequent quarter-wave retardation plate. Here, this circularly polarized external light is reflected by the surface of the image display panel, but the rotation direction of the polarization plane is reversed during this reflection. As a result, this reflected light is converted by the quarter-wave retardation plate into linearly polarized light in the direction that is blocked by the linear polarizer, in the opposite direction to when it arrived, and then is blocked by the subsequent linear polarizer, resulting in significant suppression of emission to the outside.

[0005] Regarding this quarter-wave retardation plate, Patent Document 2 proposes a method of constructing this optical film with reverse dispersion characteristics by combining a half-wave plate and a quarter-wave plate to construct a quarter-wave retardation plate. In this method, an optical film with reverse dispersion characteristics can be constructed using a liquid crystal material with positive dispersion characteristics in a wide wavelength band used for displaying color images.

[0006] Recently, liquid crystal materials having reverse dispersion characteristics have been proposed as liquid crystal materials applicable to the retardation layer (Patent Documents 3 and 4). With such liquid crystal materials having reverse dispersion characteristics, instead of forming a quarter-wave retardation plate from two retardation layers by combining a half-wave plate and a quarter-wave plate, the retardation layer can be formed from a single layer to ensure reverse dispersion characteristics, and thus an optical film capable of ensuring a desired retardation in a wide wavelength band can be realized with a simple configuration.

[0007] An alignment layer is used to align liquid crystals. Methods for forming an alignment layer include, for example, a rubbing method and a photoalignment method. The photoalignment method is useful in that it does not generate static electricity or dust, which are problems with the rubbing method, and it allows quantitative control of the alignment process.

[0008] In forming an alignment material using a photoalignment method, acrylic resins and polyimide resins having photodimerization sites such as cinnamoyl groups and chalcone groups in the side chains are known as photoalignment materials that can be used. It has been reported that these resins exhibit the ability to control the alignment of liquid crystals (hereinafter, also referred to as liquid crystal alignment) by irradiating them with polarized UV light (see Patent Documents 5 to 7).

[0009] In addition to the liquid crystal alignment ability, the alignment layer is required to have solvent resistance. For example, the alignment layer may be exposed to heat or a solvent during the manufacturing process of the retardation material. If an alignment layer with low solvent resistance is exposed to a solvent, the liquid crystal alignment ability may be significantly reduced.

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

[0011] On the other hand, in order to reduce the thermal stress on the film substrate, lowering the temperature of the manufacturing process of the retardation material is being considered. One of the processes that requires the highest temperature in manufacturing the retardation material is the process of forming the liquid crystal alignment film, and there is a demand for lowering the temperature of the film formation process of the liquid crystal alignment film.

[0012] As a method for forming a liquid crystal alignment film at low temperatures, a system has been proposed that uses an acrylic resin and a thermal crosslinking system that is catalyzed by an acid derived from a thermal acid generator and proceeds at a relatively low temperature (around 100°C) (Patent Document 9). [Prior art documents] [Patent documents]

[0013] [Patent Document 1] JP 2005-49865 A [Patent Document 2] Japanese Patent Application Publication No. 10-68816 [Patent Document 3] U.S. Patent No. 8,119,026 [Patent Document 4] JP 2009-179563 A [Patent Document 5] Patent No. 3611342 [Patent Document 6] JP 2009-058584 A [Patent Document 7] Special Publication No. 2001-517719 [Patent Document 8] Patent No. 4207430 [Patent Document 9] International Publication No. 2010 / 150748 Summary of the Invention [Problem to be solved by the invention]

[0014] The object of the present invention has been achieved based on the above findings and study results. That is, the object of the present invention is to provide a liquid crystal aligning agent for photo-alignment, which has excellent solvent resistance and can form an alignment film capable of aligning a polymerizable liquid crystal with high sensitivity under conditions of relatively low temperature and short time.

[0015] Other objects and advantages of the present invention will become apparent from the following description. [Means for solving the problem]

[0016] In order to achieve the above object, the present inventors have conducted extensive research and have found that by selecting a cured film-forming material based on a cured film-forming composition containing a component having a Michael donor site and a component having a Michael acceptor site, it is possible to obtain a cured film having excellent solvent resistance and polymerizing with high sensitivity. The present inventors have found that a cured film capable of aligning polarizable liquid crystals can be formed at a relatively low temperature in a short time, thereby completing the present invention.

[0017] That is, the present invention is directed to the following aspects [1] to

[10] . [1] As component (A), a compound containing a mercapto group and a Michael donor moiety selected from groups represented by the following formula (a1), and (B) a compound containing a Michael acceptor moiety selected from an acrylic group and a methacrylic group, At least one of the component (A) and the component (B) contains a liquid crystal aligning group represented by the following formula (2): Cured film forming composition for alignment material. [ka] (In formula (a1), R represents an alkyl group, an alkoxy group, or a phenyl group, and the dashed line represents a bond.) [ka] (In formula (2), Y 1 represents a single bond or a bonding group selected from -O-, -CHO-, -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 -CH-CH(OH)-CH- group, or represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocycle, any hydrogen atom on the cyclic group may be replaced by Z, Y 3 represents a single bond or an alkylene group having 1 to 15 carbon atoms, Y 4 represents a single bond, a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocycle, or a divalent organic group having a steroid skeleton having 17 to 30 carbon atoms, any hydrogen atom on the cyclic group may be substituted with Z, Y 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocycle, 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 may be the same or different, Y 6represents 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 fluorine atom; 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 fluorine atom; the alkylene group, alkyl group, fluorinated alkyl group, alkoxy group, and fluorinated alkoxy group may have 1 to 3 of the above bonding groups therein, as long as the bonding groups are not adjacent to each other; Y 2 ~Y 6 In the formula (I), the alkylene group, the -CH2-CH(OH)-CH2- group, the divalent cyclic group, the divalent organic group having a steroid skeleton, the alkyl group and the fluoroalkyl group may be bonded to the group adjacent thereto via the above-mentioned bonding group. 2 ~Y 6 The total number of carbon atoms of the substituent represented by is 6 to 30. [2] The cured film-forming composition for alignment material according to [1], wherein the component (A) and the component (B) are the same compound containing a Michael donor moiety, a Michael acceptor moiety, and a liquid crystal alignment group. [3] As the component (A), at least one selected from a low molecular weight compound (A1) having one Michael donor site and a liquid crystal alignment group, and a compound (A2) having two or more Michael donor sites and containing or not containing a liquid crystal alignment group, The component (B) includes at least one selected from a low molecular weight compound (B1) having one Michael acceptor moiety and a liquid crystal aligning group, and a compound (B2) having two or more Michael acceptor moieties and containing or not containing a liquid crystal aligning group, The cured film-forming composition for alignment material according to [1] or [2], wherein the component (A2) and the component (B2) may be a low molecular weight compound or a high molecular weight compound. [4] (C) The cured film-forming composition for an alignment material according to any one of [1] to [3], further comprising a Michael addition reaction catalyst. [5] The cured film-forming composition for an alignment material according to any one of [1] to [4], wherein the Michael acceptor moiety is an acrylic group. [6] The cured film-forming composition for alignment material according to any one of [1] to [5], comprising 1 to 2,000 parts by mass of the component (B) per 100 parts by mass of the component (A). [7] The cured film-forming composition for alignment material according to any one of [4] to [6], containing 0.01 to 20 parts by mass of the (C) component per 100 parts by mass of the total of the (A) component and the (B) component. [8] A cured film obtained by using the cured film-forming composition for alignment material according to any one of [1] to [7]. [9] An alignment material obtained by using the cured film-forming composition for alignment material according to any one of [1] to [7].

[10] A retardation material formed using the alignment material according to [9]. The present invention also relates to a cured film-forming composition, that is, the present invention includes the following first to eleventh aspects. The first perspective is as follows: As component (A), a compound containing a Michael donor moiety; As a component (B), a compound containing a Michael acceptor moiety is included, The present invention relates to a cured film-forming composition, wherein at least one of the component (A) and the component (B) contains a liquid crystal aligning group. As a second aspect, the present invention relates to the cured film-forming composition according to the first aspect, in which the component (A) and the component (B) are the same compound containing a Michael donor moiety, a Michael acceptor moiety, and a liquid crystal aligning group. As a third perspective, As the component (A), at least one selected from a low molecular weight compound (A1) having one Michael donor site and a liquid crystal alignment group, and a compound (A2) having two or more Michael donor sites and containing or not containing a liquid crystal alignment group, The component (B) includes at least one selected from a low molecular weight compound (B1) having one Michael acceptor moiety and a liquid crystal aligning group, and a compound (B2) having two or more Michael acceptor moieties and containing or not containing a liquid crystal aligning group, The components (A2) and (B2) may be low molecular weight compounds or high molecular weight compounds. The present invention relates to a cured film-forming composition according to the first or second aspect. As a fourth aspect, the present invention relates to the cured film-forming composition according to any one of the first to third aspects, in which the Michael donor moiety of the component (A) is an active methylene group or an active methine group. As a fifth aspect, the present invention relates to the cured film-forming composition according to any one of the first to fourth aspects, further comprising (C) a Michael addition reaction catalyst. As a sixth aspect, the present invention relates to the cured film-forming composition according to any one of the first to fifth aspects, in which the Michael acceptor moiety is an acrylic group. As a seventh aspect, the present invention relates to the cured film-forming composition according to any one of the first to sixth aspects, which contains 1 part by mass to 2,000 parts by mass of the (B) component per 100 parts by mass of the (A) component. As an eighth aspect, the present invention relates to the cured film-forming composition according to any one of the fifth to seventh aspects, which contains 0.01 to 20 parts by mass of the (C) component relative to 100 parts by mass in total of the (A) component and the (B) component. As a ninth aspect, the present invention relates to a cured film obtained by using the cured film-forming composition according to any one of the first to eighth aspects. As a tenth aspect, the present invention relates to an alignment material obtained by using the cured film-forming composition according to any one of the first to eighth aspects. According to an eleventh aspect, the present invention relates to a retardation material formed by using the alignment material according to the tenth aspect. Effect of the Invention

