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WO2018181350A1 - Composition filmogène durcie, matériau d'alignement et matériau à différence de phase - Google Patents

Composition filmogène durcie, matériau d'alignement et matériau à différence de phase Download PDF

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Publication number
WO2018181350A1
WO2018181350A1 PCT/JP2018/012488 JP2018012488W WO2018181350A1 WO 2018181350 A1 WO2018181350 A1 WO 2018181350A1 JP 2018012488 W JP2018012488 W JP 2018012488W WO 2018181350 A1 WO2018181350 A1 WO 2018181350A1
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Prior art keywords
group
carbon atoms
component
cured film
mass
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PCT/JP2018/012488
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English (en)
Japanese (ja)
Inventor
伊藤　潤
裕太 菅野
真 畑中
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Nissan Chemical Corp
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Nissan Chemical Corp
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Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Priority to JP2019509906A priority Critical patent/JP7152704B2/ja
Priority to KR1020197029831A priority patent/KR102555706B1/ko
Priority to CN201880020993.5A priority patent/CN110461964B/zh
Publication of WO2018181350A1 publication Critical patent/WO2018181350A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation

Definitions

  • the present invention relates to a cured film forming composition that can be used as a liquid crystal aligning agent for photo-alignment 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 circularly polarized glasses type 3D display 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 that can be used as a liquid crystal alignment agent for photo-alignment.
  • a retardation material is usually disposed on a display element such as a liquid crystal panel.
  • a retardation material a plurality of two kinds of retardation regions having different retardation characteristics are regularly arranged, and a patterned retardation material is formed.
  • a retardation material patterned so as to arrange a plurality of retardation regions having different retardation characteristics is referred to as a patterned retardation material.
  • the patterned retardation material can be produced, for example, by optically patterning a retardation material made of a polymerizable liquid crystal as disclosed in Patent Document 1.
  • Optical patterning of a retardation material made of a polymerizable liquid crystal utilizes a photo-alignment technique known for forming an alignment material for a liquid crystal panel. That is, a coating film made of a photo-alignment material is provided on a substrate, and two types of polarized light having different polarization directions are irradiated on the coating film. Then, a photo-alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed.
  • a solution-like retardation material containing a polymerizable liquid crystal is applied on the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Thereafter, the aligned polymerizable liquid crystal is cured to form a patterned retardation material.
  • the anti-reflective film of the organic EL display is composed of a linear polarizing plate and a quarter-wave retardation plate, converts external light directed to the panel surface of the image display panel into linear polarized light by the linear polarizing plate, and continues to the quarter wavelength. It is converted into circularly polarized light by the phase difference plate.
  • the extraneous light by the circularly polarized light is reflected by the surface of the image display panel or the like, but the rotation direction of the polarization plane is reversed during the reflection.
  • this reflected light is converted from the quarter-wave retardation plate into linearly polarized light in the direction shielded by the linear polarizing plate, and then shielded by the subsequent linear polarizing plate, As a result, the emission to the outside is remarkably suppressed.
  • Patent Document 2 discloses that this optical film has a reverse dispersion characteristic by configuring a 1/4 wavelength phase difference plate by combining a 1/2 wavelength plate and a 1/4 wavelength plate. Has been proposed. In the case of this method, an optical film can be formed with reverse dispersion characteristics using a liquid crystal material with positive dispersion characteristics in a wide wavelength band used for displaying a color image.
  • Patent Documents 3 and 4 As liquid crystal materials applicable to the retardation layer, those having reverse dispersion characteristics have been proposed (Patent Documents 3 and 4). According to the liquid crystal material having such a reverse dispersion characteristic, instead of forming a quarter-wave retardation plate by combining two half-wave plates and a quarter-wave plate to form a quarter-wave retardation plate. It is possible to achieve an optical film capable of ensuring a desired phase difference in a wide wavelength band with a simple configuration.
  • An alignment layer is used to align the liquid crystal.
  • a method for forming the alignment layer for example, a rubbing method or a photo-alignment method is known.
  • the photo-alignment method does not generate static electricity or dust, which is a problem of the rubbing method, and can control the alignment process quantitatively. It is useful in.
  • acrylic resins and polyimide resins having photodimerization sites such as cinnamoyl groups and chalcone groups in the side chain are known as usable photo-alignment materials. These resins have been reported to exhibit the ability to control the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment) when irradiated with polarized UV light (see Patent Documents 5 to 7).
  • the alignment layer is required to have solvent resistance in addition to the liquid crystal alignment ability.
  • the alignment layer may be exposed to heat or a solvent in the manufacturing process of the retardation material. When the alignment layer is exposed to a solvent, the liquid crystal alignment ability may be significantly reduced.
  • Patent Document 8 in order to obtain stable liquid crystal alignment ability, a liquid crystal aligning agent containing a polymer component having a structure capable of crosslinking reaction by light and a structure crosslinked by heat, and light.
  • a liquid crystal aligning agent containing a polymer component having a structure capable of crosslinking reaction and a compound having a structure crosslinked by heat has been proposed.
  • JP 2005-49865 A Japanese Patent Laid-Open No. 10-68816 U.S. Pat. No. 8,119,026 JP 2009-179563 A Japanese Patent No. 3611342 JP 2009-058584 A JP-T-2001-517719 Japanese Patent No. 4207430
  • the retardation material is formed by laminating a cured polymerizable liquid crystal layer on a photo-alignment film that is an alignment material. Therefore, it is necessary to develop an alignment material that can achieve both excellent liquid crystal alignment and solvent resistance.
  • an acrylic resin having a photodimerization site such as a cinnamoyl group and a chalcone group in the side chain cannot obtain sufficient characteristics when applied to the formation of a retardation material. It was issued.
  • a large amount of polarized UV exposure is required.
  • the polarized UV exposure amount is much larger than the polarized UV exposure amount (for example, about 30 mJ / cm 2) sufficient to align the liquid crystal for a normal liquid crystal panel.
  • the reason for increasing the amount of polarized UV exposure is that, in the case of retardation material formation, unlike liquid crystals for liquid crystal panels, polymerizable liquid crystals are used in the state of solution and applied onto the alignment material. Yes.
  • an alignment material is formed using an acrylic resin having a photodimerization site such as a cinnamoyl group in the side chain, and the polymerizable liquid crystal is to be aligned, the acrylic resin is subjected to photocrosslinking by a photodimerization reaction. . And it is necessary to irradiate polarized light with many exposure amounts until resistance to the polymerizable liquid crystal solution is developed. In order to align the liquid crystal of the liquid crystal panel, it is usually only necessary to dimerize only the surface of the photo-alignment alignment material.
