TWI887717B - Cured film-forming composition, alignment material and retardation material - Google Patents

Abstract

The subject of the present invention is to provide a cured film forming composition, which is used as an alignment material, and when a polymerizable liquid crystal layer is arranged on it, a cured film showing excellent liquid crystal alignment, light transmittance and solvent resistance is formed under relatively low temperature and short time conditions. The solution of the present invention is a cured film forming composition, which includes a compound containing a Michael donor site as component (A) and a compound containing a Michael acceptor site as component (B), at least one of the components (A) and (B) contains a liquid crystal alignment group; a cured film and an alignment material obtained using the composition; a phase difference material formed using the alignment material.

Description

Cured film forming composition, alignment material and phase difference material

The present invention relates to a cured film forming composition, an alignment material, and a phase difference material for forming 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 phase difference material useful for producing a phase difference material that is a patterned phase difference material that can be used for a 3D display of a circularly polarized glasses type, or a phase difference material that can be used for a circularly polarized plate used as an anti-reflection film of an organic EL display.

In the case of a 3D display of the circular polarizing glasses type, the present invention generally arranges a phase difference material on a display element such as a liquid crystal panel that forms an image. This phase difference material is a patterned phase difference material formed by arranging two phase difference regions with different phase difference characteristics in a plurality and regularly. In addition, hereinafter, in this specification, such a phase difference material patterned by arranging a plurality of phase difference regions with different phase difference characteristics is referred to as a patterned phase difference material.

Patterned phase difference materials, for example, as disclosed in Patent Document 1, can be produced by optically patterning a phase difference material composed of polymeric liquid crystals. The optical patterning of the phase difference material composed of polymeric liquid crystals utilizes the well-known photo-alignment technology formed by the alignment material of the liquid crystal panel. That is, a coating composed of a photo-aligned material is provided on a substrate, and two polarized lights with different polarization directions are irradiated thereon. Then, a photo-alignment film is obtained in the form of an alignment material having two liquid crystal alignment regions with different alignment control directions of the liquid crystal. A phase difference material in a solution state containing polymeric liquid crystals is applied on this photo-alignment film to achieve the alignment of the polymeric liquid crystals. Thereafter, the aligned polymeric liquid crystals are hardened to form a patterned phase difference material.

The anti-reflection film of the organic EL display is composed of a linear polarizer and a 1/4 wavelength phase difference plate. The linear polarizer converts the external light to the panel surface of the image display panel into linear polarization, and then converts it into circular polarization by the 1/4 wavelength phase difference plate. Here, although the external light caused by this circular polarization is reflected on the surface of the image display panel, the rotation direction of the polarization plane is reversed during this reflection. As a result, the reflected light is opposite to when it arrives, and after passing through the 1/4 wavelength phase difference plate, it is converted into linear polarization in the direction blocked by the linear polarizer, and then blocked by the linear polarizer. As a result, the emission to the outside is significantly suppressed.

Regarding this 1/4 wavelength phase difference plate, Patent Document 2 proposes a method of forming this optical film by combining a 1/2 wavelength plate and a 1/4 wavelength plate and forming this optical film by reverse dispersion characteristics. In the case of this method, in a wide wavelength band that provides a display of color images, a liquid crystal material with positive dispersion characteristics is used, and an optical film can be formed by reverse dispersion characteristics.

In recent years, liquid crystal materials that can be used for this phase difference layer have been proposed to have reverse dispersion characteristics (Patent Documents 3 and 4). If, based on such a liquid crystal material with reverse dispersion characteristics, a 1/4 wavelength phase difference plate is formed by a two-layer phase difference layer instead of combining a 1/2 wavelength plate and a 1/4 wavelength plate, a phase difference layer can be formed by a single layer and reverse dispersion characteristics can be ensured, thereby realizing an optical film that can ensure the desired phase difference in a wide wavelength band with a simple structure.

An alignment layer can be used to align liquid crystals. As methods for forming the alignment layer, for example, a rubbing method and a photo-alignment method are known. The photo-alignment method does not generate static electricity and dust, which are problems of the rubbing method, and is useful in that the alignment process can be quantitatively controlled.

In the formation of alignment materials using the photo-alignment method, acrylic resins and polyimide resins having photodimerization sites such as cinnamyl groups and chalcone groups on the side chains are known as materials with photo-alignment properties. These resins are reported to exhibit the ability to control the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment properties) by irradiating them with polarized UV light (see Patent Documents 5 to 7).

Furthermore, in addition to the liquid crystal alignment ability, the alignment layer is also required to have solvent resistance. For example, the alignment layer may be subjected to heat or solvent during the manufacturing process of the phase difference material. If a solvent is applied to an alignment layer with low solvent resistance, there is a risk that the liquid crystal alignment ability may be significantly reduced.

Therefore, for example, in Patent Document 8, in order to obtain stable liquid crystal alignment ability, a liquid crystal alignment agent containing a polymer component having a structure capable of undergoing a crosslinking reaction by light and a structure capable of undergoing a crosslinking reaction by heat is proposed; and a liquid crystal alignment agent containing a polymer component having a structure capable of undergoing a crosslinking reaction by light and a compound having a structure capable of undergoing a crosslinking reaction by heat.

On the other hand, in order to reduce the thermal stress on the film substrate, the process of lowering the temperature of the phase difference material is being studied. When manufacturing phase difference materials, one of the processes that requires the highest temperature is the step of forming the liquid crystal alignment film, and it is required to lower the temperature of the process of forming the liquid crystal alignment film.

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

[Patent Document 1] Japanese Patent Publication No. 2005-49865 [Patent Document 2] Japanese Patent Publication No. 10-68816 [Patent Document 3] U.S. Patent No. 8119026 [Patent Document 4] Japanese Patent Publication No. 2009-179563 [Patent Document 5] Japanese Patent No. 3611342 [Patent Document 6] Japanese Patent Publication No. 2009-058584 [Patent Document 7] Japanese Patent Publication No. 2001-517719 [Patent Document 8] Japanese Patent No. 4207430 [Patent Document 9] International Publication No. 2010/150748

[Invention Summary] [Problem that the invention aims to solve]

The purpose of the present invention is achieved based on the above insights and research results. That is, the purpose of the present invention is to provide a liquid crystal alignment agent for photo-alignment, which can form an alignment film with excellent solvent resistance and high sensitivity to align polymerizable liquid crystals under relatively low temperature and short time conditions.

Other purposes and advantages of the present invention can be found in the following description. [Means for solving the problem]

The inventors of the present invention have made intensive studies to achieve the above-mentioned purpose and have found that by selecting a cured film-forming composition as a base material for the cured film-forming material, and the cured film-forming composition contains a component having a Michael donor site and a component having a Michael acceptor site, a cured film having excellent solvent resistance and capable of aligning polymerizable liquid crystals with high sensitivity can be formed under relatively low temperature and short time conditions, thereby completing the present invention.

That is, the first aspect of the present invention is about a cured film forming composition, which includes a compound containing a mickel donor site as component (A) and a compound containing a mickel receptor site as component (B), and at least one of the components (A) and (B) contains a liquid crystal alignment group. The second aspect is about the cured film forming composition described in the first aspect, wherein the components (A) and (B) are the same compound containing a mickel donor site, a mickel receptor site, and a liquid crystal alignment group. The third aspect is related to the cured film forming composition described in the first aspect or the second aspect, wherein, as component (A), at least one selected from a low molecular compound (A1) having a micoke donor site and a liquid crystal alignment group, and a compound (A2) having two or more micoke donor sites and containing or not containing a liquid crystal alignment group is included; and as component (B), at least one selected from a low molecular compound (B1) having a micoke receptor site and a liquid crystal alignment group, and a compound (B2) having two or more micoke receptor sites and containing or not containing a liquid crystal alignment group is included, and the components (A2) and (B2) may be low molecular compounds or high molecular compounds. The fourth aspect is related to the cured film forming composition described in any one of the first to third aspects, wherein the micoke donor site of component (A) is an active methylene group or an active methine group. The fifth aspect is the cured film forming composition described in any one of the first to fourth aspects, further comprising (C) a mic addition reaction catalyst. The sixth aspect is the cured film forming composition described in any one of the first to fifth aspects, wherein the mic receptor site is an acrylic group. The seventh aspect is the cured film forming composition described in any one of the first to sixth aspects, wherein the (B) component is contained in an amount of 1 to 2,000 parts by mass relative to 100 parts by mass of the (A) component. The eighth aspect is the cured film forming composition described in any one of the fifth to seventh aspects, wherein the (C) component is contained in an amount of 0.01 to 20 parts by mass relative to 100 parts by mass of the total of the (A) component and the (B) component. The ninth aspect is a cured film obtained by using the cured film forming composition described in any one of the first to eighth aspects. The tenth aspect is an alignment material obtained by using the cured film forming composition described in any one of the first to eighth aspects. The eleventh aspect is a phase difference material formed by using the alignment material described in the tenth aspect. [Effect of the invention]

According to the present invention, a cured film having excellent solvent resistance and capable of aligning polymerizable liquid crystals with high sensitivity, and a cured film-forming composition suitable for forming the cured film and capable of being formed at a relatively low temperature and in a short time can be provided. According to the present invention, an alignment material having excellent liquid crystal alignment and light transmittance, and a phase difference material capable of optical patterning with high precision can be provided.