[0018] According to the present invention, it is possible to provide a cured film that has excellent solvent resistance and is capable of aligning a polymerizable liquid crystal with high sensitivity, and a cured film-forming composition that is suitable for forming the cured film and can be formed under conditions of a relatively low temperature and a short time. According to the present invention, it is possible to provide an alignment material having excellent liquid crystal alignment properties and light transmittance, and a retardation material that allows highly accurate optical patterning. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] <Cured film forming composition> The cured film-forming composition of the present invention is a cured film-forming composition that includes a component containing one or more structures selected from the group consisting of a Michael donor moiety, a Michael acceptor moiety, and a liquid crystal alignment group, and that essentially contains the above three types of structures as a whole component. In detail, the cured film-forming composition includes a compound containing a Michael donor moiety as component (A) and a compound containing a Michael acceptor moiety as component (B), and at least one of the components (A) and (B) includes a liquid crystal aligning group. The components (A) and (B) may be the same compound that includes a Michael donor moiety, a Michael acceptor moiety, and a liquid crystal aligning group. The cured film-forming composition of the present invention may also be in an embodiment, comprising, as the component (A), at least one selected from a low molecular weight compound (A1) having one Michael donor moiety and a liquid crystal aligning group, and a compound (A2) having two or more Michael donor moieties and either not containing or containing a liquid crystal aligning group, and, as the component (B), at least one selected from a low molecular weight compound (B1) having one Michael acceptor moiety and a liquid crystal aligning group, and a compound (B2) having two or more Michael acceptor moieties and either not containing or containing a liquid crystal aligning group, wherein the components (A2) and (B2) may be either low molecular weight compounds or polymer compounds. Other additives may be contained as long as they do not impair the effects of the present invention. In the above, the term "low molecular weight compound" refers to a compound other than a "high molecular weight compound (polymer)", that is, a compound other than a compound having a repeating unit formed within the compound (by polymerization).

[0020] Each component will be described in detail below.

[0021] <Michael donor part> Examples of the Michael donor site in the component (A) include a mercapto group, an amino group, an active methylene group, and an active methine group.

[0022] An active methylene group refers to a methylene group (-CH2-) that has a carbonyl group adjacent to it and is reactive to nucleophiles. In the present invention, the active methine group refers to an active methylene group in which one hydrogen atom of the methylene group (-CH2-) is replaced with an alkyl group and is reactive to nucleophiles.

[0023] As the active methylene group and the active methine group, a group represented by the following formula (a1) is more preferable. [ka] (In formula (a1), R represents an alkyl group, an alkoxy group, or a phenyl group, and the dashed line represents a bond.)

[0024] 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. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. Of these, a methyl group, an ethyl group, an n-propyl group, etc. are preferred.

[0025] In the above formula (a1), examples of the alkoxy group represented by R include alkoxy groups having 1 to 20 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are preferred. Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy and t-butoxy groups. Among these, a methoxy group, an ethoxy group, an n-propoxy group, and the like are preferable.

[0026] Examples of the group represented by the above formula (a1) include the following structures: In the structural formula, the dashed lines represent bonds. [ka]

[0027] <Method of Introducing Group Represented by Formula (a1) (Michael Donor Moiety)> 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 acyl Meldrum's acid obtained by reacting Meldrum's acid with a carboxylic acid chloride can be mentioned. This method is known. In this case, taking into consideration availability, orientation, and the like, R is preferably a methyl group. [ka]

[0028] Another method is to react a low molecular weight compound or polymer having a hydroxyl group with tert-butyl acylacetate. This method is known. Here, R is preferably a methyl group in consideration of availability and orientation. [ka]

[0029] Furthermore, by copolymerizing a monomer having a Michael donor moiety, a compound having two or more Michael donor moieties (component (A2) described below) can be obtained as a polymer. Examples of monomers having a Michael donor site include 2-acetoacetoxyethyl acrylate (ethylene glycol monoacetoacetate monoacrylate), 2-acetoacetoxyethyl methacrylate (ethylene glycol monoacetoacetate monomethacrylate), and the like.

[0030] <Michael acceptor site> Examples of the Michael acceptor moiety in the component (B) include a (meth)acrylic group and a maleimide group, i.e., a CH2=CH-C(=O)- group, a CH2=C(CH3)-C(=O)- group, and a maleimide group. In this specification, the term "(meth)acrylic group" refers to both an acrylic group and a methacrylic group.

[0031] <Method of Introducing a (Meth)acrylic Group> As a method for introducing a (meth)acrylic group into each component, a method of reacting a component having an epoxy group with (meth)acrylic acid by a known method can be mentioned. Also, a method of reacting a compound component having a (meth)acrylic group and an isocyanate group by a known method can be mentioned.

[0032] <Method for introducing maleimide group> Methods for introducing maleimide groups into each component include reacting N-(4-carboxyphenyl)maleimide or N-(4-hydroxyphenyl)maleimide with a component having an epoxy group by a known method, and also include reacting N-(4-hydroxyphenyl)maleimide with a component having an isocyanate group by a known method.

[0033] <Liquid crystal alignment group> The liquid crystal aligning group contained in at least one of the components (A) and (B) and used in the present invention includes a vertical aligning group and a photoaligning group.

[0034] <Photoalignment group> In the present invention, the photoalignable group refers to a functional group that undergoes photodimerization or photoisomerization (also referred to as a photodimerization site or a photoisomerization site).

[0035] The photodimerization moiety is a moiety that forms a dimer upon irradiation with light, and specific examples thereof include a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, etc. Among these, a cinnamoyl group is preferred because of its high transparency and photodimerization reactivity in the visible light region. The photoisomerizable portion is a portion that changes between a cis form and a trans form upon irradiation with light, and specific examples thereof include an azobenzene structure, a stilbene structure, etc. Among these, the azobenzene structure is preferred because of its high reactivity.

[0036] A more preferred example of the structure of the cinnamoyl group as the photodimerization site is shown in the following formula [1] or formula [2]. [ka] 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 which the phenyl group and the biphenyl group may be substituted with any one of a halogen atom, an alkyl group, an alkoxy group, and a cyano group. 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 which the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded to the benzene ring via a single bond, an ether bond, an ester bond, an amide bond, or a urea bond.

[0037] <Method of introducing photoalignment groups> In order to introduce such a photoalignment group into each component of the present invention, there may be mentioned a method of introducing a Michael donor moiety into a compound having a photoalignment group and a hydroxyl group by the method described above in <Method of introducing a group represented by formula (a1) (Michael donor moiety)>, a method of using an acrylic monomer having a photoalignment group as is 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 photoalignment group (cinnamoyl group) and a carboxyl group), and the like.

[0038] The compound having a photoalignable group and a hydroxy group is represented by any one of the following formulas [A1] to [A5]. [ka]

[0039] In the above formula, A 1 and A 2 each independently represents a hydrogen atom or a methyl group; X 1 represents a structure in which 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 are bonded via one or more bonds selected from a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, an amino bond, or a combination thereof. 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 which the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded to the benzene ring via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond. X 3 represents a hydroxy group, a mercapto group, an amino group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, a phenoxy group, a phenylthio group, a phenylamino group, a biphenylamino group, a phenyl group, or a biphenyl group. X 4each 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, where the alkylene group having 1 to 20 carbon atoms may be branched or linear. X represents a single bond, an oxygen atom or a sulfur atom. In these groups, hydrogen atoms on the phenyl group, biphenyl group, phenylene group and biphenylene group may be substituted with one or more identical or different substituents 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.

[0040] 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.

