WO2019027045A1 - Cured film forming composition, orienting material, and phase contrast material - Google Patents

Cured film forming composition, orienting material, and phase contrast material Download PDF

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Publication number
WO2019027045A1
WO2019027045A1 PCT/JP2018/029248 JP2018029248W WO2019027045A1 WO 2019027045 A1 WO2019027045 A1 WO 2019027045A1 JP 2018029248 W JP2018029248 W JP 2018029248W WO 2019027045 A1 WO2019027045 A1 WO 2019027045A1
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group
cured film
component
mass
parts
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PCT/JP2018/029248
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French (fr)
Japanese (ja)
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伊藤　潤
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日産化学株式会社
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Priority to CN202310790480.5A priority Critical patent/CN116789871A/en
Priority to KR1020207004627A priority patent/KR102662084B1/en
Priority to CN201880064199.0A priority patent/CN111164120A/en
Priority to JP2019534604A priority patent/JP7365003B2/en
Publication of WO2019027045A1 publication Critical patent/WO2019027045A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers

Definitions

  • the present invention relates to a cured film-forming composition for aligning liquid crystal molecules, an alignment material, and a retardation material.
  • the present invention is useful for producing a patterned retardation material used in a 3D display of a circularly polarized glasses system, and a retardation material used in a circularly polarizing plate used as an antireflection film of an organic EL display.
  • the present invention relates to a cured film-forming composition, an alignment material, and a retardation material.
  • a retardation material is usually disposed on a display element such as a liquid crystal panel that forms an image.
  • a display element such as a liquid crystal panel that forms an image.
  • a plurality of two types of retardation regions having different retardation characteristics are regularly arranged, and constitute a patterned retardation material.
  • a retardation material patterned so as to dispose a plurality of retardation regions having different retardation characteristics as described above will be referred to as a patterned retardation material.
  • the patterned retardation material can be produced, for example, by optically patterning a retardation material composed of a polymerizable liquid crystal as disclosed in Patent Document 1.
  • the optical patterning of the retardation material made of a polymerizable liquid crystal utilizes a photoalignment technique known for forming an alignment material of a liquid crystal panel. That is, a coating film made of a photoalignable material is provided on a substrate, and two types of polarized light having different polarization directions are irradiated to this. Then, a photo alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different alignment control directions of liquid crystals are formed.
  • a solution-like retardation material containing a polymerizable liquid crystal is coated on the photoalignment film to realize the alignment of the polymerizable liquid crystal. Thereafter, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.
  • the anti-reflection film of the organic EL display is composed of a linear polarizer and a quarter-wave retarder, and the extraneous light directed to the panel surface of the image display panel is converted into linearly polarized light by the linear polarizer, and the subsequent quarter-wave The light is converted to circularly polarized light by a retardation plate.
  • the extraneous light by this circularly polarized light is reflected by the surface of the image display panel or the like, the rotational direction of the polarization plane is reversed at the time of this reflection.
  • the reflected light is converted by the 1 ⁇ 4 wavelength retardation plate into linearly polarized light in the direction to be blocked by the linear polarization plate and then blocked by the subsequent linear polarization plate, contrary to the time of arrival.
  • outgoing radiation to the outside is significantly suppressed.
  • Patent Document 2 describes that this optical film has reverse dispersion characteristics by constituting a quarter-wave retarder by combining a half-wave plate and a quarter-wave plate.
  • a method of configuring by In this method it is possible to construct an optical film with reverse dispersion characteristics using a liquid crystal material with positive dispersion characteristics in a wide wavelength band for displaying a color image.
  • Patent Documents 3 and 4 As a liquid crystal material applicable to this retardation layer, one having an inverse dispersion characteristic has been proposed (Patent Documents 3 and 4). According to the liquid crystal material having such an inverse dispersion characteristic, instead of forming a 1 ⁇ 4 wavelength retardation plate by combining 2 layers of a 1 ⁇ 2 wavelength plate and a 1 ⁇ 4 wavelength plate, it is possible to use a retardation layer Can be secured by a single layer to ensure reverse dispersion characteristics, whereby an optical film capable of securing a desired retardation in a wide wavelength band can be realized with a simple configuration.
  • An alignment layer is used to align the liquid crystal.
  • a method of forming an alignment layer for example, a rubbing method or a photo-alignment method is known, and the photo-alignment method is capable of quantitative control of alignment processing without generating static electricity and dust which are problems of the rubbing method.
  • an acrylic resin, a polyimide resin, etc. which have photodimerization sites, such as a cinnamoyl group and a chalcone group, in a side chain as an available photoalignment property material are known. It has been reported that these resins exhibit the ability to control the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment) by irradiating polarized UV light (see Patent Documents 5 to 7).
  • the alignment layer is required to have adhesion to the liquid crystal layer.
  • the liquid crystal layer may be peeled off in the winding step or the like included in the production of the retardation film.
  • JP 2005-49865 A Japanese Patent Application Laid-Open No. 10-68816 U.S. Pat. No. 8,119,026 JP, 2009-179563, A Patent No. 3611342 JP, 2009-058584, A Japanese Patent Publication No. 2001-517719
  • an object of the present invention is made based on the above findings and examination results. That is, an object of the present invention is to provide a cured film-forming composition for providing an alignment material which exhibits good liquid crystal alignment and is excellent in adhesion to a liquid crystal layer.
  • the present inventors conducted intensive studies to achieve the above object, and as a result, (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond, (B) By selecting a cured film-forming composition based on a crosslinking agent, it has been found that a cured film can be formed which exhibits good liquid crystal alignment and is excellent in adhesion to a liquid crystal layer, thereby completing the present invention.
  • a cured film-forming composition comprising (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group having a polymerizable double bond and (B) a crosslinking agent.
  • A a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group having a polymerizable double bond
  • B a crosslinking agent
  • the present invention relates to, as a third aspect, the cured film-forming composition according to the first aspect or the second aspect, wherein the cinnamic acid derivative having a group containing the polymerizable double bond is a compound represented by the following formula (1).
  • each of A 1 and A 2 independently represents a hydrogen atom or a methyl group
  • R 1 is the following formula (c-2) (In the formula (c-2), the broken line represents a bond
  • R 101 represents an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of this alkylene group are replaced by a fluorine atom or an organic group
  • - M 1 is a hydrogen atom which may be substituted by a group selected from the group consisting of O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO-
  • a methyl group is represented by R 2 represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused cyclic group,
  • the present invention relates to the cured film-forming composition as described in any one of the first aspect to the third aspect, wherein the crosslinking agent of the component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group.
  • the first to fourth aspects which further contain a polymer having at least one group selected from the group consisting of (C) hydroxy group, carboxyl group, amido group, amino group, and alkoxysilyl group
  • the present invention relates to a cured film-forming composition according to any one of the above.
  • the present invention relates to the cured film forming composition according to any one of the first aspect to the fifth aspect, which further contains (D) a crosslinking catalyst.
  • the cured film-forming composition according to any one of the first to sixth aspects which contains a compound having at least one group.
  • the fifth to eighth aspects of the fifth to eighth aspects containing 1 part by mass to 400 parts by mass of the component (C) with respect to 100 parts by mass of the total amount of the crosslinking agents of the components (A) and (B)
  • the present invention relates to a cured film-forming composition according to any one of the above.
  • the sixth aspect to the ninth aspect which contain 0.01 parts by mass to 20 parts by mass of the component (D) with respect to 100 parts by mass of the total amount of the crosslinking agents of the components (A) and (B) It is related with the cured film formation composition as described in any one of a viewpoint.
  • the seventh to tenth aspects of the present invention are the seventh to tenth aspects containing 1 part by mass to 100 parts by mass of the component (E) with respect to 100 parts by mass of the total amount of the crosslinking agents
  • the present invention relates to a cured film-forming composition according to any one of the above.
  • the present invention relates to a cured film obtained from the cured film-forming composition according to any one of the first to eleventh aspects.
  • the present invention relates to, as a thirteenth aspect, an alignment material obtained from the cured film-forming composition according to any one of the first to eleventh aspects.
  • the present invention relates to, as a fourteenth aspect, a retardation material which is formed using a cured film obtained from the cured film forming composition according to any one of the first to eleventh aspects.
  • the cured film which shows favorable liquid crystal orientation, and is excellent in adhesiveness with a liquid crystal layer, and a cured film formation composition suitable for the formation can be provided.
  • a cured film formation composition suitable for the formation it is possible to provide an alignment material excellent in liquid crystal alignment and light transmission. Further, according to the present invention, it is possible to provide a retardation material capable of highly accurate optical patterning.
  • the cured film-forming composition of the present invention contains (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond, and (B) a crosslinking agent.
  • the cured film-forming composition of the present invention further comprises a group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group as the component (C) in addition to the components (A) and (B). It can also contain a polymer having at least one group selected from Furthermore, a crosslinking catalyst can also be contained as (D) component.
  • component (E) at least one group A selected from the group consisting of one or more polymerizable groups and a hydroxy group, a carboxyl group, an amido group, an amino group, and an alkoxysilyl group It can contain a compound having one group. And, as long as the effects of the present invention are not impaired, other additives can be contained. The details of each component will be described below.
  • the component (A) contained in the cured film-forming composition of the present invention is a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond.
  • the polymer having an epoxy group can be, for example, a polymer of a polymerizable unsaturated compound having an epoxy group or a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound.
  • polymerizable unsaturated compound having an epoxy group examples include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, glycidyl ⁇ -n-butyl acrylate, acrylic Acids-3,4-Epoxybutyl, Methacrylic Acid-3,4-Epoxybutyl, Acrylic Acid-6,7-Epoxyheptyl, Methacrylic Acid-6,7-Epoxyheptyl, ⁇ -Ethyl Acrylic Acid-6,7-Epoxy Examples include heptyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like.
  • polymerizable unsaturated compounds include (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compounds, maleimide Compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other polymerizable unsaturated compounds can be mentioned.
  • alkyl methacrylates such as hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, and the like.
  • Methacryloxyethyl glycoside 4-hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate Etc .; as acrylic acid alkyl esters, eg methyl acrylate Over DOO, isopropyl acrylate and the like; as methacrylic acid cyclic alkyl esters such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 2,6] decan-8-yl methacrylate, tricyclo [5.2.
  • the copolymerization ratio of the polymerizable unsaturated compound having an epoxy group in the polymer having an epoxy group is preferably 30% by mass or more, and more preferably 50% by mass or more.
  • the synthesis of the polymer having an epoxy group can be carried out by a known radical polymerization method, preferably in the presence of a suitable polymerization initiator in a solvent.
  • a commercial item may be used as a polymer which has an epoxy group.
  • EHPE3150, EHPE3150CE above, Daicel (formerly Daicel Chemical Industries, Ltd.) made
  • UG-4010, UG-4035, UG-4040, UG-4070 above, Toa Synthetic ( ALUFON series, Inc., ECN-1299 (Asahi Kasei Corporation), DEN 431, DEN 438 (above, Dow Chemical Co., Ltd.), jER-152 (Mitsubishi Chemical Co., Ltd.
  • the polymerizable double bond is preferably a carbon-carbon double bond.
  • the group containing a carbon-carbon double bond for example, a vinyl group, a (meth) acryloyl group, an acrylamide group and the like can be mentioned, and a (meth) acryloyl group is preferable.
  • each of A 1 and A 2 independently represents a hydrogen atom or a methyl group
  • R 1 is the following formula (c-2) (In the formula (c-2), the broken line represents a bond
  • R 101 represents an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of this alkylene group are replaced by a fluorine atom or an organic group
  • - M 1 is a hydrogen atom which may be substituted by a group selected from the group consisting of O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO- Or a methyl group is represented by R 2
  • Examples of the divalent aromatic group of R 2 include 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3,5,6- Tetrafluoro-1,4-phenylene group etc .;
  • a divalent alicyclic group of R 2 1,2-cyclopropylene group, 1,3-cyclobutylene group, 1,4-cyclohexylene group etc.
  • the divalent heterocyclic group for R 2 for example, 1,4-pyridine group, 2,5-pyridylene group, 1,4-furanylene group etc .; for the divalent fused cyclic group for R 2 For example, 2,6-naphthylene group etc. can be mentioned respectively.
  • R 2 a 1,4-phenylene group is preferable.
  • Preferred examples of the compound represented by the above formula (1) include the following formulas M1-1 to M1-5. (Wherein, M 1 is a hydrogen atom or a methyl group, s 1 represents the number of methylene groups, and is a natural number of 2 to 9)
  • the compound represented by the said Formula (1) can be synthesize
  • the reaction product of a polymer having an epoxy group and a specific cinnamic acid derivative contained in the liquid crystal aligning agent of the present invention comprises a polymer having an epoxy group as described above and a specific cinnamic acid derivative, preferably a catalyst. It can be synthesized by reacting in the presence, preferably in a suitable organic solvent.
  • the proportion of the cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 moles, more preferably 0.05 to 1 mole, relative to 1 mole of epoxy groups contained in the polymer having an epoxy group. It is 1.3 mol, more preferably 0.1 to 1.1 mol.
  • an organic catalyst which can be used here a compound known as a so-called curing accelerator which promotes the reaction of an organic base or an epoxy compound with an acid anhydride can be used.
  • organic base examples include primary to secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, Tertiary organic amines such as diazabicycloundecene; quaternary organic amines such as tetramethyl ammonium hydroxide can be mentioned.
  • primary to secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole
  • triethylamine tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine
  • Tertiary organic amines such as diazabicycloundecene
  • quaternary organic amines such as tetramethyl ammonium hydroxide
  • tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; and quaternary organic amines such as tetramethylammonium hydroxide preferable.
  • the curing accelerator examples include benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, tertiary amines such as triethanolamine; 2-methylimidazole, 2-n-heptylimidazole , 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2- Ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1 -(2-cyanoethyl) -2-ethyl 4-Methylimidazo
  • quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride.
  • the proportion of the catalyst used is preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, still more preferably 0.1 to 20 parts by mass, with respect to 100 parts by mass of the polymer having an epoxy group.
  • organic solvent a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, an alcohol compound etc. can be mentioned, for example.
  • ether compounds, ester compounds, ketone compounds and alcohol compounds are preferable from the viewpoint of the solubility of the raw materials and products and the ease of purification of the products.
  • the solvent is used in an amount such that the solid concentration (the ratio of the mass of components other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1% by mass or more, more preferably 5 to 50% by mass Be done.
  • the reaction temperature is preferably 0 to 200 ° C., more preferably 50 to 150 ° C.
  • the reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. In this way, a solution is obtained which contains the reaction product of a polymer having an epoxy group and a specific cinnamic acid derivative.
  • This solution may be used as it is for preparation of a liquid crystal aligning agent, or may be used for preparing a liquid crystal aligning agent after isolating a polymer contained in the solution, or after purifying the isolated polymer. You may use for preparation of a liquid crystal aligning agent.
  • the component (B) in the cured film-forming composition of the present invention is a crosslinking agent.
  • the crosslinking agent which is the component (B) is preferably a crosslinking agent having a group capable of forming a crosslink with the thermally crosslinkable functional group of the component (A), such as a methylol group or an alkoxymethyl group. Examples of compounds having these groups include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine and alkoxymethylated melamine.
  • alkoxymethylated glycoluril examples include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 , 6-Tetrakis (hydroxymethyl) glycoluril, 1, 3-bis (hydroxymethyl) urea, 1, 1, 3, 3- tetrakis (butoxymethyl) urea, 1, 1, 3, 3- tetrakis (methoxymethyl) Examples thereof include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.
  • alkoxymethylated benzoguanamine examples include tetramethoxymethylbenzoguanamine and the like.
  • Nippon Cytech Industries Co., Ltd. formerly Mitsui Cytec Co., Ltd.
  • Cymel registered trademark
  • Sanwa Chemical Co., Ltd. trade name: Nikalac (registered trademark) BX-) 4000, BX-37, BL-60, BX-55H) and the like.
  • alkoxymethylated melamine examples include, for example, hexamethoxymethylmelamine.
  • methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine Compound (trade name: Mycoat (registered trademark) 506, 508), methoxymethyl type melamine compound (trade name: Nikalac (registered trademark) MW-30, MW-22, MW-22 manufactured by Sanwa Chemical Co., Ltd.
  • it may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of such an amino group is substituted with a methylol group or an alkoxymethyl group.
  • a melamine compound a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of such an amino group is substituted with a methylol group or an alkoxymethyl group.
  • high molecular weight compounds prepared from melamine compounds and benzoguanamine compounds described in US Pat. No. 6,323,310 can be mentioned.
  • Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303
  • examples of commercially available products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 (above, Nippon Cytech Industries, Ltd. And the like (manufactured by Mitsui
  • hydroxymethyl groups such as N-hydroxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl methacrylamide or alkoxymethyl groups
  • hydroxymethyl groups such as N-hydroxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl methacrylamide or alkoxymethyl groups
  • Polymers prepared using acrylamide compounds or methacrylamide compounds substituted with can also be used.
  • polymers for example, poly (N-butoxymethyl acrylamide), a copolymer of N-butoxymethyl acrylamide and styrene, a copolymer of N-hydroxymethyl methacrylamide and methyl methacrylate, N-ethoxymethyl
  • polymers for example, poly (N-butoxymethyl acrylamide), a copolymer of N-butoxymethyl acrylamide and styrene, a copolymer of N-hydroxymethyl methacrylamide and methyl methacrylate, N-ethoxymethyl
  • examples thereof include copolymers of methacrylamide and benzyl methacrylate, and copolymers of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate, and the like.
  • the method for obtaining the polymer as described above is not particularly limited.
  • the specific functional group 1 means a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a functional group such as a phenolic hydroxy group or an isocyanate group, or a plurality of functional groups selected therefrom. say.
  • preferred combinations of the specific functional group 1 and the functional group possessed by the specific compound and involved in the reaction are a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, a phenolic hydroxy group and an epoxy group A carboxyl group and an isocyanate group, an amino group and an isocyanate group, or a hydroxy group and an acid chloride.
  • a more preferable combination is a carboxyl group and glycidyl methacrylate, or a hydroxyl group and isocyanate ethyl methacrylate.
  • the weight average molecular weight (in terms of polystyrene) of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000. More preferably, it is 3,000 to 50,000.
  • crosslinking agents can be used alone or in combination of two or more.
  • the content of the crosslinking agent of the component (B) in the cured film-forming composition of the present invention is preferably 1 part by mass to 500 parts by mass, and more preferably, based on 100 parts by mass of the polymer which is the component (A). 5 parts by mass to 400 parts by mass.
  • the content of the crosslinking agent is too small, the solvent resistance of the cured film obtained from the cured film-forming composition is lowered, and the liquid crystal alignment is lowered. On the other hand, when the content is excessive, the liquid crystal alignment and storage stability may be lowered.
  • the cured film-forming composition of the present invention comprises, as component (C), at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group (hereinafter also referred to as a specific functional group 2) May be contained in the polymer.
  • component (C) at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group (hereinafter also referred to as a specific functional group 2) May be contained in the polymer.
  • polymer which is the component (C) for example, acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polyalkyleneimine, poly Examples thereof include polymers having a linear or branched structure such as allylamine, celluloses (cellulose or derivatives thereof), phenol novolac resin, and melamine formaldehyde resin, and cyclic polymers such as cyclodextrins.
  • the polymer which is the component (C) preferably includes acrylic polymers, hydroxyalkyl cyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols and polycaprolactone polyols.
  • the acrylic polymer which is a preferable example of the polymer of the component (C) is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, vinyl compound, etc.
  • the polymer may be a polymer obtained by polymerizing a monomer containing a monomer having a functional group 2 or a mixture thereof, and the type and the like of the main chain skeleton and side chains of the polymer constituting the acrylic polymer are not particularly limited.
  • a monomer having the specific functional group 2 a monomer having a polyethylene glycol ester group, a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms, a monomer having a phenolic hydroxy group, a monomer having a carboxyl group, an amino group And monomers having an alkoxysilyl group and a group represented by Formula 2 above.
  • Examples of the above-described monomer having a polyethylene glycol ester group include monoacrylate or monomethacrylate of H- (OCH 2 CH 2 ) n -OH.
  • the value of n is 2 to 50, preferably 2 to 10.
  • Examples of the monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms described above include, for example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate And 4-hydroxybutyl methacrylate.
  • Examples of the above-mentioned monomer having a phenolic hydroxy group include p-hydroxystyrene, m-hydroxystyrene and o-hydroxystyrene.
  • acrylic acid methacrylic acid
  • vinyl benzoic acid is mentioned, for example.
  • Examples of the above-mentioned monomer having an amino group in the side chain include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate.
  • Examples of the above-mentioned monomer having an alkoxysilyl group in the side chain include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane and the like can be mentioned.
  • the acrylic polymer which is an example of the component (C)
  • Monomers which do not have any of the represented groups can be used in combination.
  • Such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
  • acrylic acid ester compound for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, Beauty, etc. 8-ethyl-8-tricyclodecyl acrylate.
  • methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Propyl-2-adamantyl methacrylate, 8-meth Le -8- tricyclodecyl methacrylate, and, 8-e
  • maleimide compound examples include maleimide, N-methyl maleimide, N-phenyl maleimide, and N-cyclohexyl maleimide.
  • styrene compounds include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.
  • vinyl compounds include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
  • the amount of the monomer having the specific functional group 2 used to obtain the acrylic polymer which is an example of the component (C) is based on the total amount of all the monomers used to obtain the acrylic polymer which is the component (C). And preferably 2 mol% or more. If the monomer having the specific functional group 2 is less than 2 mol%, the solvent resistance of the resulting cured film tends to be insufficient.
  • the method of obtaining the acrylic polymer which is an example of (C) component is not specifically limited,
  • the monomer containing the monomer which has the specific functional group 2, and the monomer which does not have the specific functional group 2 if needed, and a polymerization initiator It is obtained by a polymerization reaction at a temperature of 50.degree. C. to 110.degree. C. in a solvent in the presence of, etc.
  • the solvent to be used is not particularly limited as long as it dissolves the monomer having the specific functional group 2, and the optionally used monomer having no specific functional group 2, the polymerization initiator and the like.
  • the acrylic polymer which is an example of (C) component obtained by the above method is a state of the solution normally melt
  • the powder can be dried at normal temperature or dried by heating under normal pressure or reduced pressure to form a powder of an acrylic polymer which is an example of the component (C).
  • the polymerization initiator coexisting with the acrylic polymer which is an example of the component (C) and unreacted monomers can be removed, and as a result, the acrylic polymer which is an example of the purified component (C) Powder is obtained. If sufficient purification can not be performed by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
  • the acrylic polymer which is a preferable example of the component (C) preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and still more preferably 5,000 to 100,000. If the weight average molecular weight is more than 200,000 and is too large, the solubility in solvents may be reduced and the handling properties may be reduced. If the weight average molecular weight is less than 3000 and is too low, the curing is insufficient at the time of heat curing And the solvent resistance may be reduced.
  • the weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard material.
  • GPC gel permeation chromatography
  • polyether polyol which is a preferable example of the component (C)
  • polyethylene oxide polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, polyhydric alcohol such as sorbitol, propylene oxide, polyethylene glycol, polypropylene glycol, etc.
  • polyether polyols include Adeka Polyether P series, G series, EDP series, BPX series, FC series, CM series manufactured by Adeka, Uniox (registered trademark) HC-40, HC-60, ST- 30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400 And Nonion (registered trademark) LT-221, ST-221, OT-221 and the like.
  • polyester polyol which is a preferable example of (C) component
  • diols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, etc. were made to react with polyvalent carboxylic acids, such as adipic acid, sebacic acid, and isophthalic acid.
  • polyvalent carboxylic acids such as adipic acid, sebacic acid, and isophthalic acid.