  • an object of the present invention is to form a cured film that can be used as a liquid crystal aligning agent for photo-alignment for providing an alignment material that has excellent solvent resistance and can align a polymerizable liquid crystal with high sensitivity. It is to provide a composition.
  • the present inventors have (A) a reaction product of a monomer having an epoxy group and a specific cinnamic acid derivative, and (B) a cured film based on a crosslinking agent.
  • a forming composition it was found that a cured film (alignment material) having excellent solvent resistance and capable of aligning a polymerizable liquid crystal with high sensitivity could be formed, and the present invention was completed.
  • A a polymer obtained by using a monomer that is a reaction product of a monomer having an epoxy group and a cinnamic acid derivative represented by the following formula (1):
  • a 1 and A 2 each independently represent a hydrogen atom or a methyl group
  • R 1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms.
  • Haloalkyl groups alkoxy groups having 1 to 6 carbon atoms, haloalkoxy groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, halocycloalkyl groups having 3 to 8 carbon atoms, carbon, carbon An alkenyl group having 2 to 6 atoms, a haloalkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, a halocycloalkenyl group having 3 to 8 carbon atoms, and 2 to 6 carbon atoms Alkynyl group, haloalkynyl group having 2 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, haloalkoxy group having 1 to 6 carbon atoms, (alkyl having 1 to 6 carbon atoms) carbonyl group, (carbon C with 1-6 atoms (Alkyl) carbonyl group, (alkoxy having 1 to 6 carbon
  • (B) A cured film forming composition containing a crosslinking agent.
  • a crosslinking agent As a 2nd viewpoint, it is related with the cured film formation composition as described in a 1st viewpoint whose crosslinking agent of (B) component is a crosslinking agent which has a methylol group or an alkoxymethyl group.
  • (C) described in the first aspect or the second aspect further containing a polymer having 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.
  • the present invention relates to a cured film forming composition.
  • a 4th viewpoint it is related with the cured film formation composition as described in any one of the 1st viewpoint thru
  • the cured film formation according to any one of the first aspect to the fifth aspect containing 1 part by mass to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A) Relates to the composition.
  • a seventh aspect from the third aspect to the sixth aspect, 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 agent of the component (A) and the component (B). It is related with the cured film formation composition as described in any one.
  • the fourth aspect to the seventh aspect contain the component (D) in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the crosslinking agents of the components (A) and (B)
  • the cured film forming composition according to any one of the aspects.
  • the fourth aspect to the eighth aspect containing the component (E) in an amount of 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the total amount of the crosslinking agent of the component (A) and the component (B) It is related with the cured film formation composition as described in any one.
  • the present invention relates to a cured film obtained by curing the cured film-forming composition according to any one of the first to ninth aspects.
  • An eleventh aspect relates to an alignment material obtained by curing the cured film forming composition according to any one of the first to ninth aspects.
  • the present invention relates to a retardation material characterized by being formed using a cured film obtained from the cured film forming composition according to any one of the first aspect to the ninth aspect.
  • ADVANTAGE OF THE INVENTION According to this invention, it can provide the cured film which has the outstanding solvent resistance, can align a polymerizable liquid crystal with high sensitivity, and a cured film formation composition suitable for the formation.
  • ADVANTAGE OF THE INVENTION According to this invention, the phase difference material in which the orientation material excellent in liquid crystal orientation and light transmittance and high-precision optical patterning are possible can be provided.
  • the cured film forming composition of the present invention comprises (A) a polymer obtained by using a monomer that is a reaction product of a monomer having an epoxy group and a cinnamic acid derivative represented by the above formula (1), and (B ) Contains 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). It is also possible to 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, a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, or at least reacts with the group A Compounds having one group can be contained. And as long as the effect of this invention is not impaired, another additive can be contained.
  • group A selected from the group consisting of one or more polymerizable groups, a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group
  • the component (A) contained in the cured film forming composition of the present invention is obtained by using a monomer that is a reaction product of a monomer having an epoxy group and a cinnamic acid derivative represented by the above formula (1). It is a coalescence.
  • ⁇ Monomer having an epoxy group Specific examples of the polymerizable unsaturated compound (monomer) having an epoxy group used for the reaction with the cinnamic acid derivative represented by the above formula (1) in the present invention include, for example, glycidyl acrylate, glycidyl methacrylate, ⁇ - Glycidyl ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, glycidyl ⁇ -n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-acrylic acid Mention of epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, ⁇ -ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p
  • cinnamic acid derivative having a carboxyl group examples include compounds represented by the above formula (1).
  • halogen atom in the above formula (1) examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the notation “halo” also represents these halogen atoms.
  • the notation of an alkyl group having carbon atoms a to b in the above formula (1) represents a linear or branched hydrocarbon group having carbon atoms of a to b, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 1,1 Specific examples include dimethylbutyl group, 1,3-dimethylbutyl group, heptyl group, octyl group, nonyl group, decyl
  • the notation of the haloalkyl group having carbon atoms a to b in the above formula (1) is a straight chain comprising a to b carbon atoms, in which a hydrogen atom bonded to a carbon atom is arbitrarily substituted with a halogen atom. Alternatively, it represents a branched hydrocarbon group, and when substituted with two or more halogen atoms, these halogen atoms may be the same as or different from each other.
  • fluoromethyl group chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, chlorofluoromethyl group, dichloromethyl group, bromofluoromethyl group, trifluoromethyl group, chlorodifluoromethyl group, dichlorofluoromethyl group, trichloromethyl Group, bromodifluoromethyl group, bromochlorofluoromethyl group, dibromofluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2-chloro-2-fluoroethyl Group, 2,2-dichloroethyl group, 2-bromo-2-fluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2,2-difluoroethyl group, 2,2-dichloro-2 -Fl group, 2-chloro-2,2-
  • the notation of the cycloalkyl group having a carbon number of a to b in the above formula (1) represents a cyclic hydrocarbon group having a carbon number of a to b, a monocyclic ring having 3 to 6 members, A complex ring structure can be formed. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms.
  • cyclopropyl group 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, 2,2,3,3-tetramethylcyclopropyl group, cyclobutyl group, cyclopentyl group, 2- Specific examples include methylcyclopentyl group, 3-methylcyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, bicyclo [2.2.1] heptan-2-yl group, and the like. Each of which is selected for each specified number of carbon atoms.