[0041] Specific examples of the compound having a photoalignment group and a hydroxy group include 4-(8-hydroxyoctyloxy)cinnamic acid methyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid methyl ester, 4-(4-hydroxybutyloxy)cinnamic acid methyl ester, 4-(3-hydroxypropyloxy)cinnamic acid methyl ester, 4-(2-hydroxypropyloxy)cinnamic acid methyl ester, and the like. 4-hydroxyethyloxy)cinnamic acid methyl ester, 4-hydroxymethyloxycinnamic acid methyl ester, 4-hydroxycinnamic acid methyl ester, 4-(8-hydroxyoctyloxy)cinnamic acid ethyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid ethyl ester, 4-(4-hydroxybutyloxy)cinnamic acid ethyl ester, 4-(3-hydroxypropyloxy)cinnamic acid ethyl ester, 4-(2-hydroxyethyloxy)cinnamic acid ethyl ester, 4-hydroxymethyloxycinnamic acid ethyl ester, 4-hydroxy 4-(8-hydroxyoctyloxy)cinnamic acid phenyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid phenyl ester, 4-(4-hydroxybutyloxy)cinnamic acid phenyl ester, 4-(3-hydroxypropyloxy)cinnamic acid phenyl ester, 4-(2-hydroxyethyloxy)cinnamic acid phenyl ester, 4-hydroxymethyloxycinnamic acid phenyl ester, 4-hydroxycinnamic acid phenyl ester, 4-(8-hydroxyoctyloxy)cinnamic acid biphenyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid biphenyl ester, 4-(4-hydroxybutyloxy)cinnamic acid biphenyl ester, 4-(3-hydroxypropyloxy)cinnamic acid biphenyl ester, 4-(2-hydroxyethyloxy)cinnamic acid biphenyl ester, 4-hydroxymethyloxycinnamic acid biphenyl ester, 4-hydroxycinnamic acid biphenyl ester, cinnamic acid 8-hydroxyoctyl ester, cinnamic acid 6-hydroxyhexyl ester, cinnamic acid 4-hydroxybutyl ester, cinnamic acid 3-hydroxypropyl Pyr ester, cinnamic acid 2-hydroxyethyl ester, cinnamic acid hydroxymethyl ester, 4-(8-hydroxyoctyloxy)azobenzene, 4-(6-hydroxyhexyloxy)azobenzene, 4-(4-hydroxybutyloxy)azobenzene, 4-(3-hydroxypropyloxy)azobenzene, 4-(2-hydroxyethyloxy)azobenzene, 4-hydroxymethyloxyazobenzene, 4-hydroxyazobenzene, 4-(8-hydroxyoctyloxy)chalcone, 4-(6-hydroxyhexyloxy)chalcone,4-(4-hydroxybutyloxy)chalcone, 4-(3-hydroxypropyloxy)chalcone, 4-(2-hydroxyethyloxy)chalcone, 4-hydroxymethyloxychalcone, 4-hydroxychalcone, 4'-(8-hydroxyoctyloxy)chalcone, 4'-(6-hydroxyhexyloxy)chalcone, 4'-(4-hydroxybutyloxy)chalcone, 4'-(3-hydroxypropyloxy)chalcone, 4'-(2-hydroxyethyloxy)chalcone, 4'-hydroxymethyloxychalcone, 4'-hydroxychalcone, 7-(8-hydroxyoctyloxy) Coumarin, 7-(6-hydroxyhexyloxy)coumarin, 7-(4-hydroxybutyloxy)coumarin, 7-(3-hydroxypropyloxy)coumarin, 7-(2-hydroxyethyloxy)coumarin, 7-hydroxymethyloxycoumarin, 7-hydroxycoumarin, 6-hydroxyoctyloxycoumarin, 6-hydroxyhexyloxycoumarin, 6-(4-hydroxybutyloxy)coumarin, 6-(3-hydroxypropyloxy)coumarin, 6-(2-hydroxyethyloxy)coumarin, 6-hydroxymethyloxycoumarin, and 6-hydroxycoumarin.

[0042] The compound having a photoalignable group and a carboxyl group is represented by the following formula. [ka] In formula (1), A 11 and A 12 each independently represents a hydrogen atom or a methyl group. R 11is a hydrogen atom, a halogen atom, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, (C1-C6 alkyl)carbonyl, (C1-C6 haloalkyl)carbonyl, (C1-C6 alkoxy)carbonyl, (C1-C6 haloalkoxy)carbonyl, (C1-C6 alkylamino)carbonyl, (C1-C6 haloalkyl)aminocarbonyl, di(C1-C6 alkyl)aminocarbonyl, cyano, nitro, and the following formula (c-2): [ka] (In formula (c-2), the dashed line represents a bond, and R 101 is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of this alkylene group may be replaced by a fluorine atom or an organic group. 101 In the formula (I), -CH2CH2- may be replaced by -CH=CH-, and further, when any of the following groups are not adjacent to each other, they may be replaced by a group selected from the group consisting of -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO-; 1 is a hydrogen atom or a methyl group; R 12 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused ring group, R 13 is a single bond, an oxygen atom, -COO- or -OCO-, R 14 ~R 17 each 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, n is an integer from 0 to 3.

[0043] Preferred examples of the compound represented by the above formula (1) include compounds represented by the following formulae (1-1) to (1-5): [ka] (In the above formula, R 11 are R in the above formula (1), 11 and the like.

[0044] In the compound represented by the above formula (1), R 11 Preferred examples of the compound in which is a group represented by formula (c-2) include the following formulae M1-1 to M1-5. [ka] (In the formula, M 1 is a hydrogen atom or a methyl group, and s1 represents the number of methylene groups and is a natural number from 2 to 9.

[0045] The compound represented by the above formula (1) can be synthesized by appropriately combining standard methods in organic chemistry.

[0046] 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 these, monomers having a cinnamoyl group, which have good transparency in the visible light region and photodimerization reactivity, are particularly preferred.

[0047] In particular, monomers having a cinnamoyl group represented by the above formula [1] or [2] are more preferred. Specific examples of such monomers are shown in the following formula [3] or [4]. [ka] In the formula [3], X 11represents 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 are not limited to a halogen atom, an alkyl group, or a phenyl group. It may be substituted with any one of an alkyl group, an alkoxy group and a cyano group. In the above formula [4], 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 which the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded to the benzene ring via a single bond, an ether bond, an ester bond, an amide bond, or a urea bond. 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, where the alkylene group having 1 to 20 carbon atoms may be branched or linear, may be substituted with a hydroxy group, and 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 styrene group, a maleimide group, an acrylamide group, and a methacrylamide group.

[0048] The above-mentioned compounds having a photo-alignable group and a hydroxyl group, and monomers having a photo-alignable group are known and can be produced in accordance with the methods described in JP-A-62-284350, U.S. Pat. No. 4,696,990, JP-A-9-118717, U.S. Pat. No. 6,107,427, etc.

[0049] In addition, as the monomer having a photodimerization site, a compound obtained by reacting a cinnamic acid derivative represented by the above formulas (1-1) to (1-5) with a (meth)acrylic monomer having an epoxy group is also preferably used.

[0050] <Vertical alignment group> 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 preferable. [ka] In formula (2), Y 1 represents a single bond or a bonding group selected from -O-, -CHO-, -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 cyclohexane ring, or a heterocycle, any hydrogen atom on the cyclic group may be replaced by Z, and Y 3 represents a single bond or an alkylene group having 1 to 15 carbon atoms; Y 4 represents a single bond, a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocycle, or a divalent organic group having a steroid skeleton having 17 to 30 carbon atoms, any hydrogen atom on the cyclic group may be substituted with Z, Y 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocycle, any hydrogen atom on the cyclic group may be substituted with Z, m represents an integer of 0 to 4, and when m is 2 or more, Y 5 may be the same or different, and 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 fluorine atom; 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 fluorine atom; 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 bonding groups therein, as long as the bonding groups are not adjacent to each other; Y 2 ~Y 6In the formula (I), the alkylene group, the -CH2-CH(OH)-CH2- group, the divalent cyclic group, the divalent organic group having a steroid skeleton, the alkyl group and the fluoroalkyl group may be bonded to the group adjacent thereto via the above-mentioned bonding group. 2 ~ Y 6 The substituent represented by the formula (I) has 6 to 30 carbon atoms in total.

[0051] The alkylene group having 1 to 15 carbon atoms includes a divalent group obtained by removing one hydrogen atom from an alkyl group having 1 to 15 carbon atoms, among the alkyl groups having 1 to 18 carbon atoms described below, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group. Specific examples of the heterocycle include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, a purine ring, a thiadiazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a cinnoline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, and an acridine ring. Among these, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyrazoline ring, a carbazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, and a benzimidazole ring are preferred.

[0052] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 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 group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methylcyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 1-ethylcyclobutyl group, 2-ethyl ethylcyclobutyl group, 3-ethylcyclobutyl group, 1,2-dimethylcyclobutyl group, 1,3-dimethylcyclobutyl group, 2,2-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,4-dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-propylcyclopropyl group, 2-propylcyclopropyl group, 1-isopropylcyclopropyl group, 2-isopropylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl, 3-methyl-n-hexyl, 1,1-dimethyl-n-pentyl, 1,2-dimethyl-n-pentyl, 1,3-dimethyl-n-pentyl, 2,2-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 group, 1-methyl-3-ethyl-n-pentyl group, 2-methyl-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, and n-octadecyl group. Furthermore, examples of the alkoxy group having 1 to 18 carbon atoms include groups in which an oxygen atom (—O—) is bonded to the above-mentioned alkyl group having 1 to 18 carbon atoms.

[0053] Examples of the fluorinated alkyl group having 1 to 18 carbon atoms include the above-mentioned alkyl groups having 1 to 18 carbon atoms in which at least one hydrogen atom has been substituted with a fluorine atom. Specific examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 2,2,2-trifluoro-1-(trifluoromethyl) group, ) ethyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, undecafluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, tridecafluorohexyl group, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, and the like.

[0054] Specific examples of the fluorinated alkoxy group having 1 to 18 carbon atoms include the above-mentioned fluorinated alkyl group having 1 to 18 carbon atoms to which an oxygen atom (-O-) is bonded. Specific examples thereof include a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a pentafluoroethoxy group, a 2,2,2-trifluoroethoxy group, a heptafluoropropoxy group, a 2,2,3,3,3-pentafluoropropoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2,2-trifluoro-1-(trifluoromethyl)ethoxy group, a nonafluoro Examples of such a group include a fluorobutoxy group, a 4,4,4-trifluorobutoxy group, an undecafluoropentyloxy group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyloxy group, a 2,2,3,3,4,4,5,5-octafluoropentyloxy group, a tridecafluorohexyloxy group, a 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyloxy group, a 2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy group, and a 3,3,4,4,5,5,6,6,6-nonafluorohexyloxy group.

[0055] In addition, examples of the alkyl group having 1 to 3 carbon atoms in Z include those having 1 to 3 carbon atoms among the groups exemplified above for those having 1 to 18 carbon atoms, and examples of the alkoxy group having 1 to 3 carbon atoms include those having 1 to 3 carbon atoms among the groups exemplified above for those having 1 to 18 carbon atoms (those having 1 to 3 carbon atoms among the groups exemplified above for those having 1 to 18 carbon atoms to which an oxygen atom (-O-) is bonded). Examples of the fluorinated alkyl group having 1 to 3 carbon atoms include those having 1 to 3 carbon atoms among the groups exemplified above for the fluorinated alkyl group having 1 to 18 carbon atoms, and examples of the fluorinated alkoxy group having 1 to 3 carbon atoms include those having 1 to 3 carbon atoms among the groups exemplified above for the fluorinated alkoxy group having 1 to 18 carbon atoms.