  • Specific examples of the polyester polyol include Polylight (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, manufactured by DIC.
  • polycaprolactone polyol which is a preferable example of the component (C)
  • a polycaprolactone polyol which is a preferable example of the component (C)
  • a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator
  • Specific examples of the polycaprolactone polyol include Polylight (registered trademark) OD-X-2155, OD-X-640, and OD-X-2568 manufactured by DIC, Plaxel (registered trademark) 205 manufactured by Daicel, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320 and the like.
  • polycarbonate polyol which is a preferable example of the component (C) include those obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like.
  • polycarbonate polyols include PLACEL (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel, C-590, C-1050, C-2050, C-2090, C-3090 and the like manufactured by Kuraray.
  • Preferred examples of the component (C) include celluloses such as hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and cellulose.
  • celluloses such as hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, and hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and cellulose.
  • hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.
  • cyclodextrins which are preferable examples of the component (C) include cyclodextrins such as ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin, methyl- ⁇ -cyclodextrin, methyl- ⁇ -cyclodextrin and methyl- ⁇ Methylated cyclodextrins such as -cyclodextrin, hydroxymethyl- ⁇ -cyclodextrin, hydroxymethyl- ⁇ -cyclodextrin, hydroxymethyl- ⁇ -cyclodextrin, 2-hydroxyethyl- ⁇ -cyclodextrin, 2-hydroxyethyl- ⁇ -Cyclodextrin, 2-hydroxyethyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -
  • melamine formaldehyde resin which is a preferable example of (C) component, resin obtained by polycondensing melamine and formaldehyde is mentioned.
  • the melamine formaldehyde resin of component (C) is preferably an alkylated methylol group formed during the polycondensation of melamine and formaldehyde.
  • a melamine formaldehyde resin of (C) component resin which has a unit structure represented, for example by a following formula is mentioned.
  • R 21 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • n is a natural number representing the number of repeating units.
  • the method for obtaining the melamine formaldehyde resin of the component (C) is not particularly limited, but generally, melamine and formaldehyde are mixed, and after being weakly alkaline using sodium carbonate, ammonia and the like, heating is carried out at 60 ° C to 100 ° C.
  • the methylol group can be alkoxylated by reacting with an alcohol.
  • the weight average molecular weight of the melamine formaldehyde resin of the component (C) is preferably 250 to 5,000, more preferably 300 to 4,000, and still more preferably 350 to 3,500. If the weight average molecular weight is more than 5000, the solubility in the solvent may be reduced and the handling properties may be reduced. If the weight average molecular weight is less than 250 and the amount is too small, the curing is insufficient at the time of heat curing As a result, the effect of improving the solvent resistance may not be sufficiently exhibited.
  • the melamine formaldehyde resin of the component (C) may be used in the form of a liquid, or in the form of a solution in which the purified liquid is redissolved in a solvent described later.
  • a phenol novolak resin which is a preferable example of the component (C)
  • a phenol-formaldehyde polycondensate and the like can be mentioned.
  • the polymer of the component (C) may be used in the form of a powder or in the form of a solution in which the purified powder is redissolved in a solvent described later.
  • the component (C) may be a mixture of two or more of the polymers exemplified as the component (C).
  • the content of component (C) in the cured film-forming composition of the present invention is preferably 100 parts by mass of the total amount of the polymer as component (A) and the crosslinking agent as component (B).
  • the content is 400 parts by mass or less, more preferably 10 parts by mass to 380 parts by mass, and still more preferably 40 parts by mass to 360 parts by mass.
  • the content of the component (C) is excessive, the liquid crystal alignment tends to be deteriorated.
  • the cured film formation composition of this invention can contain the bridge
  • a crosslinking catalyst which is (D) component an acid or a thermal acid generator can be used conveniently, for example.
  • This (D) component is effective in promoting the thermosetting reaction of the cured film-forming composition of the present invention.
  • Specific examples of the component (D) include, as the acid, a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof.
  • the thermal acid generator is not particularly limited as long as it is a compound which is thermally decomposed during heat treatment to generate an acid, that is, a compound which is thermally decomposed at a temperature of 80 ° C. to 250 ° C. to generate an acid. .
  • the above-mentioned acid include, for example, hydrochloric acid or a salt thereof; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphor Sulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, Sulfonic acid group-containing compounds such as 1H, 2H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid
  • a compound capable of generating an acid by heat for example, bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, -Phenylene tris (methyl sulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morpholinium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p- Toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyan
  • the content of the component (D) in the cured film-forming composition of the present invention is preferably 0.01 parts by mass with respect to 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent of the component (B).
  • the amount is from 20 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 15 parts by mass, and still more preferably 0.5 parts by mass to 10 parts by mass.
  • component (E) at least one group A selected from the group consisting of one or more polymerizable groups and a hydroxy group, a carboxyl group, an amido group, an amino group, and an alkoxysilyl group or the group A It can also contain compounds having at least one group to react. This acts as a component that improves the adhesion of the formed cured film (hereinafter, also referred to as an adhesion improving component).
  • the adhesion of the alignment material to the layer of the polymerizable liquid crystal is improved,
  • the crosslinkable reaction site of the polymerizable functional group and the orienting material can be linked by covalent bond.
  • the phase difference material of the present embodiment formed by laminating the cured polymerizable liquid crystal on the alignment material of the present embodiment can maintain strong adhesion even under high temperature and high quality conditions, peeling etc. It can show high resistance to
  • component (E) monomers and polymers having a group selected from a hydroxy group and an N-alkoxymethyl group and a polymerizable group are preferable.
  • a compound having a hydroxy group and a (meth) acrylic group a compound having an N-alkoxymethyl group and a (meth) acrylic group, an N-alkoxymethyl group and a (meth) acrylic group And the like. Specific examples are shown below.
  • the polyfunctional acrylate (Hereafter, it is also called a hydroxy group containing polyfunctional acrylate.) Containing a hydroxy group can be mentioned.
  • the hydroxy group-containing polyfunctional acrylate which is an example of the component (E) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
  • the compound which has one acryl group and one or more hydroxy groups is also mentioned as an example of (E) component.
  • Preferred examples of such compounds having one acrylic group and one or more hydroxy groups are listed.
  • the compound of (E) component is not limited to the following compound example.
  • R 11 represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10).
  • the N of an N-alkoxymethyl group that is, the nitrogen atom of an amide, a nitrogen atom of a thioamide, a nitrogen atom of a urea, a nitrogen atom of a thiourea, a nitrogen atom of a urethane, a nitrogen atom of a urethane, a nitrogen atom of a nitrogen-containing heterocyclic ring And a nitrogen atom etc.
  • a nitrogen atom of an amide, a nitrogen atom of a thioamide, a nitrogen atom of a urea, a nitrogen atom of a thiourea, a nitrogen atom of a urethane, a nitrogen atom of a urethane, a nitrogen bonded adjacent to a nitrogen atom of a nitrogen-containing heterocyclic ring A structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from atoms and the like can be mentioned.
  • any one having the above-mentioned group may be used, and preferably, for example, a compound represented by the following formula (X1) can be mentioned.
  • R 31 represents a hydrogen atom or a methyl group
  • R 32 represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 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 group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl- n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-
  • the compound represented by the above formula (X1) include N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth)
  • An acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as acrylamide may be mentioned.
  • (meth) acrylamide means both methacrylamide and acrylamide.
  • a compound represented by the following formula (X2) is preferably exemplified.
  • R 51 represents a hydrogen atom or a methyl group.
  • R 52 represents an alkyl group having 2 to 20 carbon atoms, a monovalent aliphatic ring group having 5 to 6 carbon atoms, or a monovalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms,
  • the structure may contain an ether bond.
  • R 53 represents a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent aliphatic ring group having 5 to 6 carbon atoms, or a divalent containing an aliphatic ring having 5 to 6 carbon atoms And an ether bond may be included in the structure.
  • R 54 is a linear or branched divalent to pentavalent aliphatic group having 1 to 20 carbon atoms, a divalent to ninth divalent aliphatic ring group having 5 to 6 carbon atoms, or 5 carbon atoms And a divalent to nine-valent aliphatic group containing one to six aliphatic rings, wherein one methylene group or a plurality of non-adjacent methylene groups of these groups may be replaced by an ether bond.
  • Z is> NCOO- or -OCON ⁇ (where, "-" indicates that there is one bond, and ">" or " ⁇ " indicates that there are two bonds, and Indicates that an alkoxymethyl group (ie, -OR52 group) is bonded to any one bond.
  • r is a natural number of 2 or more and 9 or less.
  • alkylene group having 2 to 20 carbon atoms in the definition of R 53 include divalent groups in which one hydrogen atom is further removed from the alkyl group having 2 to 20 carbon atoms. Further, as a specific example of the divalent to decavalent aliphatic group having 1 to 20 carbon atoms in the definition of R 54 , 1 to 8 hydrogen atoms are further removed from the alkyl group having 1 to 20 carbon atoms Divalent to 9-valent groups may be mentioned.
  • the alkyl group having 1 carbon atom is a methyl group, and specific examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group.
  • an alkylene group having 2 to 10 carbon atoms is preferable, and it is particularly preferable that R 53 is an ethylene group and R 54 is a hexylene group from the viewpoint of availability of raw materials.
  • alkyl group having 1 to 20 carbon atoms in the definition of R 52 include the specific examples of the alkyl group having 2 to 20 carbon atoms in the definition of R 53 and a methyl group.
  • an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group or an n-butyl group is particularly preferable.
  • a natural number of 2 or more and 9 or less can be mentioned, and among them, 2 to 6 is preferable.
  • the content of the component (E) in the cured film-forming composition of the embodiment of the present invention is preferably 1 part by mass with respect to 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent of the component (B).
  • the amount is 100 parts by mass, and more preferably 5 parts by mass to 70 parts by mass.
  • the cured film-forming composition of the present invention is used mainly in the form of a solution dissolved in a solvent.
  • the solvent used at that time should just be able to dissolve the (A) component, the (B) component and, if necessary, the (C) component, the (D) component, the (E) component and / or other additives described later,
  • the type, structure, etc. are not particularly limited.
  • the solvent include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 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, ethylene
  • the cured film-forming composition of the present invention contains the polymer of component (A) and the crosslinking agent of component (B), and optionally the polymer of component (C), the crosslinking catalyst of component (D) and the component (E) adhesion It is a composition which can contain an accelerator and further other additives as long as the effect of the present invention is not impaired. And, usually, they are used in the form of a solution dissolved in a solvent.
  • the preferable example of the cured film formation composition of this invention is as follows. [1] A cured film-forming composition containing 1 part by mass to 500 parts by mass of the (B) component based on 100 parts by mass of the (A) component and the (A) component.
  • a cured film-forming composition comprising 1 to 400 parts by mass of the component (C) with respect to 100 parts by mass of the total amount of [3]
  • a cured film-forming composition containing 1 part by mass to 500 parts by mass of the component (B) and a solvent based on 100 parts by mass of the component (A) and the component (A).
  • the compounding ratio in the case of using the cured film formation composition of this invention as a solution, a preparation method, etc. are explained in full detail below.
  • the ratio of solid content in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1% by mass to 60% by mass, and preferably 2
  • the content is 50% by mass, more preferably 2% by mass to 20% by mass.
  • solid content means what remove
  • the method for preparing the cured film-forming composition of the present invention is not particularly limited.
  • a preparation method for example, the solution of the component (A) dissolved in a solvent, the component (B), and further, the components (C), (D), (E) and the like are mixed at a predetermined ratio and homogeneous.
  • the method of making it into a solution, or the method of adding and mixing other additives as needed at the appropriate stage of this preparation method may be mentioned.
  • the solution of the specific copolymer (polymer) obtained by the polymerization reaction in a solvent can be used as it is.
  • component (B), component (C), component (D), component (E) and the like are added to the solution of component (A) in the same manner as described above to obtain a uniform solution.
  • a solvent may be additionally added for the purpose of adjusting the concentration.
  • the solvent used in the process of producing the component (A) and the solvent used for adjusting the concentration of the cured film-forming composition may be the same or different.
  • the solution of the cured film forming composition of the present invention is used as a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum or chromium, a glass substrate, a quartz substrate, ITO Substrates, etc.) and film substrates (eg, triacetyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET) film, acrylic film, polyethylene film Coating film is formed on a resin film such as a film by bar coating, spin coating, flow coating, roll coating, slit coating, slit coating followed by spin coating, inkjet coating, printing, etc. Relieved Dried by heating with a plate or an oven or the like, it is possible to form a resin film such as a film by bar coating, spin
  • the conditions for the heating and drying may be such that the crosslinking reaction by the crosslinking agent proceeds to such an extent that the components of the cured film (alignment material) do not elute in the polymerizable liquid crystal solution applied thereon.
  • a heating temperature and a heating time appropriately selected from the range of 200 ° C. and 0.4 minutes to 60 minutes are employed.
  • the heating temperature and the heating time are preferably 70 ° C. to 160 ° C., for 0.5 minutes to 10 minutes.
  • the film thickness of the cured film (alignment material) formed using the curable composition of the present invention is, for example, 0.05 ⁇ m to 5 ⁇ m, and is appropriately determined in consideration of the difference in level of the substrate used and the optical and electrical properties. It can be selected.
  • the alignment material formed from the cured film composition of the present invention has solvent resistance and heat resistance, a retardation material such as a polymerizable liquid crystal solution having vertical alignment property is coated on the alignment material. And alignment on the alignment material. Then, by curing the retardation material in the oriented state as it is, the retardation material can be formed as a layer having optical anisotropy. And when the board
  • the cured film formation composition of this invention can be used suitably for manufacture of various retardation material (retardation film), a liquid crystal display element, etc.
  • the molecular weight of the acrylic copolymer in the polymerization example is as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Corp. and a column (KD-803, KD-805) manufactured by Shodex Corp. And measured.
  • the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.
  • Standard sample for calibration curve preparation Standard polystyrene manufactured by Showa Denko (molecular weight about 197,000, 55, 100, 12, 800, 3, 950, 1, 260, 580).
  • Synthesis Example 1 5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 12.0 g of CIN 1, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor It was dissolved in 0. 0g and reacted at 100 ° C for 20 hours. This solution was gradually dropped into 1000 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-1). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
  • PA-1 polymer
  • Synthesis Example 2 5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 11.0 g of CIN2, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor It was dissolved in 0. 0g and reacted at 100 ° C for 20 hours. This solution was gradually dropped into 1000 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-2). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
  • Synthesis Example 3 5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 12.0 g of CIN 3, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor It was dissolved in 0. 0g and reacted at 100 ° C for 20 hours. This solution was gradually dropped into 1000 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-3). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
  • Synthesis Example 5 5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 10.0 g of CIN 1, 2.0 g of CIN 4, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, dibutyl hydroxytoluene as a polymerization inhibitor 0.2 g of PM was dissolved in 70.0 g of PM and reacted at 100 ° C. for 20 hours. This solution was gradually dropped into 1000 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-5). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
  • Synthesis Example 6 5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 6.5 g of CIN 4, and 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst are dissolved in 48.0 g of PM, and the reaction is carried out at 100 ° C. for 20 hours It was made to react. This solution was gradually dropped into 500 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-6). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
  • Example, Comparative Example> Each cured film formation composition of the Example and the comparative example was prepared with the composition shown in Table 1. Next, a cured film was formed using each retardation material formation composition, and evaluation of orientation and adhesiveness was performed about each obtained cured film.
  • the coating film was exposed at 300 mJ / cm 2 to prepare a retardation material.
  • the phase difference material on the manufactured substrate is sandwiched between a pair of polarizing plates, and the expression state of the phase difference characteristic of the phase difference material is observed, and the phase difference is expressed without defects ⁇ , the phase difference is not expressed
  • the thing was described in the column of "orientation" as x.
  • the evaluation results are summarized in Table 2 later.
  • the coating film was exposed at 300 mJ / cm 2 to prepare a retardation material.
  • This retardation material was incised with a cutter knife so as to be 10 ⁇ 10 squares at intervals of 1 mm in length and width.
  • a cellophane tape peel test was conducted using scotch tape on the incisions. The evaluation results were “adhesion”, and 100 squares were left without peeling, and those with even 1 square were marked ⁇ . The evaluation results are summarized in Table 2 later.
  • the alignment material obtained using the cured film-forming composition of the example exhibited good alignment and adhesion.
  • the alignment material obtained by using the cured film forming composition of the comparative example showed a good alignment, but no adhesion was obtained.
  • the cured film-forming composition according to the present invention is very useful as a material for forming an alignment material for forming a liquid crystal alignment film of a liquid crystal display element or an optically anisotropic film provided inside or outside of a liquid crystal display element.
  • it is suitable as a material for a retardation material of a circularly polarizing plate used as an antireflective film for IPS-LCDs and organic EL displays.

Abstract

[Problem] To provide a cured film forming composition for providing an orienting material that exhibits good liquid crystal orientability and superior adhesion to a liquid crystal layer. [Solution] A cured film forming composition containing (A) a reaction product of a polymer comprising an epoxy group and a cinnamic acid derivative comprising a group having a polymerizable double bond and (B) a crosslinker; and a cured film, orienting material, and phase-contrast material which are obtained from the same.

Description

硬化膜形成組成物、配向材および位相差材Cured film forming composition, alignment material and retardation material
　本発明は液晶分子を配向させる硬化膜形成組成物、配向材および位相差材に関する。特に本発明は、円偏光メガネ方式の３Ｄディスプレイに用いられるパターニングされた位相差材や、有機ＥＬディスプレイの反射防止膜として使用される円偏光板に用いられる位相差材を作製するのに有用な硬化膜形成組成物、配向材および位相差材に関する。 The present invention relates to a cured film-forming composition for aligning liquid crystal molecules, an alignment material, and a retardation material. In particular, the present invention is useful for producing a patterned retardation material used in a 3D display of a circularly polarized glasses system, and a retardation material used in a circularly polarizing plate used as an antireflection film of an organic EL display. The present invention relates to a cured film-forming composition, an alignment material, and a retardation material.
　円偏光メガネ方式の３Ｄディスプレイの場合、液晶パネル等の画像を形成する表示素子の上に位相差材が配置されるのが通常である。この位相差材は、位相差特性の異なる２種類の位相差領域がそれぞれ複数、規則的に配置されており、パターニングされた位相差材を構成している。尚、以下、本明細書においては、このような位相差特性の異なる複数の位相差領域を配置するようにパターン化された位相差材をパターン化位相差材と称する。 In the case of a circularly polarizing glasses 3D display, a retardation material is usually disposed on a display element such as a liquid crystal panel that forms an image. In this retardation material, a plurality of two types of retardation regions having different retardation characteristics are regularly arranged, and constitute a patterned retardation material. Hereinafter, in the present specification, a retardation material patterned so as to dispose a plurality of retardation regions having different retardation characteristics as described above will be referred to as a patterned retardation material.
　パターン化位相差材は、例えば、特許文献１に開示されるように、重合性液晶からなる位相差材料を光学パターニングすることで作製することができる。重合性液晶からなる位相差材料の光学パターニングは、液晶パネルの配向材形成で知られている光配向技術を利用する。すなわち、基板上に光配向性の材料からなる塗膜を設け、これに偏光方向が異なる２種類の偏光を照射する。そして、液晶の配向制御方向の異なる２種類の液晶配向領域が形成された配向材として光配向膜を得る。この光配向膜の上に重合性液晶を含む溶液状の位相差材料を塗布し、重合性液晶の配向を実現する。その後、配向された重合性液晶を硬化してパターン化位相差材を形成する。 The patterned retardation material can be produced, for example, by optically patterning a retardation material composed of a polymerizable liquid crystal as disclosed in Patent Document 1. The optical patterning of the retardation material made of a polymerizable liquid crystal utilizes a photoalignment technique known for forming an alignment material of a liquid crystal panel. That is, a coating film made of a photoalignable material is provided on a substrate, and two types of polarized light having different polarization directions are irradiated to this. Then, a photo alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different alignment control directions of liquid crystals are formed. A solution-like retardation material containing a polymerizable liquid crystal is coated on the photoalignment film to realize the alignment of the polymerizable liquid crystal. Thereafter, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.
　有機ＥＬディスプレイの反射防止膜は、直線偏光板、１／４波長位相差板により構成され、画像表示パネルのパネル面に向かう外来光を直線偏光板により直線偏光に変換し、続く１／４波長位相差板により円偏光に変換する。ここでこの円偏光による外来光は、画像表示パネルの表面等で反射するものの、この反射の際に偏光面の回転方向が逆転する。その結果、この反射光は、到来時とは逆に、１／４波長位相差板より、直線偏光板により遮光される方向の直線偏光に変換された後、続く直線偏光板により遮光され、その結果、外部への出射が著しく抑制される。 The anti-reflection film of the organic EL display is composed of a linear polarizer and a quarter-wave retarder, and the extraneous light directed to the panel surface of the image display panel is converted into linearly polarized light by the linear polarizer, and the subsequent quarter-wave The light is converted to circularly polarized light by a retardation plate. Here, although the extraneous light by this circularly polarized light is reflected by the surface of the image display panel or the like, the rotational direction of the polarization plane is reversed at the time of this reflection. As a result, the reflected light is converted by the 1⁄4 wavelength retardation plate into linearly polarized light in the direction to be blocked by the linear polarization plate and then blocked by the subsequent linear polarization plate, contrary to the time of arrival. As a result, outgoing radiation to the outside is significantly suppressed.
　この１／４波長位相差板に関して、特許文献２には、１／２波長板、１／４波長板を組み合わせて１／４波長位相差板を構成することにより、この光学フィルムを逆分散特性により構成する方法が提案されている。この方法の場合、カラー画像の表示に供する広い波長帯域において、正の分散特性による液晶材料を使用して逆分散特性により光学フィルムを構成することができる。 With regard to this quarter-wave retarder, Patent Document 2 describes that this optical film has reverse dispersion characteristics by constituting a quarter-wave retarder by combining a half-wave plate and a quarter-wave plate. A method of configuring by In this method, it is possible to construct an optical film with reverse dispersion characteristics using a liquid crystal material with positive dispersion characteristics in a wide wavelength band for displaying a color image.
　また近年、この位相差層に適用可能な液晶材料として、逆分散特性を備えるものが提案されている（特許文献３、４）。このような逆分散特性の液晶材料によれば、１／２波長板、１／４波長板を組み合わせて２層の位相差層により１／４波長位相差板を構成する代わりに、位相差層を単層により構成して逆分散特性を確保することができ、これにより広い波長帯域において所望の位相差を確保することが可能な光学フィルムを簡易な構成により実現することができる。 Further, in recent years, as a liquid crystal material applicable to this retardation layer, one having an inverse dispersion characteristic has been proposed (Patent Documents 3 and 4). According to the liquid crystal material having such an inverse dispersion characteristic, instead of forming a 1⁄4 wavelength retardation plate by combining 2 layers of a 1⁄2 wavelength plate and a 1⁄4 wavelength plate, it is possible to use a retardation layer Can be secured by a single layer to ensure reverse dispersion characteristics, whereby an optical film capable of securing a desired retardation in a wide wavelength band can be realized with a simple configuration.