[Form for implementing the invention]

<Cured film forming composition> The cured film forming composition of the present invention is a cured film forming composition containing a component containing one or more structures selected from the group consisting of a mic donor site, a mic receptor site, and a liquid crystal alignment group, and the composition as a whole must contain the aforementioned three structures. Specifically, it is a cured film forming composition, which contains a compound containing a mic donor site as component (A) and a compound containing a mic receptor site as component (B), and at least one of the components (A) and (B) contains a liquid crystal alignment group. The aforementioned component (A) and the aforementioned component (B) may also be the same compound containing a mic donor site, a mic receptor site, and a liquid crystal alignment group. The cured film forming composition of the present invention may also be in the following form: it contains at least one selected from a low molecular compound (A1) having one mickel donor site and a liquid crystal alignment group, and a compound (A2) having two or more mickel donor sites and containing or not containing a liquid crystal alignment group as the above-mentioned (A) component, and at least one selected from a low molecular compound (B1) having one mickel receptor site and a liquid crystal alignment group, and a compound (B2) having two or more mickel receptor sites and containing or not containing a liquid crystal alignment group as the above-mentioned (B) component, in which case, the (A2) component and the (B2) component may be a low molecular compound or a high molecular compound. Moreover, other additives may be contained as long as the effects of the present invention are not impaired. In addition, the so-called "low molecular weight compounds" mentioned above include compounds other than "high molecular weight compounds (polymers)", that is, compounds other than compounds having repeating units formed within the compound (by polymerization).

The following is a detailed description of each ingredient.

<Milk donor site> As the miclk donor site of component (A), there can be listed, for example, methyl group, amino group, active methylene group and active methine group.

The active methylene group refers to a methylene group (-CH ₂ -) having a carbonyl group adjacent to the methylene group and being reactive toward nucleophilic reagents. In the present invention, the active methine group refers to a methylene group (-CH ₂ -) having a structure in which one hydrogen atom is replaced by an alkyl group and being reactive toward nucleophilic reagents.

As the active methylene group and the active methine group, a group represented by the following formula (a1) is more preferred. (In formula (a1), R represents an alkyl group, an alkoxy group or a phenyl group, and the dotted line represents an atomic bonding).

In the above formula (a1), as the alkyl group represented by R, for example, an alkyl group having 1 to 20 carbon atoms can be listed, and an alkyl group having 1 to 5 carbon atoms is preferred. As such an alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, etc. can be listed. Among them, a methyl group, an ethyl group, an n-propyl group, etc. are preferred.

In the above formula (a1), as the alkoxy group represented by R, for example, an alkoxy group having 1 to 20 carbon atoms can be listed, and preferably an alkoxy group having 1 to 5 carbon atoms can be listed. As such an alkoxy group, for example, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a tertiary butoxy group, etc. can be listed. Among them, a methoxy group, an ethoxy group, and an n-propoxy group are preferred.

Examples of the group represented by the above formula (a1) include the following structures. In the structural formula, a dotted line represents an atomic bond.

<Method for introducing the group represented by formula (a1) (Michael donor site)> As a method for introducing the group represented by formula (a1) into each component, for example, a method in which Meldrum's acid and carboxylic acid chloride are reacted in a low molecular weight compound or polymer having a hydroxyl group, and the resulting acylated Meldrum's acid is reacted. This method is well known. Here, as R, a methyl group is preferably used to increase the availability or orientation.

As another method, there is a method of reacting acylated tertiary butyl acetate in a low molecular weight compound or polymer having a hydroxyl group. This method is well known. Here, as R, a methyl group is preferably used to increase the availability or orientation.

Furthermore, by copolymerizing a monomer having a micagonist moiety, a compound having two or more micagonist moieties (component (A2) described later) can be obtained in the form of a polymer. As monomers having a micagonist moiety, 2-acetylacetoxyethyl acrylate (ethylene glycol monoacetyl acetate monoacrylate), 2-acetylacetoxyethyl methacrylate (ethylene glycol monoacetyl acetate monomethacrylate) and the like can be cited.

<Mycoacrylic acid receptor moiety> Examples of the mycoacrylic acid receptor moiety of component (B) include (meth)acrylic acid groups and cis-imide groups, i.e., _CH2 =CH-C(=O)- groups, _CH2 =C( _CH3 )-C(=O)- groups, and cis-imide groups. In addition, in the present specification, the description of "(meth)acrylic acid group" etc. means both acrylic acid groups and methacrylic acid groups.

<Method for introducing (meth)acrylic acid group> As a method for introducing (meth)acrylic acid group into each component, there can be cited a method of reacting a component having an epoxy group with (meth)acrylic acid by a known method. Also, there can be cited a method of reacting a copolymer obtained by using a monomer having a hydroxyl group such as hydroxyethyl (meth)acrylate with a compound component having a (meth)acrylic acid group and an isocyanate group by a known method.

<Method for introducing cis-butenediimide group> As a method for introducing cis-butenediimide group into each component, there can be cited a method of reacting N-(4-carboxyphenyl)cis-butenediimide or N-(4-hydroxyphenyl)cis-butenediimide with a component having an epoxy group by a known method. In addition, there can be cited a method of reacting N-(4-hydroxyphenyl)cis-butenediimide with a component having an isocyanate group by a known method.

<Liquid crystal alignment group> The liquid crystal alignment group that can be used in the present invention and is contained in at least one of the components (A) and (B) includes a vertical alignment group and a photoalignment group.

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

The so-called photodimerization site is a site that forms a dimer by light irradiation, and specific examples thereof include cinnamyl, chalcone, coumarin, anthracene, etc. Among these, cinnamyl, which has high transparency and photodimerization reactivity in the visible light region, is preferred. In addition, the so-called photoisomerization site is a site where the cis-isomer and the trans-isomer change by light irradiation, and specific examples thereof include azobenzene structure, stilbene structure, etc. Among these, the azobenzene structure is preferred because of its high reactivity.

An example of a more preferable cinnamyl structure as a photoinduced dimerization site is disclosed in the following formula [1] or formula [2]. In the above formula [1], ^X11 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a biphenyl group. In this case, the phenyl group and the biphenyl group may be substituted by any of a halogen atom, an alkyl group, an alkoxy group, and a cyano group. In the above formula [2], ^X12 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. In this case, the alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group may be bonded to the benzene ring via a single bond, an ether bond, an ester bond, an amide bond, or a urea bond.

<Method for introducing photo-alignment group> For introducing such photo-alignment group into each component of the present invention, there can be listed a method of introducing the photo-alignment group into the hydroxyl group compound by the method described in the above <Method for introducing the group represented by formula (a1) (the hydroxyl group) into the hydroxyl group part>; a method of using the acrylic monomer having the photo-alignment group directly or copolymerizing it; a method of reacting a cinnamic acid derivative having a carboxyl group (a compound having a photo-alignment group (cinnamic acid group) and a carboxyl group) in a component having an epoxy group, etc.

The compound having a photoalignment group and a hydroxyl group is represented by any one of the following formulas [A1] to [A5].

In the above formula, ^A1 and ^A2 each independently represent a hydrogen atom or a methyl group, ^X1 represents a structure formed by bonding to one to three divalent groups selected from alkylene groups having 1 to 18 carbon atoms, phenylene groups, biphenylene groups, or combinations thereof, through one or more bonds selected from single bonds, ether bonds, ester bonds, amide bonds, urethane bonds, amine bonds, or combinations thereof. ^X2 represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. In this case, the alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, and a cyclohexyl group may also be bonded to the benzene ring through a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond. ^X3 represents a hydroxyl group, an alkyl 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, an anilino group, a benzidine group, a phenyl group or a biphenyl group. ^X4 independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group or a divalent alicyclic group. Here, 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 addition, in these groups, the hydrogen atoms on the phenyl group, the biphenyl group, the phenylene group and the phenylene group may be substituted by one or more substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group and a cyano group.

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group or a cyano group.

Specific examples of the compound having a photoalignment group and a hydroxyl 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-hydroxyethyloxy)cinnamic acid methyl ester, 4-hydroxymethyloxycinnamic acid methyl 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-hydroxycinnamic acid ethyl ester, 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-(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, 8-hydroxyoctyl cinnamic acid, 6-hydroxyhexyl cinnamic acid, 4-Hydroxybutyl cinnamate, 3-hydroxypropyl cinnamate, 2-hydroxyethyl cinnamate, hydroxymethyl cinnamate, 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 ) chalcone, 4'-(4-hydroxybutyloxy) chalcone, 4'-(3-hydroxypropyloxy) chalcone, 4'-(2-hydroxyethyloxy) chalcone, 4'-hydroxymethyloxy chalcone, 4'-hydroxychalcone, 7-(8-hydroxyoctyloxy) coumarin, 7-(6-hydroxyhexyloxy) coumarin, 7-(4-hydroxybutyloxy) coumarin, 7-(3-hydroxypropyloxy) 6-(4-hydroxybutyloxy)coumarin, 6-(3-hydroxypropyloxy)coumarin, 6-(2-hydroxyethyloxy)coumarin, 6-hydroxymethyloxycoumarin, 6-hydroxycoumarin.