[0056] Also, Y 2 ~Y 6 The total number of carbon atoms of each of the substituents represented by each is 6 to 30, but 6 to 20 is preferred. In particular, taking into consideration the vertical alignment property and coatability of the resulting liquid crystal polymer, the vertical alignment group is preferably a group containing an alkyl group having 7 to 18 carbon atoms, particularly 8 to 15 carbon atoms.

[0057] Specific examples of the vertical alignment group include hydrocarbon groups having about 6 to 20 carbon atoms. Examples of the hydrocarbon group having 6 to 20 carbon atoms include linear, branched, or cyclic alkyl groups having 6 to 20 carbon atoms or hydrocarbon groups having 6 to 20 carbon atoms including an aromatic group. Therefore, in the above formula (2), the above Y 1 , Y 2 and Y 4 is a single bond, and 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, and Y 6 is an alkyl group having 1 to 18 carbon atoms, and Y 3 and Y 6The alkyl group (a-1) is preferably an alkyl group having a total of 6 to 20 carbon atoms, more preferably an alkyl group having a total of 7 to 18 carbon atoms, and even more preferably an alkyl group having a total of 8 to 15 carbon atoms. Specific examples of such vertically aligning groups (a-1) include, in addition to the alkyl groups having 6 to 18 carbon atoms exemplified above as the alkyl groups having 1 to 18 carbon atoms, n-nonadecyl and n-eicosynyl groups.

[0058] In addition to the vertical alignment group (a-1), for example, the above Y 1 ~Y 4 is a single bond, m is 2 or 3, and Y 5 is a benzene ring or a cyclohexane ring, and Y 6 However, a vertically aligning group (a-2) which is an alkyl group having 1 to 18 carbon atoms can also be suitably used. Specific examples of such vertically aligning groups (a-2) include the following groups (a-2-1) to (a-2-6), but are not limited thereto. [ka] (In the formula, Y 6 is Y in the above formula (2) 6 is equivalent to

[0059] <Method of Introducing Vertically Aligning Group> To introduce the vertical alignment group described above into each component of the present invention, there may be mentioned a method of introducing a Michael donor moiety into a compound having a vertical alignment group and a hydroxy group by the method described in the above <Method of introducing a group (Michael donor moiety) represented by formula (a1)>, a method of using an acrylic monomer having a vertical alignment group as is or copolymerizing it, a method of reacting a compound having a carboxyl group bonded to a vertical alignment group with a component having an epoxy group, and the like.

[0060] Examples of monomers having a vertical alignment group include alkyl esters of (meth)acrylic acid, alkyl vinyl ethers, 2-alkylstyrenes, 3-alkylstyrenes, 4-alkylstyrenes, and N-alkylmaleimides in which the alkyl group has 6 to 20 carbon atoms. These monomers can be produced by known methods, and some are commercially available. In addition, 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'): As shown. [ka] (In the formula, Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 and m are the same as those in formula (2).

[0061] <(A1) A low molecular weight compound having one Michael donor site and a liquid crystal alignment group> Examples of the low molecular weight compound (A1) having one Michael donor moiety and a liquid crystal alignment group include a compound obtained by introducing a Michael donor moiety into a compound having the above-mentioned photoalignment group and a hydroxyl group by the method described in the above-mentioned <Method for introducing a group represented by formula (a1) (Michael donor moiety)>, and a compound obtained by introducing a Michael donor moiety into a compound having the above-mentioned vertical alignment group and a hydroxyl group by the method described in the above-mentioned <Method for introducing a group represented by formula (a1) (Michael donor moiety)>.

[0062] <(A2) Compounds having two or more Michael donor sites (low molecular weight compounds)> When the compound (A2) having two or more Michael donor moieties is a low molecular weight compound, examples of the low molecular weight compound (A2) include a compound obtained by introducing a Michael donor moiety into a low molecular weight compound having two or more hydroxyl groups by the method described in the above <Method for introducing a group represented by formula (a1) (Michael donor moiety)>, polyfunctional thiol, diamine, etc.

[0063] <Low molecular weight compounds with two or more hydroxyl groups> Specific examples of dihydric alcohols having two alcoholic hydroxy groups include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, trimethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, pentanediol, hexanediol, heptanediol, nonanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, dioxane glycol, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-tert-butyldiethanolamine, N-lauryldiethanolamine, stearyldiethanolamine, N-phenyldiethanolamine, m-tolyldiethanolamine, and p-tolyldiethanolamine.

[0064] Specific examples of trihydric alcohols having three alcoholic hydroxy groups include trimethylolethane, trimethylolpropane, glycerin, tris(2-hydroxyethyl)isocyanurate, hexanetriol, octanetriol, decanetriol, triethanolamine, and triisopropanolamine.

[0065] Specific examples of tetrahydric alcohols having four alcoholic hydroxy groups include ditrimethylolethane, ditrimethylolpropane, diglycerin, and pentaerythritol.

[0066] In the present invention, these polyhydric alcohols can be used alone or in any combination of two or more.

[0067] <Multifunctional thiol compounds> The polyfunctional thiol compound can be obtained as an addition reaction product between a polyhydric alcohol and a monofunctional and / or polyfunctional thiol compound. Specific examples of the compound include 1,3,5-tris(3-mercaptopropionyloxyethyl)-isocyanurate, 1,3,5-tris( Examples of the thiol compounds include trifunctional thiol compounds such as pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko K.K., Karenz MT (registered trademark) PEI), and tetrafunctional thiol compounds such as pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko K.K., Karenz MT (registered trademark) PEI), and hexafunctional thiol compounds such as dipentaerythritol hexakis(3-propionate).

[0068] <Diamine> The diamine component used is not particularly limited, but specific examples are as follows: Examples of the alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, and isophoronediamine.

[0069] Examples of 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.

[0070] Examples of 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-aminopropyl)aniline, 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.

[0071] Examples of 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.

[0072] <(A2) Compound (polymer) having two or more Michael donor sites> When the compound (A2) having two or more Michael donor moieties is a polymer (polymer compound), the polymer (A2) can be a polymer obtained by introducing a Michael donor moiety into a precursor of the polymer (A2) and polymer (B2) described below by the method described in the above <Method for introducing a group represented by formula (a1) (Michael donor moiety)>.

[0073] In addition, when it is desired to introduce a liquid crystal alignment group into the polymer (A2) having two or more Michael donor sites, the liquid crystal alignment group is introduced into the precursors of the polymer (A2) and the polymer (B2) described later by the above-mentioned method, or the precursors of the polymer (A2) and the polymer (B2) are produced. In this case, the above-mentioned monomer having a liquid crystal alignment group is copolymerized, and then a Michael donor site is introduced by the above-mentioned method.

[0074] <(B1) A low molecular weight compound having one Michael acceptor site and a liquid crystal alignment group> Examples of the low molecular weight compound (B1) having one Michael acceptor site and a liquid crystal alignment group include an ester obtained by using the compound having the above-mentioned photoalignment group and a hydroxyl group with (meth)acrylic acid chloride, and an ester obtained by using the compound having the above-mentioned vertical alignment group and a hydroxyl group with (meth)acrylic acid chloride.

[0075] <(B2) Compounds having two or more Michael acceptor sites (low molecular weight compounds)> When the compound (B2) having two or more Michael acceptor sites is a low molecular weight compound, examples of the low molecular weight compound (B2) include polyfunctional (meth)acrylates and bismaleimides.

[0076] [Multifunctional urethane (meth)acrylate compound having three or more (meth)acryloyl groups] (1) Trifunctional (having three (meth)acryloyl groups) urethane (meth)acrylate Specific examples of commercially available polyfunctional urethane (meth)acrylate compounds having three (meth)acryloyl groups include NK Oligo UA-7100 [manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 204, 205, 264, 265, 294 / 25HD, 1259, 4820, 8311, 8465, 8701, 9260, KRM (registered trademark) 8296, and 8667 [all manufactured by Daicel-Allnex Corporation]; and Shikoh (registered trademark) UV-7550B, 7000B, 7510B, 7461TE, and 2750B [all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.].

[0077] (2) Tetrafunctional (having four (meth)acryloyl groups) urethane (meth)acrylate Specific examples of commercially available polyfunctional urethane (meth)acrylate compounds having four (meth)acryloyl groups include EBECRYL (registered trademark) 8210, EBECRYL 8405, and KRM (registered trademark) 8528 [all manufactured by Daicel-Allnex Co., Ltd.]; Shikoh (registered trademark) UV-7650B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd.]; and the like.

[0078] (3) Pentafunctional or higher (having 5 or more (meth)acryloyl groups) urethane (meth)acrylate Examples of polyfunctional urethane (meth)acrylate compounds having five or more (meth)acryloyl groups (penta- or higher-functional urethane (meth)acrylates) 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.

[0079] The pentafunctional or higher urethane (meth)acrylate may be a commercially available product, such as UA-306H, UA-306T, UA-306I, and UA-510H (all manufactured by Kyoeisha Chemical Co., Ltd.); NK Oligo U-6LPA, U-10HA, U-10PA, U-1100H, U-15HA, UA-53H, and UA-33H (all manufactured by Shin-Nakamura Chemical Co., Ltd.); EBECRYL (registered trademark) (registered trademark) 220, 1290, 5129, 8254, 8301R, KRM (registered trademark) 8200, 8200AE, 8904, and 8452 (all manufactured by Daicel-Allnex Co., Ltd.); Shiko (registered trademark) UV-1700B, 6300B, 7600B, 7605B, 7610B, 7620EA, 7630B, 7640B, and 7650B (all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). etc.