  • the description of the halocycloalkyl group having a carbon number of a to b is a cyclic group in which the hydrogen atom bonded to the carbon atom is optionally substituted with a halogen atom and having a carbon number of a to b. And can form a monocyclic or complex ring structure of 3 to 6 membered rings.
  • Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the substitution with a halogen atom may be a ring structure part, a side chain part, They may be both, and when they are substituted by two or more halogen atoms, the halogen atoms may be the same as or different from each other.
  • 2,2-difluorocyclopropyl group, 2,2-dichlorocyclopropyl group, 2,2-dibromocyclopropyl group, 2,2-difluoro-1-methylcyclopropyl group, 2,2-dichloro-1-methyl Cyclopropyl group, 2,2-dibromo-1-methylcyclopropyl group, 2,2,3,3-tetrafluorocyclobutyl group, 2- (trifluoromethyl) cyclohexyl group, 3- (trifluoromethyl) cyclohexyl group , 4- (trifluoromethyl) cyclohexyl group and the like are listed as specific examples, and each is selected within the range of the designated number of carbon atoms.
  • the alkenyl group having a carbon number of a to b is linear or branched having a carbon number of a to b, and one or two or more carbon atoms in the molecule.
  • Represents an unsaturated hydrocarbon group having a heavy bond for example, vinyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 2-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2 -Propenyl group, 2-pentenyl group, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 2-ethyl-2-propenyl group, 1,1-dimethyl-2-propenyl group, 2-hexenyl Group, 2-methyl-2-pentenyl group, 2,4-dimethyl-2,6-heptadienyl group, 3,7-dimethyl-2,6-octadienyl group, etc. In a range of numbers Be-option.
  • the haloalkenyl group having a carbon number of a to b is a straight chain composed of a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom.
  • the halogen atoms may be the same as or different from each other.
  • the description of the cycloalkenyl group having a carbon number of a to b is a cyclic unsaturated hydrocarbon having 1 to 2 carbon atoms and having one or more double bonds.
  • Each ring may be optionally substituted with an alkyl group within a range of the specified number of carbon atoms, and the double bond may be in an endo- or exo- form.
  • 2-cyclopenten-1-yl group, 3-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, bicyclo [2.2.1] -5-heptene- A 2-yl group or the like is given as a specific example, and is selected within the range of each designated number of carbon atoms.
  • a halocycloalkenyl group having a carbon number of a to b in the above formula (1) is a cyclic structure having a carbon number of a to b, wherein a hydrogen atom bonded to the carbon atom is optionally substituted with a halogen atom And an unsaturated hydrocarbon group having one or two or more double bonds, and can form a monocyclic or complex ring structure having 3 to 6 members.
  • Each ring may be optionally substituted with an alkyl group within a range of the specified number of carbon atoms, and the double bond may be in an endo- or exo- form.
  • substitution by a halogen atom may be a ring structure part, a side chain part or both of them, and when substituted by two or more halogen atoms, those halogen atoms May be the same as or different from each other.
  • a 2-chlorobicyclo [2.2.1] -5-hepten-2-yl group and the like can be mentioned as specific examples, and each group is selected within the range of the designated number of carbon atoms.
  • the alkynyl group having a carbon number of a to b is linear or branched having a carbon number of a to b and one or more triples in the molecule.
  • Specific examples include butynyl group, 1,1-dimethyl-2-propynyl group, 2-hexynyl group and the like, and each is selected within the range of the designated number of carbon atoms.
  • a haloalkynyl group having a carbon number of a to b is a straight chain composed of a to b carbon atoms in which a hydrogen atom bonded to the carbon atom is arbitrarily substituted with a halogen atom.
  • the halogen atoms may be the same as or different from each other.
  • Specific examples include 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 3-iodo-2-propynyl group and the like. Each of which is selected for each specified number of carbon atoms.
  • the notation of an alkoxy group having carbon atoms a to b represents an alkyl-O— group having the above-mentioned meaning consisting of a to b carbon atoms, such as methoxy group, ethoxy group, n
  • alkyl-O— group having the above-mentioned meaning consisting of a to b carbon atoms, such as methoxy group, ethoxy group, n
  • Specific examples include -propyloxy group, i-propyloxy group, n-butyloxy group, i-butyloxy group, s-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, and the like.
  • Each selected range of carbon atoms is selected.
  • a haloalkoxy group having carbon atoms a to b in the above formula (1) represents a haloalkyl-O— group having the above-mentioned meaning consisting of a to b carbon atoms, such as a difluoromethoxy group, trifluoro Methoxy group, chlorodifluoromethoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2, -tetrafluoroethoxy group, 2-chloro-1,1,2-trifluoroethoxy group, 2-bromo-1,1,2-trifluoroethoxy group, pentafluoroethoxy group, 2,2-dichloro-1,1,2-trifluoroethoxy group 2,2,2-trichloro-1,1-difluoroethoxy group, 2-bromo-1,1,2,2-tetrafluoroethoxy group
  • the notation of (alkyl of carbon atoms a to b) carbonyl group represents an alkyl-C (O) -group having the above meaning consisting of a to b carbon atoms, for example acetyl
  • acetyl Specific examples include a group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, 2-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanoyl group, etc. Selected.
  • the notation of (haloalkyl having a carbon number of a to b) carbonyl group represents a haloalkyl-C (O) -group having the above-mentioned meaning consisting of a to b carbon atoms.
  • Acetyl group chloroacetyl group, difluoroacetyl group, dichloroacetyl group, trifluoroacetyl group, chlorodifluoroacetyl group, bromodifluoroacetyl group, trichloroacetyl group, pentafluoropropionyl group, heptafluorobutanoyl group, 3-chloro-2
  • Specific examples include, 2-dimethylpropanoyl group, and the like, and each is selected within the range of the designated number of carbon atoms.
  • the notation of (alkoxy having carbon atoms a to b) carbonyl group in the above formula (1) represents an alkyl-O—C (O) — group having the above-mentioned meaning consisting of a to b carbon atoms, Specific examples include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, i-propyloxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group and the like. Selected within the specified number of carbon atoms.
  • the expression of (haloalkoxy having a carbon number of a to b) carbonyl group represents a haloalkyl-O—C (O) — group having the above meaning consisting of a carbon number of a to b.
  • Specific examples include 2-chloroethoxycarbonyl group, 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, etc. Selected within the specified number of carbon atoms.