　液晶を配向させるためには配向層が用いられる。配向層の形成方法としては、例えばラビング法や光配向法が知られており、光配向法はラビング法の問題点である静電気や塵の発生がなく、定量的な配向処理の制御ができる点で有用である。 An alignment layer is used to align the liquid crystal. As a method of forming an alignment layer, for example, a rubbing method or a photo-alignment method is known, and the photo-alignment method is capable of quantitative control of alignment processing without generating static electricity and dust which are problems of the rubbing method. Useful for
　光配向法を用いた配向材形成では、利用可能な光配向性の材料として、側鎖にシンナモイル基およびカルコン基等の光二量化部位を有するアクリル樹脂やポリイミド樹脂等が知られている。これらの樹脂は、偏光ＵＶ照射することにより、液晶の配向を制御する性能（以下、液晶配向性とも言う。）を示すことが報告されている（特許文献５～特許文献７を参照。）。 In the alignment material formation using the photoalignment method, an acrylic resin, a polyimide resin, etc. which have photodimerization sites, such as a cinnamoyl group and a chalcone group, in a side chain as an available photoalignment property material are known. It has been reported that these resins exhibit the ability to control the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment) by irradiating polarized UV light (see Patent Documents 5 to 7).
　また、配向層には、液晶配向能の他、液晶層との密着性が要求される。例えば、配向層とこの上に形成された液晶層との密着力が不十分な場合、位相差フィルムの製造に含まれる巻き取り工程等において、上記液晶層が剥離してしまうことがある。 In addition to the liquid crystal alignment ability, the alignment layer is required to have adhesion to the liquid crystal layer. For example, when the adhesion between the alignment layer and the liquid crystal layer formed thereon is insufficient, the liquid crystal layer may be peeled off in the winding step or the like included in the production of the retardation film.
特開２００５－４９８６５号公報JP 2005-49865 A 特開平１０－６８８１６号公報Japanese Patent Application Laid-Open No. 10-68816 米国特許第８１１９０２６号明細書U.S. Pat. No. 8,119,026 特開２００９－１７９５６３号公報JP, 2009-179563, A 特許第３６１１３４２号公報Patent No. 3611342 特開２００９－０５８５８４号公報JP, 2009-058584, A 特表２００１－５１７７１９号公報Japanese Patent Publication No. 2001-517719
　本発明の目的は、以上の知見や検討結果に基づいてなされたものである。すなわち、本発明の目的は、良好な液晶配向性を示し、かつ液晶層との密着性に優れる配向材を提供するための硬化膜形成組成物を提供することである。　 The object of the present invention is made based on the above findings and examination results. That is, an object of the present invention is to provide a cured film-forming composition for providing an alignment material which exhibits good liquid crystal alignment and is excellent in adhesion to a liquid crystal layer.
　本発明の他の目的および利点は、以下の記載から明らかとなるであろう。 Other objects and advantages of the present invention will become apparent from the following description.
　本発明者らは上記目的を達成するため、鋭意検討を重ねた結果、（Ａ）エポキシ基を有するポリマーと重合性二重結合を含む基を有する桂皮酸誘導体との反応生成物、（Ｂ）架橋剤をベースとする硬化膜形成組成物を選択することにより、良好な液晶配向性を示し、かつ液晶層との密着性に優れる硬化膜を形成できることを見出し、本発明を完成させた。 The present inventors conducted intensive studies to achieve the above object, and as a result, (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond, (B) By selecting a cured film-forming composition based on a crosslinking agent, it has been found that a cured film can be formed which exhibits good liquid crystal alignment and is excellent in adhesion to a liquid crystal layer, thereby completing the present invention.
　すなわち、本発明は第１観点として、（Ａ）エポキシ基を有するポリマーと重合性二重結合を含む基を有する桂皮酸誘導体との反応生成物及び（Ｂ）架橋剤を含有する硬化膜形成組成物に関する。 That is, as a first aspect of the present invention, a cured film-forming composition comprising (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group having a polymerizable double bond and (B) a crosslinking agent. Related to things.
　第２観点として、上記重合性二重結合を含む基が、（メタ）アクリロイル基である第１観点に記載の硬化膜形成組成物に関する。 It is related with the cured film formation composition as described in a 1st viewpoint whose group containing the said polymerizable double bond is a (meth) acryloyl group as a 2nd viewpoint.
　第３観点として、上記重合性二重結合を含む基を有する桂皮酸誘導体が、下記式（１）で表される化合物である第１観点または第２観点に記載の硬化膜形成組成物に関する。
Figure JPOXMLDOC01-appb-C000003
 　式（１）中、Ａ１とＡ２はそれぞれ独立に、水素原子またはメチル基を表し、
　Ｒ１は下記式（ｃ－２）
Figure JPOXMLDOC01-appb-C000004
 （式（ｃ－２）中、破線は結合手を表し、Ｒ１０１は炭素数１～３０のアルキレン基を表し、このアルキレン基の１つ若しくは複数の水素原子は、フッ素原子又は有機基で置き換えられていてもよい。また、Ｒ１０１中の－ＣＨ２ＣＨ２－は－ＣＨ＝ＣＨ－に置き換えられていてもよく、さらに、次に挙げるいずれかの基が互いに隣り合わない場合において、－Ｏ－、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－ＮＨＣＯＮＨ－及び－ＣＯ－からなる群から選ばれる基に置き換えられていてもよく、Ｍ１は水素原子又はメチル基を表す。）で表される基を表し、
　Ｒ２は２価の芳香族基、２価の脂環族基、２価の複素環式基または２価の縮合環式基を表し、
　Ｒ３は単結合、酸素原子、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ＝ＣＨＣＯＯ－または－ＯＣＯＣＨ＝ＣＨ－を表し、
　Ｒ４～Ｒ７はそれぞれ独立に水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のハロアルキル基、炭素数１～６のアルコキシ基、炭素数１～６のハロアルコキシ基、シアノ基、及びニトロ基からなる群から選ばれる置換基を表し、
　また、Ｒ２、Ｒ３及びＲ４又はＲ２、Ｒ３及びＲ６は一緒になって芳香族基を形成してもよく、
　ｎは０～３の整数である。） The present invention relates to, as a third aspect, the cured film-forming composition according to the first aspect or the second aspect, wherein the cinnamic acid derivative having a group containing the polymerizable double bond is a compound represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000003
 In formula (1), each of A 1 and A 2 independently represents a hydrogen atom or a methyl group,
R 1 is the following formula (c-2)
Figure JPOXMLDOC01-appb-C000004
 (In the formula (c-2), the broken line represents a bond, R 101 represents an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of this alkylene group are replaced by a fluorine atom or an organic group In addition, -CH 2 CH 2-in R 101 may be replaced by -CH = CH-, and further, in the case where any of the following groups are not adjacent to each other,- M 1 is a hydrogen atom which may be substituted by a group selected from the group consisting of O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO- Or a methyl group is represented by
R 2 represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused cyclic group,
R 3 represents a single bond, an oxygen atom, -COO-, -OCO-, -CH = CHCOO- or -OCOCH = CH-,
R 4 to R 7 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy having 1 to 6 carbon atoms Represents a substituent selected from the group consisting of a group, a cyano group, and a nitro group,
Also, R 2 , R 3 and R 4 or R 2 , R 3 and R 6 may together form an aromatic group,
n is an integer of 0 to 3. )
　第４観点として、（Ｂ）成分の架橋剤がメチロール基またはアルコキシメチル基を有する架橋剤である、第１観点乃至第３観点のうち何れか一に記載の硬化膜形成組成物に関する。
　第５観点として、（Ｃ）ヒドロキシ基、カルボキシル基、アミド基、アミノ基、およびアルコキシシリル基からなる群から選ばれる少なくとも１つの基を有するポリマーをさらに含有する第１観点乃至第４観点のうち何れか一項に記載の硬化膜形成組成物に関する。
　第６観点として、（Ｄ）架橋触媒をさらに含有する第１観点乃至第５観点のうち何れか一項に記載の硬化膜形成組成物に関する。
　第７観点として、（Ｅ）１つ以上の重合性基と、ヒドロキシ基、カルボキシル基、アミド基、アミノ基、およびアルコキシシリル基からなる群から選ばれる少なくとも１つの基Ａ又は該基Ａと反応する少なくとも１つの基とを有する化合物を含有する第１観点乃至第６観点のうち何れか一項に記載の硬化膜形成組成物に関する。
　第８観点として、（Ａ）成分１００質量部に基づいて、１質量部～５００質量部の（Ｂ）成分を含有する第１観点乃至第７観点のうち何れか一項に記載の硬化膜形成組成物に関する。
　第９観点として、（Ａ）成分及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して１質量部～４００質量部の（Ｃ）成分を含有する第５観点乃至第８観点のいずれか一項に記載の硬化膜形成組成物に関する。
　第１０観点として、（Ａ）成分及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して０．０１質量部～２０質量部の（Ｄ）成分を含有する第６観点乃至第９観点のいずれか一項に記載の硬化膜形成組成物に関する。
　第１１観点として、（Ａ）成分及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して１質量部～１００質量部の（Ｅ）成分を含有する第７観点乃至第１０観点のいずれか一項に記載の硬化膜形成組成物に関する。 As a fourth aspect, the present invention relates to the cured film-forming composition as described in any one of the first aspect to the third aspect, wherein the crosslinking agent of the component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group.
As a fifth aspect, among the first to fourth aspects, which further contain a polymer having at least one group selected from the group consisting of (C) hydroxy group, carboxyl group, amido group, amino group, and alkoxysilyl group The present invention relates to a cured film-forming composition according to any one of the above.
As a sixth aspect, the present invention relates to the cured film forming composition according to any one of the first aspect to the fifth aspect, which further contains (D) a crosslinking catalyst.
As a seventh aspect, (E) at least one group A selected from the group consisting of one or more polymerizable groups and a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group or a reaction with the group A The cured film-forming composition according to any one of the first to sixth aspects, which contains a compound having at least one group.
The cured film formation as described in any one of 1st viewpoint thru | or 7th viewpoint which contains 1 mass part-500 mass parts (B) component based on 100 mass parts of (A) ingredient as an 8th viewpoint. It relates to a composition.
As a ninth aspect, the fifth to eighth aspects of the fifth to eighth aspects containing 1 part by mass to 400 parts by mass of the component (C) with respect to 100 parts by mass of the total amount of the crosslinking agents of the components (A) and (B) The present invention relates to a cured film-forming composition according to any one of the above.
As a tenth aspect, the sixth aspect to the ninth aspect which contain 0.01 parts by mass to 20 parts by mass of the component (D) with respect to 100 parts by mass of the total amount of the crosslinking agents of the components (A) and (B) It is related with the cured film formation composition as described in any one of a viewpoint.
As an eleventh aspect, the seventh to tenth aspects of the present invention are the seventh to tenth aspects containing 1 part by mass to 100 parts by mass of the component (E) with respect to 100 parts by mass of the total amount of the crosslinking agents The present invention relates to a cured film-forming composition according to any one of the above.
　第１２観点として、第１観点乃至第１１観点のうち何れか一項に記載の硬化膜形成組成物から得られることを特徴とする硬化膜に関する。 According to a twelfth aspect, the present invention relates to a cured film obtained from the cured film-forming composition according to any one of the first to eleventh aspects.
　第１３観点として、第１観点乃至第１１観点のうち何れか一項に記載の硬化膜形成組成物から得られることを特徴とする配向材に関する。 The present invention relates to, as a thirteenth aspect, an alignment material obtained from the cured film-forming composition according to any one of the first to eleventh aspects.
　第１４観点として、第１観点乃至第１１観点のうち何れか一項に記載の硬化膜形成組成物から得られる硬化膜を使用して形成されることを特徴とする位相差材に関する。 The present invention relates to, as a fourteenth aspect, a retardation material which is formed using a cured film obtained from the cured film forming composition according to any one of the first to eleventh aspects.
　本発明によれば、良好な液晶配向性を示し、かつ液晶層との密着性に優れる硬化膜と、その形成に好適な硬化膜形成組成物を提供することができる。本発明によれば、液晶配向性と光透過性に優れた配向材を提供することができる。また、本発明によれば、高精度な光学パターニングが可能な位相差材を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the cured film which shows favorable liquid crystal orientation, and is excellent in adhesiveness with a liquid crystal layer, and a cured film formation composition suitable for the formation can be provided. According to the present invention, it is possible to provide an alignment material excellent in liquid crystal alignment and light transmission. Further, according to the present invention, it is possible to provide a retardation material capable of highly accurate optical patterning.
＜硬化膜形成組成物＞
　本発明の硬化膜形成組成物は、（Ａ）エポキシ基を有するポリマーと重合性二重結合を含む基を有する桂皮酸誘導体との反応生成物、及び（Ｂ）架橋剤を含有する。本発明の硬化膜形成組成物は、上記（Ａ）成分及び（Ｂ）成分に加えて、さらに、（Ｃ）成分としてヒドロキシ基、カルボキシル基、アミド基、アミノ基、およびアルコキシシリル基からなる群から選ばれる少なくとも１つの基を有するポリマーを含有することもできる。さらに、（Ｄ）成分として架橋触媒をも含有することができる。さらに（Ｅ）成分として１つ以上の重合性基と、ヒドロキシ基、カルボキシル基、アミド基、アミノ基、およびアルコキシシリル基からなる群から選ばれる少なくとも１つの基Ａ又は該基Ａと反応する少なくとも１つの基とを有する化合物を含有することができる。そして、本発明の効果を損なわない限りにおいて、その他の添加剤を含有することができる。
　以下、各成分の詳細を説明する。    <Curing film forming composition>
The cured film-forming composition of the present invention contains (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond, and (B) a crosslinking agent. The cured film-forming composition of the present invention further comprises a group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group as the component (C) in addition to the components (A) and (B). It can also contain a polymer having at least one group selected from Furthermore, a crosslinking catalyst can also be contained as (D) component. Furthermore, as component (E), at least one group A selected from the group consisting of one or more polymerizable groups and a hydroxy group, a carboxyl group, an amido group, an amino group, and an alkoxysilyl group It can contain a compound having one group. And, as long as the effects of the present invention are not impaired, other additives can be contained.
The details of each component will be described below.
＜（Ａ）成分＞
　本発明の硬化膜形成組成物に含有される（Ａ）成分は、エポキシ基を有するポリマーと重合性二重結合を含む基を有する桂皮酸誘導体との反応生成物である。 <(A) component>
The component (A) contained in the cured film-forming composition of the present invention is a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond.
＜エポキシ基を有するポリマー＞
　エポキシ基を有するポリマーは、例えばエポキシ基を有する重合性不飽和化合物の重合体またはエポキシ基を有する重合性不飽和化合物とその他の重合性不飽和化合物との共重合体であることができる。 <Polymer having an epoxy group>
The polymer having an epoxy group can be, for example, a polymer of a polymerizable unsaturated compound having an epoxy group or a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound.
　エポキシ基を有する重合性不飽和化合物の具体例としては、例えばアクリル酸グリシジル、メタクリル酸グリシジル、α－エチルアクリル酸グリシジル、α－ｎ－プロピルアクリル酸グリシジル、α－ｎ－ブチルアクリル酸グリシジル、アクリル酸－３，４－エポキシブチル、メタクリル酸－３，４－エポキシブチル、アクリル酸－６，７－エポキシヘプチル、メタクリル酸－６，７－エポキシヘプチル、α－エチルアクリル酸－６，７－エポキシヘプチル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル等を挙げることができる。 Specific examples of the polymerizable unsaturated compound having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic Acids-3,4-Epoxybutyl, Methacrylic Acid-3,4-Epoxybutyl, Acrylic Acid-6,7-Epoxyheptyl, Methacrylic Acid-6,7-Epoxyheptyl, α-Ethyl Acrylic Acid-6,7-Epoxy Examples include heptyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like.
　その他の重合性不飽和化合物としては、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸環状アルキルエステル、メタクリル酸アリールエステル、アクリル酸アリールエステル、不飽和ジカルボン酸ジエステル、ビシクロ不飽和化合物類、マレイミド化合物類、不飽和芳香族化合物、共役ジエン系化合物、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和ジカルボン酸無水物、これら以外の重合性不飽和化合物を挙げることができる。 Other polymerizable unsaturated compounds include (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compounds, maleimide Compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other polymerizable unsaturated compounds can be mentioned.
　これらの具体例としては、メタクリル酸アルキルエステルとして、例えばヒドロキシメチルメタクリレート、２－ヒドロキシエチルメタクリレート、３－ヒドロキシプロピルメタクリレート、４－ヒドロキシブチルメタクリレート、ジエチレングリコールモノメタクリレート、２，３－ジヒドロキシプロピルメタクリレート、２－メタクリロキシエチルグリコサイド、４－ヒドロキシフェニルメタクリレート、メチルメタクリレート、エチルメタクリレート、ｎ－ブチルメタクリレート、ｓｅｃ－ブチルメタクリレート、２－エチルヘキシルメタクリレート、イソデシルメタクリレート、ｎ－ラウリルメタクリレート、トリデシルメタクリレート、ｎ－ステアリルメタクリレート等；アクリル酸アルキルエステルとして、例えばメチルアクリレート、イソプロピルアクリレート等；メタクリル酸環状アルキルエステルとして、例えばシクロヘキシルメタクリレート、２－メチルシクロヘキシルメタクリレート、トリシクロ［５．２．１．０２，６］デカン－８－イルメタクリレート、トリシクロ［５．２．１．０２，６］デカン－８－イルオキシエチルメタクリレート、イソボロニルメタクリレート、コレスタニルメタクリレート等；アクリル酸環状アルキルエステルとして、例えばシクロヘキシルアクリレート、２－メチルシクロヘキシルアクリレート、トリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート、トリシクロ［５．２．１．０２，６］デカン－８－イルオキシエチルアクリレート、イソボロニルアクリレート、コレスタニルアクリレート等；メタクリル酸アリールエステルとして、フェニルメタクリレート、ベンジルメタクリレート等；アクリル酸アリールエステルとして、例えばフェニルアクリレート、ベンジルアクリレート等；不飽和ジカルボン酸ジエステルとして、例えばマレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチル等；ビシクロ不飽和化合物類として、例えばビシクロ［２．２．１］ヘプト－２－エン、５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－メトキシビシクロ［２．２．１］ヘプト－２－エン、５－エトキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジメトキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジエトキシビシクロ［２．２．１］ヘプト－２－エン、５－（２’－ヒドロキシエチル）ビシクロ［２．２．１］ヘプト－２－エン、５，６－ジヒドロキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジ（ヒドロキシメチル）ビシクロ［２．２．１］ヘプト－２－エン、５，６－ジ（２’－ヒドロキシエチル）ビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシ－５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシ－５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシメチル－５－メチルビシクロ［２．２．１］ヘプト－２－エン等；マレイミド化合物類として、例えばフェニルマレイミド、シクロヘキシルマレイミド、ベンジルマレイミド、Ｎ－スクシンイミジル－３－マレイミドベンゾエート、Ｎ－スクシンイミジル－４－マレイミドブチレート、Ｎ－スクシンイミジル－６－マレイミドカプロエート、Ｎ－スクシンイミジル－３－マレイミドプロピオネート、Ｎ－（９－アクリジニル）マレイミド等；不飽和芳香族化合物として、例えばスチレン、α－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、ビニルトルエン、ｐ－メトキシスチレン等；共役ジエン系化合物として、１，３－ブタジエン、イソプレン、２，３－ジメチル－１，３－ブタジエン等；不飽和モノカルボン酸として、例えばアクリル酸、メタクリル酸、クロトン酸等；不飽和ジカルボン酸として、マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸等；不飽和ジカルボン酸無水物として、上記不飽和ジカルボン酸の各無水物；上記以外の重合性不飽和化合物として、例えばアクリロニトリル、メタクリロニトリル、塩化ビニル、塩化ビニリデン、アクリルアミド、メタクリルアミド、酢酸ビニル等をそれぞれ挙げることができる。 Specific examples of these include alkyl methacrylates such as hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, and the like. Methacryloxyethyl glycoside, 4-hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate Etc .; as acrylic acid alkyl esters, eg methyl acrylate Over DOO, isopropyl acrylate and the like; as methacrylic acid cyclic alkyl esters such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 2,6] decan-8-yl methacrylate, tricyclo [5.2. 1.0 2,6 ! Decane-8-yloxyethyl methacrylate, isoboronyl methacrylate, cholestanyl methacrylate etc .; as acrylic acid cyclic alkyl ester, for example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1 .0 2,6 ] decane-8-yl acrylate, tricyclo [5.2.1.0 2,6 ] decane-8-yloxyethyl acrylate, isoboronyl acrylate, cholestanyl acrylate, etc .; As aryl acrylates, phenyl methacrylate, benzyl methacrylate, etc .; aryl acrylates, such as phenyl acrylate, benzyl acrylate, etc .; Unsaturated dicarboxylic acid diesters, such as diethyl maleate, diethyl fumarate, diethyl itaconate, etc .; As saturated compounds, for example, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1 Hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, -(2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) Bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2 .2.1] Hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene and the like; maleimide compounds such as phenyl maleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimidyl 3-maleimidobenzoate, N-succinimidyl 4-maleimidobutyl Rates, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide etc .; unsaturated aromatic compounds such as styrene, α-methylstyrene, m -Methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene etc .; Conjugated diene compounds such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc .; unsaturated monocarboxylic acid As, for example, acrylic acid, methacrylic acid, crotonic acid etc .; As unsaturated dicarboxylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc .; As unsaturated dicarboxylic acid anhydride, each of the above unsaturated dicarboxylic acids Anhydrides; as polymerizable unsaturated compounds other than the above, for example, acryl Tolyl, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, etc. may be mentioned, respectively.
　エポキシ基を有する重合体におけるエポキシ基を有する重合性不飽和化合物の共重合割合は、好ましくは３０質量％以上であり、より好ましくは５０質量％以上である。 The copolymerization ratio of the polymerizable unsaturated compound having an epoxy group in the polymer having an epoxy group is preferably 30% by mass or more, and more preferably 50% by mass or more.
　エポキシ基を有する重合体の合成は、好ましくは溶媒中、適当な重合開始剤の存在下における公知のラジカル重合法により行うことができる。 The synthesis of the polymer having an epoxy group can be carried out by a known radical polymerization method, preferably in the presence of a suitable polymerization initiator in a solvent.
　エポキシ基を有する重合体としては、市販品を使用してもよい。かかる市販品としては、例えばＥＨＰＥ３１５０、ＥＨＰＥ３１５０ＣＥ（以上、（株）ダイセル（旧　ダイセル化学工業（株））製）、ＵＧ－４０１０、ＵＧ－４０３５、ＵＧ－４０４０、ＵＧ－４０７０（以上、東亜合成（株）製ＡＬＵＦＯＮシリーズ）、ＥＣＮ－１２９９（旭化成（株）製）、ＤＥＮ４３１、ＤＥＮ４３８（以上、ダウケミカル社製）、ｊＥＲ－１５２（三菱ケミカル（株）（旧　ジャパンエポキシレジン（株））製）、エピクロンＮ－６６０、Ｎ－６６５、Ｎ－６７０、Ｎ－６７３、Ｎ－６９５、Ｎ－７４０、Ｎ－７７０、Ｎ－７７５（以上、ＤＩＣ（株）（旧　大日本インキ化学工業（株））製）、ＥＯＣＮ－１０２０、ＥＯＣＮ－１０２Ｓ、ＥＯＣＮ－１０４Ｓ（以上、日本化薬（株）製）などが挙げられる。 A commercial item may be used as a polymer which has an epoxy group. As such commercial products, for example, EHPE3150, EHPE3150CE (above, Daicel (formerly Daicel Chemical Industries, Ltd.) made), UG-4010, UG-4035, UG-4040, UG-4070 (above, Toa Synthetic ( ALUFON series, Inc., ECN-1299 (Asahi Kasei Corporation), DEN 431, DEN 438 (above, Dow Chemical Co., Ltd.), jER-152 (Mitsubishi Chemical Co., Ltd. (formerly Japan Epoxy Resins Co., Ltd.)) , Epiclon N-660, N-665, N-670, N-673, N- 705, N- 770, N- 770, N- 775 (above, DIC Corporation) (formerly Dai Nippon Ink Chemical Industry Co., Ltd.) And EOCN-1020, EOCN-102S, and EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.).