[0080] (1) Trifunctional compounds (having three (meth)acryloyl groups) Examples of compounds having three (meth)acryloyl groups include 1,1,1-trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and glycerin tri(meth)acrylate.

[0081] The compound having three (meth)acryloyl groups may be a commercially available product, such as Viscoat #295 or #300 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light Acrylate TMP-A, PE-3A, or Light Ester TMP (all manufactured by Kyoeisha Chemical Co., Ltd.); NK Ester A-9300, A-9300-1CL, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, or TMPT (all manufactured by Shin-Nakamura Chemical Co., Ltd.); PETIA, PETRA, TMPTA, or EBECRYL (registered trademark) 180 (all manufactured by Daicel-Allnex Co., Ltd.).

[0082] (2) Tetrafunctional (having four (meth)acryloyl groups) compounds Examples of the compound having four (meth)acryloyl groups include ditrimethylolpropane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate.

[0083] The compound having four (meth)acryloyl groups may be suitably a commercially available product, such as Viscoat #300 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Light Acrylate PE-4A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester AD-TMP, NK Ester A-TMMT [all manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 140, 1142, 180 [all manufactured by Daicel-Allnex Corporation], and the like.

[0084] (3) Compounds with five or more functional groups (containing five or more (meth)acryloyl groups) 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.

[0085] As the compound having five or more (meth)acryloyl groups, commercially available products can be suitably used, such as Viscoat #802 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Light Acrylate DPE-6A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester A-9550, NK Ester A-DPH [all manufactured by Shin-Nakamura Chemical Co., Ltd.]; DPHA [manufactured by Daicel-Allnex Co., Ltd.], and the like.

[0086] <Bismaleimide> The bismaleimide compound used as the component (B2) in the present invention is represented by the following formula (3). [ka] In the formula, R 33 is an organic group selected from the group consisting of an aliphatic group, an aliphatic group containing a cyclic structure, and an aromatic group, or an organic group consisting of a combination of a plurality of organic groups selected from the group. And R33 may contain bonds such as ester bonds, ether bonds, amide bonds, and urethane bonds.

[0087] 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'-p-benzophenone bismaleimide, N,N'-diphenylethane bismaleimide, N,N'-diphenylether bismaleimide, N,N'-(methylenedi-ditetrahydro (3-chlorophenyl) bismaleimide, N,N'-(3-ethyl)-4,4-diphenylmethane bismaleimide, N,N'-(3,3-dimethyl)-4,4-diphenylmethane 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 Imide, N,N'-5-methoxy-1,3-phenylenebismaleimide, 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, 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 Examples of the bismaleimide compounds include N,N'-hexamethylene bismaleimide, N,N'-dodecamethylene bismaleimide, N,N'-m-xylene bismaleimide, N,N'-p-xylene bismaleimide, N,N'-1,3-bismethylenecyclohexane bismaleimide, N,N'-2,4-tolylene bismaleimide, and N,N'-2,6-tolylene bismaleimide. These bismaleimide compounds are not particularly limited to those mentioned above. These compounds can be used alone or in combination of two or more kinds.

[0088] <(B2) Compound (polymer) having two or more Michael acceptor sites> When the compound having two or more Michael acceptor sites is a polymer (polymer compound), examples of the polymer (B2) include polymer compounds having a side chain in the molecule with one or more terminals that are polymerizable unsaturated bonds. As such a polymer compound having a side chain whose terminal is a polymerizable unsaturated bond, a polymer compound having (meth)acryloyl groups in two or more side chains in the molecule is preferably mentioned.

[0089] The above-mentioned polymeric compounds include polymeric compounds containing a (meth)acryloyl group, such as urethane acrylic compounds, epoxy acrylic compounds, and various (meth)acrylate compounds. Examples of the polyfunctional polymer compound include a polyfunctional polymer compound having three or more acryloyl groups.

[0090] As the preferred example of the polymer compound having a (meth)acryloyl group, commercially available products can be suitably used, such as Acrylit 8KX-077, 8KX-078, 8KX-089, 8KX-127, 8KX-128, 8KX-012C, 8KX-014C, 8KX-018C, 8KX-052C, 8KQ-2001, 8BR-600, 8UH-1006, and 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.); SMP-220A, SMP-250A, SMP-360A, and SMP-550A (all manufactured by Kyoeisha Chemical Co., Ltd.).

[0091] In addition, examples of the polymer (B2) having two or more Michael acceptor sites include polymers in which a Michael acceptor site has been introduced into the precursors of the polymer (A2) and polymer (B2) described below, using the above-mentioned method for introducing a (meth)acrylic group or a method for introducing a maleimide group.

[0092] When it is desired to introduce a liquid crystal aligning group into a polymer (B2) having two or more Michael acceptor sites, the liquid crystal aligning group can be introduced into the precursors of the polymer (A2) and polymer (B2) described below by the above-mentioned method, or when producing the precursors of the polymer (A2) and polymer (B2), a monomer having the above-mentioned liquid crystal aligning group can be copolymerized and then the Michael acceptor site can be introduced by the above-mentioned method.

[0093] <Precursors of polymer (A2) and polymer (B2)> When introducing a side chain (specific side chain) having a liquid crystal alignment group or a Michael addition reaction site into a polymer, a specific functional group that is easily reactive with each other is arranged (or reacted with a specific compound), and the specific side chain can be generated by reacting them. In the reaction for generating the specific side chain, preferred combinations of specific functional groups and combinations of specific functional groups and specific compounds are combinations of a carboxyl group and an epoxy group, a hydroxyl group and an isocyanate group, a phenolic hydroxyl group and an epoxy group, a carboxyl group and an isocyanate group, an amino group and an isocyanate group, a hydroxyl group and an acid chloride, etc. More specific preferred examples include a carboxyl group and a glycidyl (meth)acrylate, and a hydroxyl group and an isocyanate ethyl (meth)acrylate.

[0094] The polymer having a specific functional group (also called a specific copolymer) is a copolymer obtained by polymerizing a monomer having a functional group (specific functional group) for reacting with a specific compound as an essential component, and has a number average molecular weight of 2,000 to 25,000. In this case, the monomer having a specific functional group may be used alone, or multiple types may be used in combination as long as the specific functional group does not react during polymerization. Specific examples of the monomer having a specific functional group are listed below, but the present invention is not limited thereto.

[0095] Examples of monomers 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.

[0096] Examples of monomers having a phenolic hydroxy group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleimide.

[0097] Examples of monomers having a hydroxy group other than a phenolic hydroxy 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.

[0098] Examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

[0099] Examples of monomers having an epoxy group include glycidyl methacrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

[0100] Examples of monomers having an isocyanate group include acryloylethyl isocyanate, methacryloylethyl isocyanate, and m-tetramethylxylene isocyanate.

[0101] In the present invention, when obtaining the specific copolymer, in addition to the monomer having the specific functional group, another monomer copolymerizable with the monomer can be used in combination. Specific examples of such other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

[0102] Specific examples of the other monomers are listed below, but the present invention is not limited thereto. Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, acrylic acid, mono-(2-(acryloyloxy)ethyl)phthalate, glycidyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, and acrylate. Examples of the acrylate acrylate include anthryl acrylate, anthryl 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.

[0103] Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2-(methacryloyloxy)ethyl ester, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, glycidyl methacrylate, isopropyl methacrylate, and the like. methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl 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-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

[0104] 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, etc. Note that (meth)acrylamide means both acrylamide and methacrylamide.

[0105] Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

[0106] Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

[0107] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-(hydroxyphenyl)maleimide, N-(hydroxyphenyl)maleimide, N-(carboxyphenyl)maleimide, and N-cyclohexylmaleimide.

[0108] When introducing a liquid crystal alignment group into the (A2) component or the (B2) component (polymer), the amount of each monomer used to obtain the specific copolymer is preferably 25 to 90 mol% of a monomer having a liquid crystal alignment group or a monomer having a group for introducing it, 10 to 75 mol% of a monomer having a Michael addition reaction site (Michael donor site, Michael acceptor site) or a monomer having a group for introducing it, and 0 to 65 mol% of other monomers that do not have a specific functional group, based on the total amount of all monomers. Alternatively, it is preferably 25 to 100 mol% of a monomer having a liquid crystal alignment group and a Michael addition reaction site, and 0 to 75 mol% of a monomer that does not have a specific functional group.

[0109] When a liquid crystal alignment group is not introduced into the component (A2) or the component (B2) (polymer), the amount of each monomer used to obtain the specific copolymer is preferably 5 to 100 mol % of a monomer having a Michael addition reaction site or a monomer having a group for introducing the same, and 0 to 95 mol % of other monomers not having the specific functional group, based on the total amount of all monomers.

[0110] The method for obtaining the specific copolymer used in the present invention is not particularly limited, but for example, the specific copolymer can be obtained by a polymerization reaction at a temperature of 50 to 110° C. in a solvent in which a monomer having a specific functional group, optionally another monomer not having a specific functional group, and a polymerization initiator are present. The solvent used is not particularly limited as long as it dissolves the monomer having the specific functional group, the monomer not having the specific functional group that is used if desired, and the polymerization initiator, etc. Specific examples are described in the section "Solvent" below. The specific copolymer obtained by the above method is usually in the state of a solution dissolved in a solvent.

[0111] The solution of the specific copolymer obtained by the above method can be poured into diethyl ether or water under stirring to cause reprecipitation, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal or reduced pressure to obtain a powder of the specific copolymer. By the above operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a powder of the purified specific copolymer can be obtained. If the specific copolymer cannot be sufficiently purified by one operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated.