Furthermore, the compound having a photoalignment group and a carboxyl group is represented by the following formula. In formula (1), A ¹¹ and A ¹² each independently represent a hydrogen atom or a methyl group. R ¹¹ represents a hydrogen atom, a halogen atom, a C ₁ ~ C ₆ alkyl group, a C ₁ ~ C ₆ haloalkyl group, a C ₁ ~ C ₆ alkoxy group, a C ₁ ~ C ₆ haloalkoxy group, a C ₃ ~ C ₈ cycloalkyl group, a C ₃ ~ C ₈ halocycloalkyl group, a C ₂ ~ C ₆ alkenyl group, a C ₂ ~ C ₆ haloalkenyl group, a C ₃ ~ C ₈ cycloalkenyl group, a C ₃ ~ C ₈ halocycloalkenyl group, a C ₂ ~ C ₆ alkynyl group, a C ₂ ~ C ₆ haloalkynyl group, a C ₁ ~ C ₆ alkoxy group, a C ₁ ~ C ₆ haloalkoxy group, a (C ₁ ~ C ₆ alkyl)carbonyl group, a (C ₁ ~ C ₆ haloalkyl)carbonyl group, a (C ₁ ~ C ₆ alkoxy)carbonyl group, a (C ₁ ~ C 6 ₆ halogen alkoxy)carbonyl, (C ₁ ~C ₆ alkylamino)carbonyl, (C ₁ ~C ₆ halogen alkyl)aminocarbonyl, di(C ₁ ~C ₆ alkyl)aminocarbonyl, cyano, nitro and the following formula (c-2) (In formula (c-2), the dotted line represents an atomic bond, R ¹⁰¹ is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted by a fluorine atom or an organic group. Furthermore, -CH ₂ CH ₂ - in R ¹⁰¹ may be substituted by -CH=CH-, and further, in the case where any of the following groups are not adjacent to each other, they may be substituted by a group selected from the group consisting of -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO-, and M 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 condensed 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 halogenalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogenalkoxy group having 1 to 6 carbon atoms, a cyano group, and a nitro group, and n is an integer of 0 to 3).

Preferred examples of the compound represented by the above formula (1) include the following formulas (1-1) to (1-5): (In the above formula, R ¹¹ has the same meaning as R ¹¹ in the above formula (1)) and the like.

Among the compounds represented by the above formula (1), preferred examples of the compounds in which R ¹¹ is a group represented by the formula (c-2) include the following formulas M1-1 to M1-5. (wherein, ^M1 is a hydrogen atom or a methyl group, and s1 represents the number of methylene groups, which is a natural number from 2 to 9).

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

Examples of monomers having a photodimerization site include monomers having a cinnamyl group, a chalcone group, a coumarin group, an anthracene group, etc. Among these, monomers having a cinnamyl group which has good transparency in the visible light region and photodimerization reactivity are particularly preferred.

In particular, a cinnamyl monomer having a structure represented by the above formula [1] or formula [2] is more preferred. Specific examples of such monomers are disclosed in the following formula [3] or formula [4]. In the above formula [3], ^X11 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. In this case, the phenyl group and the biphenyl group may be substituted by any of a halogen atom, an alkyl group, an alkoxy group and a cyano group. In the above formula [4], ^X12 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group. In this case, the alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group may be bonded to the benzene ring via a single bond, an ether bond, an ester bond, an amide bond or a urea bond. In the above formula [3] or formula [4], ^X13 and ^X15 each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group or a divalent alicyclic group. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear, may be substituted by a hydroxyl group, or may be interrupted by at least one bond selected from an ether bond, an ester bond, an amide bond, a urea bond, and a urethane bond. ^X14 and ^X16 represent polymerizable groups. Specific examples of such polymerizable groups include acryl, methacryl, styryl, cis-butylene diimide, acrylamide, and methacrylamide.

In addition, the above-mentioned compounds having photo-alignment groups and hydroxyl groups, and monomers having photo-alignment groups are well known and can be produced according to the methods described in Japanese Patent Publication No. 62-284350, U.S. Patent No. 4,696,990, Japanese Patent Publication No. 9-118717, U.S. Patent No. 6,107,427, etc.

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

<Vertical Alignment Group> The vertical alignment group is not particularly limited, but is preferably a group containing a alkyl group having about 6 to 20 carbon atoms. Specifically, a group represented by formula (2) is preferred. In formula (2), ^Y1 represents a single bond or a bonding group selected from -O-, _-CH2O- , -COO-, -OCO-, -NHCO-, -NH-CO-O- and -NH-CO-NH-; ^Y2 represents a single bond, an alkylene group having 1 to 15 carbon atoms, or a _-CH2 -CH(OH) _-CH2- group, or a benzene ring, a cyclohexane ring or a divalent cyclic group selected from a heterocyclic ring, and any hydrogen atom on the cyclic group may be substituted by Z; ^Y3 represents a single bond or an alkylene group having 1 to 15 carbon atoms; ^Y4 represents a single bond, a benzene ring, a cyclohexane ring, or a divalent cyclic group selected from a heterocyclic ring, or a divalent organic group having 17 to 30 carbon atoms and a steroid skeleton, and any hydrogen atom on the cyclic group may be substituted by Z, ^Y5 represents a benzene ring, a cyclohexane ring, or a divalent cyclic group selected from a heterocyclic ring, and any hydrogen atom on such a cyclic group may be substituted by Z, m represents an integer of 0 to 4, and when m is 2 or more, ^Y5 may be the same or different from each other, and Y ^Y2 to Y6 represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorinated alkoxy group having 1 to 18 carbon atoms; Z represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom; the alkylene group, the alkyl group, the fluorinated alkyl group, the alkoxy group, and the fluorinated alkoxy group may have 1 to 3 of the above-mentioned bonding groups as long as the bonding groups are not adjacent to each other; and in ^Y2 to ^Y6 , 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 fluorinated alkyl group may be bonded to a group adjacent thereto via the above-mentioned bonding groups. However, the total number of carbon atoms of the substituents represented by Y ² to Y ⁶ is 6 to 30.

The above-mentioned alkylene group with 1 to 15 carbon atoms can be a divalent group formed by removing one hydrogen atom from an alkyl group with 1 to 15 carbon atoms among the alkyl groups with 1 to 18 carbon atoms described later. Specific examples thereof include methylene, ethyl, propyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, etc. Specific examples of the heterocyclic ring include a pyrrole ring, an imidazole ring, an oxadiazole 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 pyridine ring, a pyrazoline ring, a triazole ring, a pyrazolidine ring, a triazole ring, a pyridine ring, a benzimidazole ring, a pyridine ring, Phenanthrene ring, indole ring, quinoline ring, benzothiazole ring, phenanthrene ring, oxadiazole ring, acridine ring, etc. Among them, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridine ring, pyrazoline ring, triazole ring, pyrazolidine ring, triazole ring, pyridine ring, benzimidazole ring are preferred.

Examples of the alkyl group having 1 to 18 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, dibutyl, tertiary butyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl , 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methylcyclopentyl, 2- Methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-propylcyclopropyl, 2-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclobutyl Propyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl, 3-methyl-n-hexyl, 1,1-dimethyl-n-pentyl, 1,2-dimethyl-n-pentyl, 1,3-dimethylcyclopropyl Methyl-n-pentyl, 2,2-dimethyl-n-pentyl, 2,3-dimethyl-n-pentyl, 3,3-dimethyl-n-pentyl, 1-ethyl-n-pentyl, 2-ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1-ethyl-n-butyl, 1-methyl-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n -butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1,1-dimethyl-n-hexyl, 1,2-dimethyl-n-hexyl, 1,3-dimethyl-n-hexyl, 2,2-dimethyl-n-hexyl, 2,3-dimethyl-n-hexyl, 3,3-dimethyl-n-hexyl, 1-ethyl-n-hexyl, 2-ethyl-n-hexyl, 3-ethyl-n-hexyl, 1 -methyl-1-ethyl-n-pentyl, 1-methyl-2-ethyl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2-ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl, 3-methyl-3-ethyl-n-pentyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, etc. Also, as the alkoxy group having 1 to 18 carbon atoms, there can be listed groups in which the above-mentioned alkyl groups having 1 to 18 carbon atoms are bonded to an oxygen atom (-O-).