＜重合性二重結合を含む基を有する桂皮酸誘導体＞
　上記重合性二重結合としては、炭素－炭素間の二重結合が好ましい。この炭素－炭素間の二重結合を含む基としては、例えば、ビニル基、（メタ）アクリロイル基、アクリルアミド基等が挙げられるが、（メタ）アクリロイル基が好ましい。 <Cinamic acid derivative having a group containing a polymerizable double bond>
The polymerizable double bond is preferably a carbon-carbon double bond. As the group containing a carbon-carbon double bond, for example, a vinyl group, a (meth) acryloyl group, an acrylamide group and the like can be mentioned, and a (meth) acryloyl group is preferable.
　上記重合性二重結合を含む基を有する桂皮酸誘導体としては、下記式（１）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000005
 　式（１）中、Ａ１とＡ２はそれぞれ独立に、水素原子またはメチル基を表し、
　Ｒ１は下記式（ｃ－２）
Figure JPOXMLDOC01-appb-C000006
 （式（ｃ－２）中、破線は結合手を表し、Ｒ１０１は炭素数１～３０のアルキレン基を表し、このアルキレン基の１つ若しくは複数の水素原子は、フッ素原子又は有機基で置き換えられていてもよい。また、Ｒ１０１中の－ＣＨ２ＣＨ２－は－ＣＨ＝ＣＨ－に置き換えられていてもよく、さらに、次に挙げるいずれかの基が互いに隣り合わない場合において、－Ｏ－、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－ＮＨＣＯＮＨ－及び－ＣＯ－からなる群から選ばれる基に置き換えられていてもよく、Ｍ１は水素原子又はメチル基を表す。）で表される基を表し、
　Ｒ２は２価の芳香族基、２価の脂環族基、２価の複素環式基または２価の縮合環式基を表し、
　Ｒ３は単結合、酸素原子、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ＝ＣＨＣＯＯ－または－ＯＣＯＣＨ＝ＣＨ－を表し、
　Ｒ４～Ｒ７はそれぞれ独立に水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のハロアルキル基、炭素数１～６のアルコキシ基、炭素数１～６のハロアルコキシ基、シアノ基、及びニトロ基からなる群から選ばれる置換基を表し、
　また、Ｒ２、Ｒ３及びＲ４又はＲ２、Ｒ３及びＲ６は一緒になって芳香族基を形成してもよく、
　ｎは０～３の整数である。） As the cinnamic acid derivative having a group containing a polymerizable double bond, a compound represented by the following formula (1) is preferable.
Figure JPOXMLDOC01-appb-C000005
 In formula (1), each of A 1 and A 2 independently represents a hydrogen atom or a methyl group,
R 1 is the following formula (c-2)
Figure JPOXMLDOC01-appb-C000006
 (In the formula (c-2), the broken line represents a bond, R 101 represents an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of this alkylene group are replaced by a fluorine atom or an organic group In addition, -CH 2 CH 2-in R 101 may be replaced by -CH = CH-, and further, in the case where any of the following groups are not adjacent to each other,- M 1 is a hydrogen atom which may be substituted by a group selected from the group consisting of O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO- Or a methyl group is represented by
R 2 represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused cyclic group,
R 3 represents a single bond, an oxygen atom, -COO-, -OCO-, -CH = CHCOO- or -OCOCH = CH-,
R 4 to R 7 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy having 1 to 6 carbon atoms Represents a substituent selected from the group consisting of a group, a cyano group, and a nitro group,
Also, R 2 , R 3 and R 4 or R 2 , R 3 and R 6 may together form an aromatic group,
n is an integer of 0 to 3. )
　Ｒ２の２価の芳香族基としては、例えば１，４－フェニレン基、２－フルオロ－１，４－フェニレン基、３－フルオロ－１，４－フェニレン基、２，３，５，６－テトラフルオロ－１，４－フェニレン基等を；Ｒ２の２価の脂環族基としては、１，２－シクロプロピレン基、１，３－シクロブチレン基、１，４－シクロヘキシレン基等を；Ｒ２の２価の複素環式基としては、例えば１，４－ピリジレン基、２，５－ピリジレン基、１，４－フラニレン基等を；Ｒ２の２価の縮合環式基としては、例えば２，６－ナフチレン基等を、それぞれ挙げることができる。Ｒ２としては１，４－フェニレン基が好ましい。 Examples of the divalent aromatic group of R 2 include 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3,5,6- Tetrafluoro-1,4-phenylene group etc .; As a divalent alicyclic group of R 2 , 1,2-cyclopropylene group, 1,3-cyclobutylene group, 1,4-cyclohexylene group etc. As the divalent heterocyclic group for R 2 , for example, 1,4-pyridine group, 2,5-pyridylene group, 1,4-furanylene group etc .; for the divalent fused cyclic group for R 2 For example, 2,6-naphthylene group etc. can be mentioned respectively. As R 2 , a 1,4-phenylene group is preferable.
　上記式（１）で表される化合物の好ましい例としては、例えば、下記式Ｍ１－１～Ｍ１－５が挙げられる。
Figure JPOXMLDOC01-appb-C000007
 （式中、Ｍ１は水素原子又はメチル基であり、ｓ１はメチレン基の数を表し、２乃至９の自然数である。） Preferred examples of the compound represented by the above formula (1) include the following formulas M1-1 to M1-5.
Figure JPOXMLDOC01-appb-C000007
 (Wherein, M 1 is a hydrogen atom or a methyl group, s 1 represents the number of methylene groups, and is a natural number of 2 to 9)
　上記式（１）で表される化合物は、有機化学の定法を適宜に組み合わせて合成することができる。 The compound represented by the said Formula (1) can be synthesize | combined combining the usual method of organic chemistry suitably.
＜エポキシ基を有するポリマーと特定の桂皮酸誘導体の反応＞
　本発明の液晶配向剤に含有される、エポキシ基を有するポリマーと特定の桂皮酸誘導体との反応生成物は、上記の如きエポキシ基を有するポリマーと特定の桂皮酸誘導体とを、好ましくは触媒の存在下、好ましくは適当な有機溶媒中で反応させることにより合成することができる。
　反応に際して使用される桂皮酸誘導体の使用割合は、エポキシ基を有する重合体に含まれるエポキシ基１モルに対して、好ましくは０．０１～１．５モルであり、より好ましくは０．０５～１．３モルであり、さらに好ましくは０．１～１．１モルである。
　ここで使用することのできる有機触媒としては、有機塩基またはエポキシ化合物と酸無水物との反応を促進するいわゆる硬化促進剤として公知の化合物を用いることができる。 <Reaction of polymer having epoxy group and specific cinnamic acid derivative>
The reaction product of a polymer having an epoxy group and a specific cinnamic acid derivative contained in the liquid crystal aligning agent of the present invention comprises a polymer having an epoxy group as described above and a specific cinnamic acid derivative, preferably a catalyst. It can be synthesized by reacting in the presence, preferably in a suitable organic solvent.
The proportion of the cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 moles, more preferably 0.05 to 1 mole, relative to 1 mole of epoxy groups contained in the polymer having an epoxy group. It is 1.3 mol, more preferably 0.1 to 1.1 mol.
As an organic catalyst which can be used here, a compound known as a so-called curing accelerator which promotes the reaction of an organic base or an epoxy compound with an acid anhydride can be used.
　上記有機塩基としては、例えばエチルアミン、ジエチルアミン、ピペラジン、ピペリジン、ピロリジン、ピロールの如き１～２級有機アミン；トリエチルアミン、トリ－ｎ－プロピルアミン、トリ－ｎ－ブチルアミン、ピリジン、４－ジメチルアミノピリジン、ジアザビシクロウンデセンの如き３級の有機アミン；テトラメチルアンモニウムヒドロキシドの如き４級の有機アミン等を挙げることができる。これらの有機塩基のうち、トリエチルアミン、トリ－ｎ－プロピルアミン、トリ－ｎ－ブチルアミン、ピリジン、４－ジメチルアミノピリジンの如き３級の有機アミン；テトラメチルアンモニウムヒドロキシドの如き４級の有機アミンが好ましい。 Examples of the organic base include primary to secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, Tertiary organic amines such as diazabicycloundecene; quaternary organic amines such as tetramethyl ammonium hydroxide can be mentioned. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; and quaternary organic amines such as tetramethylammonium hydroxide preferable.
　上記硬化促進剤としては、例えばベンジルジメチルアミン、２，４，６－トリス（ジメチルアミノメチル）フェノール、シクロヘキシルジメチルアミン、トリエタノールアミンの如き３級アミン；２－メチルイミダゾール、２－ｎ－ヘプチルイミダゾール、２－ｎ－ウンデシルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール、１，２－ジメチルイミダゾール、２－エチル－４－メチルイミダゾール、１－（２－シアノエチル）－２－メチルイミダゾール、１－（２－シアノエチル）－２－ｎ－ウンデシルイミダゾール、１－（２－シアノエチル）－２－フェニルイミダゾール、１－（２－シアノエチル）－２－エチル－４－メチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、２－フェニル－４，５－ジ（ヒドロキシメチル）イミダゾール、１－（２－シアノエチル）－２－フェニル－４，５－ジ〔（２’－シアノエトキシ）メチル〕イミダゾール、１－（２－シアノエチル）－２－ｎ－ウンデシルイミダゾリウムトリメリテート、１－（２－シアノエチル）－２－フェニルイミダゾリウムトリメリテート、１－（２－シアノエチル）－２－エチル－４－メチルイミダゾリウムトリメリテート、２，４－ジアミノ－６－〔２’－メチルイミダゾリル－（１’）〕エチル－ｓ－トリアジン、２，４－ジアミノ－６－（２’－ｎ－ウンデシルイミダゾリル）エチル－ｓ－トリアジン、２，４－ジアミノ－６－〔２’－エチル－４’－メチルイミダゾリル－（１’）〕エチル－ｓ－トリアジン、２－メチルイミダゾールのイソシアヌル酸付加物、２－フェニルイミダゾールのイソシアヌル酸付加物、２，４－ジアミノ－６－〔２’－メチルイミダゾリル－（１’）〕エチル－ｓ－トリアジンのイソシアヌル酸付加物の如きイミダゾール化合物；ジフェニルフォスフィン、トリフェニルフォスフィン、亜リン酸トリフェニルの如き有機リン化合物；ベンジルトリフェニルフォスフォニウムクロライド、テトラ－ｎ－ブチルフォスフォニウムブロマイド、メチルトリフェニルフォスフォニウムブロマイド、エチルトリフェニルフォスフォニウムブロマイド、ｎ－ブチルトリフェニルフォスフォニウムブロマイド、テトラフェニルフォスフォニウムブロマイド、エチルトリフェニルフォスフォニウムヨーダイド、エチルトリフェニルフォスフォニウムアセテート、テトラ－ｎ－ブチルフォスフォニウムｏ，ｏ－ジエチルフォスフォロジチオネート、テトラ－ｎ－ブチルフォスフォニウムベンゾトリアゾレート、テトラ－ｎ－ブチルフォスフォニウムテトラフルオロボレート、テトラ－ｎ－ブチルフォスフォニウムテトラフェニルボレート、テトラフェニルフォスフォニウムテトラフェニルボレートの如き４級フォスフォニウム塩；１，８－ジアザビシクロ［５．４．０］ウンデセン－７やその有機酸塩の如きジアザビシクロアルケン；オクチル酸亜鉛、オクチル酸錫、アルミニウムアセチルアセトン錯体の如き有機金属化合物；テトラエチルアンモニウムブロマイド、テトラ－ｎ－ブチルアンモニウムブロマイド、テトラエチルアンモニウムクロライド、テトラ－ｎ－ブチルアンモニウムクロライドの如き４級アンモニウム塩；三フッ化ホウ素、ホウ酸トリフェニルの如きホウ素化合物；塩化亜鉛、塩化第二錫の如き金属ハロゲン化合物；ジシアンジアミドやアミンとエポキシ樹脂との付加物等のアミン付加型促進剤等の高融点分散型潜在性硬化促進剤；前記イミダゾール化合物、有機リン化合物や４級フォスフォニウム塩等の硬化促進剤の表面をポリマーで被覆したマイクロカプセル型潜在性硬化促進剤；アミン塩型潜在性硬化剤促進剤；ルイス酸塩、ブレンステッド酸塩等の高温解離型の熱カチオン重合型潜在性硬化促進剤等の潜在性硬化促進剤等を挙げることができる。
　これらのうち、好ましくはテトラエチルアンモニウムブロマイド、テトラ－ｎ－ブチルアンモニウムブロマイド、テトラエチルアンモニウムクロライド、テトラ－ｎ－ブチルアンモニウムクロライドの如き４級アンモニウム塩である。 Examples of the curing accelerator include benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, tertiary amines such as triethanolamine; 2-methylimidazole, 2-n-heptylimidazole , 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2- Ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1 -(2-cyanoethyl) -2-ethyl 4-Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-phenyl-4,5- Di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 2,4 -Diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methane -Imidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- ( 1 ′) imidazole compounds such as isocyanuric acid adducts of ethyl-s-triazines; organophosphorus compounds such as diphenyl phosphine, triphenyl phosphine, triphenyl phosphite; benzyl triphenyl phosphonium chloride, tetra-n -Butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenyl phosphite Ionium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butyl phosphinate Quaternary phosphonium salts such as phonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate; 1,8-diazabicyclo [5.4.0] undecene-7 And diazobicycloalkenes such as organic acid salts thereof; organometal compounds such as zinc octylate, tin octylate, and aluminum acetylacetone complex; tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethyl alcohol Quaternary ammonium salts such as monium chloride and tetra-n-butyl ammonium chloride; boron compounds such as boron trifluoride and triphenyl borate; metal halide compounds such as zinc chloride and stannic chloride; dicyandiamide and amines and epoxy resins High-melting point dispersion type latent curing accelerators such as amine addition type accelerators such as adducts thereof; micro coats coated with polymer on the surface of curing accelerators such as the above-mentioned imidazole compounds, organic phosphorus compounds and quaternary phosphonium salts Capsule type latent curing accelerator; Amine salt type latent curing agent accelerator; Potential curing accelerator such as high temperature dissociation thermal cationic polymerization type latent curing accelerator such as Lewis acid salt, Bronsted acid salt It can be mentioned.
Among these, preferred are quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride.
　触媒の使用割合としては、エポキシ基を有する重合体１００質量部に対して、好ましくは１００質量部以下であり、より好ましくは０．０１～１００質量部、さらに好ましくは０．１～２０質量部である。
　上記有機溶媒としては、例えば炭化水素化合物、エーテル化合物、エステル化合物、ケトン化合物、アミド化合物、アルコール化合物等を挙げることができる。これらのうち、エーテル化合物、エステル化合物、ケトン化合物、アルコール化合物が原料および生成物の溶解性ならびに生成物の精製のし易さの観点から好ましい。溶媒は、固形分濃度（反応溶液中の溶媒以外の成分の質量が溶液の全質量に占める割合）が、好ましくは０．１質量％以上、より好ましくは５～５０質量％となる量で使用される。
　反応温度は、好ましくは０～２００℃であり、より好ましくは５０～１５０℃である。反応時間は、好ましくは０．１～５０時間であり、より好ましくは０．５～２０時間である。
　このようにして、エポキシ基を有するポリマーと特定の桂皮酸誘導体との反応生成物を含有する溶液が得られる。この溶液はそのまま液晶配向剤の調製に供してもよく、溶液中に含まれる重合体を単離したうえで液晶配向剤の調製に供してもよく、または単離した重合体を精製したうえで液晶配向剤の調製に供してもよい。 The proportion of the catalyst used is preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, still more preferably 0.1 to 20 parts by mass, with respect to 100 parts by mass of the polymer having an epoxy group. It is.
As said organic solvent, a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, an alcohol compound etc. can be mentioned, for example. Among these, ether compounds, ester compounds, ketone compounds and alcohol compounds are preferable from the viewpoint of the solubility of the raw materials and products and the ease of purification of the products. The solvent is used in an amount such that the solid concentration (the ratio of the mass of components other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1% by mass or more, more preferably 5 to 50% by mass Be done.
The reaction temperature is preferably 0 to 200 ° C., more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.
In this way, a solution is obtained which contains the reaction product of a polymer having an epoxy group and a specific cinnamic acid derivative. This solution may be used as it is for preparation of a liquid crystal aligning agent, or may be used for preparing a liquid crystal aligning agent after isolating a polymer contained in the solution, or after purifying the isolated polymer. You may use for preparation of a liquid crystal aligning agent.
＜（Ｂ）成分＞
　本発明の硬化膜形成組成物における（Ｂ）成分は、架橋剤である。
　（Ｂ）成分である架橋剤は、前記（Ａ）成分の熱架橋可能な官能基と架橋を形成する基、例えばメチロール基またはアルコキシメチル基を有する架橋剤であることが好ましい。
　これらの基を有する化合物としては、例えば、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミンおよびアルコキシメチル化メラミン等のメチロール化合物が挙げられる。 <(B) component>
The component (B) in the cured film-forming composition of the present invention is a crosslinking agent.
The crosslinking agent which is the component (B) is preferably a crosslinking agent having a group capable of forming a crosslink with the thermally crosslinkable functional group of the component (A), such as a methylol group or an alkoxymethyl group.
Examples of compounds having these groups include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine and alkoxymethylated melamine.
　アルコキシメチル化グリコールウリルの具体例としては、例えば、１，３，４，６－テトラキス（メトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ブトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ヒドロキシメチル）グリコールウリル、１，３－ビス（ヒドロキシメチル）尿素、１，１，３，３－テトラキス（ブトキシメチル）尿素、１，１，３，３－テトラキス（メトキシメチル）尿素、１，３－ビス（ヒドロキシメチル）－４，５－ジヒドロキシ－２－イミダゾリノン、および１，３－ビス（メトキシメチル）－４，５－ジメトキシ－２－イミダゾリノン等が挙げられる。市販品として、日本サイテック・インダストリーズ（株）（旧　三井サイテック（株））製グリコールウリル化合物（商品名：サイメル（登録商標）１１７０、パウダーリンク（登録商標）１１７４）等の化合物、メチル化尿素樹脂（商品名：ＵＦＲ（登録商標）６５）、ブチル化尿素樹脂（商品名：ＵＦＲ（登録商標）３００、Ｕ－ＶＡＮ１０Ｓ６０、Ｕ－ＶＡＮ１０Ｒ、Ｕ－ＶＡＮ１１ＨＶ）、ＤＩＣ（株）（旧　大日本インキ化学工業（株））製尿素／ホルムアルデヒド系樹脂（高縮合型、商品名：ベッカミン（登録商標）Ｊ－３００Ｓ、同Ｐ－９５５、同Ｎ）等が挙げられる。 Specific examples of alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 , 6-Tetrakis (hydroxymethyl) glycoluril, 1, 3-bis (hydroxymethyl) urea, 1, 1, 3, 3- tetrakis (butoxymethyl) urea, 1, 1, 3, 3- tetrakis (methoxymethyl) Examples thereof include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercially available products, compounds such as Nippon Cytech Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) glycoluril compound (trade name: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174), methylated urea resin (Trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN 10 S60, U-VAN 10 R, U-VAN 11 HV), DIC Corporation (formerly Dai Nippon Ink Chemical Co., Ltd.) Urea / formaldehyde resin (manufactured by Kogyo Co., Ltd.) (high condensation type, trade name: Beckamine (registered trademark) J-300S, P-955, N) and the like can be mentioned.
　アルコキシメチル化ベンゾグアナミンの具体例としてはテトラメトキシメチルベンゾグアナミン等が挙げられる。市販品として、日本サイテック・インダストリーズ（株）（旧　三井サイテック（株））製（商品名：サイメル（登録商標）１１２３）、（株）三和ケミカル製（商品名：ニカラック（登録商標）ＢＸ－４０００、同ＢＸ－３７、同ＢＬ－６０、同ＢＸ－５５Ｈ）等が挙げられる。 Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. As commercially available products, Nippon Cytech Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: Nikalac (registered trademark) BX-) 4000, BX-37, BL-60, BX-55H) and the like.
　アルコキシメチル化メラミンの具体例としては、例えば、ヘキサメトキシメチルメラミン等が挙げられる。市販品として、日本サイテック・インダストリーズ（株）（旧　三井サイテック（株））製メトキシメチルタイプメラミン化合物（商品名：サイメル（登録商標）３００、同３０１、同３０３、同３５０）、ブトキシメチルタイプメラミン化合物（商品名：マイコート（登録商標）５０６、同５０８）、（株）三和ケミカル製メトキシメチルタイプメラミン化合物（商品名：ニカラック（登録商標）ＭＷ－３０、同ＭＷ－２２、同ＭＷ－１１、同ＭＳ－００１、同ＭＸ－００２、同ＭＸ－７３０、同ＭＸ－７５０、同ＭＸ－０３５）、ブトキシメチルタイプメラミン化合物（商品名：ニカラック（登録商標）ＭＸ－４５、同ＭＸ－４１０、同ＭＸ－３０２）等が挙げられる。 Examples of alkoxymethylated melamine include, for example, hexamethoxymethylmelamine. As a commercial product, Nippon Cytech Industries Ltd. (formerly Mitsui Cytec Co., Ltd.) methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine Compound (trade name: Mycoat (registered trademark) 506, 508), methoxymethyl type melamine compound (trade name: Nikalac (registered trademark) MW-30, MW-22, MW-22 manufactured by Sanwa Chemical Co., Ltd. 11, MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compound (trade name: Nicarak (registered trademark) MX-45, MX-410 , MX-302) and the like.
　また、このようなアミノ基の水素原子がメチロール基またはアルコキシメチル基で置換されたメラミン化合物、尿素化合物、グリコールウリル化合物及びベンゾグアナミン化合物を縮合させて得られる化合物であってもよい。例えば、米国特許第６３２３３１０号に記載されているメラミン化合物およびベンゾグアナミン化合物から製造される高分子量の化合物が挙げられる。前記メラミン化合物の市販品としては、商品名：サイメル（登録商標）３０３等が挙げられ、前記ベンゾグアナミン化合物の市販品としては、商品名：サイメル（登録商標）１１２３（以上、日本サイテック・インダストリーズ（株）（旧　三井サイテック（株））製）等が挙げられる。 In addition, it may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of such an amino group is substituted with a methylol group or an alkoxymethyl group. For example, high molecular weight compounds prepared from melamine compounds and benzoguanamine compounds described in US Pat. No. 6,323,310 can be mentioned. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303, and examples of commercially available products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 (above, Nippon Cytech Industries, Ltd. And the like (manufactured by Mitsui Cytec Co., Ltd.) and the like.
　さらに、（Ｂ）成分の架橋剤として、Ｎ－ヒドロキシメチルアクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－エトキシメチルアクリルアミド、Ｎ－ブトキシメチルメタクリルアミド等のヒドロキシメチル基（すなわちメチロール基）またはアルコキシメチル基で置換されたアクリルアミド化合物またはメタクリルアミド化合物を使用して製造されるポリマーも用いることができる。 Further, as a crosslinking agent for the component (B), hydroxymethyl groups (ie, methylol groups) such as N-hydroxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl methacrylamide or alkoxymethyl groups Polymers prepared using acrylamide compounds or methacrylamide compounds substituted with can also be used.