[0112] In the present invention, the specific copolymer may be used in the form of a powder, or in the form of a solution obtained by redissolving the purified powder in a solvent described below.

[0113] The acrylic copolymer used as component (A2) or component (B2) of the present invention may have a weight average molecular weight of, for example, 3,000 to 200,000, or may have a weight average molecular weight of, for example, 4,000 to 150,000, or may have a weight average molecular weight of, for example, 5,000 to 100,000. If the weight average molecular weight of the copolymer is too high, exceeding 200,000, the solubility in solvents may decrease, leading to poor handling properties, whereas if the weight average molecular weight is too low, less than 3,000, the copolymer may be insufficiently cured during heat curing, resulting in poor solvent resistance and heat resistance.

[0114] As the precursor of the component (A2) or the component (B2), a polymer having multiple hydroxy groups other than those mentioned above can also be used.

[0115] Examples of polyether polyols, which are preferred examples of polymers having multiple hydroxyl groups, include those obtained by adding propylene oxide, polyethylene glycol, polypropylene glycol, etc. to polyhydric alcohols such as polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, and sorbitol. Specific examples of polyether polyols include the Adeka Polyether P series, G series, EDP series, BPX series, FC series, and CM series manufactured by ADEKA CORPORATION, Uniox (registered trademark) HC-40, HC-60, ST-30E, ST-40E, G-450, and G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, and DB-400, and Nonion LT-221, ST-221, and OT-221 manufactured by NOF Corporation.

[0116] Examples of polyester polyols, which are preferred examples of polymers having multiple hydroxyl groups, include those obtained by reacting polycarboxylic acids such as adipic acid, sebacic acid, and isophthalic acid with diols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, and polypropylene glycol. Specific examples of polyester polyols include 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-2547 ... OD-2523, OD-X-2555, OD-X-2560, and polyols 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, and PNNA-2016 manufactured by Kuraray Co., Ltd.

[0117] A preferred example of a polymer having multiple hydroxyl groups is polycaprolactone polyol, which is obtained by ring-opening polymerization of ε-caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of polycaprolactone polyol include Polylite (registered trademark) OD-X-2155, OD-X-640, and OD-X-2568 manufactured by DIC Corporation, and Plaxel (registered trademark) 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, and 410 manufactured by Daicel Corporation.

[0118] A polycarbonate polyol, which is a preferred example of a polymer having multiple hydroxyl groups, can be obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc. Specific examples of polycarbonate polyols include PLACCEL (registered trademark) CD205, CD205PL, CD210, and CD220 manufactured by Daicel Corporation, and C-590, C-1050, C-2050, C-2090, and C-3090 manufactured by Kuraray Co., Ltd.

[0119] Examples of cellulose, which is a preferred example of a polymer having multiple hydroxy groups, include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and cellulose, and for example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferred.

[0120] Cyclodextrin, which is a preferred example of a polymer having a plurality of hydroxy groups, includes 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 ... Examples of hydroxyalkyl cyclodextrins include diethyl-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.

[0121] Examples of urethane-modified acrylic polymers, which are preferred examples of polymers having multiple hydroxy groups, include commercially available products such as ACRYT (registered trademark) 8UA-017, 8UA-239, 8UA-239H, 8UA-140, 8UA-146, 8UA-585H, 8UA-301, 8UA-318, 8UA-347A, 8UA-347H, and 8UA-366 manufactured by Taisei Fine Chemical Co., Ltd.

[0122] An example of a phenol novolac resin, which is a preferred example of a polymer having a plurality of hydroxy groups, is a phenol-formaldehyde polycondensate.

[0123] When the above-mentioned (B) component is contained (when the later-described (A2) component and (B2) component are not the same compound), the content of the (B) component is 1 part by mass to 2000 parts by mass, for example, 5 parts by mass to 2000 parts by mass, and preferably, is 1 part by mass to 2000 parts by mass, per 100 parts by mass of the (A) component. The amount is usually from 15 parts by weight to 700 parts by weight, or alternatively from 1 part by weight to 400 parts by weight.

[0124] <When components (A) and (B) are the same compound> In such a case, the above-mentioned introduction methods may be combined to introduce both the Michael donor site and the Michael acceptor site, and further introduce a liquid crystal alignment group as necessary. For example, such a method may be a copolymerization of a monomer having an active methylene group, a monomer having an epoxy group, and a monomer having a liquid crystal alignment group as necessary, and react the copolymer with (meth)acrylic acid.

[0125] <(C) Michael addition reaction catalyst> The cured film-forming composition of the present invention may further contain, in addition to the components (A) and (B), a Michael addition reaction catalyst that promotes the Michael addition reaction as component (C). More specifically, the Michael addition reaction catalyst may be the basic compounds shown below, but is not limited thereto. Examples of basic compounds include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; alkoxides of alkali metals such as sodium methoxide and potassium ethoxide; quaternary ammonium hydroxides such as tetrabutylammonium hydroxide and benzyltrimethylammonium hydroxide; quaternary ammonium carbonates such as tetrabutylammonium carbonate, benzyltrimethylammonium carbonate, triethylmonomethylammonium 2-ethylhexanoate and tetrabutylammonium acetate; quaternary ammonium fluorides such as tetrabutylammonium fluoride and benzyltrimethylammonium fluoride; quaternary ammonium tetrahydroborate and benzyltrimethylammonium tetrahydroborate; tertiary amines such as tetramethylguanidine, 1,8-diazabicyclo[5,4,0]undecene-7 and diazabicyclo[4,3,0]nonene-5; and tertiary phosphines such as guanidine, azine and triphenylphosphine.

[0126] Furthermore, an acidic compound may be added together with the Michael addition reaction catalyst in order to improve storage stability during storage. In particular, when a strongly basic compound with high catalytic activity is used, the addition of an acidic compound is effective in improving 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.

[0127] From the viewpoints of reactivity and storage stability, quaternary ammonium carbonates, quaternary ammonium hydroxides, and tertiary amines are more preferable as the component (C).

[0128] The content of the (C) component in the cured film-forming composition of the present invention, when included, is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the total of the (A) and (B) components. By making the content of the (C) component 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, if it is more than 20 parts by mass, the storage stability of the composition may decrease.

[0129] <Solvent> The cured film-forming composition of the present invention is mainly used in a state of solution 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), and optionally component (C), and further other additives described below as necessary.

[0130] 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 ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ether, propylene glycol mono ... methyl 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 ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, cyclopentyl methyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

[0131] For example, when an alignment material is produced by forming a cured film on a resin film using the cured film-forming composition of the present invention, it is preferable to use methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol, 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, etc., since these are solvents to which the resin film exhibits resistance.

[0132] These solvents can be used alone or in combination of two or more.

[0133] <Other additives> Furthermore, the cured film-forming composition of the present invention may contain, as necessary, an adhesion improver, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, an antioxidant, inorganic oxide particles, etc., as long as the effects of the present invention are not impaired.

[0134] <Preparation of Cured Film-Forming Composition> The cured film-forming composition of the present invention is a composition that can contain a compound having a Michael donor site (A), a compound having a Michael acceptor site (B), and a Michael addition reaction catalyst (C) as well as other additives as long as they do not impair the effects of the present invention. Usually, they are used in the form of a solution in which they are dissolved in a solvent.

[0135] Preferred examples of the cured film-forming composition of the present invention are as follows. [1]: A cured film-forming composition containing a compound having a Michael donor moiety as a component (A) and a compound having a Michael acceptor moiety as a component (B), and containing 0.01 to 20 parts by mass of a component (C) relative to 100 parts by mass in total of the components (A) and (B), and a solvent.

[0136] The blending ratio, preparation method, etc. when the cured film-forming composition of the present invention is used in the form of a solution will be described in detail below. The solid content of the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1% by mass to 60% by mass, preferably 2% by mass to 50% by mass, and more preferably 2% by mass to 20% by mass. refers to all components of the cured film-forming composition excluding the solvent.

[0137] The method for preparing the cured film-forming composition of the present invention is not particularly limited. For example, the method for preparing the composition includes a method in which the solution of the component (A) dissolved in a solvent is mixed with the components (B) and (C) in a predetermined ratio to prepare a homogeneous solution, or a method in which other additives are further added and mixed as necessary at an appropriate stage of the preparation method.

[0138] In preparing the cured film-forming composition of the present invention, the solution of the specific copolymer (polymer) obtained by polymerization reaction in a solvent can be used as is. In this case, for example, the (A) component or the (B) component and the (C) component are added to the solution of the (A) component or the (B) component polymer to make a homogeneous solution. At this time, a solvent may be added for the purpose of adjusting the concentration. At this time, the solvent used in the process of producing the (A) component or the (B) component polymer and the solvent used to adjust the concentration of the cured film-forming composition may be the same or different.

[0139] The prepared solution of the cured film-forming composition is preferably filtered using a filter having a pore size of about 0.2 μm before use.

[0140] <Curing film, alignment material and retardation material> A solution of the cured film-forming composition of the present invention is applied onto a substrate (e.g., a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, an ITO substrate, or the like) or a film substrate (e.g., a resin film such as a triacetyl cellulose (TAC) film, a polycarbonate (PC) film, a cycloolefin polymer (COP) film, a cycloolefin copolymer (COC) film, a polyethylene terephthalate (PET) film, an acrylic film, or a polyethylene film) by bar coating, spin coating, flow coating, roll coating, slit coating, spin coating followed by slit coating, inkjet coating, printing, or the like to form a coating film, and then the coating is dried by heating on a hot plate or in an oven, or the like to form a cured film. The cured film can be used as an alignment material as it is.