  • the notation of (alkylamino having a carbon number of a to b) carbonyl group is carbamoyl substituted with an alkyl group as defined above, wherein one of the hydrogen atoms is composed of a to b carbon atoms.
  • Specific examples are given, each selected in the range of the specified number of carbon atoms.
  • the notation of (haloalkylamino of carbon atoms a to b) carbonyl group in the above formula (1) is a carbamoyl group substituted by a haloalkyl group as defined above, wherein one of the hydrogen atoms is composed of a carbon atom of a to b
  • Specific examples include 2-fluoroethylcarbamoyl group, 2-chloroethylcarbamoyl group, 2,2-difluoroethylcarbamoyl group, 2,2,2-trifluoroethylcarbamoyl group, and the like. Selected in the range of the number of carbon atoms.
  • the notation of di (alkyl having a carbon number of ab) aminocarbonyl group is such that both hydrogen atoms may be the same or different from each other from ab.
  • a carbamoyl group substituted by an alkyl group as defined above for example, N, N-dimethylcarbamoyl group, N-ethyl-N-methylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-di- Specific examples include n-propylcarbamoyl group, N, N-di-n-butylcarbamoyl group and the like, and each is selected within the range of the designated number of carbon atoms.
  • the substituents R 1 , R 4 , R 5 , R 6 and R 7 of the cinnamic acid derivative represented by the formula (1) are each independently a hydrogen atom, a halogen atom, or an alkyl having 1 to 6 carbon atoms.
  • the substituent R 1 is preferably a substituent other than a hydrogen atom in the above definition from the viewpoint of orientation sensitivity, and is preferably a halogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. And more preferably a substituent selected from the group consisting of a haloalkyl group, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group, and a nitro group.
  • Examples of the divalent aromatic group of the substituent R 2 include 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5, 6-tetrafluoro-1,4-phenylene group and the like; as the divalent alicyclic group for R 2 , for example, 1,2-cyclopropylene group, 1,3-cyclobutylene group, 1,4-cyclohexylene
  • the divalent heterocyclic group represented by R 2 includes, for example, a 1,4-pyridylene group, a 2,5-pyridylene group, a 1,4-furylene group, and the like; a divalent condensed cyclic group represented by R 2 Examples of the group include a 2,6-naphthylene group.
  • R 2 is preferably a 1,4-phenylene group.
  • Preferred examples of the compound represented by the above formula (1) include, for example, the following formulas (1-1) to (1-5): (In the above formulas, R 1 are each the same meaning as R 1 in the formula (1).) Of can be mentioned cinnamic acid derivatives represented by each.
  • the cinnamic acid derivative represented by the above formula (1) can be synthesized by appropriately combining organic chemistry methods.
  • the reaction product (monomer) of the monomer having an epoxy group and the specific cinnamic acid derivative used for the preparation of the polymer as the component (A) of the present invention is the monomer having the epoxy group as described above and the specific cinnamic It can be synthesized by reacting an acid derivative, preferably in the presence of a catalyst, preferably in a suitable organic solvent.
  • the use ratio of the cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 mol, more preferably 0.05 to 1 with respect to 1 mol of the epoxy group contained in the monomer having an epoxy group. .3 mole, more preferably 0.1 to 1.1 mole.
  • a compound known as a so-called curing accelerator that accelerates the reaction between an organic base or an epoxy compound and an acid anhydride can be used.
  • organic base examples include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, And tertiary organic amines such as diazabicycloundecene; quaternary organic amines such as tetramethylammonium hydroxide.
  • primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole
  • triethylamine tri-n-propylamine
  • tri-n-butylamine pyridine
  • 4-dimethylaminopyridine 4-dimethylaminopyridine
  • tertiary organic amines such as diazabicycloundecene
  • quaternary organic amines such
  • tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; quaternary organic amines such as tetramethylammonium hydroxide preferable.
  • the curing accelerator examples include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and 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,
  • Benzyltriphenylphosphonium chloride tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide , Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra -N-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate Quaternary phosphonium salts such as salts; Dia
  • Organic metal compounds tetraethylammonium bromide, tetra-n-butylammonium bromide, quaternary ammonium salts such as tetraethylammonium chloride, tetra-n-butylammonium chloride; boron compounds such as boron trifluoride and triphenylborate; Metal halide compounds such as zinc and stannic chloride; high melting point dispersion type latent curing accelerators such as amine addition accelerators such as dicyandiamide and adducts of amine and epoxy resin; imidazole compounds, organophosphorus compounds and 4 Table of curing accelerators such as grade phosphonium salts Microcapsule-type latent curing accelerator coated with polymer; amine salt-type latent curing accelerator; high-temperature dissociation type thermal cationic polymerization type latent curing accelerator such as Lewis acid salt and Bronsted acid salt Can be mentioned.
  • quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride are preferable.
  • the ratio of the catalyst used is preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, and further preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the monomer having an epoxy group. is there.
  • the organic solvent examples include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, alcohol compounds, and the like. Of these, ether compounds, ester compounds, ketone compounds, and alcohol compounds are preferred from the viewpoints of solubility of raw materials and products and ease of purification of the products.
  • the solvent is used in such an amount that the solid content 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. Is 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.
  • a solution containing a monomer which is a reaction product of the monomer having an epoxy group and a cinnamic acid derivative represented by the above formula (1) is obtained.
  • This solution may be used as it is for the preparation of the polymer as the component (A), may be used for the preparation of the polymer as the component (A) after isolating the monomer contained in the solution.
  • the separated monomer may be purified and then used for the preparation of the polymer as component (A).
  • the polymer which is the component (A) used in the present invention is a polymer obtained by polymerizing a monomer which is a reaction product of the monomer having an epoxy group and a cinnamic acid derivative represented by the above formula (1).
  • the polymer of the component (A) is a copolymer of a monomer that is a reaction product of the monomer having an epoxy group and a cinnamic acid derivative represented by the above formula (1) and another polymerizable unsaturated compound. Can be.
  • 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, bicyclounsaturated compounds, maleimide
  • examples include compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other polymerizable unsaturated compounds.
  • methacrylic acid alkyl esters such as hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2- Methacryloxyethylglycoside, 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 .; alkyl acrylate esters such as methyl acrylate Over DOO, isopropyl acrylate and the like; as methacrylic acid cyclic alkyl esters such as cyclohexy
  • bicyclo unsaturated compounds include 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, 5- (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]
  • unsaturated dicarboxylic acid maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .
  • unsaturated dicarboxylic acid anhydride each unsaturated dicarboxylic acid anhydride
  • polymerizable unsaturated compound other than the above Examples thereof include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate and the like.
  • the copolymerization ratio of the monomer which is a reaction product of the monomer having an epoxy group and the cinnamic acid derivative represented by the above formula (1) in the polymer as the component (A) is preferably 30 mol% or more. More preferably, it is 50 mol% or more. From the viewpoint of orientation sensitivity, it is more preferably 70 mol% or more.
  • the synthesis of the polymer as component (A) can be carried out by a known radical polymerization method, preferably in a solvent and in the presence of a suitable polymerization initiator.
  • a solution containing the polymer as the component (A) is obtained.
  • This solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polymer contained in the solution, or after the isolated polymer is purified. You may use for preparation of a liquid crystal aligning agent.
  • Component (B) in the cured film forming composition of the present invention is a crosslinking agent.
  • a crosslinking agent as component (B), a compound having at least two groups capable of forming a crosslink with the thermally crosslinkable functional group of component (A) is preferable.
  • a crosslinking having at least two methylol groups or alkoxymethyl groups is preferable.
  • the compound 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 include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.
  • glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Nippon Cytec Industries Co., Ltd. (former Mitsui Cytec Co., Ltd.), methylated urea resins (Trade name: UFR (registered trademark) 65), butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Corporation (formerly Dainippon Ink Chemical Co., Ltd.) Urea / formaldehyde resin (high condensation type, trade name: Beccamin (registered trademark) J-300S, P-955, N) manufactured by Kogyo Co., Ltd.).
  • alkoxymethylated benzoguanamine examples include tetramethoxymethylbenzoguanamine.
  • Commercially available products are made by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) (trade name: Cymel (registered trademark) 1123), manufactured by Sanwa Chemical Co., Ltd. (product name: Nicarak (registered trademark) BX-) 4000, BX-37, BL-60, BX-55H) and the like.
  • alkoxymethylated melamine examples include, for example, hexamethoxymethylmelamine.
  • methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Nippon Cytec Industries Co., Ltd. (former Mitsui Cytec Co., Ltd.), butoxymethyl type melamine Compound (trade name: My Coat (registered trademark) 506, 508), methoxymethyl type melamine compound (trade name: Nicalac (registered trademark) MW-30, MW-22, MW-) manufactured by Sanwa Chemical Co., Ltd. 11, MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compound (trade name: Nicalac (registered trademark) MX-45, MX-410) , MX-302).
  • a crosslinking agent a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which a hydrogen atom of an amino group is substituted with a methylol group or an alkoxymethyl group may be used.
  • the high molecular weight compound manufactured from the melamine compound and the benzoguanamine compound which are described in US Patent 6,323,310 is mentioned.
  • Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 and the like.
  • Examples of commercially available products of the benzoguanamine compound include product name: Cymel (registered trademark) 1123 (Nippon Cytec Industries, Ltd.). ) (Formerly Mitsui Cytec Co., Ltd.).
  • hydroxymethyl groups that is, methylol groups
  • alkoxymethyl groups such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, etc.
  • Polymers produced using an acrylamide compound or a methacrylamide compound substituted with a can also be used.
  • Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl. And a copolymer of methacrylamide and benzyl methacrylate, a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.
  • a polymer having an N-alkoxymethyl group and a polymerizable group containing a C ⁇ C double bond can also be used.
  • 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.
  • the method for obtaining the polymer as described above is not particularly limited.
  • an acrylic polymer having a specific functional group is generated in advance by a polymerization method such as radical polymerization.
  • a specific compound a compound having an unsaturated bond at the terminal
  • a polymerizable group containing can be introduced.
  • the specific functional group possessed by the acrylic polymer is a functional group such as a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group or an isocyanate group, or a plurality of types selected from these functional groups.
  • a functional group such as a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group or an isocyanate group, or a plurality of types selected from these functional groups.
  • the preferred combination of the specific functional group possessed by the acrylic polymer and the functional group possessed by the specific compound and involved in the reaction is a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, or a phenolic hydroxy group.
  • a more preferable combination is an epoxy group in a carboxy group and glycidyl methacrylate, or an isocyanate group in a hydroxy group and isocyanate ethyl methacrylate.
  • the weight average molecular weight (polystyrene equivalent value) 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.
  • cross-linking agents can be used alone or in combination of two or more.
  • the content of the crosslinking agent as the component (B) in the cured film forming composition of the present invention is preferably 1 part by mass to 500 parts by mass, more preferably based on 100 parts by mass of the polymer as the component (A). 5 parts by mass to 400 parts by mass.
  • content of a crosslinking agent is too small, the solvent tolerance of the cured film obtained from a cured film formation composition will fall, and liquid crystal orientation will fall. On the other hand, when the content is excessive, the liquid crystal orientation and storage stability may be lowered.
  • the cured film forming composition of the present invention may contain a polymer having 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 as the component (C). good.
  • polymer as the component (C) examples include acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polyalkyleneimine, poly Examples include allylamines, celluloses (cellulose or derivatives thereof), polymers having a linear or branched structure such as phenol novolac resins and melamine formaldehyde resins, and cyclic polymers such as cyclodextrins.
  • the polymer as the component (C) preferably includes acrylic polymers, hydroxyalkylcyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols.
  • the acrylic polymer which is a preferred example of the polymer of 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. It may be a polymer obtained by polymerizing a monomer containing a monomer having a functional group or a mixture thereof, and is not particularly limited with respect to the skeleton of the main chain of the polymer constituting the acrylic polymer and the type of side chain.
  • the monomer having a specific functional group includes 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, and an amino group.
  • Examples of the monomer having a polyethylene glycol ester group described above 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 include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate. 4-hydroxybutyl methacrylate.
  • Examples of the above-mentioned monomer having a phenolic hydroxy group include p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene.
  • Examples of the above-mentioned monomer having a carboxyl group include acrylic acid, methacrylic acid, and vinyl benzoic acid.
  • Examples of the monomer having an amino group described above include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate.
  • Examples of the monomer having an alkoxysilyl group include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyl, and the like. Examples include trimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.
  • the alkyl group having 1 to 12 carbon atoms and the alkoxy group having 1 to 12 carbon atoms in R 62 are groups having the corresponding number of carbon atoms among the alkyl groups and alkoxy groups exemplified above. Is mentioned.
  • Examples of the monomer having a group represented by the above formula (2) include monomers having groups represented by the following formulas [2-1] to [2-5].