　そのようなポリマーとしては、例えば、ポリ（Ｎ－ブトキシメチルアクリルアミド）、Ｎ－ブトキシメチルアクリルアミドとスチレンとの共重合体、Ｎ－ヒドロキシメチルメタクリルアミドとメチルメタクリレートとの共重合体、Ｎ－エトキシメチルメタクリルアミドとベンジルメタクリレートとの共重合体、及びＮ－ブトキシメチルアクリルアミドとベンジルメタクリレートと２－ヒドロキシプロピルメタクリレートとの共重合体等が挙げられる。 As such polymers, for example, poly (N-butoxymethyl acrylamide), a copolymer of N-butoxymethyl acrylamide and styrene, a copolymer of N-hydroxymethyl methacrylamide and methyl methacrylate, N-ethoxymethyl Examples thereof include copolymers of methacrylamide and benzyl methacrylate, and copolymers of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate, and the like.
　また、そのようなポリマーとして、Ｎ－アルコキシメチル基とＣ＝Ｃ二重結合とを含む重合性基とを有する重合体を用いることも出来る。 In addition, as such a polymer, a polymer having an N-alkoxymethyl group and a polymerizable group containing a C = C double bond can also be used.
　Ｃ＝Ｃ二重結合を含む重合性基としては、アクリル基、メタクリル基、ビニル基、アリル基、マレイミド基等が挙げられる。 Examples of the polymerizable group containing a C = C double bond include an acryl group, a methacryl group, a vinyl group, an allyl group and a maleimide group.
　上記のようなポリマーを得る方法は、特に限定されない。一例を挙げれば、予めラジカル重合などの重合方法によって、特定官能基１を有するアクリル重合体を生成する。次いで、この特定官能基１と、末端に不飽和結合を有する化合物（以下、特定化合物と称す。）とを反応させることにより、（Ｂ）成分であるポリマーにＣ＝Ｃ二重結合を含む重合性基を導入することができる。 The method for obtaining the polymer as described above is not particularly limited. As an example, an acrylic polymer having a specific functional group 1 is formed in advance by a polymerization method such as radical polymerization. Then, the specific functional group 1 is reacted with a compound having an unsaturated bond at the end (hereinafter, referred to as a specific compound) to polymerize the polymer which is the component (B) including a C = C double bond Sex groups can be introduced.
　ここで、特定官能基１とは、カルボキシル基、グリシジル基、ヒドロキシ基、活性水素を有するアミノ基、フェノール性ヒドロキシ基若しくはイソシアネート基などの官能基、または、これらから選ばれる複数種の官能基を言う。 Here, the specific functional group 1 means a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a functional group such as a phenolic hydroxy group or an isocyanate group, or a plurality of functional groups selected therefrom. say.
　上述した反応において、特定官能基１と、特定化合物が有する官能基であって反応に関与する基との好ましい組み合わせは、カルボキシル基とエポキシ基、ヒドロキシ基とイソシアネート基、フェノール性ヒドロキシ基とエポキシ基、カルボキシル基とイソシアネート基、アミノ基とイソシアネート基、または、ヒドロキシ基と酸クロリドなどである。さらに、より好ましい組み合わせは、カルボキシル基とグリシジルメタクリレート、または、ヒドロキシ基とイソシアネートエチルメタクリレートである。 In the above-mentioned reaction, preferred combinations of the specific functional group 1 and the functional group possessed by the specific compound and involved in the reaction are a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, a phenolic hydroxy group and an epoxy group A carboxyl group and an isocyanate group, an amino group and an isocyanate group, or a hydroxy group and an acid chloride. Furthermore, a more preferable combination is a carboxyl group and glycidyl methacrylate, or a hydroxyl group and isocyanate ethyl methacrylate.
　このようなポリマーの重量平均分子量（ポリスチレン換算値）は、１，０００～５００，０００であり、好ましくは、２，０００～２００，０００であり、より好ましくは３，０００～１５０，０００であり、更に好ましくは３，０００～５０，０００である。 The weight average molecular weight (in terms of polystyrene) of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000. More preferably, it is 3,000 to 50,000.
　これらの架橋剤は、単独でまたは２種以上を組み合わせて使用することができる。 These crosslinking agents can be used alone or in combination of two or more.
　本発明の硬化膜形成組成物における（Ｂ）成分の架橋剤の含有量は、（Ａ）成分であるポリマー１００質量部に基づいて１質量部～５００質量部であることが好ましく、より好ましくは５質量部～４００質量部である。架橋剤の含有量が過小である場合には、硬化膜形成組成物から得られる硬化膜の溶剤耐性が低下し、液晶配向性が低下する。他方、含有量が過大である場合には液晶配向性および保存安定性が低下することがある。 The content of the crosslinking agent of the component (B) in the cured film-forming composition of the present invention is preferably 1 part by mass to 500 parts by mass, and more preferably, based on 100 parts by mass of the polymer which is the component (A). 5 parts by mass to 400 parts by mass. When the content of the crosslinking agent is too small, the solvent resistance of the cured film obtained from the cured film-forming composition is lowered, and the liquid crystal alignment is lowered. On the other hand, when the content is excessive, the liquid crystal alignment and storage stability may be lowered.
＜（Ｃ）成分＞
　本発明の硬化膜形成組成物は、（Ｃ）成分として、ヒドロキシ基、カルボキシル基、アミド基、アミノ基、およびアルコキシシリル基からなる群から選ばれる少なくとも１つの基（以下、特定官能基２ともいう）を有するポリマーを含有しても良い。 <(C) component>
The cured film-forming composition of the present invention comprises, as component (C), at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group (hereinafter also referred to as a specific functional group 2) May be contained in the polymer.
　（Ｃ）成分であるポリマーとしては、例えば、アクリル重合体、ポリアミック酸、ポリイミド、ポリビニルアルコール、ポリエステル、ポリエステルポリカルボン酸、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリカプロラクトンポリオール、ポリアルキレンイミン、ポリアリルアミン、セルロース類（セルロースまたはその誘導体）、フェノールノボラック樹脂、メラミンホルムアルデヒド樹脂等の直鎖構造または分岐構造を有するポリマー、シクロデキストリン類等の環状ポリマー等が挙げられる。 As a polymer which is the component (C), for example, acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polyalkyleneimine, poly Examples thereof include polymers having a linear or branched structure such as allylamine, celluloses (cellulose or derivatives thereof), phenol novolac resin, and melamine formaldehyde resin, and cyclic polymers such as cyclodextrins.
　（Ｃ）成分であるポリマーとしては、好ましくは、アクリル重合体、ヒドロキシアルキルシクロデキストリン類、セルロース類、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール並びにポリカプロラクトンポリオールが挙げられる。 The polymer which is the component (C) preferably includes acrylic polymers, hydroxyalkyl cyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols and polycaprolactone polyols.
　（Ｃ）成分のポリマーの好ましい一例であるアクリル重合体としては、アクリル酸、メタクリル酸、スチレン、ビニル化合物等の不飽和二重結合を有するモノマーを重合して得られる重合体であって、特定官能基２を有するモノマーを含むモノマーまたはその混合物を重合させることにより得られる重合体であればよく、アクリル重合体を構成する高分子の主鎖の骨格および側鎖の種類などについて特に限定されない。 The acrylic polymer which is a preferable example of the polymer of the component (C) is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, vinyl compound, etc. The polymer may be a polymer obtained by polymerizing a monomer containing a monomer having a functional group 2 or a mixture thereof, and the type and the like of the main chain skeleton and side chains of the polymer constituting the acrylic polymer are not particularly limited.
　特定官能基２を有するモノマーとしては、ポリエチレングリコールエステル基を有するモノマー、炭素原子数２～５のヒドロキシアルキルエステル基を有するモノマー、フェノール性ヒドロキシ基を有するモノマー、カルボキシル基を有するモノマー、アミノ基を有するモノマー、アルコキシシリル基および上記式２で表される基を有するモノマーが挙げられる。 As the monomer having the specific functional group 2, a monomer having a polyethylene glycol ester group, a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms, a monomer having a phenolic hydroxy group, a monomer having a carboxyl group, an amino group And monomers having an alkoxysilyl group and a group represented by Formula 2 above.
　上述したポリエチレングリコールエステル基を有するモノマーとしては、Ｈ－（ＯＣＨ２ＣＨ２）ｎ－ＯＨのモノアクリレートまたはモノメタクリレートが挙げられる。そのｎの値は２～５０であり、好ましくは２～１０である。 Examples of the above-described monomer having a polyethylene glycol ester group include monoacrylate or monomethacrylate of H- (OCH 2 CH 2 ) n -OH. The value of n is 2 to 50, preferably 2 to 10.
　上述した炭素原子数２～５のヒドロキシアルキルエステル基を有するモノマーとしては、例えば、２－ヒドロキシエチルメタクリレート、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルメタクリレート、２－ヒドロキシプロピルアクリレート、４－ヒドロキシブチルアクリレート、４－ヒドロキシブチルメタクリレートが挙げられる。 Examples of the monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms described above include, for example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate And 4-hydroxybutyl methacrylate.
　上述したフェノール性ヒドロキシ基を有するモノマーとしては、例えば、ｐ－ヒドロキシスチレン、ｍ－ヒドロキシスチレン、ｏ－ヒドロキシスチレンが挙げられる。 Examples of the above-mentioned monomer having a phenolic hydroxy group include p-hydroxystyrene, m-hydroxystyrene and o-hydroxystyrene.
　上述したカルボキシル基を有するモノマーとしては、例えば、アクリル酸、メタクリル酸、ビニル安息香酸が挙げられる。 As a monomer which has the carboxyl group mentioned above, acrylic acid, methacrylic acid, vinyl benzoic acid is mentioned, for example.
　上述したアミノ基を側鎖に有するモノマーとしては、例えば、２－アミノエチルアクリレート、２－アミノエチルメタクリレート、アミノプロピルアクリレート及びアミノプロピルメタクリレートが挙げられる。 Examples of the above-mentioned monomer having an amino group in the side chain include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate.
　上述したアルコキシシリル基を側鎖に有するモノマーとしては、例えば、３－アクリロキシプロピルトリメトキシシラン、３－アクリロキシプロピルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルトリメトキシシラン及びアリルトリエトキシシラン等が挙げられる。 Examples of the above-mentioned monomer having an alkoxysilyl group in the side chain include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane and the like can be mentioned.
　また、本実施形態においては、（Ｃ）成分の例であるアクリル重合体を合成するに際し、本発明の効果を損なわない限り、ヒドロキシ基、カルボキシル基、アミド基、アミノ基、およびアルコキシシリル基で表される基のいずれも有さないモノマーを併用することができる。 Further, in the present embodiment, when synthesizing the acrylic polymer which is an example of the component (C), it is preferable to use a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group as long as the effect of the present invention is not impaired. Monomers which do not have any of the represented groups can be used in combination.
　そのようなモノマーの具体例としては、アクリル酸エステル化合物、メタクリル酸エステル化合物、マレイミド化合物、アクリロニトリル、マレイン酸無水物、スチレン化合物及びビニル化合物等が挙げられる。 Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
　アクリル酸エステル化合物としては、例えば、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、ベンジルアクリレート、ナフチルアクリレート、アントリルアクリレート、アントリルメチルアクリレート、フェニルアクリレート、２，２，２－トリフルオロエチルアクリレート、ｔｅｒｔ－ブチルアクリレート、シクロヘキシルアクリレート、イソボルニルアクリレート、２－メトキシエチルアクリレート、メトキシトリエチレングリコールアクリレート、２－エトキシエチルアクリレート、テトラヒドロフルフリルアクリレート、３－メトキシブチルアクリレート、２－メチル－２－アダマンチルアクリレート、２－プロピル－２－アダマンチルアクリレート、８－メチル－８－トリシクロデシルアクリレート、及び、８－エチル－８－トリシクロデシルアクリレート等が挙げられる。 As an acrylic acid ester compound, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, Beauty, etc. 8-ethyl-8-tricyclodecyl acrylate.
　メタクリル酸エステル化合物としては、例えば、メチルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、ベンジルメタクリレート、ナフチルメタクリレート、アントリルメタクリレート、アントリルメチルメタクリレート、フェニルメタクリレート、２，２，２－トリフルオロエチルメタクリレート、ｔｅｒｔ－ブチルメタクリレート、シクロヘキシルメタクリレート、イソボルニルメタクリレート、２－メトキシエチルメタクリレート、メトキシトリエチレングリコールメタクリレート、２－エトキシエチルメタクリレート、テトラヒドロフルフリルメタクリレート、３－メトキシブチルメタクリレート、２－メチル－２－アダマンチルメタクリレート、２－プロピル－２－アダマンチルメタクリレート、８－メチル－８－トリシクロデシルメタクリレート、及び、８－エチル－８－トリシクロデシルメタクリレート等が挙げられる。 Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Propyl-2-adamantyl methacrylate, 8-meth Le -8- tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate.
　マレイミド化合物としては、例えば、マレイミド、Ｎ－メチルマレイミド、Ｎ－フェニルマレイミド、及びＮ－シクロヘキシルマレイミド等が挙げられる。 Examples of the maleimide compound include maleimide, N-methyl maleimide, N-phenyl maleimide, and N-cyclohexyl maleimide.
　スチレン化合物としては、例えば、スチレン、メチルスチレン、クロロスチレン、ブロモスチレン等が挙げられる。 Examples of styrene compounds include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.
　ビニル化合物としては、例えば、ビニルエーテル、メチルビニルエーテル、ベンジルビニルエーテル、２－ヒドロキシエチルビニルエーテル、フェニルビニルエーテル、及び、プロピルビニルエーテル等が挙げられる。 Examples of vinyl compounds include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
　（Ｃ）成分の例であるアクリル重合体を得るために用いる特定官能基２を有するモノマーの使用量は、（Ｃ）成分であるアクリル重合体を得るために用いる全モノマーの合計量に基づいて、２モル％以上であることが好ましい。特定官能基２を有するモノマーが２モル％よりも過小の場合は、得られる硬化膜の耐溶剤性が不充分となり易い。 The amount of the monomer having the specific functional group 2 used to obtain the acrylic polymer which is an example of the component (C) is based on the total amount of all the monomers used to obtain the acrylic polymer which is the component (C). And preferably 2 mol% or more. If the monomer having the specific functional group 2 is less than 2 mol%, the solvent resistance of the resulting cured film tends to be insufficient.
　（Ｃ）成分の例であるアクリル重合体を得る方法は特に限定されないが、例えば、特定官能基２を有するモノマーを含むモノマーと、所望により特定官能基２を有さないモノマーと、重合開始剤等とを共存させた溶剤中において、５０℃～１１０℃の温度下で重合反応により得られる。その際、用いられる溶剤は、特定官能基２を有するモノマーと、所望により用いられる特定官能基２を有さないモノマーおよび重合開始剤等を溶解するものであれば特に限定されない。具体例としては、後述する［溶剤］の項に記載する。 Although the method of obtaining the acrylic polymer which is an example of (C) component is not specifically limited, For example, the monomer containing the monomer which has the specific functional group 2, and the monomer which does not have the specific functional group 2 if needed, and a polymerization initiator It is obtained by a polymerization reaction at a temperature of 50.degree. C. to 110.degree. C. in a solvent in the presence of, etc. In that case, the solvent to be used is not particularly limited as long as it dissolves the monomer having the specific functional group 2, and the optionally used monomer having no specific functional group 2, the polymerization initiator and the like. As a specific example, it describes in the term of the "solvent" mentioned later.
　以上の方法により得られる（Ｃ）成分の例であるアクリル重合体は、通常、溶剤に溶解した溶液の状態である。 The acrylic polymer which is an example of (C) component obtained by the above method is a state of the solution normally melt | dissolved in the solvent.
　また、上記方法で得られた（Ｃ）成分の例であるアクリル重合体の溶液を、攪拌下のジエチルエーテルや水等に投入して再沈殿させ、生成した沈殿物を濾過・洗浄した後に、常圧または減圧下で、常温乾燥または加熱乾燥し、（Ｃ）成分の例であるアクリル重合体の粉体とすることができる。上述の操作により、（Ｃ）成分の例であるアクリル重合体と共存する重合開始剤および未反応のモノマーを除去することができ、その結果、精製した（Ｃ）成分の例であるアクリル重合体の粉体が得られる。一度の操作で充分に精製できない場合は、得られた粉体を溶剤に再溶解させ、上述の操作を繰り返し行えば良い。 In addition, after a solution of an acrylic polymer which is an example of the component (C) obtained by the above method is added to diethyl ether under stirring, water or the like to cause reprecipitation, and the formed precipitate is filtered and washed, The powder can be dried at normal temperature or dried by heating under normal pressure or reduced pressure to form a powder of an acrylic polymer which is an example of the component (C). By the above-mentioned operation, the polymerization initiator coexisting with the acrylic polymer which is an example of the component (C) and unreacted monomers can be removed, and as a result, the acrylic polymer which is an example of the purified component (C) Powder is obtained. If sufficient purification can not be performed by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
　（Ｃ）成分の好ましい例であるアクリル重合体は、重量平均分子量が３０００～２０００００であることが好ましく、４０００～１５００００であることがより好ましく、５０００～１０００００であることがさらに好ましい。重量平均分子量が２０００００を超えて過大なものであると、溶剤に対する溶解性が低下しハンドリング性が低下する場合があり、重量平均分子量が３０００未満で過小なものであると、熱硬化時に硬化不足になり溶剤耐性が低下する場合がある。尚、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、標準資料としてポリスチレンを用いて得られる値である。以下、本明細書においても同様とする。 The acrylic polymer which is a preferable example of the component (C) preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and still more preferably 5,000 to 100,000. If the weight average molecular weight is more than 200,000 and is too large, the solubility in solvents may be reduced and the handling properties may be reduced. If the weight average molecular weight is less than 3000 and is too low, the curing is insufficient at the time of heat curing And the solvent resistance may be reduced. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard material. Hereinafter, the same applies to the present specification.
　次に、（Ｃ）成分の好ましい一例であるポリエーテルポリオールとしては、ポリエチレングリコール、ポリプロピレングリコール、プロピレングリコールやビスフェノールＡ、トリエチレングリコール、ソルビトール等の多価アルコールにプロピレンオキサイドやポリエチレングリコール、ポリプロピレングリコール等を付加したものが挙げられる。ポリエーテルポリオールの具体例としてはＡＤＥＫＡ製アデカポリエーテルＰシリーズ、Ｇシリーズ、ＥＤＰシリーズ、ＢＰＸシリーズ、ＦＣシリーズ、ＣＭシリーズ、日油製ユニオックス（登録商標）ＨＣ－４０、ＨＣ－６０、ＳＴ－３０Ｅ、ＳＴ－４０Ｅ、Ｇ－４５０、Ｇ－７５０、ユニオール（登録商標）ＴＧ－３３０、ＴＧ－１０００、ＴＧ－３０００、ＴＧ－４０００、ＨＳ－１６００Ｄ、ＤＡ－４００、ＤＡ－７００、ＤＢ－４００、ノニオン（登録商標）ＬＴ－２２１、ＳＴ－２２１、ＯＴ－２２１等が挙げられる。 Next, as a polyether polyol which is a preferable example of the component (C), polyethylene oxide, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, polyhydric alcohol such as sorbitol, propylene oxide, polyethylene glycol, polypropylene glycol, etc. The thing which added Specific examples of polyether polyols include Adeka Polyether P series, G series, EDP series, BPX series, FC series, CM series manufactured by Adeka, Uniox (registered trademark) HC-40, HC-60, ST- 30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400 And Nonion (registered trademark) LT-221, ST-221, OT-221 and the like.
　（Ｃ）成分の好ましい一例であるポリエステルポリオールとしては、アジピン酸、セバシン酸、イソフタル酸等の多価カルボン酸にエチレングリコール、プロピレングリコール、ブチレングリコール、ポリエチレングリコール、ポリプロピレングリコール等のジオールを反応させたものが挙げられる。ポリエステルポリオールの具体例としてはＤＩＣ製ポリライト（登録商標）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、クラレ製ポリオールＰ－５１０、Ｐ－１０１０、Ｐ－２０１０、Ｐ－３０１０、Ｐ－４０１０、Ｐ－５０１０、Ｐ－６０１０、Ｆ－５１０、Ｆ－１０１０、Ｆ－２０１０、Ｆ－３０１０、Ｐ－１０１１、Ｐ－２０１１、Ｐ－２０１３、Ｐ－２０３０、Ｎ－２０１０、ＰＮＮＡ－２０１６等が挙げられる。 As polyester polyol which is a preferable example of (C) component, diols, such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, etc. were made to react with polyvalent carboxylic acids, such as adipic acid, sebacic acid, and isophthalic acid. The thing is mentioned. Specific examples of the polyester polyol include Polylight (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, manufactured by DIC. OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD- X-2555, OD-X-2560, Kuraray polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F -2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016 and the like.
　（Ｃ）成分の好ましい一例であるポリカプロラクトンポリオールとしては、トリメチロールプロパンやエチレングリコール等の多価アルコールを開始剤としてε－カプロラクトンを開環重合させたものが挙げられる。ポリカプロラクトンポリオールの具体例としてはＤＩＣ製ポリライト（登録商標）ＯＤ－Ｘ－２１５５、ＯＤ－Ｘ－６４０、ＯＤ－Ｘ－２５６８、ダイセル製プラクセル（登録商標）２０５、Ｌ２０５ＡＬ、２０５Ｕ、２０８、２１０、２１２、Ｌ２１２ＡＬ、２２０、２３０、２４０、３０３、３０５、３０８、３１２、３２０等が挙げられる。 As a polycaprolactone polyol which is a preferable example of the component (C), one obtained by ring-opening-polymerizing ε-caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator can be mentioned. Specific examples of the polycaprolactone polyol include Polylight (registered trademark) OD-X-2155, OD-X-640, and OD-X-2568 manufactured by DIC, Plaxel (registered trademark) 205 manufactured by Daicel, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320 and the like.
　（Ｃ）成分の好ましい一例であるポリカーボネートポリオールとしては、トリメチロールプロパンやエチレングリコール等の多価アルコールと炭酸ジエチル、炭酸ジフェニル、エチレンカーボネート等を反応させたものが挙げられる。ポリカーボネートポリオールの具体例としてはダイセル製プラクセル（登録商標）ＣＤ２０５、ＣＤ２０５ＰＬ、ＣＤ２１０、ＣＤ２２０、クラレ製のＣ－５９０、Ｃ－１０５０、Ｃ－２０５０、Ｃ－２０９０、Ｃ－３０９０等が挙げられる。 Examples of the polycarbonate polyol which is a preferable example of the component (C) include those obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like. Specific examples of polycarbonate polyols include PLACEL (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel, C-590, C-1050, C-2050, C-2090, C-3090 and the like manufactured by Kuraray.
　（Ｃ）成分の好ましい一例であるセルロース類としては、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース等のヒドロキシアルキルセルロース類、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシエチルエチルセルロース等のヒドロキシアルキルアルキルセルロース類およびセルロース等が挙げられ、例えば、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース等のヒドロキシアルキルセルロース類が好ましい。 Preferred examples of the component (C) include celluloses such as hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and cellulose. For example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.
　（Ｃ）成分の好ましい一例であるシクロデキストリン類としては、α－シクロデキストリン、β－シクロデキストリンおよびγシクロデキストリン等のシクロデキストリン、メチル－α－シクロデキストリン、メチル－β－シクロデキストリンならびにメチル－γ－シクロデキストリン等のメチル化シクロデキストリン、ヒドロキシメチル－α－シクロデキストリン、ヒドロキシメチル－β－シクロデキストリン、ヒドロキシメチル－γ－シクロデキストリン、２－ヒドロキシエチル－α－シクロデキストリン、２－ヒドロキシエチル－β－シクロデキストリン、２－ヒドロキシエチル－γ－シクロデキストリン、２－ヒドロキシプロピル－α－シクロデキストリン、２－ヒドロキシプロピル－β－シクロデキストリン、２－ヒドロキシプロピル－γ－シクロデキストリン、３－ヒドロキシプロピル－α－シクロデキストリン、３－ヒドロキシプロピル－β－シクロデキストリン、３－ヒドロキシプロピル－γ－シクロデキストリン、２，３－ジヒドロキシプロピル－α－シクロデキストリン、２，３－ジヒドロキシプロピル－β－シクロデキストリン、２，３－ジヒドロキシプロピル－γ－シクロデキストリン等のヒドロキシアルキルシクロデキストリン等が挙げられる。 Examples of cyclodextrins which are preferable examples of the component (C) include cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, methyl-α-cyclodextrin, methyl-β-cyclodextrin and methyl-γ Methylated cyclodextrins such as -cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxyethyl-β -Cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ Cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2,3-dihydroxy And hydroxyalkyl cyclodextrins such as propyl-β-cyclodextrin, 2,3-dihydroxypropyl-γ-cyclodextrin and the like.