[0141] The conditions for the heat drying are such that the crosslinking reaction by the crosslinking agent proceeds to such an extent that the components of the cured film (alignment material) are not dissolved in the polymerizable liquid crystal solution applied thereon, and for example, a heating temperature and a heating time appropriately selected from the ranges of 60°C to 200°C and 0.4 minutes to 60 minutes are adopted. The heating temperature and heating time are preferably 70°C to 160°C and 0.5 minutes to 10 minutes.

[0142] The thickness of the cured film (alignment material) formed using the curable composition of the present invention is, for example, 0.05 μm to 5 μm, and can be appropriately selected taking into consideration the step height and optical and electrical properties of the substrate to be used.

[0143] Since the alignment material formed from the cured film composition of the present invention has solvent resistance and heat resistance, a retardation material such as a polymerizable liquid crystal solution having vertical alignment properties can be applied onto the alignment material and aligned on the alignment material. Then, the retardation material in the aligned state can be cured as it is to form a retardation material as a layer having optical anisotropy. And, when the substrate on which the alignment material is formed is a film, it is useful as a retardation film.

[0144] In addition, two substrates having the alignment material of the present invention formed as described above can be used, bonded together via a spacer so that the alignment materials on both substrates face each other, and then liquid crystal can be injected between the substrates to create a liquid crystal display element in which the liquid crystal is aligned. In this way, the cured film-forming composition of the present invention can be used in various retardation materials (retardation films) and liquid crystal displays. It can be suitably used for manufacturing elements and the like. EXAMPLES

[0145] The present invention will be specifically described below by way of examples of the present invention, but the present invention should not be construed as being limited to these.

[0146] [Abbreviations used in the Examples] The meanings of the abbreviations used in the following examples are as follows. <Raw material> GMA: Glycidyl methacrylate M100: 3,4-Epoxycyclohexylmethyl methacrylate EGAMA: Ethylene glycol monoacetoacetate monomethacrylate LA: Lauryl acrylate HA: Hexyl acrylate AIBN: α,α’-Azobisisobutyronitrile CIN1:

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[0147] <Component A2> TMPI: 1,3,5-Tris(3-mercaptopropionyloxyethyl)-isocyanurate

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[0148] <Component B> DPHA: Dipentaerythritol hexaacrylate [A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)] UA: Urethane acrylate [UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.)] SMP: Acrylic group-containing acrylic polymer [SMP-220A (manufactured by Kyoeisha Chemical Co., Ltd.)]<Component C> UCAT: Triethylmethylammonium 2-ethylhexanoate [U-CAT18X (manufactured by San-Apro Ltd.)] TBAAc: Tetrabutylammonium acetate TBAH: Tetrabutylammonium hydroxide DBU: 1,8-Diazabicyclo[5.4.0]-7-undecene <Other components (Component D)> PGM-AC: Organosilica sol [PGM-AC-2140Z (manufactured by Nissan Chemical Industries, Ltd.)] <Solvent> The compositions of the examples and comparative examples contain a solvent, and as the solvent, propylene glycol monomethyl ether (PM), propylene glycol monomethyl ether acetate (PMA), butyl acetate (BA), and ethyl acetate (EA) were used.

[0149] <Measurement of the molecular weight of the polymer> The molecular weight of the acrylic copolymer in the polymerization example was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co., Ltd. The number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene. Column temperature: 40℃ Eluent: Tetrahydrofuran Flow rate: 1.0mL / min Standard samples for creating calibration curves: Standard polystyrene manufactured by Showa Denko (molecular weights: approximately 197,000, 55,100, 12,800, 3,950, 1,260, and 580). <Synthesis of raw materials>

[0150] <Synthesis Example 1> Synthesis of CIN3 8.3g of GMA, 20.7g of 4-methoxycinnamic acid, 0.2g of dibutylhydroxytoluene, 0.3g of triphenylethylphosphonium bromide, and 80mL of 1.4-dioxane were mixed and heated at 90℃ for 3 days. After the reaction was completed, 1.4-dioxane was distilled off under reduced pressure, 150mL of ethyl acetate was added, insoluble matter was filtered off, and then 100mL of sodium bicarbonate solution was added and washed three times to remove excess methoxycinnamic acid. Ethyl acetate was distilled off under reduced pressure to obtain 16.5g of the target product, CIN3.

[0151] <Synthesis Example 2> Synthesis of acetyl Meldrum's acid Meldrum's acid (18.3g) and pyridine (20.0g) were dissolved in chloroform (150mL), cooled to -20℃, and acetyl chloride (13.5g) was added dropwise. The mixture was slowly warmed to room temperature and reacted for 20 hours. 2N hydrochloric acid (40mL) and water (150mL) were added, extracted in a separatory funnel, and concentrated to obtain an orange solid. Chloroform (100mL) was added, and the bottom was cut with a silica gel (neutral) short column. The solvent was distilled off to obtain acetyl Meldrum's acid (20.5g) shown below. [ka]

[0152] <Synthesis Example 3> Synthesis of CIN4 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.

[0153] <Synthesis Example 4> Synthesis of CIN5 4.9 g of M100, 8.9 of 4-methoxycinnamic acid, 0.1 g of dibutylhydroxytoluene, 0.18 g of triphenylethylphosphonium bromide, and 40 mL of 1,4-dioxane were heated at 90 °C for 3 days. After completion of the reaction, 1,4-dioxane was distilled off under reduced pressure, 100 mL of ethyl acetate was added, insolubles were filtered off, and 100 mL of aqueous sodium bicarbonate was added and washed three times. Ethyl acetate was distilled off under reduced pressure to obtain 6.3 g of the target CIN5.

[0154] <Synthesis Example 5> Synthesis of CIN6 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.

[0155] <Synthesis of Component A1> <Synthesis Example 6> Synthesis of CIN8 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.

[0156] <Synthesis of Component A2> <Synthesis Example 7> 10.0 g of CIN1, 4.3 g of EGAMA, and 0.43 g of AIBN as a polymerization catalyst 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 an acetoacetyl group in the side chain. The Mn of the obtained acrylic copolymer was 12,000 and the Mw was 23,000.

[0157] <Synthesis Example 8> 10.0g of CIN2, 2.5g of EGAMA, and 0.38g of AIBN as a polymerization catalyst were dissolved in 115.9g of PM, and the mixture was 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 the side chain. The Mn and Mw of the obtained acrylic copolymer were 18,000 and 35,000, respectively.

[0158] <Synthesis Example 9> 15.0 g of CIN4 and 0.3 g of AIBN as a polymerization catalyst were dissolved in 61.2 g of PM, and the mixture was reacted at 80° C. for 20 hours to obtain a solution containing 20% ​​by mass of an acrylic copolymer (A2-3) having an acetoacetyl group in the side chain. The Mn and Mw of the obtained acrylic copolymer were 17,000 and 32,000, respectively.

[0159] <Synthesis Example 10> 15.0g of CIN6 and 0.3g of AIBN as a polymerization catalyst were dissolved in 61.2g of PM, and the mixture was reacted at 80°C for 20 hours to obtain a solution containing 20% ​​by mass of an acrylic copolymer (A2-4) having an acetoacetyl group in the side chain. The Mn of the obtained acrylic copolymer was 23,000 and the Mw was 40,000.

[0160] <Synthesis Example 11> 10.0 g of PLACCEL 410 (polycaprolactone tetraol manufactured by Daicel Corporation) and 6.3 g of tert-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 a compound (A2-5) having an acetoacetyl group.

[0161] <Synthesis Example 12> 8.0g of EGAMA and 0.3g of AIBN as a polymerization catalyst were dissolved in 33.2g of PM, and the mixture was reacted at 80°C for 20 hours to obtain a solution containing 20% ​​by mass of an acrylic copolymer (A2-6) having an acetoacetyl group in the side chain. The Mn of the obtained acrylic copolymer was 10,000 and the Mw was 22,000.

[0162] <Synthesis Example 13> 10.0 g of CIN3, 4.3 g of EGAMA, and 0.4 g of AIBN as a polymerization catalyst 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 the side chain. The Mn of the obtained acrylic copolymer was 17,000, and the Mw was 32,000.

[0163] <Synthesis Example 14> 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 dissolved in 68.7 g of PM, and reacted at 90°C for 20 hours to obtain an acrylic copolymer solution having an acetoacetyl group in the side chain. Next, 2.0 g of acrylic acid, 0.1 g of triphenylethylphosphonium bromide, and 0.2 g of dibutylhydroxytoluene were added, and reacted at 100°C for 18 hours to introduce an acrylic group into the side chain of the acrylic copolymer. Then, it was reprecipitated with hexane to obtain an acrylic copolymer (A2-8) having an acetoacetyl group and an acrylic group in the side chain. The Mn of the obtained acrylic copolymer was 23,000, and the Mw was 42,000.

[0164] <Synthesis of Component B2> <Synthesis Example 15> 8.0 g of CIN1, 3.4 g of GMA, and 0.3 g of AIBN as a polymerization catalyst 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, 0.1 g of triphenylethylphosphonium bromide, and 0.2 g of dibutylhydroxytoluene were added, and reacted at 100°C for 18 hours to introduce an acrylic group into the side chain of the acrylic copolymer. Then, it was reprecipitated with hexane to obtain an acrylic copolymer (B2-1) having an acrylic group in the side chain. The Mn of the obtained acrylic copolymer was 12,000, and the Mw was 32,000.

[0165] <Example 1> As the component (A-1), an amount equivalent to 100 parts by mass of a solution containing 10% by mass of the acrylic copolymer (A2-1) obtained in Synthesis Example 7 above (solid content) was mixed with 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 were added thereto to prepare an alignment material forming composition (A-1) having a solvent composition of PM:PMA=80:20 (mass ratio) and a solid content concentration of 5.0% by mass.