  • a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group are used as long as the effects of the present invention are not impaired.
  • Monomers that do not have any of the groups represented can be used in combination.
  • Such monomers include acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
  • acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl.
  • 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.
  • maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
  • styrene compound examples include styrene, methylstyrene, chlorostyrene, and bromostyrene.
  • vinyl compound examples include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
  • the usage-amount of the monomer which has a specific functional group used in order to obtain the acrylic polymer which is an example of a component is based on the total amount of all the monomers used in order to obtain the acrylic polymer which is (C) component, It is preferable that it is 2 mol% or more. If the monomer having a specific functional group is too small, the solvent resistance of the resulting cured film tends to be insufficient.
  • the method to obtain the acrylic polymer which is an example of a component is not specifically limited,
  • the monomer containing the monomer which has a specific functional group, the monomer which does not have a specific functional group depending on necessity, a polymerization initiator, etc. Can be obtained by a polymerization reaction at a temperature of 50 ° C. to 110 ° C. in a solvent coexisting with.
  • the solvent used will not be specifically limited if it dissolves the monomer which has a specific functional group, the monomer which does not have the specific functional group used depending on necessity, a polymerization initiator, etc. Specific examples are described in the section of [Solvent] described later.
  • the acrylic polymer which is an example of the component (C) obtained by the above method is usually in a solution state dissolved in a solvent.
  • the acrylic polymer solution which is an example of the component (C) obtained by the above method, is poured into diethyl ether or water under stirring to cause reprecipitation, and the generated precipitate is filtered and washed. Under normal or reduced pressure, it can be dried at room temperature or by heating to obtain an acrylic polymer powder as an example of the component (C).
  • the polymerization initiator and unreacted monomer coexisting with the acrylic polymer which is an example of the component (C) can be removed, and as a result, the acrylic polymer which is an example of the purified component (C) Of powder is obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
  • the acrylic polymer which is a preferred example of the component (C) has a weight average molecular weight of preferably 3000 to 200000, more preferably 4000 to 150,000, and further preferably 5000 to 100,000. If the weight average molecular weight exceeds 200,000, the solvent solubility may decrease and handling may decrease. If the weight average molecular weight is less than 3,000, the curing may be insufficient during thermal curing. And solvent resistance may be reduced.
  • the weight average molecular weight is a value obtained by using gel as a standard material by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • polyether polyol which is a preferable example of the polymer of component (C)
  • polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, polyhydric alcohol such as sorbitol, propylene oxide, polyethylene glycol, polypropylene The thing which added glycol etc. is mentioned.
  • polyether polyols include ADEKA Adeka Polyether P Series, G Series, EDP Series, BPX Series, FC Series, CM Series, NOF 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 Nonion (registered trademark) LT-221, ST-221, OT-221 and the like.
  • a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol or polypropylene glycol is reacted with a polyvalent carboxylic acid such as adipic acid, sebacic acid or isophthalic acid.
  • a polyvalent carboxylic acid such as adipic acid, sebacic acid or isophthalic acid.
  • polyester polyol examples include DIC polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD- X-2555, OD-X-2560, Kuraray polyols P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F -2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016 and the like.
  • DIC polylite registered trademark
  • the polycaprolactone polyol which is a preferred example of the polymer of component (C), includes those obtained by ring-opening polymerization of ⁇ -caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator.
  • Specific examples of the polycaprolactone polyol include DIC polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, Daicel Plaxel (registered trademark) 205, 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 polymer of 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.
  • a polyhydric alcohol such as trimethylolpropane or ethylene glycol
  • diethyl carbonate diethyl carbonate
  • diphenyl carbonate ethylene carbonate or the like.
  • Specific examples of the polycarbonate polyol include Placel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel, C-590, C-1050, C-2050, C-2090, C-3090 manufactured by Kuraray, and the like.
  • cellulose examples include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkylalkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl ethyl cellulose, and cellulose.
  • hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.
  • the cyclodextrin which is a preferred example of the polymer of component (C) includes 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-hydroxyethyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -cyclodextrin, 2-hydroxypro Pill- ⁇
  • a melamine formaldehyde resin includes a resin obtained by polycondensation of melamine and formaldehyde.
  • the methylol group generated during the polycondensation of melamine and formaldehyde is alkylated from the viewpoint of storage stability.
  • the melamine formaldehyde resin include a resin having a unit structure represented by the following formula.
  • 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 as component (C) is not particularly limited, but in general, melamine and formaldehyde are mixed, made weakly alkaline using sodium carbonate, ammonia, etc., and then heated at 60 ° C. to 100 ° C. Is synthesized. Further, the methylol group can be alkoxylated by reacting with alcohol.
  • the (C) component melamine formaldehyde resin preferably has a weight average molecular weight of 250 to 5000, more preferably 300 to 4000, and even more preferably 350 to 3500. If the weight average molecular weight exceeds 5,000, the solubility in the solvent may decrease and handling may decrease. If the weight average molecular weight is less than 250, the curing may be insufficient during thermal curing. In some cases, the effect of improving the solvent resistance is not sufficiently exhibited.
  • the melamine formaldehyde resin as the component (C) may be used in a liquid form or a solution form in which a purified liquid is redissolved in a solvent described later.
  • phenol novolak resin that is a preferred example of the specific polymer of the component (C) include phenol-formaldehyde polycondensate.
  • the polymer of component (C) may be used in the form of a powder or in the form of a solution obtained by re-dissolving the purified powder in a solvent described later.
  • the component (C) may be a mixture of a plurality of types of polymers exemplified as the component (C).
  • the content of the component (C) in the cured film forming composition of the present invention is preferably 400 parts by mass or less 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). More preferably, it is 10 to 380 parts by mass, and still more preferably 40 to 360 parts by mass. When the content of the component (C) is excessive, the liquid crystal orientation tends to be lowered.
  • the cured film forming composition of the present invention can further contain a crosslinking catalyst as the component (D) in addition to the components (A) and (B).
  • a crosslinking catalyst as component (D)
  • an acid or a thermal acid generator can be preferably used as the crosslinking catalyst as component (D).
  • This component (D) is effective in promoting the thermosetting reaction of the cured film forming composition of the present invention.
  • Specific examples of the component (D) include sulfonic acid group-containing compounds, hydrochloric acid or salts thereof as the acid.
  • the thermal acid generator is not particularly limited as long as it is a compound that thermally decomposes during heat treatment to generate an acid, that is, a compound that thermally decomposes at a temperature of 80 ° C. to 250 ° C. to generate an acid. .