　（Ｃ）成分の好ましい一例であるメラミンホルムアルデヒド樹脂としては、メラミンとホルムアルデヒドを重縮合して得られる樹脂が挙げられる。 As a melamine formaldehyde resin which is a preferable example of (C) component, resin obtained by polycondensing melamine and formaldehyde is mentioned.
　（Ｃ）成分のメラミンホルムアルデヒド樹脂は、保存安定性の観点からメラミンとホルムアルデヒドの重縮合の際に生成したメチロール基がアルキル化されていることが好ましい。（Ｃ）成分のメラミンホルムアルデヒド樹脂としては、例えば下記式で表される単位構造を有する樹脂が挙げられる。
Figure JPOXMLDOC01-appb-C000008
 　上記式中、Ｒ２１は水素原子または炭素原子数１～４のアルキル基を表し、ｎは繰り返し単位の数を表す自然数である。 From the viewpoint of storage stability, the melamine formaldehyde resin of component (C) is preferably an alkylated methylol group formed during the polycondensation of melamine and formaldehyde. As a melamine formaldehyde resin of (C) component, resin which has a unit structure represented, for example by a following formula is mentioned.
Figure JPOXMLDOC01-appb-C000008
 In the above formulas, R 21 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is a natural number representing the number of repeating units.
　（Ｃ）成分のメラミンホルムアルデヒド樹脂を得る方法は特には限定されないが、一般的にメラミンとホルムアルデヒドを混合し、炭酸ナトリウムやアンモニア等を用いて弱アルカリ性にした後６０℃～１００℃にて加熱することにより合成される。さらにアルコールと反応させることでメチロール基をアルコキシ化することができる。 The method for obtaining the melamine formaldehyde resin of the component (C) is not particularly limited, but generally, melamine and formaldehyde are mixed, and after being weakly alkaline using sodium carbonate, ammonia and the like, heating is carried out at 60 ° C to 100 ° C. Are synthesized by Furthermore, the methylol group can be alkoxylated by reacting with an alcohol.
　（Ｃ）成分のメラミンホルムアルデヒド樹脂は、重量平均分子量が２５０～５０００であることが好ましく、３００～４０００であることがより好ましく、３５０～３５００であることがさらに好ましい。重量平均分子量が５０００を超えて過大なものであると、溶剤に対する溶解性が低下しハンドリング性が低下する場合があり、重量平均分子量が２５０未満で過小なものであると、熱硬化時に硬化不足になり溶剤耐性の向上効果が十分に現れない場合がある。 The weight average molecular weight of the melamine formaldehyde resin of the component (C) is preferably 250 to 5,000, more preferably 300 to 4,000, and still more preferably 350 to 3,500. If the weight average molecular weight is more than 5000, the solubility in the solvent may be reduced and the handling properties may be reduced. If the weight average molecular weight is less than 250 and the amount is too small, the curing is insufficient at the time of heat curing As a result, the effect of improving the solvent resistance may not be sufficiently exhibited.
　本発明の実施形態においては、（Ｃ）成分のメラミンホルムアルデヒド樹脂は液体形態で、あるいは精製した液体を後述する溶剤に再溶解した溶液形態で用いてもよい。 In the embodiment of the present invention, the melamine formaldehyde resin of the component (C) may be used in the form of a liquid, or in the form of a solution in which the purified liquid is redissolved in a solvent described later.
　（Ｃ）成分の好ましい一例であるフェノールノボラック樹脂としては、例えば、フェノール－ホルムアルデヒド重縮合物などが挙げられる。 As a phenol novolak resin which is a preferable example of the component (C), for example, a phenol-formaldehyde polycondensate and the like can be mentioned.
　本実施形態の硬化膜形成組成物において、（Ｃ）成分のポリマーは、粉体形態で、または精製した粉末を後述する溶剤に再溶解した溶液形態で用いてもよい。 In the cured film-forming composition of the present embodiment, the polymer of the component (C) may be used in the form of a powder or in the form of a solution in which the purified powder is redissolved in a solvent described later.
　また、本実施の形態の硬化膜形成組成物において、（Ｃ）成分は、（Ｃ）成分として例示されたポリマーの複数種の混合物であってもよい。 Further, in the cured film-forming composition of the present embodiment, the component (C) may be a mixture of two or more of the polymers exemplified as the component (C).
　本発明の硬化膜形成組成物における（Ｃ）成分を含有させる場合の含有量は、（Ａ）成分であるポリマー及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して、好ましくは４００質量部以下、より好ましくは１０質量部～３８０質量部、更に好ましくは４０質量部～３６０質量部である。（Ｃ）成分の含有量が過大の場合は液晶配向性が低下し易い。 The content of component (C) in the cured film-forming composition of the present invention is preferably 100 parts by mass of the total amount of the polymer as component (A) and the crosslinking agent as component (B). The content is 400 parts by mass or less, more preferably 10 parts by mass to 380 parts by mass, and still more preferably 40 parts by mass to 360 parts by mass. When the content of the component (C) is excessive, the liquid crystal alignment tends to be deteriorated.
＜（Ｄ）成分＞
　本発明の硬化膜形成組成物は、前記（Ａ）成分及び（Ｂ）成分に加えて、さらに（Ｄ）成分として架橋触媒を含有することができる。
　（Ｄ）成分である架橋触媒としては、例えば、酸または熱酸発生剤を好適に使用できる。この（Ｄ）成分は、本発明の硬化膜形成組成物の熱硬化反応を促進させることにおいて有効である。
　（Ｄ）成分は、具体的には、上記酸としてスルホン酸基含有化合物、塩酸またはその塩が挙げられる。そして上記熱酸発生剤としては、加熱処理時に熱分解して酸を発生する化合物、すなわち温度８０℃から２５０℃で熱分解して酸を発生する化合物であれば、特に限定されるものではない。 <(D) component>
In addition to the said (A) component and (B) component, the cured film formation composition of this invention can contain the bridge | crosslinking catalyst as (D) component further.
As a crosslinking catalyst which is (D) component, an acid or a thermal acid generator can be used conveniently, for example. This (D) component is effective in promoting the thermosetting reaction of the cured film-forming composition of the present invention.
Specific examples of the component (D) include, as the acid, a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof. The thermal acid generator is not particularly limited as long as it is a compound which is thermally decomposed during heat treatment to generate an acid, that is, a compound which is thermally decomposed at a temperature of 80 ° C. to 250 ° C. to generate an acid. .
　上記酸の具体例としては、例えば、塩酸またはその塩；メタンスルホン酸、エタンスルホン酸、プロパンスルホン酸、ブタンスルホン酸、ペンタンスルホン酸、オクタンスルホン酸、ベンゼンスルホン酸、ｐ－トルエンスルホン酸、カンファースルホン酸、トリフルオロメタンスルホン酸、ｐ－フェノールスルホン酸、２－ナフタレンスルホン酸、メシチレンスルホン酸、ｐ－キシレン－２－スルホン酸、ｍ－キシレン－２－スルホン酸、４－エチルベンゼンスルホン酸、１Ｈ，１Ｈ，２Ｈ，２Ｈ－パーフルオロオクタンスルホン酸、パーフルオロ（２－エトキシエタン）スルホン酸、ペンタフルオロエタンスルホン酸、ノナフルオロブタン－１－スルホン酸、ドデシルベンゼンスルホン酸等のスルホン酸基含有化合物またはその水和物や塩等が挙げられる。 Specific examples of the above-mentioned acid include, for example, hydrochloric acid or a salt thereof; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphor Sulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, Sulfonic acid group-containing compounds such as 1H, 2H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid or Its hydrate or Etc. The.
　また熱により酸を発生する化合物としては、例えば、ビス（トシルオキシ）エタン、ビス（トシルオキシ）プロパン、ビス（トシルオキシ）ブタン、ｐ－ニトロベンジルトシレート、ｏ－ニトロベンジルトシレート、１，２，３－フェニレントリス（メチルスルホネート）、ｐ－トルエンスルホン酸ピリジニウム塩、ｐ－トルエンスルホン酸モルホニウム塩、ｐ－トルエンスルホン酸エチルエステル、ｐ－トルエンスルホン酸プロピルエステル、ｐ－トルエンスルホン酸ブチルエステル、ｐ－トルエンスルホン酸イソブチルエステル、ｐ－トルエンスルホン酸メチルエステル、ｐ－トルエンスルホン酸フェネチルエステル、シアノメチルｐ－トルエンスルホネート、２，２，２－トリフルオロエチルｐ－トルエンスルホネート、２－ヒドロキシブチルｐ－トルエンスルホネート、Ｎ－エチル－ｐ－トルエンスルホンアミド、さらに下記式で表される化合物： Further, as a compound capable of generating an acid by heat, for example, bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, -Phenylene tris (methyl sulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morpholinium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p- Toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydro Shibuchiru p- toluenesulfonate, N- ethyl -p- toluenesulfonamide, further represented by the following compound:
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
 等が挙げられる。
Figure JPOXMLDOC01-appb-C000014
 Etc.
　本発明の硬化膜形成組成物における（Ｄ）成分の含有量は、（Ａ）成分であるポリマー及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して、好ましくは０．０１質量部～２０質量部、より好ましくは０．１質量部～１５質量部、更に好ましくは０．５質量部～１０質量部である。（Ｄ）成分の含有量を０．０１質量部以上とすることで、充分な熱硬化性および溶剤耐性を付与することができる。しかし、２０質量部より多い場合、組成物の保存安定性が低下する場合がある。 The content of the component (D) in the cured film-forming composition of the present invention is preferably 0.01 parts by mass with respect to 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent of the component (B). The amount is from 20 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 15 parts by mass, and still more preferably 0.5 parts by mass to 10 parts by mass. By setting the content of the component (D) to 0.01 parts by mass or more, sufficient thermosetting and solvent resistance can be imparted. However, if it is more than 20 parts by mass, the storage stability of the composition may be reduced.
＜（Ｅ）成分＞
　本発明は（Ｅ）成分として、１つ以上の重合性基と、ヒドロキシ基、カルボキシル基、アミド基、アミノ基、およびアルコキシシリル基からなる群から選ばれる少なくとも１つの基Ａ又は該基Ａと反応する少なくとも１つの基とを有する化合物を含有することもできる。これは、形成される硬化膜の接着性を向上させる成分（以下、密着向上成分とも言う。）として作用する。 <(E) component>
The present invention provides as component (E) at least one group A selected from the group consisting of one or more polymerizable groups and a hydroxy group, a carboxyl group, an amido group, an amino group, and an alkoxysilyl group or the group A It can also contain compounds having at least one group to react. This acts as a component that improves the adhesion of the formed cured film (hereinafter, also referred to as an adhesion improving component).
　（Ｅ）成分を含有する本実施形態の硬化膜形成組成物から形成される硬化膜を配向材として用いる場合、配向材と重合性液晶の層との密着性が向上するよう、重合性液晶の重合性官能基と配向材の架橋反応部位を共有結合によりリンクさせることができる。その結果、本実施形態の配向材上に硬化した重合性液晶を積層してなる本実施形態の位相差材は、高温高質の条件下でも、強い密着性を維持することができ、剥離等に対する高い耐久性を示すことができる。 When a cured film formed from the cured film-forming composition of the present embodiment containing the component (E) is used as an alignment material, the adhesion of the alignment material to the layer of the polymerizable liquid crystal is improved, The crosslinkable reaction site of the polymerizable functional group and the orienting material can be linked by covalent bond. As a result, the phase difference material of the present embodiment formed by laminating the cured polymerizable liquid crystal on the alignment material of the present embodiment can maintain strong adhesion even under high temperature and high quality conditions, peeling etc. It can show high resistance to
　（Ｅ）成分としては、ヒドロキシ基及びＮ－アルコキシメチル基から選ばれる基と、重合性基とを有するモノマー及びポリマーが好ましい。
このような（Ｅ）成分としては、ヒドロキシ基と（メタ）アクリル基とを有する化合物、Ｎ－アルコキシメチル基と（メタ）アクリル基とを有する化合物、Ｎ－アルコキシメチル基と（メタ）アクリル基を有するポリマー等が挙げられる。以下、それぞれ具体例を示す。 As the component (E), monomers and polymers having a group selected from a hydroxy group and an N-alkoxymethyl group and a polymerizable group are preferable.
As such (E) component, a compound having a hydroxy group and a (meth) acrylic group, a compound having an N-alkoxymethyl group and a (meth) acrylic group, an N-alkoxymethyl group and a (meth) acrylic group And the like. Specific examples are shown below.
　（Ｅ）成分の一例として、ヒドロキシ基を含有した多官能アクリレート（以下、ヒドロキシ基含有多官能アクリレートとも言う。）を挙げることができる。
　（Ｅ）成分の例であるヒドロキシ基含有多官能アクリレートとしては、例えば、ペンタエリスリトールトリアクリレートおよびジペンタエリトリトールペンタアクリレート等を挙げることができる。 As an example of (E) component, the polyfunctional acrylate (Hereafter, it is also called a hydroxy group containing polyfunctional acrylate.) Containing a hydroxy group can be mentioned.
Examples of the hydroxy group-containing polyfunctional acrylate which is an example of the component (E) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
　（Ｅ）成分の一例として、１つのアクリル基と、１つ以上のヒドロキシ基とを有する化合物も挙げられる。このような、１つのアクリル基と、１つ以上のヒドロキシ基とを有する化合物の好ましい例を挙げる。尚、（Ｅ）成分の化合物は、以下の化合物例に限定されるものではない。 The compound which has one acryl group and one or more hydroxy groups is also mentioned as an example of (E) component. Preferred examples of such compounds having one acrylic group and one or more hydroxy groups are listed. In addition, the compound of (E) component is not limited to the following compound example.
Figure JPOXMLDOC01-appb-C000015
 （上記式中、Ｒ１１は水素原子またはメチル基を表し、ｍは１～１０の整数を表す。）
Figure JPOXMLDOC01-appb-C000015
 (Wherein, R 11 represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10).
　また、（Ｅ）成分の化合物としては、１分子中にＣ＝Ｃ二重結合を含む重合性基を少なくとも１つと、Ｎ－アルコキシメチル基を少なくとも１つ有する化合物が挙げられる。 Further, examples of the compound of the component (E) include a compound having at least one polymerizable group containing a C = C double bond in one molecule and at least one N-alkoxymethyl group.
　Ｃ＝Ｃ二重結合を含む重合性基としては、アクリル基、メタクリル基、ビニル基、アリル基、マレイミド基等が挙げられる。 Examples of the polymerizable group containing a C = C double bond include an acryl group, a methacryl group, a vinyl group, an allyl group and a maleimide group.
　Ｎ－アルコキシメチル基のＮ、すなわち窒素原子としては、アミドの窒素原子、チオアミドの窒素原子、ウレアの窒素原子、チオウレアの窒素原子、ウレタンの窒素原子、含窒素へテロ環の窒素原子の隣接位に結合した窒素原子等が挙げられる。従って、Ｎ－アルコキシメチル基としては、アミドの窒素原子、チオアミドの窒素原子、ウレアの窒素原子、チオウレアの窒素原子、ウレタンの窒素原子、含窒素へテロ環の窒素原子の隣接位に結合した窒素原子等から選ばれる窒素原子にアルコキシメチル基が結合した構造が挙げられる。 The N of an N-alkoxymethyl group, that is, the nitrogen atom of an amide, a nitrogen atom of a thioamide, a nitrogen atom of a urea, a nitrogen atom of a thiourea, a nitrogen atom of a urethane, a nitrogen atom of a urethane, a nitrogen atom of a nitrogen-containing heterocyclic ring And a nitrogen atom etc. bonded to Accordingly, as the N-alkoxymethyl group, a nitrogen atom of an amide, a nitrogen atom of a thioamide, a nitrogen atom of a urea, a nitrogen atom of a thiourea, a nitrogen atom of a urethane, a nitrogen atom of a urethane, a nitrogen bonded adjacent to a nitrogen atom of a nitrogen-containing heterocyclic ring A structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from atoms and the like can be mentioned.
　（Ｅ）成分としては、上記の基を有するものであればよいが、好ましくは、例えば下記の式（Ｘ１）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000016
 （式中、Ｒ３１は水素原子又はメチル基を表し、Ｒ３２は水素原子、若しくは直鎖又は分岐の炭素原子数１乃至１０のアルキル基を表す） As the component (E), any one having the above-mentioned group may be used, and preferably, for example, a compound represented by the following formula (X1) can be mentioned.
Figure JPOXMLDOC01-appb-C000016
 (Wherein, R 31 represents a hydrogen atom or a methyl group, and R 32 represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms)
　上記アルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、１－メチル－ｎ－ブチル基、２－メチル－ｎ－ブチル基、３－メチル－ｎ－ブチル基、１，１－ジメチル－ｎ－プロピル基、１，２－ジメチル－ｎ－プロピル基、２，２－ジメチル－ｎ－プロピル基、１－エチル－ｎ－プロピル基、ｎ－ヘキシル基、１－メチル－ｎ－ペンチル基、２－メチル－ｎ－ペンチル基、３－メチル－ｎ－ペンチル基、４－メチル－ｎ－ペンチル基、１，１－ジメチル－ｎ－ブチル基、１，２－ジメチル－ｎ－ブチル基、１，３－ジメチル－ｎ－ブチル基、２，２－ジメチル－ｎ－ブチル基、２，３－ジメチル－ｎ－ブチル基、３，３－ジメチル－ｎ－ブチル基、１－エチル－ｎ－ブチル基、２－エチル－ｎ－ブチル基、１，１，２－トリメチル－ｎ－プロピル基、１，２，２－トリメチル－ｎ－プロピル基、１－エチル－１－メチル－ｎ－プロピル基、１－エチル－２－メチル－ｎ－プロピル基、ｎ－ヘプチル基、１－メチル－ｎ－ヘキシル基、２－メチル－ｎ－ヘキシル基、３－メチル－ｎ－ヘキシル基、１，１－ジメチル－ｎ－ペンチル基、１，２－ジメチル－ｎ－ペンチル基、１，３－ジメチル－ｎ－ペンチル基、２，２－ジメチル－ｎ－ペンチル基、２，３－ジメチル－ｎ－ペンチル基、３，３－ジメチル－ｎ－ペンチル基、１－エチル－ｎ－ペンチル基、２－エチル－ｎ－ペンチル基、３－エチル－ｎ－ペンチル基、１－メチル－１－エチル－ｎ－ブチル基、１－メチル－２－エチル－ｎ－ブチル基、１－エチル－２－メチル－ｎ－ブチル基、２－メチル－２－エチル－ｎ－ブチル基、２－エチル－３－メチル－ｎ－ブチル基、ｎ－オクチル基、１－メチル－ｎ－ヘプチル基、２－メチル－ｎ－ヘプチル基、３－メチル－ｎ－ヘプチル基、１，１－ジメチル－ｎ－ヘキシル基、１，２－ジメチル－ｎ－ヘキシル基、１，３－ジメチル－ｎ－ヘキシル基、２，２－ジメチル－ｎ－ヘキシル基、２，３－ジメチル－ｎ－ヘキシル基、３，３－ジメチル－ｎ－ヘキシル基、１－エチル－ｎ－ヘキシル基、２－エチル－ｎ－ヘキシル基、３－エチル－ｎ－ヘキシル基、１－メチル－１－エチル－ｎ－ペンチル基、１－メチル－２－エチル－ｎ－ペンチル基、１－メチル－３－エチル－ｎ－ペンチル基、２－メチル－２－エチル－ｎ－ペンチル基、２－メチル－３－エチル－ｎ－ペンチル基、３－メチル－３－エチル－ｎ－ペンチル基、ｎ－ノニル基、ｎ－デシル基等が挙げられる。 Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 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 group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl- n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2 , 3-Dimethyl-n-butyl, 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 group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1-methyl-n-hexyl group, 2-methyl-n-hexyl group Group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1,3-dimethyl-n-pentyl group, 2,2-dimethyl- n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n -Pentyl group, 1-methyl-1-ethyl-n-butyl group 1-methyl-2-ethyl-n-butyl group, 1-ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group Group, n-octyl group, 1-methyl-n-heptyl group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl -N-hexyl group, 1,3-dimethyl-n-hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n- group Pentyl group, 1-methyl-3-ethyl-n-pentyl group, 2-methane And ethyl 2-ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl, 3-methyl-3-ethyl-n-pentyl, n-nonyl and n-decyl groups. .
　上記式（Ｘ１）で表される化合物の具体例としては、Ｎ－ヒドロキシメチル（メタ）アクリルアミド、Ｎ－メトキシメチル（メタ）アクリルアミド、Ｎ－エトキシメチル（メタ）アクリルアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド等のヒドロキシメチル基又はアルコキシメチル基で置換されたアクリルアミド化合物又はメタクリルアミド化合物が挙げられる。なお（メタ）アクリルアミドとはメタクリルアミドとアクリルアミドの双方を意味する。 Specific examples of the compound represented by the above formula (X1) include N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) An acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as acrylamide may be mentioned. In addition, (meth) acrylamide means both methacrylamide and acrylamide.
　（Ｅ）成分のＣ＝Ｃ二重結合を含む重合性基とＮ－アルコキシメチル基を有する化合物の別の態様としては、好ましくは、例えば下記の式（Ｘ２）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000017
 　式中、Ｒ５１は水素原子又はメチル基を表す。
　Ｒ５２は炭素原子数２乃至２０のアルキル基、炭素原子数５乃至６の１価の脂肪族環基、若しくは炭素原子数５乃至６の脂肪族環を含む１価の脂肪族基を表し、構造中にエーテル結合を含んでいてもよい。
　Ｒ５３は直鎖又は分枝鎖の炭素原子数２乃至２０のアルキレン基、炭素原子数５乃至６の２価の脂肪族環基、若しくは炭素原子数５乃至６の脂肪族環を含む２価の脂肪族基を表し、構造中にエーテル結合を含んでいてもよい。
　Ｒ５４は直鎖又は分枝鎖の炭素原子数１乃至２０の２価乃至９価の脂肪族基、炭素原子数５乃至６の２価乃至９価の脂肪族環基、若しくは炭素原子数５乃至６の脂肪族環を含む２価乃至９価の脂肪族基を表し、これらの基の一つのメチレン基または隣り合わない複数のメチレン基がエーテル結合に置き換わっていてもよい。
　Ｚは＞ＮＣＯＯ－、または－ＯＣＯＮ＜（ここで「－」は結合手が１つであることを示す。また、「＞」「＜」は結合手が２つであることを示し、かつ、どちらか１つの結合手にアルコキシメチル基（即ち－ＯＲ５２基）が結合していることを示す。）を表す。
　ｒは２以上９以下の自然数である。 As another embodiment of the compound having a polymerizable group containing a C = C double bond of component (E) and an N-alkoxymethyl group, a compound represented by the following formula (X2) is preferably exemplified. .
Figure JPOXMLDOC01-appb-C000017
 In the formula, R 51 represents a hydrogen atom or a methyl group.