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

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

In addition, examples of the alkyl group having 1 to 3 carbon atoms in the above-mentioned Z include those having 1 to 3 carbon atoms among the groups exemplified above having 1 to 18 carbon atoms, examples of the alkoxy group having 1 to 3 carbon atoms include those having 1 to 3 carbon atoms among the groups exemplified above having 1 to 18 carbon atoms (those having 1 to 3 carbon atoms among the groups exemplified above having 1 to 18 carbon atoms bonded to an oxygen atom (—O—)), 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 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 having 1 to 18 carbon atoms.

Furthermore, the total carbon number of the substituents represented by ^Y2 to ^Y6 is 6 to 30, preferably 6 to 20. In particular, considering the vertical alignment and coating properties of the obtained liquid crystal polymer, the vertical alignment group is preferably a group containing an alkyl group having 7 to 18 carbon atoms, and particularly preferably a group containing an alkyl group having 8 to 15 carbon atoms.

As a specific vertical aligning group, for example, a alkyl group having about 6 to 20 carbon atoms can be listed. As the alkyl group having 6 to 20 carbon atoms, a alkyl group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms in a linear, branched or cyclic form can be listed. Therefore, in the above formula (2), it is preferred that Y ¹ , Y ² and Y ⁴ are a single bond, Y ³ is a single bond or an alkylene group having 1 to 15 carbon atoms (preferably an alkylene group having 1 to 15 carbon atoms), m is 0, Y ⁶ is an alkyl group having 1 to 18 carbon atoms, and the total carbon number of Y ³ and Y ⁶ is an alkyl group having 6 to 20 carbon atoms (a-1), more preferably an alkyl group having 7 to 18 carbon atoms, and still more preferably an alkyl group having 8 to 15 carbon atoms. Specific examples of such vertical alignment 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-nonadecanyl groups, n-eicosyl groups, and the like.

In addition to the vertical alignment group (a-1), a vertical alignment group (a-2) in which, for example, Y ¹ to Y ⁴ are single bonds, m is 2 or 3, Y ⁵ is a benzene ring or a cyclohexane ring, and Y ⁶ is an alkyl group having 1 to 18 carbon atoms can also be preferably used. Specific examples of such vertical alignment groups (a-2) include the groups shown in the following (a-2-1) to (a-2-6), but are not limited thereto. (wherein, ^Y6 has the same meaning as ^Y6 in the above formula (2)).

<Method for introducing vertical alignment group> For introducing the vertical alignment group described above into the components of the present invention, there can be listed a method of introducing the vertical alignment group into the hydroxyl group compound by the method described in the above <Method for introducing the group represented by formula (a1) (the hydroxyl group) into the hydroxyl group donor site>; a method of directly using an acrylic monomer having a vertical alignment group or copolymerizing it; a method of reacting a compound in which the vertical alignment group is bonded to a carboxyl group in a component having an epoxy group, etc.

Examples of monomers having a vertical alignment group include (meth)acrylic acid alkyl esters, alkyl vinyl ethers, 2-alkylstyrenes, 3-alkylstyrenes, 4-alkylstyrenes, and N-alkyl butylene diimides, wherein the carbon number of the alkyl group in these compounds is 6 to 20. These monomers can be produced by known methods, and some are available as commercial products. In addition, when a (meth)acrylic monomer having a vertical alignment group represented by the above formula (2) is used to introduce a vertical alignment group into a polymer, the vertical alignment side chain is represented by the following formula (2'). (wherein, Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , and m have the same meanings as those of the groups in formula (2)).

<(A1) Low molecular compound having a micoke donor site and a liquid crystal alignment group> As the low molecular compound (A1) having a micoke donor site and a liquid crystal alignment group, there can be listed compounds obtained by introducing the micoke donor site into the aforementioned compound having a photoalignment group and a hydroxyl group by the method described in the aforementioned <Method for introducing the group represented by formula (a1) (micoke donor site)>; compounds obtained by introducing the micoke donor site into the aforementioned compound having a vertical alignment group and a hydroxyl group by the method described in the aforementioned <Method for introducing the group represented by formula (a1) (micoke donor site)>, etc.

<(A2) Compounds having two or more hydroxyl groups (low molecular weight compounds)> When the compound (A2) having two or more hydroxyl groups is a low molecular weight compound, the low molecular weight compound (A2) includes compounds obtained by introducing a hydroxyl group 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) (hydroxyl group)>, polyfunctional alkyl groups, diamines, etc.

<Low molecular weight compounds having two or more hydroxyl groups> Specific examples of divalent alcohols having two alcoholic hydroxyl 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, dialkylene glycol, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-tert-butyldiethanolamine, N-lauryldiethanolamine, stearyldiethanolamine, N-phenyldiethanolamine, m-tolyldiethanolamine, p-tolyldiethanolamine, etc.

Specific examples of the trivalent alcohol having three alcoholic hydroxyl groups include tri(hydroxymethyl)ethane, trihydroxymethylpropane, glycerol, tris(2-hydroxyethyl)isocyanurate, hexanetriol, octanetriol, decantriol, triethanolamine, tris(isopropanolamine) and the like.

Specific examples of the tetravalent alcohol having four alcoholic hydroxyl groups include di-tri(hydroxymethyl)ethane, di-trihydroxymethylpropane, diglycerol, and neopentyltriol.

In the present invention, these polyols can be used alone or in any combination of two or more.

<Multifunctional olefinic compounds> Multifunctional olefinic compounds can be obtained in the form of addition reaction products of polyols and monofunctional and/or multifunctional olefinic compounds. Specific compounds include trifunctional olefin compounds such as 1,3,5-tris(3-butylenepropionylethoxy)-isocyanurate, 1,3,5-tris(3-butylenebutyrylethoxy)-isocyanurate (produced by Showa Denko, Karenz MT (registered trademark) NR1), and trihydroxymethylpropane tris(3-butylenepropionate); tetrafunctional olefin compounds such as pentaerythritol tetra(3-butylenepropionate), pentaerythritol tetra(3-butylenebutyrate) (produced by Showa Denko, Karenz MT (registered trademark) PEI); and hexafunctional olefin compounds such as dipentaerythritol hexa(3-propionate).

<Diamine> The components used are not particularly limited. If specific examples are required, they are as follows. Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, and isophoronediamine.

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.

As examples of aromatic-aliphatic diamines, there can be mentioned 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-(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.

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.

<(A2) Compounds (polymers) having two or more micester donor sites> When the compound (A2) having two or more micester donor sites is a polymer (high molecular weight compound), the polymer (A2) may include a polymer obtained by introducing a micester donor site into a precursor of the polymer (A2) and the polymer (B2) described later by the method described in the <Method for introducing a group (micester donor site) represented by formula (a1)>, etc.

Furthermore, in the case of introducing a liquid crystal alignment group into a polymer (A2) having two or more micagon-donating sites, it is sufficient to introduce the liquid crystal alignment group into the precursors of the polymers (A2) and (B2) described later by the above method, or to introduce the micagon-donating sites by the above method after copolymerizing the monomers having the liquid crystal alignment group during the production of the precursors of the polymers (A2) and (B2).

<(B1) Low molecular compound having a micoke receptor site and a liquid crystal alignment group> As the low molecular compound (B1) having a micoke receptor site and a liquid crystal alignment group, there can be esters obtained by using the aforementioned compound having a photoalignment group and a hydroxyl group and (meth) acrylic acid chloride, and esters obtained by using the aforementioned compound having a vertical alignment group and a hydroxyl group and (meth) acrylic acid chloride, etc.

<(B2) Compounds having two or more mic receptor sites (low molecular weight compounds)> When the compound having two or more mic receptor sites (B2) is a low molecular weight compound, examples of the low molecular weight compound (B2) include polyfunctional (meth)acrylates, dibutylene diimide, and the like.

[Multifunctional urethane (meth)acrylate compounds having three or more (meth)acryl groups] (1) Trifunctional (having three (meth)acryl groups) urethane (meth)acrylate Specific examples of commercially available multifunctional urethane (meth)acrylate compounds having three (meth)acryl groups include NK OLIGO UA-7100 [produced by Shin-Nakamura Chemical Industry (Co., Ltd.)]; EBECRYL (registered trademark) 204, 205, 264, 265, 294/25HD, 1259, 4820, 8311, 8465, 8701, 9260, KRM (registered trademark) 8296, 8667 [all manufactured by DAICEL-ALLNEX (Co., Ltd.)]; Ziguang (registered trademark) UV-7550B, 7000B, 7510B, 7461TE, 2750B [all manufactured by Nippon Gosei Chemical Industry (Co., Ltd.)], etc.

(2) Tetrafunctional (having four (meth)acryl groups) urethane (meth)acrylate Specific examples of commercially available products of multifunctional urethane (meth)acrylate compounds having four (meth)acryl groups include EBECRYL (registered trademark) 8210, 8405, KRM (registered trademark) 8528 [all manufactured by DAICEL-ALLNEX (Co., Ltd.)]; Ziguang (registered trademark) UV-7650B [manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.], etc.