[0166] <Examples 2 to 25 and Comparative Examples 1 to 4> Except for the type and amount of each component being as shown in Table 1, the same procedure as in Example 1 was carried out to prepare alignment material forming compositions A-2 to A-29, respectively (the values ​​of components (A) to (D) are all converted to solid contents). [Table 1]

[0167] <Example 26> [Evaluation of orientation] The alignment material forming composition A-1 obtained in Example 1 was applied to a TAC film with a wet film thickness of 4 μm using a bar coater. The film was dried by heating at a temperature of 110° C. for 2 minutes in a heat circulation oven to form a cured film on the TAC film. Each of the cured films was irradiated with linearly polarized light of 313 nm at 20 mJ / cm. 2 An alignment material was formed by irradiating the TAC film with an exposure amount of 300 mJ / cm. A polymerizable liquid crystal solution RMS03-013c (Merck) was applied to the alignment material on the TAC film with a wet film thickness of 6 μm using a bar coater. This coating was dried by heating for 2 minutes on a hot plate set at a temperature of 65° C., and then irradiated with 300 mJ / cm. 2 The retardation material on the substrate thus prepared was sandwiched between a pair of polarizing plates, and the state of expression of retardation characteristics in the retardation material was observed. The retardation material in which the retardation was expressed without defects was marked with an O, and the retardation material in which the retardation was not expressed was marked with an X. These are shown in the "Orientation" column in Table 2.

[0168] <Examples 27 to 50 and Comparative Examples 5 to 8> A retardation material was prepared and the alignment property was evaluated in the same manner as in Example 26, except that the alignment material forming composition and the heating temperature and heating time in the heat circulation oven were as shown in Table 2. The evaluation results are summarized in Table 2 below. [Table 2]

[0169] In Examples 26 to 50, retardation materials exhibiting good alignment properties could be produced by firing at low temperatures for short periods of time. In contrast, in Comparative Examples 5 to 8, retardation materials exhibiting good alignment properties could not be produced by firing at low temperatures for a short period of time.

[0170] [Adhesion evaluation] <Examples 51 to 53> The retardation materials on the films prepared in Examples 48 to 50 were cut with a cutter knife to form 10 × 10 squares at 1 mm intervals vertically and horizontally. A cellophane tape peeling test was performed on the cuts using Scotch (registered trademark) tape. After the tape was peeled off, those that remained without peeling off were evaluated as ○, and those that peeled off even one square were evaluated as ×. The evaluation results are summarized in the "Initial" column in Table 3 described later.

[0171] [Evaluation of durable adhesion] The retardation material prepared in the same manner as in the above-mentioned adhesion evaluation was placed in an oven set at a temperature of 80°C and a humidity of 90%, and left to stand for 200 hours or more. After that, the retardation material was taken out, and the adhesion was evaluated in the same manner as in the above-mentioned adhesion evaluation. The evaluation results are summarized in the "Durability" column in Table 3 described later. [Table 3]

[0172] From Examples 51 to 53, the prepared retardation materials exhibited excellent adhesion and excellent durability.

[0173] <Synthesis of component (A)> <Synthesis Example 16> 14.1g of LA, 7.2g of EGAMA, and 0.68g of AIBN as a polymerization catalyst were dissolved in 107.0g of PM, and the mixture was reacted at 80°C for 16 hours to obtain a solution containing 30% by mass of acrylic copolymer (A2-9). The Mn and Mw of the obtained acrylic copolymer were 13,300 and 27,800, respectively.

[0174] <Synthesis Example 17> 14.1g of HA, 7.2g of EGAMA, and 0.68g of AIBN as a polymerization catalyst were dissolved in 107.0g of PM, and the mixture was reacted at 80°C for 16 hours to obtain a solution containing 30% by mass of acrylic copolymer (A2-10). The Mn and Mw of the obtained acrylic copolymer were 13,300 and 27,800, respectively.

[0175] <Examples 54 to 57 and Comparative Examples 9 to 10> Except for the type and amount of each component being as shown in Table 4, the same procedure as in Example 1 was carried out to prepare alignment material forming compositions A-30 to A-35, respectively (the values ​​of components (A) to (D) are all converted to solid contents). [Table 4]

[0176] <Example 58> [Evaluation of vertical alignment] The alignment material forming composition A-30 obtained in Example 54 was applied to a TAC film with a wet film thickness of 4 μm using a bar coater. Heat drying was performed in a heat circulation oven at a temperature of 120° C. for 2 minutes to form an alignment material on the TAC film. A polymerizable liquid crystal solution RMS03-015 (manufactured by Merck Ltd.) was applied to the alignment material on the TAC film with a wet film thickness of 6 μm using a bar coater. This coating film was heated and dried for 2 minutes on a hot plate set at a temperature of 65° C., and then 300 mJ / cm 2A retardation material was prepared by exposing the film to light at 1000 W at 400 Hz to prepare a retardation material. The retardation material thus prepared was measured for the incidence angle dependency of the in-plane retardation using a retardation measuring device RETS100 manufactured by Otsuka Electronics Co., Ltd. The retardation material was determined to be vertically aligned when the in-plane retardation value was 0 at an incidence angle of 0 degrees and the in-plane retardation value was in the range of 38±5 nm at an incidence angle of ±50 degrees. The evaluation results are shown in the "Vertical Alignment" column of Table 5.

[0177] <Examples 59 to 61 and Comparative Examples 11 to 12> A retardation material was prepared in the same manner as in Example 58, except that the alignment material-forming compositions were as shown in Table 5, and the vertical alignment property was evaluated. The evaluation results are shown in Table 5 later. [Table 5]

[0178] In Examples 58 to 61, retardation materials exhibiting good vertical alignment properties could be produced by firing at low temperatures for short periods of time. In contrast, in Comparative Examples 11 and 12, retardation materials exhibiting good alignment properties could not be produced by firing at low temperatures for a short period of time. [Industrial Applicability]

[0179] The cured film-forming composition according to the present invention is very useful as a material for forming a liquid crystal alignment film of a liquid crystal display element or an alignment material for forming an optically anisotropic film provided inside or outside a liquid crystal display element, and is particularly suitable as a material for a retardation material of a circular polarizing plate used as an anti-reflection film in an IPS-LCD or an organic EL display.

Claims

1. As component (A), a compound containing a mercapto group and a Michael donor moiety selected from groups represented by the following formula (a1), As component (B), a compound containing a Michael acceptor moiety selected from an acrylic group and a methacrylic group is included, At least one of the component (A) and the component (B) contains a liquid crystal aligning group represented by the following formula (2): Cured film forming composition for alignment material. 【Chemistry 1】 (In formula (a1), R represents an alkyl group, an alkoxy group, or a phenyl group, and the dashed line represents a bond.) 【Chemistry 2】 (In formula (2), Y １ is a single bond, or -O-, -CH ２ represents a bonding group selected from the group consisting of O-, -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 -CH ２ -CH(OH)-CH ２ represents a - group or a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocycle, any hydrogen atom on the cyclic group may be replaced by Z, Y ３ represents a single bond or an alkylene group having 1 to 15 carbon atoms, Y ４ represents a single bond, a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocycle, or a divalent organic group having a steroid skeleton having 17 to 30 carbon atoms, any hydrogen atom on the cyclic group may be substituted with Z, Y ５ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocycle, 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 may be the same or different, 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 fluorine atom; Z represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom, and the alkylene group, alkyl group, fluorinated alkyl group, alkoxy group, and fluorinated alkoxy group may have 1 to 3 of the above-mentioned bonding groups therein, as long as the bonding groups are not adjacent to each other; Y ２ ~Y ６ In the formula (I), an alkylene group, —CH ２ -CH(OH)-CH ２ The - group, the divalent cyclic group, the divalent organic group having a steroid skeleton, the alkyl group and the fluoroalkyl group may be bonded to the adjacent group via the above-mentioned bonding group. ２ ~Y ６ The total number of carbon atoms of the substituent represented by is 6 to 30.

2. The (A) component and the (B) component are the same compound containing a Michael donor moiety, a Michael acceptor moiety, and a liquid crystal alignment group; The cured film-forming composition for alignment material according to claim 1 .

3. As the component (A), at least one selected from a low molecular weight compound (A1) having one Michael donor site and a liquid crystal alignment group, and a compound (A2) having two or more Michael donor sites and not containing or containing a liquid crystal alignment group, The component (B) includes at least one selected from a low molecular weight compound (B1) having one Michael acceptor moiety and a liquid crystal aligning group, and a compound (B2) having two or more Michael acceptor moieties and containing or not containing a liquid crystal aligning group, The cured film-forming composition for an alignment material according to claim 1 or 2, wherein the component (A2) and the component (B2) may be a low molecular weight compound or a high molecular weight compound.

4. The cured film-forming composition for an alignment material according to claim 1 , further comprising (C) a Michael addition reaction catalyst.

5. The cured film-forming composition for an alignment material according to claim 1 , wherein the Michael acceptor moiety is an acrylic group.

6. The cured film-forming composition for alignment material according to any one of claims 1 to 5, comprising 1 to 2,000 parts by mass of the (B) component per 100 parts by mass of the (A) component.

7. The cured film-forming composition for alignment material according to any one of claims 4 to 6, comprising 0.01 parts by mass to 20 parts by mass of the (C) component relative to 100 parts by mass in total of the (A) component and the (B) component.

8. A cured film obtained by using the cured film forming composition for alignment material according to claim 1 .

9. An alignment material obtained by using the cured film-forming composition for alignment material according to claim 1 .

10. A retardation material formed by using the alignment material according to claim 9 .

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