R 52 represents an alkyl group having 2 to 20 carbon atoms, a monovalent aliphatic ring group having 5 to 6 carbon atoms, or a monovalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, The structure may contain an ether bond.
R 53 represents a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent aliphatic ring group having 5 to 6 carbon atoms, or a divalent containing an aliphatic ring having 5 to 6 carbon atoms And an ether bond may be included in the structure.
R 54 is a linear or branched divalent to pentavalent aliphatic group having 1 to 20 carbon atoms, a divalent to ninth divalent aliphatic ring group having 5 to 6 carbon atoms, or 5 carbon atoms And a divalent to nine-valent aliphatic group containing one to six aliphatic rings, wherein one methylene group or a plurality of non-adjacent methylene groups of these groups may be replaced by an ether bond.
Z is> NCOO- or -OCON <(where, "-" indicates that there is one bond, and ">" or "<" indicates that there are two bonds, and Indicates that an alkoxymethyl group (ie, -OR52 group) is bonded to any one bond.
r is a natural number of 2 or more and 9 or less.
　Ｒ５３の定義における炭素原子数２乃至２０のアルキレン基の具体例としては、炭素原子数２乃至２０のアルキル基から、さらに１個の水素原子を取り去った２価の基が挙げられる。
　またＲ５４の定義における炭素原子数１乃至２０の２価乃至９価の脂肪族基の具体例としては、炭素原子数１乃至２０のアルキル基から、さらに１乃至８個の水素原子を取り去った２価乃至９価の基が挙げられる。 Specific examples of the alkylene group having 2 to 20 carbon atoms in the definition of R 53 include divalent groups in which one hydrogen atom is further removed from the alkyl group having 2 to 20 carbon atoms.
Further, as a specific example of the divalent to decavalent aliphatic group having 1 to 20 carbon atoms in the definition of R 54 , 1 to 8 hydrogen atoms are further removed from the alkyl group having 1 to 20 carbon atoms Divalent to 9-valent groups may be mentioned.
　炭素原子数１のアルキル基はメチル基であり、また炭素原子数２乃至２０のアルキル基の具体例としては、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、１－メチル－ｎ－ブチル基、２－メチル－ｎ－ブチル基、３－メチル－ｎ－ブチル基、１，１－ジメチル－ｎ－プロピル基、ｎ－ヘキシル基、１－メチル－ｎ－ペンチル基、２－メチル－ｎ－ペンチル基、１，１－ジメチル－ｎ－ブチル基、１－エチル－ｎ－ブチル基、１，１，２－トリメチル－ｎ－プロピル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ウンデシル基、ｎ－ドデシル基、ｎ－トリデシル基、ｎ－テトラデシル基、ｎ－ペンタデシル基、ｎ－ヘキサデシル基、ｎ－ヘプタデシル基、ｎ－オクタデシル基、ｎ－ノナデシル基、ｎ－エイコシル基、シクロペンチル基、シクロヘキシル基、それらの一種または複数種が炭素原子数２０までの範囲で結合した基と、これらの基の一つのメチレンまたは隣り合わない複数のメチレン基がエーテル結合に置き換わった基等が一例として挙げられる。 The alkyl group having 1 carbon atom is a methyl group, and specific examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group. Group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl- n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 1, 1,2-trimethyl-n-propyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group , N-pentadecyl group, n-hexadecyl group, -Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, cyclopentyl group, cyclohexyl group, a group in which one or more of them are bonded in a range of up to 20 carbon atoms, and one of these groups A group in which two methylenes or a plurality of non-adjacent methylene groups are replaced by ether bonds is an example.
　これらのうち、炭素原子数２乃至１０のアルキレン基が好ましく、Ｒ５３がエチレン基であり、Ｒ５４がヘキシレン基であるのが原料の入手性等の点から特に好ましい。 Among them, an alkylene group having 2 to 10 carbon atoms is preferable, and it is particularly preferable that R 53 is an ethylene group and R 54 is a hexylene group from the viewpoint of availability of raw materials.
　Ｒ５２の定義における炭素原子数１乃至２０のアルキル基の具体例としては、Ｒ５３の定義における炭素原子数２乃至２０のアルキル基の具体例及びメチル基が挙げられる。これらのうち、炭素原子数１乃至６のアルキル基が好ましく、メチル基、エチル基、n－プロピル基またはn－ブチル基が特に好ましい。 Specific examples of the alkyl group having 1 to 20 carbon atoms in the definition of R 52 include the specific examples of the alkyl group having 2 to 20 carbon atoms in the definition of R 53 and a methyl group. Among these, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group or an n-butyl group is particularly preferable.
　ｒとしては、２以上９以下の自然数が挙げられるが、中でも、２乃至６が好ましい。 As r, a natural number of 2 or more and 9 or less can be mentioned, and among them, 2 to 6 is preferable.
　本発明の実施形態の硬化膜形成組成物における（Ｅ）成分の含有量は、（Ａ）成分であるポリマー及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して、好ましくは１質量部～１００質量部であり、更に好ましくは５質量部～７０質量部である。（Ｅ）成分の含有量を１質量部以上とすることで、形成される硬化膜に充分な密着性を付与することができる。しかし、１００質量部より多い場合、液晶配向性が低下し易い。 The content of the component (E) in the cured film-forming composition of the embodiment of the present invention is preferably 1 part by mass with respect to 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent of the component (B). The amount is 100 parts by mass, and more preferably 5 parts by mass to 70 parts by mass. By making content of (E) component into 1 mass part or more, sufficient adhesiveness can be provided to the cured film formed. However, if the amount is more than 100 parts by mass, the liquid crystal alignment tends to be degraded.
　また、本実施形態の硬化膜形成組成物において、（Ｅ）成分は、（Ｅ）成分の化合物の複数種の混合物であってもよい。 Moreover, in the cured film formation composition of this embodiment, multiple types of mixtures of the compound of (E) component may be sufficient as (E) component.
＜溶剤＞
　本発明の硬化膜形成組成物は、主として溶剤に溶解した溶液状態で用いられる。その際に使用する溶剤は、（Ａ）成分、（Ｂ）成分および必要に応じて（Ｃ）成分、（Ｄ）成分、（Ｅ）成分および／または後述するその他添加剤を溶解できればよく、その種類および構造などは特に限定されるものでない。 <Solvent>
The cured film-forming composition of the present invention is used mainly in the form of a solution dissolved in a solvent. The solvent used at that time should just be able to dissolve the (A) component, the (B) component and, if necessary, the (C) component, the (D) component, the (E) component and / or other additives described later, The type, structure, etc. are not particularly limited.
　溶剤の具体例としては、例えば、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、イソブタノール、２－メチル－１－ブタノール、ｎ－ペンタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテル、プロピレングリコールプロピルエーテル、プロピレングリコールプロピルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、イソブチルメチルケトン、シクロペンタノン、シクロヘキサノン、２－ブタノン、３－メチル－２－ペンタノン、２－ペンタノン、２－ヘプタノン、γ－ブチロラクトン、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、シクロペンチルメチルエーテル、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、およびＮ－メチル－２－ピロリドン等が挙げられる。 Specific examples of the solvent include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, Toluene, xylene, methyl Ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, cyclopentyl methyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone Etc.
　本発明の硬化膜形成組成物を用い、樹脂フィルム上に硬化膜を形成して配向材を製造する場合は、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、２－メチル－１－ブタノール、２－ヘプタノン、イソブチルメチルケトン、ジエチレングリコール、プロピレングリコール、プロピレングリコールモノメチルエーテル、シクロペンチルメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、酢酸エチル、酢酸ブチル等が、樹脂フィルムが耐性を示す溶剤であるという点から好ましい。 When a cured film is formed on a resin film using the cured film-forming composition of the present invention to produce an alignment material, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate and the like are preferable from the viewpoint that the resin film exhibits resistance. .
　これらの溶剤は、１種単独でまたは２種以上の組合せで使用することができる。 These solvents can be used singly or in combination of two or more.
＜その他添加剤＞
　さらに、本発明の硬化膜形成組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、密着向上剤、シランカップリング剤、界面活性剤、レオロジー調整剤、顔料、染料、保存安定剤、消泡剤、酸化防止剤等を含有することができる。 <Other additives>
Furthermore, as long as the cured film forming composition of the present invention does not impair the effects of the present invention, as necessary, an adhesion improver, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, storage stability An agent, an antifoamer, an antioxidant etc. can be contained.
＜硬化膜形成組成物の調製＞
　本発明の硬化膜形成組成物は、（Ａ）成分のポリマーおよび（Ｂ）成分の架橋剤を含有し、所望により（Ｃ）成分のポリマー、（Ｄ）成分の架橋触媒および（Ｅ）成分密着促進剤、そして更に本発明の効果を損なわない限りにおいてその他の添加剤を含有することができる組成物である。そして通常は、それらが溶剤に溶解した溶液の形態として用いられる。 <Preparation of Cured Film Forming Composition>
The cured film-forming composition of the present invention contains the polymer of component (A) and the crosslinking agent of component (B), and optionally the polymer of component (C), the crosslinking catalyst of component (D) and the component (E) adhesion It is a composition which can contain an accelerator and further other additives as long as the effect of the present invention is not impaired. And, usually, they are used in the form of a solution dissolved in a solvent.
　本発明の硬化膜形成組成物の好ましい例は、以下のとおりである。
　［１］：（Ａ）成分、（Ａ）成分１００質量部に基づいて、１質量部～５００質量部の（Ｂ）成分を含有する硬化膜形成組成物。
　［２］：（Ａ）成分、（Ａ）成分１００質量部に基づいて、１質量部～５００質量部の（Ｂ）成分、並びに、（Ａ）成分であるポリマー及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して１～４００質量部の（Ｃ）成分を含有する硬化膜形成組成物。
　［３］：（Ａ）成分、（Ａ）成分１００質量部に基づいて、１質量部～５００質量部の（Ｂ）成分、並びに、溶剤を含有する硬化膜形成組成物。
　［４］：（Ａ）成分、（Ａ）成分１００質量部に基づいて、１質量部～５００質量部の（Ｂ）成分、（Ａ）成分であるポリマー及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して１～４００質量部の（Ｃ）成分、並びに、溶剤を含有する硬化膜形成組成物。
　［５］：（Ａ）成分、（Ａ）成分１００質量部に基づいて、１質量部～５００質量部の（Ｂ）成分、（Ａ）成分であるポリマー及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して１～４００質量部の（Ｃ）成分、（Ａ）成分であるポリマー及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して０．０１質量部～２０質量部の（Ｄ）成分、溶剤を含有する硬化膜形成組成物。
　［６］：（Ａ）成分、（Ａ）成分１００質量部に基づいて、１質量部～５００質量部の（Ｂ）成分、（Ａ）成分であるポリマー及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して１～４００質量部の（Ｃ）成分、（Ａ）成分であるポリマー及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して０．０１質量部～２０質量部の（Ｄ）成分、（Ａ）成分であるポリマー及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して１質量部～１００質量部の（Ｅ）成分、並びに、溶剤を含有する硬化膜形成組成物。 The preferable example of the cured film formation composition of this invention is as follows.
[1] A cured film-forming composition containing 1 part by mass to 500 parts by mass of the (B) component based on 100 parts by mass of the (A) component and the (A) component.
[2]: 1 part by mass to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A), and a polymer as the component (A) and a crosslinking agent of the component (B) A cured film-forming composition comprising 1 to 400 parts by mass of the component (C) with respect to 100 parts by mass of the total amount of
[3] A cured film-forming composition containing 1 part by mass to 500 parts by mass of the component (B) and a solvent based on 100 parts by mass of the component (A) and the component (A).
[4]: A total of 1 to 500 parts by mass of the component (B), the polymer which is the component (A) and the crosslinking agent of the component (B) based on 100 parts by mass of the component (A) or (A) A cured film-forming composition comprising 1 to 400 parts by mass of the component (C) per 100 parts by mass of the composition, and a solvent.
[5]: A total of 1 to 500 parts by mass of the component (B), the polymer which is the component (A) and the crosslinking agent of the component (B) based on 100 parts by mass of the component (A) or (A) 0.01 parts by mass to 100 parts by mass of the total amount of 1 to 400 parts by mass of the component (C), the polymer which is the component (A) and the crosslinking agent of the component (B) per 100 parts by mass of The cured film formation composition containing 20 mass parts (D) component and a solvent.
[6]: A total of 1 to 500 parts by mass of the component (B), the polymer which is the component (A) and the crosslinking agent of the component (B) based on 100 parts by mass of the component (A) or (A) 0.01 parts by mass to 100 parts by mass of the total amount of 1 to 400 parts by mass of the component (C), the polymer which is the component (A) and the crosslinking agent of the component (B) per 100 parts by mass of 1 part by mass to 100 parts by mass of the component (E) with respect to 100 parts by mass of the total amount of 20 parts by mass of the component (D), the polymer which is the component (A) and the crosslinking agent of the component (B) A cured film-forming composition containing:
　本発明の硬化膜形成組成物を溶液として用いる場合の配合割合、調製方法等を以下に詳述する。
　本発明の硬化膜形成組成物における固形分の割合は、各成分が均一に溶剤に溶解している限り、特に限定されるものではないが、１質量％～６０質量％であり、好ましくは２質量％～５０質量％であり、より好ましくは２質量％～２０質量％である。ここで、固形分とは、硬化膜形成組成物の全成分から溶剤を除いたものをいう。 The compounding ratio in the case of using the cured film formation composition of this invention as a solution, a preparation method, etc. are explained in full detail below.
The ratio of solid content in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1% by mass to 60% by mass, and preferably 2 The content is 50% by mass, more preferably 2% by mass to 20% by mass. Here, solid content means what remove | eliminated the solvent from all the components of a cured film formation composition.
　本発明の硬化膜形成組成物の調製方法は、特に限定されない。調製法としては、例えば、溶剤に溶解した（Ａ）成分の溶液に（Ｂ）成分、さらには（Ｃ）成分、（Ｄ）成分、（Ｅ）成分等を所定の割合で混合し、均一な溶液とする方法、或いは、この調製法の適当な段階において、必要に応じてその他添加剤をさらに添加して混合する方法が挙げられる。 The method for preparing the cured film-forming composition of the present invention is not particularly limited. As a preparation method, for example, the solution of the component (A) dissolved in a solvent, the component (B), and further, the components (C), (D), (E) and the like are mixed at a predetermined ratio and homogeneous. The method of making it into a solution, or the method of adding and mixing other additives as needed at the appropriate stage of this preparation method may be mentioned.
　本発明の硬化膜形成組成物の調製においては、溶剤中の重合反応によって得られる特定共重合体（ポリマー）の溶液をそのまま使用することができる。この場合、例えば、（Ａ）成分の溶液に前記と同様に（Ｂ）成分、さらには（Ｃ）成分、（Ｄ）成分、（Ｅ）成分等を入れて均一な溶液とする。この際に、濃度調整を目的としてさらに溶剤を追加投入してもよい。このとき、（Ａ）成分の生成過程で用いられる溶剤と、硬化膜形成組成物の濃度調整に用いられる溶剤とは同一であってもよく、また異なってもよい。 In preparation of the cured film formation composition of this invention, the solution of the specific copolymer (polymer) obtained by the polymerization reaction in a solvent can be used as it is. In this case, for example, component (B), component (C), component (D), component (E) and the like are added to the solution of component (A) in the same manner as described above to obtain a uniform solution. At this time, a solvent may be additionally added for the purpose of adjusting the concentration. At this time, the solvent used in the process of producing the component (A) and the solvent used for adjusting the concentration of the cured film-forming composition may be the same or different.
　また、調製された硬化膜形成組成物の溶液は、孔径が０．２μｍ程度のフィルタなどを用いて濾過した後、使用することが好ましい。 Moreover, it is preferable to use, after filtering the solution of the prepared cured film formation composition using a filter with a pore diameter of about 0.2 μm or the like.
＜硬化膜、配向材および位相差材＞
　本発明の硬化膜形成組成物の溶液を基板（例えば、シリコン／二酸化シリコン被覆基板、シリコンナイトライド基板、金属、例えば、アルミニウム、モリブデン、クロムなどが被覆された基板、ガラス基板、石英基板、ＩＴＯ基板等）やフィルム基板（例えば、トリアセチルセルロース（ＴＡＣ）フィルム、ポリカーボネート（ＰＣ）フィルム、シクロオレフィンポリマー（ＣＯＰ）フィルム、シクロオレフィンコポリマー（ＣＯＣ）フィルム、ポリエチレンテレフタレート（ＰＥＴ）フィルム、アクリルフィルム、ポリエチレンフィルム等の樹脂フィルム）等の上に、バーコート、回転塗布、流し塗布、ロール塗布、スリット塗布、スリットに続いた回転塗布、インクジェット塗布、印刷などによって塗布して塗膜を形成し、その後、ホットプレートまたはオーブン等で加熱乾燥することにより、硬化膜を形成することができる。該硬化膜はそのまま配向材として適用できる。 <Cured film, alignment material and retardation material>
The solution of the cured film forming composition of the present invention is used as a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum or chromium, a glass substrate, a quartz substrate, ITO Substrates, etc.) and film substrates (eg, triacetyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET) film, acrylic film, polyethylene film Coating film is formed on a resin film such as a film by bar coating, spin coating, flow coating, roll coating, slit coating, slit coating followed by spin coating, inkjet coating, printing, etc. Relieved Dried by heating with a plate or an oven or the like, it is possible to form a cured film. The cured film can be applied as an alignment material as it is.
　加熱乾燥の条件としては、硬化膜（配向材）の成分が、その上に塗布される重合性液晶溶液に溶出しない程度に、架橋剤による架橋反応が進行すればよく、例えば、温度６０℃～２００℃、時間０．４分間～６０分間の範囲の中から適宜選択された加熱温度および加熱時間が採用される。加熱温度および加熱時間は、好ましくは７０℃～１６０℃、０．５分間～１０分間である。 The conditions for the heating and drying may be such that the crosslinking reaction by the crosslinking agent proceeds to such an extent that the components of the cured film (alignment material) do not elute in the polymerizable liquid crystal solution applied thereon. A heating temperature and a heating time appropriately selected from the range of 200 ° C. and 0.4 minutes to 60 minutes are employed. The heating temperature and the heating time are preferably 70 ° C. to 160 ° C., for 0.5 minutes to 10 minutes.
　本発明の硬化性組成物を用いて形成される硬化膜（配向材）の膜厚は、例えば、０．０５μｍ～５μｍであり、使用する基板の段差や光学的、電気的性質を考慮し適宜選択することができる。 The film thickness of the cured film (alignment material) formed using the curable composition of the present invention is, for example, 0.05 μm to 5 μm, and is appropriately determined in consideration of the difference in level of the substrate used and the optical and electrical properties. It can be selected.
　本発明の硬化膜組成物から形成された配向材は耐溶剤性および耐熱性を有しているため、この配向材上に、垂直配向性を有する重合性液晶溶液などの位相差材料を塗布し、配向材上で配向させることができる。そして、配向状態となった位相差材料をそのまま硬化させることにより、光学異方性を有する層として位相差材を形成することができる。そして、配向材を形成する基板がフィルムである場合には、位相差フィルムとして有用となる。 Since the alignment material formed from the cured film composition of the present invention has solvent resistance and heat resistance, a retardation material such as a polymerizable liquid crystal solution having vertical alignment property is coated on the alignment material. And alignment on the alignment material. Then, by curing the retardation material in the oriented state as it is, the retardation material can be formed as a layer having optical anisotropy. And when the board | substrate which forms an orientation material is a film, it becomes useful as retardation film.
　また、上記のようにして形成された、本発明の配向材を有する２枚の基板を用い、スペーサを介して両基板上の配向材が互いに向かい合うように張り合わせた後、それらの基板の間に液晶を注入して、液晶が配向した液晶表示素子とすることもできる。
　このように本発明の硬化膜形成組成物は、各種位相差材（位相差フィルム）や液晶表示素子等の製造に好適に用いることができる。 Also, using the two substrates having the alignment material of the present invention formed as described above, after the alignment materials on both substrates are pasted so as to face each other through the spacers, the space between those substrates A liquid crystal can be injected to form a liquid crystal display element in which the liquid crystal is aligned.
Thus, the cured film formation composition of this invention can be used suitably for manufacture of various retardation material (retardation film), a liquid crystal display element, etc.
　以下、本発明の実施例を挙げて、本発明を具体的に説明するが、本発明はこれらに限定して解釈されるものではない。 EXAMPLES Hereinafter, the present invention will be specifically described by way of examples of the present invention, but the present invention is not construed as being limited thereto.
［実施例で用いる略記号］
　以下の実施例で用いる略記号の意味は、次のとおりである。
＜原料＞
ＧＭＡ：グリシジルメタクリレート
ＡＩＢＮ：α，α’－アゾビスイソブチロニトリル
ＢＭＡＡ：Ｎ－ブトキシメチルアクリルアミド
ＭＭＡ：メタクリル酸メチル
ＨＥＭＡ：２－ヒドロキシエチルメタクリレート
＜重合性基を有する桂皮酸化合物＞
ＣＩＮ１：４－（６－メタクリルオキシヘキシル－１－オキシ）桂皮酸
Figure JPOXMLDOC01-appb-C000018
 ＣＩＮ２：４－（３－メタクリルオキシプロピル－１－オキシ）桂皮酸
Figure JPOXMLDOC01-appb-C000019
 ＣＩＮ３：４－（６－アクリルオキシヘキシル－１－オキシ）桂皮酸
Figure JPOXMLDOC01-appb-C000020
 ＜重合性基を有さない桂皮酸化合物＞
ＣＩＮ４：４－メトキシ桂皮酸
Figure JPOXMLDOC01-appb-C000021
 ＜Ｂ成分＞
ＨＭＭ：下記の構造式で表されるメラミン架橋剤［サイメル（ＣＹＭＥＬ）（登録商標）３０３（三井サイテック（株）製）］
Figure JPOXMLDOC01-appb-C000022
 ＜Ｄ成分＞
ＰＴＳＡ：ｐ－トルエンスルホン酸・一水和物
＜Ｅ成分＞
Ｅ－１：下記の構造式で示されるＮ－アルコキシメチル基およびアクリル基を有する化合物
Figure JPOXMLDOC01-appb-C000023
 ＜溶剤＞
実施例及び比較例の各樹脂組成物は溶剤を含有し、その溶剤として、プロピレングリコールモノメチルエーテル（ＰＭ）を用いた。 [Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<Raw material>
GMA: glycidyl methacrylate AIBN: α, α'-azobis isobutyro nitrile BMAA: N-butoxymethyl acrylamide MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate <cinnamic acid compound having a polymerizable group>
CIN 1: 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid
Figure JPOXMLDOC01-appb-C000018
 CIN2: 4- (3-methacryloxypropyl-1-oxy) cinnamic acid
Figure JPOXMLDOC01-appb-C000019
 CIN 3: 4- (6-acryloxyhexyl-1-oxy) cinnamic acid
Figure JPOXMLDOC01-appb-C000020
 <Cinnamic acid compound having no polymerizable group>
CIN 4: 4-methoxycinnamic acid
Figure JPOXMLDOC01-appb-C000021
 <B component>
HMM: Melamine crosslinker represented by the following structural formula [Cymel (CYMEL) (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.)]
Figure JPOXMLDOC01-appb-C000022
 <D component>
PTSA: p-toluenesulfonic acid monohydrate <E component>
E-1: a compound having an N-alkoxymethyl group and an acrylic group represented by the following structural formula
Figure JPOXMLDOC01-appb-C000023
 <Solvent>
Each resin composition of Examples and Comparative Examples contained a solvent, and propylene glycol monomethyl ether (PM) was used as the solvent.