(3) Pentafunctional or higher (having five or more (meth)acryl groups) urethane (meth)acrylates As polyfunctional urethane (meth)acrylate compounds having five or more (meth)acryl groups (pentafunctional or higher urethane (meth)acrylates), for example, urethane compounds of pentaerythritol tri(meth)acrylate and hexamethylene diisocyanate, urethane compounds of pentaerythritol tri(meth)acrylate and toluene diisocyanate, urethane compounds of pentaerythritol tri(meth)acrylate and isophorone diisocyanate, urethane compounds of dipentaerythritol penta(meth)acrylate and hexamethylene diisocyanate, etc. can be cited.

The pentafunctional or higher urethane (meth)acrylates may preferably be commercially available products, such as UA-306H, UA-306T, UA-306I, UA-510H [all manufactured by Kyoeisha Chemical Co., Ltd.]; NK OLIGO U-6LPA, U-10HA, U-10PA, U-1100H, U-15HA, UA-53H, UA-33H [all manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 220, 1290, 5129, 8254, 8301R, KRM (registered trademark) 8200, 82 00AE, 8904, 8452 [all manufactured by DAICEL-ALLNEX (Co., Ltd.)]; Unisplendour (registered trademark) UV-1700B, 6300B, 7600B, 7605B, 7610B, 7620EA, 7630B, 7640B, 7650B [all manufactured by Nippon Gosei Kagaku Kogyo (Co., Ltd.)], etc.

(1) Trifunctional (having three (meth)acryloyl) compounds As compounds having three (meth)acryloyl groups, there can be listed 1,1,1-tri(hydroxymethyl)ethane tri(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, di-trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, etc.

The above-mentioned compound having three (meth)acryloyl groups may preferably be a commercially available product, such as VISCOAT #295, #300 [all manufactured by Osaka Organic Chemical Industry Co., Ltd.]; LIGHT ACRYLATE TMP-A, PE-3A, LIGHTESTER 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, TMPT [all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; PETIA, PETRA, TMPTA, EBECRYL (registered trademark) 180 [all manufactured by DAICEL-ALLNEX Co., Ltd.], etc.

(2) Tetrafunctional (having four (meth)acryloyl) compounds As compounds having four (meth)acryloyl groups, di-trihydroxymethylpropane tetra(meth)acrylate, neopentyltriol tetra(meth)acrylate, etc. can be cited.

The above-mentioned compound having four (meth)acryloyl groups can preferably be a commercially available product, for example, VISCOAT #300 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; LIGHT ACRYLATE PE-4A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK ESTER AD-TMP, A-TMMT [all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 140, 1142, 180 [all manufactured by DAICEL-ALLNEX Co., Ltd.], etc.

(3) Pentafunctional or higher compounds (compounds having five or more (meth)acryloyl groups) Compounds having five or more (meth)acryloyl groups include dipentatriol penta(meth)acrylate, dipentatriol hexa(meth)acrylate, tripentatriol octa(meth)acrylate, etc.

The above-mentioned compound having five or more (meth)acryloyl groups may preferably be a commercially available product, for example, VISCOAT #802 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; LIGHT ACRYLATE DPE-6A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK ESTER A-9550 and A-DPH [all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; DPHA [manufactured by DAICEL-ALLNEX Co., Ltd.], etc.

<Bis-cis-butylenediimide> The bis-cis-butylenediimide compound used as the component (B2) in the present invention is represented by the following formula (3). In the formula, R ³³ is an organic group selected from the group consisting of an aliphatic group, an aliphatic group including a cyclic structure, and an aromatic group, or an organic group consisting of a combination of a plurality of organic groups selected from these groups. In addition, R ³³ may also include an ester bond, an ether bond, an amide bond, a urethane bond, and the like.

Examples of such bis-cis-butylenediamide compounds include N,N'-3,3-diphenylmethane bis-cis-butylenediamide, N,N'-(3,3-diethyl-5,5-dimethyl)-4,4-diphenyl-methane bis-cis-butylenediamide, N,N'-4,4-diphenylmethane bis-cis-butylenediamide, 3,3 -Diphenylsulfone dicis-butylenediamide, 4,4-diphenylsulfone dicis-butylenediamide, N,N'-p-diphenylketone dicis-butylenediamide, N,N'-diphenylethane dicis-butylenediamide, N,N'-diphenylether dicis-butylenediamide, N,N'-(methylenebis-tetrahydrophenyl)dicis-butylenediamide 、N,N'-(3-ethyl)-4,4-diphenylmethanebis(cis-butylene)diimide、N,N'-(3,3-dimethyl)-4,4-diphenylmethanebis(cis-butylene)diimide、N,N'-(3,3-diethyl)-4,4-diphenylmethanebis(cis-butylene)diimide、N,N'-(3,3-dichloro)-4 ,4-diphenylmethane di-butene diimide, N,N'-isophorone di-butene diimide, N,N'-tolidine di-butene diimide, N,N'-diphenylpropane di-butene diimide, N,N'-naphthalene di-butene diimide, N,N'-m-phenylene di-butene diimide (phenylene bismaleimide), N,N'-5-methoxy-1,3-phenylene bis(imide), 2,2-bis(4-(4-imide phenoxy)phenyl)propane, 2,2-bis(3-chloro-4-(4-imide phenoxy)phenyl)propane, 2,2-bis(3-bromo-4-(4-imide phenoxy)phenyl)propane, 2,2-bis(3-ethyl-4-(4-imide phenoxy)phenyl)propane, 2,2-bis(3-propyl-4-(4-imide 2,2-bis(3-isopropyl-4-(4-cis-butylenediimidephenoxy)phenyl)propane, 2,2-bis(3-butyl-4-(4-cis-butylenediimidephenoxy)phenyl)propane, 2,2-bis(3-methoxy-4-(4-cis-butylenediimidephenoxy)phenyl)propane, 1,1-bis(4-(4-cis-butylenediimidephenoxy)phenyl)ethane, 1,1-bis(3-methyl-4-(4-cis-butylenediimidephenoxy)phenyl)ethane, 1,1-bis(3-chloro ... 1,1-bis(3-bromo-4-(4-cis-butylenediimidephenoxy)phenyl)ethane, 3,3-bis(4-(4-cis-butylenediimidephenoxy)phenyl)pentane, 1,1,1,3,3,3-hexafluoro-2,2-bis(4-(4-cis-butylenediimidephenoxy)phenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,5-dimethyl-4-(4-cis-butylenediimidephenoxy)phenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis( 3,5-dibromo-4-(4-cis-butylenediamidephenoxy)phenyl)propane, N,N'-ethylenebis(cis-butylenediamide), N,N'-hexamethylenebis(cis-butylenediamide), N,N'-dodecamethylenebis(cis-butylenediamide), N,N'-m-xylenebis(cis-butylenediamide), N,N'-p-xylenebis(cis-butylenediamide), N,N'-1,3-bis(methylenecyclohexane)bis(cis-butylenediamide), N,N'-2,4-methylenephenylbis(cis-butylenediamide), N,N'-2,6-methylenephenylbis(cis-butylenediamide), etc. These bis(cis-butylene diimide) compounds are not limited to the above ones. These can be used alone or in combination of two or more components.

<(B2) Compounds (polymers) having two or more Michel receptor sites> When the compound having two or more Michel receptor sites is a polymer (high molecular weight compound), the polymer (B2) may include high molecular weight compounds having one or more side chains with polymerizable unsaturated bonds at the end in the molecule. As such high molecular weight compounds having side chains with polymerizable unsaturated bonds at the end, preferably, high molecular weight compounds having (meth)acryloyl groups at two or more side chains in the molecule can be listed.

Examples of the above-mentioned polymer compounds include polymer compounds containing a (meth)acryl group such as urethane acrylate, epoxy acrylate, and various (meth)acrylates, and in particular, the above-mentioned multifunctional polymer compounds containing three or more (meth)acryl groups.

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

Furthermore, as the polymer (B2) having two or more micker receptor sites, there can be exemplified a polymer into which a micker receptor site is introduced using the aforementioned method for introducing a (meth)acrylic acid group or the aforementioned method for introducing a cis-butylenediimide group in the precursor of the polymer (A2) and the polymer (B2) described later.

Furthermore, in the case of introducing a liquid crystal alignment group into a polymer (B2) having two or more MICR receptor sites, it is sufficient to introduce the liquid crystal alignment group into the precursors of the polymers (A2) and (B2) described later by the above method, or to introduce the MICR receptor sites by the above method after copolymerizing the monomers having the liquid crystal alignment group during the production of the precursors of the polymers (A2) and (B2).