  • the 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, 1H, 2H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, non
  • Examples of the compound that generates an acid by heat include, for example, bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3 -Phenylenetris (methyl sulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium 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,
  • the content of the component (D) in the cured film forming composition of the present invention is preferably 0.01 mass with respect to 100 mass parts of the total amount of the polymer as the component (A) and the crosslinking agent of the component (B). Part to 20 parts by weight, more preferably 0.1 part by weight to 15 parts by weight, still more preferably 0.5 part by weight to 10 parts by weight.
  • This invention can also contain the component (henceforth an adhesion improvement component) which improves the adhesiveness of the cured film formed as (E) component.
  • the polymerizable liquid crystal of the polymerizable liquid crystal is improved so that the adhesion between the alignment material and the polymerizable liquid crystal layer is improved.
  • the polymerizable functional group and the crosslinking reaction site of the alignment material can be linked by a covalent bond.
  • the retardation material of this embodiment formed by laminating a cured polymerizable liquid crystal on the alignment material of this embodiment can maintain strong adhesion even under conditions of high temperature and high humidity , such as peeling. High durability can be exhibited.
  • the component (E) reacts with one or more polymerizable groups and at least one group A selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, or the group A.
  • group A selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, or the group A.
  • Compounds having at least one group can be used.
  • monomers and polymers having a group selected from a hydroxy group and an N-alkoxymethyl group and a polymerizable group are preferred.
  • Such (E) component includes a compound having a hydroxy group and a (meth) acryl group, a compound having an N-alkoxymethyl group and a (meth) acryl group, an N-alkoxymethyl group and a (meth) acryl group.
  • the polymer etc. which have are mentioned. Specific examples are shown below.
  • the polyfunctional acrylate containing a hydroxyl group (henceforth a hydroxy group containing polyfunctional acrylate) can be mentioned.
  • the hydroxy group-containing polyfunctional acrylate that is an example of the component (E) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
  • (E) As an example of a component, the compound which has one (meth) acryl group and one or more hydroxy groups is also mentioned. Preferred examples of such a compound having one (meth) acryl group and one or more hydroxy groups are given below.
  • the compound of (E) component is not limited to the following compound examples.
  • R 11 represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10.
  • the compound of component (E) includes a compound having at least one polymerizable group containing a C ⁇ C double bond and at least one N-alkoxymethyl group in one molecule.
  • 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 of N-alkoxymethyl group that is, nitrogen atom is adjacent to amide nitrogen atom, thioamide nitrogen atom, urea nitrogen atom, thiourea nitrogen atom, urethane nitrogen atom, nitrogen atom of nitrogen-containing heterocycle And a nitrogen atom bonded to. Therefore, the N-alkoxymethyl group includes an amide nitrogen atom, a thioamide nitrogen atom, a urea nitrogen atom, a thiourea nitrogen atom, a urethane nitrogen atom, and a nitrogen bonded to the adjacent position of the nitrogen atom of the nitrogen-containing heterocyclic ring. Examples include a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from atoms and the like.
  • any compound having the above-described group may be used, and a compound represented by the following formula (X1) is preferable.
  • 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, and 1-methyl-n.
  • Specific examples of the compound represented by the formula (X1) include N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth).
  • Examples thereof include acrylamide compounds and methacrylamide compounds substituted with a hydroxymethyl group such as acrylamide or an alkoxymethyl group.
  • (Meth) acrylamide means both methacrylamide and acrylamide.
  • 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 cyclic group having 5 to 6 carbon atoms, or a monovalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, An ether bond may be included in the structure.
  • R 53 is a divalent group containing a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent aliphatic ring group having 5 to 6 carbon atoms, or 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 9-valent aliphatic group having 1 to 20 carbon atoms, a divalent to 9-valent aliphatic cyclic group having 5 to 6 carbon atoms, or a carbon number of 5 It represents a divalent to a 9-valent aliphatic group containing 6 to 6 aliphatic rings, and one methylene group or a plurality of non-adjacent methylene groups in these groups may be replaced with an ether bond.
  • Z is> NCOO-, or -OCON ⁇ (where "-" indicates that there is one bond, and ">” and “ ⁇ ” indicate that there are two bonds, and It represents an alkoxymethyl group (that is, —OR 52 group) is bonded to any one of the bonds.)
  • 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 a divalent group obtained by further removing one hydrogen atom from an alkyl group having 2 to 20 carbon atoms.
  • specific examples of the divalent to 9-valent aliphatic group having 1 to 20 carbon atoms in the definition of R 54 include further removing 1 to 8 hydrogen atoms from the alkyl group having 1 to 20 carbon atoms. Examples thereof include divalent to 9-valent groups.
  • 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 an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group.
  • R 53 is an ethylene group
  • 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 a specific example of an alkyl group having 2 to 20 carbon atoms in the definition of R 53 and a methyl group. Of 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 may be a natural number of 2 to 9, but a natural number of 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 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 100 parts by weight to 100 parts by weight, and more preferably from 5 parts by weight to 70 parts by weight.
  • (E) By making content of a component into 1 mass part or more, sufficient adhesiveness can be provided to the cured film formed. However, when the amount is more than 100 parts by mass, the liquid crystal orientation tends to decrease.
  • the component (E) may be a mixture of a plurality of compounds of the component (E).
  • the cured film forming composition of the present invention is mainly used in a solution state dissolved in a solvent.
  • the solvent used in that case is only required to be able to dissolve the component (A), the component (B) and, if necessary, the component (C), the component (D), the component (E) and / or other additives described below.
  • Kinds and structures 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, 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
  • the cured film-forming composition of the present invention is used to produce an alignment material by forming a cured film on a resin film
  • solvents can be used alone or in combination of two or more.
  • the cured film-forming composition of the present invention is, as necessary, an adhesion improver, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stability, as long as the effects of the present invention are not impaired.
  • an adhesion improver e.g., a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stability, as long as the effects of the present invention are not impaired.
  • Agents, antifoaming agents, antioxidants, and the like are examples of the like.
  • the cured film forming composition of the present invention contains (A) component polymer and (B) component cross-linking agent, and (C) component polymer, (D) cross-linking catalyst, and (E) component adhesion as desired. It is a composition that can contain an accelerator and further other additives as long as the effects of the present invention are not impaired. Usually, they are used in the form of a solution in which they are dissolved in a solvent.