＜重合体の分子量の測定＞
　重合例におけるアクリル共重合体の分子量は、（株）Ｓｈｏｄｅｘ社製常温ゲル浸透クロマトグラフィー（ＧＰＣ）装置（ＧＰＣ－１０１）、Ｓｈｏｄｅｘ社製カラム（ＫＤ―８０３、ＫＤ－８０５）を用い以下のようにして測定した。
なお、下記の数平均分子量（以下、Ｍｎと称す。）及び重量平均分子量（以下、Ｍｗと称す。）は、ポリスチレン換算値にて表した。
カラム温度：４０℃
溶離液：テトラヒドロフラン
流速：１．０ｍＬ／分
検量線作成用標準サンプル：昭和電工社製　標準ポリスチレン（分子量　約１９７，０００、５５，１００、１２，８００、３，９５０、１，２６０、５８０）。 <Measurement of Molecular Weight of Polymer>
The molecular weight of the acrylic copolymer in the polymerization example is as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Corp. and a column (KD-803, KD-805) manufactured by Shodex Corp. And measured.
The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.
Column temperature: 40 ° C
Eluent: tetrahydrofuran Flow rate: 1.0 mL / min Standard sample for calibration curve preparation: Standard polystyrene manufactured by Showa Denko (molecular weight about 197,000, 55, 100, 12, 800, 3, 950, 1, 260, 580).
＜Ａ成分の合成＞
＜重合例１＞　
　ＧＭＡ　１５．０ｇ、重合触媒としてＡＩＢＮ　０．５ｇをテトラヒドロフラン　４６．４ｇに溶解し、加熱還流下にて２０時間反応させることによりアクリル重合体溶液を得た。得られたアクリル共重合体溶液をヘキサン５００．０ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することで、エポキシ基を有するアクリル重合体（Ｐ１）を得た。得られたアクリル重合体のＭｎは２５，０００、Ｍｗは１０，０００であった。 <Composition of A component>
Polymerization Example 1
An acrylic polymer solution was obtained by dissolving 15.0 g of GMA and 0.5 g of AIBN as a polymerization catalyst in 46.4 g of tetrahydrofuran and reacting for 20 hours under heating and reflux. The obtained acrylic copolymer solution was gradually added dropwise to 500.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic polymer (P1) having an epoxy group. Mn of the obtained acrylic polymer was 25,000 and Mw was 10,000.
＜合成例１＞
　重合例１で得たエポキシ基を有するアクリル重合体（Ｐ１）５．２ｇ、ＣＩＮ１　１２．０ｇ、反応触媒としてエチルトリフェニルホスホニウムブロミド　０．１ｇ、重合禁止剤としてジブチルヒドロキシトルエン　０．２ｇをＰＭ　７０．０ｇに溶解させ、１００℃で２０時間反応させた。この溶液をジエチルエーテル　１０００ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することで、重合体（ＰＡ－１）を得た。得られた重合体のエポキシ価を測定し、エポキシ基が消失したことを確認した。 Synthesis Example 1
5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 12.0 g of CIN 1, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor It was dissolved in 0. 0g and reacted at 100 ° C for 20 hours. This solution was gradually dropped into 1000 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-1). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
＜合成例２＞
　重合例１で得たエポキシ基を有するアクリル重合体（Ｐ１）５．２ｇ、ＣＩＮ２　１１．０ｇ、反応触媒としてエチルトリフェニルホスホニウムブロミド　０．１ｇ、重合禁止剤としてジブチルヒドロキシトルエン　０．２ｇをＰＭ　７０．０ｇに溶解させ、１００℃で２０時間反応させた。この溶液をジエチルエーテル　１０００ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することで、重合体（ＰＡ－２）を得た。得られた重合体のエポキシ価を測定し、エポキシ基が消失したことを確認した。 Synthesis Example 2
5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 11.0 g of CIN2, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor It was dissolved in 0. 0g and reacted at 100 ° C for 20 hours. This solution was gradually dropped into 1000 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-2). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
＜合成例３＞
　重合例１で得たエポキシ基を有するアクリル重合体（Ｐ１）５．２ｇ、ＣＩＮ３　１２．０ｇ、反応触媒としてエチルトリフェニルホスホニウムブロミド　０．１ｇ、重合禁止剤としてジブチルヒドロキシトルエン　０．２ｇをＰＭ　７０．０ｇに溶解させ、１００℃で２０時間反応させた。この溶液をジエチルエーテル　１０００ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することで、重合体（ＰＡ－３）を得た。得られた重合体のエポキシ価を測定し、エポキシ基が消失したことを確認した。 Synthesis Example 3
5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 12.0 g of CIN 3, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor It was dissolved in 0. 0g and reacted at 100 ° C for 20 hours. This solution was gradually dropped into 1000 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-3). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
＜合成例４＞
　フェノ－ルノボラック型エポキシ樹脂Ｎ－７７５（ＤＩＣ（株）製ＥＰＩＣＬＯＮシリーズ）５．７ｇ、ＣＩＮ１　１１．０ｇ、反応触媒としてエチルトリフェニルホスホニウムブロミド　０．２ｇ、重合禁止剤としてジブチルヒドロキシトルエン　０．２ｇをＰＭ　４０．０ｇに溶解させ、１００℃で２０時間反応させた。この溶液をジエチルエーテル　５００ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することで、重合体（ＰＡ－４）を得た。得られた重合体のエポキシ価を測定し、エポキシ基が消失したことを確認した。 Synthesis Example 4
5.7 g of phenol novolac type epoxy resin N-775 (EPICLON series manufactured by DIC Corporation), 11.0 g of CIN 1, 0.2 g of ethyltriphenylphosphonium bromide as a reaction catalyst, 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor It was dissolved in 40.0 g of PM and reacted at 100 ° C. for 20 hours. This solution was gradually dropped into 500 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-4). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
＜合成例５＞
　重合例１で得たエポキシ基を有するアクリル重合体（Ｐ１）５．２ｇ、ＣＩＮ１　１０．０ｇ、ＣＩＮ４　２．０ｇ、反応触媒としてエチルトリフェニルホスホニウムブロミド　０．１ｇ、重合禁止剤としてジブチルヒドロキシトルエン　０．２ｇをＰＭ　７０．０ｇに溶解させ、１００℃で２０時間反応させた。この溶液をジエチルエーテル　１０００ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することで、重合体（ＰＡ－５）を得た。得られた重合体のエポキシ価を測定し、エポキシ基が消失したことを確認した。 Synthesis Example 5
5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 10.0 g of CIN 1, 2.0 g of CIN 4, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, dibutyl hydroxytoluene as a polymerization inhibitor 0.2 g of PM was dissolved in 70.0 g of PM and reacted at 100 ° C. for 20 hours. This solution was gradually dropped into 1000 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-5). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
＜合成例６＞
　重合例１で得たエポキシ基を有するアクリル重合体（Ｐ１）５．２ｇ、ＣＩＮ４　６．５ｇ、反応触媒としてエチルトリフェニルホスホニウムブロミド　０．１ｇをＰＭ　４８．０ｇに溶解させ、１００℃で２０時間反応させた。この溶液をジエチルエーテル　５００ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することで、重合体（ＰＡ－６）を得た。得られた重合体のエポキシ価を測定し、エポキシ基が消失したことを確認した。 Synthesis Example 6
5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 6.5 g of CIN 4, and 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst are dissolved in 48.0 g of PM, and the reaction is carried out at 100 ° C. for 20 hours It was made to react. This solution was gradually dropped into 500 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-6). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
＜合成例７＞
　フェノ－ルノボラック型エポキシ樹脂Ｎ－７７５（ＤＩＣ（株）製ＥＰＩＣＬＯＮシリーズ）５．３ｇ、ＣＩＮ４　５．０ｇ、反応触媒としてエチルトリフェニルホスホニウムブロミド　０．２ｇをＰＭ　２５．０ｇに溶解させ、１００℃で２０時間反応させた。この溶液をジエチルエーテル　５００ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することで、重合体（ＰＡ－７）を得た。得られた重合体のエポキシ価を測定し、エポキシ基が消失したことを確認した。 Synthesis Example 7
Phenol novolak type epoxy resin N-775 (DIC Corporation EPICLON series) 5.3g, CIN 4 5.0g, Ethyl triphenyl phosphonium bromide 0.2g as a reaction catalyst is dissolved in 25.0g PM, It was allowed to react for 20 hours. This solution was gradually dropped into 500 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-7). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
＜Ｂ成分の合成＞
＜重合例２＞
　ＢＭＡＡ　１００．０ｇ、重合触媒としてＡＩＢＮ　４．２ｇをＰＭ　１９３．５ｇに溶解し、９０℃にて２０時間反応させることによりアクリル重合体溶液を得た。得られたアクリル重合体のＭｎは２，７００、Ｍｗは３，９００であった。アクリル重合体溶液をヘキサン２０００．０ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することで、重合体（ＰＢ－１）を得た。 <Composition of B component>
Polymerization Example 2
An acrylic polymer solution was obtained by dissolving 100.0 g of BMAA and 4.2 g of AIBN as a polymerization catalyst in 193.5 g of PM and reacting at 90 ° C. for 20 hours. Mn of the obtained acrylic polymer was 2,700 and Mw was 3,900. The acrylic polymer solution was gradually dropped into 2000.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PB-1).
＜Ｃ成分の合成＞
＜重合例３＞
　ＭＭＡ　３０．０ｇ、ＨＥＭＡ　３．０ｇ、重合触媒としてＡＩＢＮ　０．３ｇをＰＭ１４６．０ｇに溶解し、８０℃にて２０時間反応させることによりアクリル共重合体溶液を得た。アクリル共重合体溶液をヘキサン１０００．０ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することでアクリル共重合体（ＰＣ－１）を得た。得られたアクリル共重合体のＭｎは１８，０００、Ｍｗは３２，８００であった。 <Composition of C component>
<Polymerization Example 3>
An acrylic copolymer solution was obtained by dissolving 30.0 g of MMA, 3.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst in 146.0 g of PM and reacting at 80 ° C. for 20 hours. The acrylic copolymer solution was gradually dropped into 1000.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PC-1). The Mn and Mw of the obtained acrylic copolymer were 18,000 and 32,800, respectively.
＜実施例、比較例＞
　表１に示す組成にて実施例及び比較例の各硬化膜形成組成物を調製した。次に、各位相差材形成組成物を用いて硬化膜を形成し、得られた硬化膜それぞれについて、配向性および密着性の評価を行った。 <Example, Comparative Example>
Each cured film formation composition of the Example and the comparative example was prepared with the composition shown in Table 1. Next, a cured film was formed using each retardation material formation composition, and evaluation of orientation and adhesiveness was performed about each obtained cured film.
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
［配向性の評価］
　実施例及び比較例の各硬化膜形成組成物を、オゾン処理を施したＣＯＰフィルム上にバーコーターを用いてＷｅｔ膜厚４μｍにて塗布した。それぞれ温度１１０℃で６０秒間、熱循環式オーブン中で加熱乾燥を行い、ＣＯＰフィルム上にそれぞれ硬化膜を形成した。この各硬化膜に３１３ｎｍの直線偏光を１０ｍＪ／ｃｍ２の露光量で垂直に照射し、配向材を形成した。ＣＯＰフィルム上の配向材の上に、メルク株式会社製の水平配向用重合性液晶溶液ＲＭＳ０３－０１３Ｃを、バーコーターを用いてＷｅｔ膜厚６μｍにて塗布した。この塗膜を３００ｍＪ／ｃｍ２で露光し、位相差材を作製した。作製した基板上の位相差材を一対の偏光板で挟み込み、位相差材における位相差特性の発現状況を観察し、位相差が欠陥なく発現しているものを○、位相差が発現していないものを×として「配向性」の欄に記載した。評価結果は、後に表２にまとめて示す。 [Evaluation of orientation]
Each cured film formation composition of an Example and a comparative example was apply | coated by Wet film thickness 4 micrometers using the bar coater on the COP film which gave the ozone treatment. It heat-dried in a thermal circulation type oven at temperature 110 degreeC respectively for 60 seconds, and formed the cured film on COP film, respectively. Each cured film was vertically irradiated with 313 nm linearly polarized light at an exposure amount of 10 mJ / cm 2 to form an alignment material. On the alignment material on the COP film, a horizontal alignment polymerizable liquid crystal solution RMS03-013C manufactured by Merck Co., Ltd. was applied at a wet film thickness of 6 μm using a bar coater. The coating film was exposed at 300 mJ / cm 2 to prepare a retardation material. The phase difference material on the manufactured substrate is sandwiched between a pair of polarizing plates, and the expression state of the phase difference characteristic of the phase difference material is observed, and the phase difference is expressed without defects ○, the phase difference is not expressed The thing was described in the column of "orientation" as x. The evaluation results are summarized in Table 2 later.
［密着性の評価］
　実施例及び比較例の各硬化膜形成組成物を、オゾン処理を施したＣＯＰフィルム上にバーコーターを用いてＷｅｔ膜厚４μｍにて塗布した。それぞれ温度１１０℃で６０秒間、熱循環式オーブン中で加熱乾燥を行い、ＣＯＰフィルム上にそれぞれ硬化膜を形成した。この各硬化膜に３１３ｎｍの直線偏光を１０ｍＪ／ｃｍ２の露光量で垂直に照射し、配向材を形成した。ＣＯＰフィルム上の配向材の上に、メルク株式会社製の水平配向用重合性液晶溶液ＲＭＳ０３－０１３Ｃを、バーコーターを用いてＷｅｔ膜厚６μｍにて塗布した。この塗膜を３００ｍＪ／ｃｍ２で露光し、位相差材を作製した。この位相差材に縦横１ｍｍ間隔で１０×１０マスとなるようカッターナイフで切込みをつけた。この切り込みの上にスコッチテープを用いてセロハンテープ剥離試験を行った。評価結果は「密着性」とし、１００マス全て剥がれずに残っているものを○、１マスでも剥がれているものを×とした。評価結果は、後に表２にまとめて示す。 [Evaluation of adhesion]
Each cured film formation composition of an Example and a comparative example was apply | coated by Wet film thickness 4 micrometers using the bar coater on the COP film which gave the ozone treatment. It heat-dried in a thermal circulation type oven at temperature 110 degreeC respectively for 60 seconds, and formed the cured film on COP film, respectively. Each cured film was vertically irradiated with 313 nm linearly polarized light at an exposure amount of 10 mJ / cm 2 to form an alignment material. On the alignment material on the COP film, a horizontal alignment polymerizable liquid crystal solution RMS03-013C manufactured by Merck Co., Ltd. was applied at a wet film thickness of 6 μm using a bar coater. The coating film was exposed at 300 mJ / cm 2 to prepare a retardation material. This retardation material was incised with a cutter knife so as to be 10 × 10 squares at intervals of 1 mm in length and width. A cellophane tape peel test was conducted using scotch tape on the incisions. The evaluation results were “adhesion”, and 100 squares were left without peeling, and those with even 1 square were marked ×. The evaluation results are summarized in Table 2 later.
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
　表２に示すように、実施例の硬化膜形成組成物を用いて得られた配向材は、良好な配向性と密着性を示した。 As shown in Table 2, the alignment material obtained using the cured film-forming composition of the example exhibited good alignment and adhesion.
　それに対して、比較例の硬化膜形成組成物を用いて得られた配向材は、良好な配向性は示したが、密着性が得られなかった。 On the other hand, the alignment material obtained by using the cured film forming composition of the comparative example showed a good alignment, but no adhesion was obtained.
　本発明による硬化膜形成組成物は、液晶表示素子の液晶配向膜や、液晶表示素子に内部や外部に設けられる光学異方性フィルムを形成するための配向材を形成する材料として非常に有用であり、特に、ＩＰＳ－ＬＣＤや有機ＥＬディスプレイの反射防止膜として使用される円偏光板の位相差材向け材料として好適である。 The cured film-forming composition according to the present invention is very useful as a material for forming an alignment material for forming a liquid crystal alignment film of a liquid crystal display element or an optically anisotropic film provided inside or outside of a liquid crystal display element. In particular, it is suitable as a material for a retardation material of a circularly polarizing plate used as an antireflective film for IPS-LCDs and organic EL displays.

Claims (14)

  1. （Ａ）エポキシ基を有するポリマーと重合性二重結合を含む基を有する桂皮酸誘導体との反応生成物及び（Ｂ）架橋剤を含有する硬化膜形成組成物。 A cured film-forming composition comprising (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond, and (B) a crosslinking agent.
  2. 上記重合性二重結合を含む基が、（メタ）アクリロイル基である請求項１に記載の硬化膜形成組成物。 The cured film-forming composition according to claim 1, wherein the group containing a polymerizable double bond is a (meth) acryloyl group.
  3. 上記重合性二重結合を含む基を有する桂皮酸誘導体が、下記式（１）で表される化合物である、請求項１または請求項２に記載の硬化膜形成組成物。
    Figure JPOXMLDOC01-appb-C000001
     式（１）中、Ａ１とＡ２はそれぞれ独立に、水素原子またはメチル基を表し、
    Ｒ１は下記式（ｃ－２）
    Figure JPOXMLDOC01-appb-C000002
     （式（ｃ－２）中、破線は結合手を表し、Ｒ１０１は炭素数１～３０のアルキレン基を表し、このアルキレン基の１つ若しくは複数の水素原子は、フッ素原子又は有機基で置き換えられていてもよい。また、Ｒ１０１中の－ＣＨ２ＣＨ２－は－ＣＨ＝ＣＨ－に置き換えられていてもよく、さらに、次に挙げるいずれかの基が互いに隣り合わない場合において、－Ｏ－、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－ＮＨＣＯＮＨ－及び－ＣＯ－からなる群から選ばれる基に置き換えられていてもよく、Ｍ１は水素原子又はメチル基を表す。）で表される基を表し、
    　Ｒ２は２価の芳香族基、２価の脂環族基、２価の複素環式基または２価の縮合環式基を表し、
    　Ｒ３は単結合、酸素原子、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ＝ＣＨＣＯＯ－または－ＯＣＯＣＨ＝ＣＨ－を表し、
    　Ｒ４～Ｒ７はそれぞれ独立に水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のハロアルキル基、炭素数１～６のアルコキシ基、炭素数１～６のハロアルコキシ基、シアノ基、及びニトロ基からなる群から選ばれる置換基を表し、
    　また、Ｒ２、Ｒ３及びＲ４又はＲ２、Ｒ３及びＲ６は一緒になって芳香族基を形成してもよく、
    　ｎは０～３の整数である。）     The cured film formation composition of Claim 1 or Claim 2 whose cinnamic acid derivative which has group which contains the said polymerizable double bond is a compound represented by following formula (1).
    Figure JPOXMLDOC01-appb-C000001
     In formula (1), each of A 1 and A 2 independently represents a hydrogen atom or a methyl group,
    R 1 is the following formula (c-2)
    Figure JPOXMLDOC01-appb-C000002
     (In the formula (c-2), the broken line represents a bond, R 101 represents an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of this alkylene group are replaced by a fluorine atom or an organic group In addition, -CH 2 CH 2-in R 101 may be replaced by -CH = CH-, and further, in the case where any of the following groups are not adjacent to each other,- M 1 is a hydrogen atom which may be substituted by a group selected from the group consisting of O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO- Or a methyl group is represented by
    R 2 represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused cyclic group,
    R 3 represents a single bond, an oxygen atom, -COO-, -OCO-, -CH = CHCOO- or -OCOCH = CH-,
    R 4 to R 7 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy having 1 to 6 carbon atoms Represents a substituent selected from the group consisting of a group, a cyano group, and a nitro group,
    Also, R 2 , R 3 and R 4 or R 2 , R 3 and R 6 may together form an aromatic group,
    n is an integer of 0 to 3. )
  4. （Ｂ）成分の架橋剤がメチロール基またはアルコキシメチル基を有する架橋剤である、請求項１乃至請求項３のうち何れか一項に記載の硬化膜形成組成物。 The cured film formation composition as described in any one of Claims 1 thru | or 3 whose crosslinking agent of (B) component is a crosslinking agent which has a methylol group or an alkoxymethyl group.
  5. （Ｃ）ヒドロキシ基、カルボキシル基、アミド基、アミノ基、およびアルコキシシリル基からなる群から選ばれる少なくとも１つの基を有するポリマーをさらに含有する請求項１乃至請求項４のうち何れか一項に記載の硬化膜形成組成物。 The polymer according to any one of claims 1 to 4, further comprising a polymer having at least one group selected from the group consisting of (C) a hydroxy group, a carboxyl group, an amido group, an amino group, and an alkoxysilyl group. The cured film formation composition as described.
  6. （Ｄ）架橋触媒をさらに含有する請求項１乃至請求項５のうち何れか一項に記載の硬化膜形成組成物。 The cured film forming composition according to any one of claims 1 to 5, further comprising (D) a crosslinking catalyst.
  7. （Ｅ）１つ以上の重合性基と、ヒドロキシ基、カルボキシル基、アミド基、アミノ基、およびアルコキシシリル基からなる群から選ばれる少なくとも１つの基Ａ又は該基Ａと反応する少なくとも１つの基とを有する化合物を含有する請求項１乃至請求項６のうち何れか一項に記載の硬化膜形成組成物。 (E) At least one group A selected from the group consisting of one or more polymerizable groups and a hydroxy group, a carboxyl group, an amido group, an amino group, and an alkoxysilyl group or at least one group reactive with the group A The cured film formation composition as described in any one of the Claims 1 thru | or 6 containing the compound which has these.
  8. （Ａ）成分１００質量部に基づいて、１質量部～５００質量部の（Ｂ）成分を含有する請求項１乃至請求項７のうち何れか一項に記載の硬化膜形成組成物。 The cured film-forming composition according to any one of claims 1 to 7, which contains 1 part by mass to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A).
  9. （Ａ）成分及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して１質量部～４００質量部の（Ｃ）成分を含有する請求項５乃至請求項８のいずれか一項に記載の硬化膜形成組成物。 The component (C) is contained in an amount of 1 part by mass to 400 parts by mass with respect to 100 parts by mass of the total amount of the crosslinking agent of the components (A) and (B). The cured film formation composition as described.
  10. （Ａ）成分及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して０．０１質量部～２０質量部の（Ｄ）成分を含有する請求項６乃至請求項９のいずれか一項に記載の硬化膜形成組成物。 The component (D) according to any one of claims 6 to 9, which contains 0.01 to 20 parts by mass of the component (D) relative to 100 parts by mass of the total amount of the crosslinking agent of the components (A) and (B). The cured film formation composition as described in a term.
  11. （Ａ）成分及び（Ｂ）成分の架橋剤の合計量の１００質量部に対して１質量部～１００質量部の（Ｅ）成分を含有する請求項７乃至請求項１０のいずれか一項に記載の硬化膜形成組成物。 The component (E) according to any one of claims 7 to 10, comprising 1 part by mass to 100 parts by mass of the component (E) with respect to 100 parts by mass of the total amount of the crosslinking agent of the component (A) and the component (B). The cured film formation composition as described.
  12. 請求項１乃至請求項１１のうち何れか一項に記載の硬化膜形成組成物から得られることを特徴とする硬化膜。 It is obtained from the cured film formation composition as described in any one of Claims 1 thru | or 11, The cured film characterized by the above-mentioned.
  13. 請求項１乃至請求項１１のうち何れか一項に記載の硬化膜形成組成物から得られることを特徴とする配向材。 An alignment material obtained from the cured film-forming composition according to any one of claims 1 to 11.
  14. 請求項１乃至請求項１１のうち何れか一項に記載の硬化膜形成組成物から得られる硬化膜を使用して形成されることを特徴とする位相差材。 A retardation material formed by using a cured film obtained from the cured film forming composition according to any one of claims 1 to 11.
PCT/JP2018/029248 2017-08-03 2018-08-03 Cured film forming composition, orienting material, and phase contrast material WO2019027045A1 (en)

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