<Precursor of polymer (A2) and polymer (B2)> When a side chain (specific side chain) having a liquid crystal alignment group or a macrol addition reaction site is introduced into the polymer, specific functional groups (or specific compounds) that are easy to react with each other are arranged to react with each other, thereby generating specific side chains. In the reaction to generate the specific side chain, the preferred combination of specific functional groups and the combination of specific functional groups and specific compounds are a combination of carboxyl group and epoxy group, hydroxyl group and isocyanate group, phenolic hydroxyl group and epoxy group, carboxyl group and isocyanate group, amine group and isocyanate group, hydroxyl group and acyl chloride, etc. As more specific examples, carboxyl and epoxypropyl (meth)acrylate, and hydroxy and isocyanate ethyl (meth)acrylate can be cited.

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 its number average molecular weight is 2,000 to 25,000. At this time, the monomer having a specific functional group can be used alone, or a combination of multiple monomers can be used as long as the specific functional group does not react during polymerization. Specific examples of monomers having specific functional groups are listed below, but are not limited to these.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloxy)ethyl)phthalic acid, mono-(2-(methacryloxy)ethyl)phthalic acid, N-(carboxyphenyl)butenediamide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide.

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

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

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

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

Examples of the monomer having an isocyanate group include acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, and m-tetramethylxylene isocyanate.

Furthermore, in the present invention, when obtaining a specific copolymer, in addition to the monomer having a specific functional group, other monomers that can be copolymerized with the monomer can also be used. Specific examples of such other monomers include acrylate compounds, methacrylate compounds, succinimidyl compounds, acrylamide compounds, acrylonitrile, succinic anhydride, styrene compounds, and vinyl compounds.

Specific examples of the aforementioned other monomers are listed below, but are not limited thereto. As the aforementioned acrylate compound, for example, methacrylate, ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, 5-acryloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, acrylic acid, mono-(2-(acryloxy)ethyl)phthalic acid, epoxypropyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracenyl acrylate , anthracene methacrylate, phenyl acrylate, epoxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, tertiary butyl acrylate, cyclohexyl acrylate, isoborneol acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofuran methacrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, etc.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, 2-(methacryloxy)ethyl caprolactone, 5-methacryloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, glycidyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracenyl methacrylate, anthracenyl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, and isopropyl methacrylate. methacrylate, 2,2,2-trifluoroethyl methacrylate, tertiary butyl methacrylate, cyclohexyl methacrylate, isoborneol methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofuranyl 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.

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

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

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

Examples of the cis-butenediamide compound include cis-butenediamide, N-methyl cis-butenediamide, N-phenyl cis-butenediamide, N-(hydroxyphenyl) cis-butenediamide, N-(hydroxyphenyl) cis-butenediamide, N-(carboxyphenyl) cis-butenediamide, and N-cyclohexyl cis-butenediamide.

When introducing a liquid crystal alignment group into component (A2) or component (B2) (polymer), the amount of each monomer used to obtain a specific copolymer is preferably 25 to 90 mol% of a monomer having a liquid crystal alignment group or a monomer having a group for introducing the same, 10 to 75 mol% of a monomer having a Michel addition reaction site (Michel donor site, Michel acceptor site) or a monomer having a group for introducing the same, and 0 to 65 mol% of other monomers without 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 Michel addition reaction site, and 0 to 75 mol% of a monomer without a specific functional group.

In the case where no liquid crystal alignment group is introduced into component (A2) or component (B2) (polymer), the amount of each monomer used to obtain a specific copolymer is preferably 5 to 100 mol% of a monomer having a Michel addition reaction site or a monomer having a group for introducing the same, and 0 to 95 mol% of other monomers without a specific functional group, based on the total amount of all monomers.

The method for obtaining the specific copolymer used in the present invention is not particularly limited, but it can be obtained by, for example, performing a polymerization reaction at a temperature of 50 to 110°C in a solvent in which a monomer having a specific functional group, another monomer not having a specific functional group as desired, and a polymerization initiator coexist. At this time, the solvent used is not particularly limited as long as it can dissolve the monomer having a specific functional group, the monomer not having a specific functional group used as desired, and the polymerization initiator. As a specific example, it is described in <Solvent> described later. The specific copolymer obtained by the above method is usually in a solution state dissolved in a solvent.

Furthermore, the solution of the specific copolymer obtained by the above method can be put into ether or water under stirring to reprecipitate, and the resulting precipitate can be filtered and washed, and then dried at room temperature or heated under normal pressure or reduced pressure to obtain a powder of the specific copolymer. Through the above operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a refined powder of the specific copolymer can be obtained. In the case where the purification cannot be fully achieved by a single operation, the obtained powder can be dissolved in a solvent again and the above operation can be repeated.

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

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

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

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

As a preferred example of the polymer having a plurality of hydroxyl groups, polyester polyols include those obtained by reacting polycarboxylic acids such as adipic acid, sebacic acid, and isophthalic acid with diols such as ethylene glycol, propylene glycol, butanediol, polyethylene glycol, and polypropylene glycol. Specific examples of polyester polyols include DIC Corporation's Poly-Lite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD-X-2555, OD-X-2560, KURARAY Corporation's 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, PNNA-2016, etc.

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

As a preferred example of a polymer having a plurality of hydroxyl groups, polycarbonate polyols include those obtained by reacting a polyol such as trihydroxymethylene propane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc. Specific examples of polycarbonate polyols include PLACCEL (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel Co., Ltd., and C-590, C-1050, C-2050, C-2090, C-3090 manufactured by KURARAY Co., Ltd.

As a preferred example of the polymer having a plurality of hydroxyl groups, cellulose includes hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyalkylalkylcelluloses such as hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, and hydroxyethylethylcellulose, and cellulose. For example, hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose are preferred.

Preferred examples of cyclodextrins of polymers having multiple hydroxyl groups include cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, methylated cyclodextrins such as methyl-α-cyclodextrin, methyl-β-cyclodextrin, and methyl-γ-cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxyethyl-β-cyclodextrin, 2 2-Hydroxypropyl-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, 2,3-dihydroxypropyl-γ-cyclodextrin and the like.

As a preferred example of the polymer having a plurality of hydroxyl groups, urethane-modified acrylic polymers are commercially available, such as ACRIT (registered trademark) 8UA-017, 8UA-239, 8UA-239H, 8UA-140, 8UA-146, 8UA-585H, 8UA-301, 8UA-318, 8UA-347A, 8UA-347H, 8UA-366, etc. manufactured by Taisei Fine Chemical Co., Ltd.

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

When the component (B) is contained (not when the component (A2) and the component (B2) described later are the same compound), the content of the component (B) is 1 to 2000 parts by mass, for example, 5 to 2000 parts by mass, preferably 15 to 700 parts by mass, or 1 to 400 parts by mass, per 100 parts by mass of the component (A).

<When component (A) and component (B) are the same compound> In this case, the above-mentioned introduction methods can be combined to introduce both the micoke donor site and the micoke acceptor site, and further introduce the liquid crystal alignment group as needed. As such a method, for example, a polymer obtained by copolymerizing a monomer having an active methylene group, a monomer having an epoxy group, and a monomer having a liquid crystal alignment group as needed can be reacted with (meth) acrylic acid.

<(C) Michelobacterium addition reaction catalyst> The curable film forming composition of the present invention may further contain a Michelobacterium addition reaction catalyst for promoting Michelobacterium addition reaction as component (C) in addition to the aforementioned components (A) and (B). More specifically, the Michelobacterium addition reaction catalyst may include the alkaline compounds shown below, but is not limited thereto. Examples of the alkaline compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal alkoxides such as sodium methoxide and potassium ethoxide; quaternary ammonium hydroxides such as tetrabutylammonium hydroxide and benzyltrimethylammonium hydroxide; tetrabutylammonium carbonate, benzyltrimethylammonium carbonate, triethylmonomethylammonium 2-ethylhexanoate, and tetrabutylammonium acetate; 1. primary ammonium carbonate; quaternary ammonium fluorides such as tetrabutylammonium fluoride and benzyltrimethylammonium fluoride; quaternary ammonium tetrahydroborates such as tetrabutylammonium tetrahydroborate and benzyltrimethylammonium tetrahydroborate; tertiary amines such as tetramethylguanidine, 1,8-diazabicyclo[5,4,0]undecene-7, and diazabicyclo[4,3,0]nonene-5; tertiary phosphines such as guanidine, azanol, and triphenylphosphine, etc.

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

As the component (C), from the viewpoint of reactivity and storage stability, quaternary ammonium carbonate, quaternary ammonium hydroxide and tertiary amine are more preferred.

When the cured film forming composition of the present invention contains the component (C), the content 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 components (A) and (B). By setting the content of the component (C) to 0.01 parts by mass or more, sufficient heat curing and solvent resistance can be imparted. However, when the content is greater than 20 parts by mass, the storage stability of the composition may be reduced.

<Solvent> The curable film forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used at this time can dissolve the (A) component, the (B) component, and the desired (C) component, and further other additives described below as needed, and its type and structure are not particularly limited.

Specific examples of the solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiourea acetate, ethyl thiourea acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-butylene glycol, 2-butylene glycol ... -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.

For example, in the case of manufacturing an alignment material by forming a cured film on a resin film using the cured film forming composition of the present invention, from the viewpoint of providing the resin film with a solvent resistant thereto, preferably used are methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol, 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, and the like.

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

<Other additives> Furthermore, the curing film forming composition of the present invention may contain adhesion promoters, silane coupling agents, surfactants, rheology modifiers, pigments, dyes, storage stabilizers, defoamers, antioxidants, inorganic oxide particles, etc. as needed within the scope that does not impair the effects of the present invention.

<Preparation of Cured Film Forming Composition> The cured film forming composition of the present invention may contain a compound having a micak donor site as component (A), a compound having a micak acceptor site as component (B), and a micak addition reaction catalyst as component (C), and other additives that do not impair the effects of the present invention. In addition, they are usually used in the form of a solution dissolved in a solvent.

Preferred examples of the cured film forming composition of the present invention are as follows. [1]: A cured film forming composition comprising a compound having a micagonist donor site as component (A) and a compound having a micagonist acceptor site as component (B), and 0.01 to 20 parts by weight of a component (C) and a solvent, relative to 100 parts by weight of the total of the components (A) and (B).

When the cured film forming composition of the present invention is used as a solution, the blending ratio, preparation method, etc. are described in detail below. The ratio of the solid component in the cured film forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1 mass% to 60 mass%, preferably 2 mass% to 50 mass%, and more preferably 2 mass% to 20 mass%. Here, the so-called solid component refers to the components of the cured film forming composition minus the solvent.

The method for preparing the curable film forming composition of the present invention is not particularly limited. For example, the preparation method includes a method of mixing the component (B) and the component (C) at a predetermined ratio in a solution of the component (A) dissolved in a solvent to prepare a uniform solution; or a method of further adding other additives and mixing them as needed at an appropriate stage of the preparation method.

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

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

<Curing film, alignment material and phase difference material> The solution of the curing film forming composition of the present invention is applied on a substrate (e.g., a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, an ITO substrate, etc.) or a film substrate (e.g., 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, a polyethylene film, etc.) by bar coating, rotary coating, flow coating, etc. The coating is formed by coating with roller coating, slit coating, continuous slit rotary coating, inkjet coating, printing, etc., and then a cured film is formed by heating and drying with a hot plate or oven. The cured film can be directly used as an alignment material.

As the conditions for heat drying, as long as the components of the hardened film (alignment material) are subjected to crosslinking reaction by the crosslinking agent to a degree that the polymerizable liquid crystal solution applied thereon is not eluted, for example, a heating temperature and a heating time appropriately selected from the range of 60°C to 200°C and 0.4 minutes to 60 minutes are adopted. The heating temperature and the heating time are preferably 70°C to 160°C and 0.5 minutes to 10 minutes.

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

Since the alignment material formed by the cured film composition of the present invention has solvent resistance and heat resistance, a phase difference material such as a polymerizable liquid crystal solution having vertical alignment can be coated on the alignment material to align the alignment material. Moreover, by directly curing the phase difference material in an aligned state, the phase difference material can be formed as a layer having optical anisotropy. Moreover, in the case where the substrate on which the alignment material is formed is a thin film, it becomes useful as a phase difference film.

Furthermore, two substrates with the alignment material of the present invention formed as described above can be used, and after the alignment materials on the two substrates are connected face to face with each other through a spacer, liquid crystal is injected between the substrates to make a liquid crystal display element with aligned liquid crystal. In this way, the cured film forming composition of the present invention can be suitable for the manufacture of various phase difference materials (phase difference films), liquid crystal display elements, etc. [Example]

The present invention is described in detail below by way of examples, but the present invention is not to be construed as being limited thereto.

[Abbreviations used in Examples] The meanings of the abbreviations used in the following Examples are as follows. <Raw Materials> GMA: Epoxypropyl methacrylate M100: 3,4-Epoxycyclohexyl methyl methacrylate EGAMA: Ethylene glycol monoacetate monomethacrylate LA: Lauryl acrylate HA: Hexyl acrylate AIBN: α,α'-azobisisobutyronitrile CIN1: CIN2: CIN3: CIN4: CIN5: (mixture of the following isomers) CIN6: (mixture of the following isomers) CIN7: CIN8: CIN9:

<Component A2> TMPI: 1,3,5-tris(3-butylenepropionylethoxy)-isocyanurate TMBI: 1,3,5-tris(3-butylene-ethoxy)-isocyanurate

<B2 component> DPHA: Dipentatriol hexaacrylate [A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)] UA: Urethane acrylate [UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.)] SMP: Acrylic acid group-containing acrylic polymer [SMP-220A (manufactured by Kyoeisha Chemical Co., Ltd.)] <C component> UCAT: Triethylmonomethylammonium 2-ethylhexanoate [U-CAT18X (manufactured by San-Apro Co., Ltd.)] TBAAc: Tetrabutylammonium acetate TBAH: Tetrabutylammonium hydroxide DBU: 1,8-Diazabicyclo[5.4.0]-7-undecene <Other components (D component)> PGM-AC: Organic silica sol [PGM-AC-2140Z (manufactured by Nissan Chemical Industries, Ltd.)] <Solvent> Each composition of the embodiment and comparative example contains a solvent, and propylene glycol monomethyl ether (PM), propylene glycol monomethyl ether acetate (PMA), butyl acetate (BA), and ethyl acetate (EA) are used as the solvent.

<Determination of molecular weight of 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. In addition, the number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) described below are expressed as polystyrene conversion values. Column temperature: 40°C Solvent: tetrahydrofuran Flow rate: 1.0 mL/min Standard sample for calibration curve preparation: Standard polystyrene manufactured by Showa Denko K.K. (molecular weight of about 197,000, 55,100, 12,800, 3,950, 1,260, 580). <Synthesis of raw materials>

<Synthesis Example 1> Synthesis of CIN3 Mix 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, and heat at 90°C for 3 days. After the reaction is completed, 1,4-dioxane is distilled off under reduced pressure, 150mL of ethyl acetate is added, and insoluble matter is filtered off. Then, 100mL of sodium bicarbonate water is added and washed 3 times to remove excess methoxycinnamic acid. Ethyl acetate is distilled off under reduced pressure to obtain 16.5g of the target CIN3.

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

<Synthesis Example 3> Synthesis of CIN4 16.3 g of CIN3 and 9.5 g of acetyl Michaelis acid obtained in Synthesis Example 2 were dissolved in 80 mL of 1,4-dioxane and heated at 80°C for 1 hour. 20.4 g of CIN4 was obtained by distilling off 1,4-dioxane under reduced pressure.

<Synthesis Example 4> Synthesis of CIN5 4.9 g of M100, 8.9 g 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 the reaction was completed, 1,4-dioxane was distilled off under reduced pressure, 100 mL of ethyl acetate was added, insoluble matter was removed by filtration, and 100 mL of sodium bicarbonate water was added to wash 3 times. Ethyl acetate was distilled off under reduced pressure to obtain 6.3 g of the target CIN5.

<Synthesis Example 5> Synthesis of CIN6 5.0 g of CIN5 and 2.4 g of acetyl Michaelis acid obtained in Synthesis Example 2 were dissolved in 40 mL of 1,4-dioxane and heated at 80°C for 1 hour. 7.1 g of CIN6 was obtained by distilling off the 1,4-dioxane under reduced pressure.

<Synthesis of component A1> <Synthesis Example 6> Synthesis of CIN8 5.0 g of CIN7 and 3.3 g of acetyl Michaelis acid obtained in Synthesis Example 2 were dissolved in 40 mL of 1,4-dioxane and heated at 80°C for 1 hour. 8.0 g of CIN8 was obtained by distilling off 1,4-dioxane under reduced pressure.

<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 of an acrylic copolymer (A2-1) containing 10% by mass of acetylacetyl groups in the side chains. The Mn of the obtained acrylic copolymer was 12,000 and the Mw was 23,000.

<Synthesis Example 8> 10.0 g of CIN2, 2.5 g of EGAMA, and 0.38 g of AIBN as a polymerization catalyst were dissolved in 115.9 g of PM and reacted at 80°C for 20 hours to obtain a solution of an acrylic copolymer (A2-2) containing 10% by mass of acetylacetyl groups in the side chains. The Mn of the obtained acrylic copolymer was 18,000 and the Mw was 35,000.

<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 reacted at 80°C for 20 hours to obtain a solution of an acrylic copolymer (A2-3) containing 20% by mass of acetylacetyl groups in the side chains. The Mn of the obtained acrylic copolymer was 17,000 and the Mw was 32,000.

<Synthesis Example 10> 15.0 g of CIN6 and 0.3 g of AIBN as a polymerization catalyst were dissolved in 1.2 g of PM and reacted at 80°C for 20 hours to obtain a solution of an acrylic copolymer (A2-4) containing 20% by mass of acetylacetyl groups in the side chains. The Mn of the obtained acrylic copolymer was 23,000 and the Mw was 40,000.

<Synthesis Example 11> 10.0 g of PLACCEL 410 (polycaprolactone tetraol produced by Daicel Co., Ltd.) and 6.3 g of tertiary butyl acetoacetate were dissolved in 38.1 g of PMA and reacted at 130°C for 10 hours to obtain a solution containing 30% by mass of a compound (A2-5) having an acetoacetyl group.

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

<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 of an acrylic copolymer (A2-7) containing 20% by mass of acetyl groups in the side chains. The Mn of the obtained acrylic copolymer was 17,000 and the Mw was 32,000.

<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 acetyl acetyl groups in the side chain. Then, 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 acrylic acid groups into the side chains of the acrylic copolymer. Thereafter, reprecipitation was performed with hexane to obtain an acrylic copolymer (A2-8) having acetyl acetyl groups and acrylic acid groups in the side chains. The obtained acrylic copolymer has a Mn of 23,000 and a Mw of 42,000.

<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. Then, 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 acrylic groups into the side chains of the acrylic copolymer. Thereafter, reprecipitation was performed with hexane to obtain an acrylic copolymer (B2-1) having acrylic groups in the side chains. The obtained acrylic copolymer had an Mn of 12,000 and an Mw of 32,000.

<Example 1> The acrylic copolymer (A2-1) (solid content) equivalent to 100 parts by mass of the solution containing 10% by mass of the acrylic copolymer (A2-1) obtained in the above-mentioned Synthesis Example 7 was used as the component (A-1), 30 parts by mass of DPHA was used as the component (B), and 3 parts by mass of UCAT was used as the component (C). PM and PMA were added thereto to prepare an alignment material composition (A-1) having a solvent composition of PM:PMA=80:20 (mass ratio) and a solid content concentration of 5.0% by mass.

<Examples 2 to 25 and Comparative Examples 1 to 4> Alignment material compositions A-2 to A-29 (components (A) to (D) are values converted to solid components) were prepared in the same manner as in Example 1 except that the types and amounts of the components were set as shown in Table 1.

<Example 26> [Evaluation of alignment] Using a rod coater, the alignment material obtained in Example 1 is formed into composition A-1, and coated on a TAC film with a wet film thickness of 4μm. Heat drying is performed in a heat circulation oven at a temperature of 110°C for 2 minutes to form a cured film on the TAC film. For each of these cured films, 313nm linear polarized light is vertically irradiated at an exposure amount of 20mJ/ ^cm2 to form an alignment material. On the alignment material on the TAC film, a polymerizable liquid crystal solution RMS03-013c (manufactured by Merck Co., Ltd.) is applied with a wet film thickness of 6μm using a rod coater. This coating is heat dried on a hot plate set to a temperature of 65°C for 2 minutes, and then exposed to 300mJ/ ^cm2 to produce a phase difference material. The phase difference material on the manufactured substrate was sandwiched between a pair of polarizing plates, and the phase difference characteristics of the phase difference material were observed. Those that exhibited a flawless phase difference were marked as ○, and those that did not exhibit a phase difference were marked as ×, and the results were recorded in the "Orientation" column of Table 2.

<Examples 27 to 50 and Comparative Examples 5 to 8> Phase difference materials were prepared in the same manner as in Example 26, except that the alignment material forming composition, the heating temperature and the heating time in the heat circulation oven were set to the same as those in Table 2. The evaluation results are summarized in Table 2 below.

In Examples 26 to 50, a phase difference material showing good orientation can be produced by sintering at a low temperature and in a short time. In contrast, in Comparative Examples 5 to 8, a phase difference material showing good orientation cannot be produced by sintering at a low temperature and in a short time.

[Evaluation of adhesion] <Examples 51-53> The phase difference material on the film produced by Examples 48-50 was cut with a cutter at 1 mm intervals in the vertical and horizontal directions to form a mass of 10×10. On this cut, a Scotch (registered trademark) tape was used to perform a transparent tape peeling test. After peeling off the tape, 100 masses that were not peeled off and remained were evaluated as ○, and even 1 mass that was peeled off was evaluated as ×. The evaluation results are collectively disclosed in the "Initial" column in Table 3 described later.

[Evaluation of durable adhesion] The phase difference material produced by the same method as the above-mentioned adhesion evaluation was placed in an oven set to a temperature of 80°C and a humidity of 90% for more than 200 hours. Afterwards, the phase difference material was taken out and the adhesion was evaluated by the same method as the above-mentioned adhesion evaluation. The evaluation results are collectively disclosed in the "durability" column in Table 3 described below.

According to Examples 51 to 53, the phase difference materials prepared exhibit excellent durability and good adhesion.

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

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

<Examples 54 to 57 and Comparative Examples 9 to 10> Except for setting the types and amounts of each component as shown in Table 4, the same method as Example 1 was followed to prepare alignment material forming compositions A-30 to A-35 ((A) to (D) components are all values converted into solid components).

<Example 58> [Evaluation of vertical alignment] Using a rod coater, the alignment material obtained in Example 54 is formed into composition A-30 and coated on a TAC film with a wet film thickness of 4 μm. Heat drying is performed in a heat circulation oven at a temperature of 120°C for 2 minutes to form an alignment material on the TAC film. On top of the alignment material on the TAC film, a polymerizable liquid crystal solution RMS03-015 (manufactured by Merck Co., Ltd.) is coated with a wet film thickness of 6 μm using a rod coater. This coating is heat dried on a hot plate set to a temperature of 65°C for 2 minutes, and then exposed to 300 mJ/ ^cm2 to produce a phase difference material. The prepared phase difference material was used to measure the incident angle dependence of the in-plane phase difference using the phase difference measurement device RETS100 manufactured by Otsuka Electronics Co., Ltd. The in-plane phase difference value of 0 at an incident angle of 0 degrees and the in-plane phase difference within the range of 38±5nm at an incident angle of ±50 degrees were judged to be vertically aligned. The evaluation results are recorded in the "Vertical Alignment" column of Table 5.

<Examples 59-61 and Comparative Examples 11-12> Phase difference materials were prepared in the same manner as in Example 58, except that the alignment material forming compositions were set as described in Table 5. The vertical alignment properties were evaluated. The evaluation results are summarized in Table 5 below.

In Examples 58 to 61, a phase difference material showing good vertical orientation can be produced by sintering at a low temperature and for a short time. In contrast, in Comparative Examples 11 to 12, a phase difference material showing good orientation cannot be produced by sintering at a low temperature and for a short time. [Industrial Applicability]

The cured film-forming composition of the present invention is very useful as a material for forming an alignment material, which is used to form a liquid crystal alignment film of a liquid crystal display element, and an optically anisotropic film disposed inside or outside the liquid crystal display element; in particular, it is suitable as a material for a phase difference material of a circular polarizing plate, which is used as an anti-reflection film of an IPS-LCD or an organic EL display.

Claims (10)

A cured film forming composition comprising a compound containing a Michael donor site selected from a phthalate group and a group represented by formula (a1) as component (A), and a compound containing a Michael acceptor site selected from an acrylic group and a methacrylic group as component (B), wherein at least one of the components (A) and (B) contains a liquid crystal alignment group represented by the following formula [1] or [2], In formula (a1), R represents an alkyl group, an alkoxy group or a phenyl group, and the dotted line represents an atomic bond. In the above formula [1], ^X11 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group; in this case, the phenyl group and the biphenyl group may be substituted by any one of a halogen atom, an alkyl group, an alkoxy group and a cyano group. In the above formula [2], ^X12 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group; in this case, the alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group may be bonded to the benzene ring via a single bond, an ether bond, an ester bond, an amide bond or a urea bond. The cured film forming composition of claim 1, wherein the component (A) and the component (B) are the same compound containing a micor donor site, a micor acceptor site, and a liquid crystal alignment group. The cured film forming composition of claim 1, wherein, as component (A), at least one selected from a low molecular compound (A1) having a micoke donor site and a liquid crystal alignment group, and a compound (A2) having two or more micoke donor sites and containing or not containing a liquid crystal alignment group; and as component (B), at least one selected from a low molecular compound (B1) having a micoke receptor site and a liquid crystal alignment group, and a compound (B2) having two or more micoke receptor sites and containing or not containing a liquid crystal alignment group, and components (A2) and (B2) may be low molecular compounds or high molecular compounds. The hardened film forming composition of claim 1 further comprises (C) a Michel addition reaction catalyst. The hardened film forming composition of claim 1, wherein the mikroreceptor site is an acrylic group. The cured film forming composition of claim 1, wherein the component (B) is contained in an amount of 1 part by mass to 2,000 parts by mass relative to 100 parts by mass of the component (A). The cured film forming composition of claim 4, wherein the component (C) is contained in an amount of 0.01 to 20 parts by mass relative to 100 parts by mass of the total of the components (A) and (B). A cured film obtained by using the cured film forming composition according to any one of claims 1 to 7. An alignment material is obtained by using the hardened film forming composition as described in any one of claims 1 to 7. A phase difference material is formed using the alignment material as claimed in claim 9.