  • Preferred examples of the cured film forming composition of the present invention are as follows. [1]: A cured film forming composition containing 1 part by mass to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A) and the component (A).
  • component based on 100 parts by mass of component (A), 1 part by mass to 500 parts by mass of component (B), polymer of component (A) and crosslinking agent of component (B)
  • a cured film forming composition containing 1 to 400 parts by mass of component (C) and a solvent with respect to 100 parts by mass of the amount.
  • component based on 100 parts by mass of component (A), 1 part by mass to 500 parts by mass of component (B), the polymer as component (A) and the crosslinking agent for component (B) 1 to 400 parts by mass of component (C), 100 parts by mass of the polymer as component (A) and 100 parts by mass of the crosslinking agent of component (B)
  • a cured film forming composition containing 20 parts by mass of component (D) and a solvent.
  • component based on 100 parts by mass of component (A), 1 part by mass to 500 parts by mass of component (B), (A) component polymer and (B) component cross-linking agent 1 to 400 parts by mass of component (C), 100 parts by mass of the polymer as component (A) and 100 parts by mass of the crosslinking agent of component (B) 20 parts by mass of component (D), 1 part by mass to 100 parts by mass of component (E) with respect to 100 parts by mass of the total amount of the polymer as component (A) and the crosslinking agent of component (B), and solvent
  • a cured film-forming composition comprising:
  • the blending ratio, preparation method, and the like when the cured film forming composition of the present invention is used as a solution are described in detail below.
  • the ratio of the solid content in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1% by mass to 60% by mass, preferably 2%.
  • the mass is from 50% by mass to 50% by mass, and more preferably from 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, a component (B), a component (C), a component (D), a component (E), and the like are mixed in a predetermined ratio in a solution of the component (A) dissolved in a solvent, and uniform. Examples thereof include a solution method, and a method in which other additives are further added and mixed as necessary at an appropriate stage of the preparation method.
  • a solution of a specific copolymer (polymer) obtained by a polymerization reaction in a solvent can be used as it is.
  • the (B) component, (C) component, (D) component, (E) component, etc. are added to the (A) component solution in the same manner as described above to obtain a uniform solution.
  • a solvent may be further added for the purpose of adjusting the concentration.
  • the solvent used in the production process of the component (A) and the solvent used for adjusting the concentration of the cured film forming composition may be the same or different.
  • the prepared cured film-forming composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 ⁇ m.
  • a solution of the cured film forming composition of the present invention is applied to 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, or ITO.
  • 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, or ITO.
  • Substrates) 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
  • TAC triacetyl cellulose
  • PC polycarbonate
  • COP cycloolefin polymer
  • COC cycloolefin copolymer
  • PET polyethylene terephthalate
  • acrylic film e.g., acrylic film, polyethylene
  • a resin film such as a film, etc., a bar coating, spin coating, flow coating, roll coating, slit coating, spin coating following slits, ink jet coating, printing, etc.
  • the cured film can be used as an alignment material as it is.
  • the heating and drying conditions may be such that the crosslinking reaction with the crosslinking agent proceeds to such an extent that the components of the cured film (alignment material) do not elute into the polymerizable liquid crystal solution applied thereon.
  • a heating temperature and a heating time appropriately selected from the range of 200 ° C. and a time of 0.4 minutes to 60 minutes are adopted.
  • the heating temperature and the heating time are preferably 70 to 160 ° C. and 0.5 to 10 minutes.
  • the thickness of the cured film (alignment material) formed using the curable composition of the present invention is, for example, 0.05 ⁇ m to 5 ⁇ m, and is appropriately determined in consideration of the level difference of the substrate to be used and optical and electrical properties. You can choose.
  • phase difference material such as a polymerizable liquid crystal solution having vertical alignment property is applied onto the alignment material.
  • the phase difference material can be formed as a layer which has optical anisotropy by hardening the phase difference material which became the orientation state as it is.
  • substrate which forms an orientation material is a film, it becomes useful as a phase difference film.
  • the alignment materials on both substrates are bonded to each other via a spacer, and then between the substrates.
  • a liquid crystal display element in which liquid crystal is injected to align the liquid crystal may be used.
  • the cured film forming composition of this invention can be used suitably for manufacture of various retardation materials (retardation film), a liquid crystal display element, etc.
  • the molecular weight of the acrylic copolymer in the polymerization example was as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co. And measured.
  • the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) were expressed in terms of polystyrene.
  • ⁇ Polymerization example 9> CIN1 10.0 g, HEMA 2.7 g, and AIBN 0.4 g as a polymerization catalyst were dissolved in 118.2 g of PM, and reacted for 20 hours under reflux with heating to give 10% by mass of an acrylic copolymer (PA-7). A solution containing was obtained. Mn of the obtained acrylic copolymer was 22,000 and Mw was 41,000.
  • Preparation of polymerizable liquid crystal solution ⁇ Preparation Example 1> Polymeric liquid crystal LC242 (manufactured by BASF) 29.0g, Irgacure 907 (manufactured by BASF) 0.9g as a polymerization initiator, BYK-361N (manufactured by BYK) 0.2g as a leveling agent, and MIBK as a solvent were added. A polymerizable liquid crystal solution (RM-1) having a solid content concentration of 30% by mass was obtained.
  • PA-1 acrylic copolymer
  • the alignment agent compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were applied on a TAC film at a wet film thickness of 4 ⁇ m using a bar coater. Each was heated and dried in a heat circulation oven at a temperature of 110 ° C. for 60 seconds to form a cured film on the TAC film. Each cured film was irradiated vertically with 313 nm linearly polarized light at an exposure amount of 20 mJ / cm 2 to form an alignment material.
  • a polymerizable liquid crystal solution (RM-1) or (RM-2) was applied with a wet film thickness of 6 ⁇ m using a bar coater.
  • This coating film was dried on a hot plate at a temperature of 90 ° C. for 60 seconds and then exposed at 300 mJ / cm 2 to produce a retardation material.
  • the phase difference material on the prepared substrate is sandwiched between a pair of polarizing plates, the state of the phase difference characteristic in the phase difference material is observed, ⁇ if the phase difference is expressed without defects, and no phase difference is expressed The thing was described as "x" in the column of "orientation”. The evaluation results are summarized in Table 2 later.
  • the obtained retardation material showed good alignment even when any of the polymerizable liquid crystal solutions RM-1 and RM-2 was used.
  • Examples 20 to 22> [Evaluation of orientation]
  • the alignment agent compositions of Examples 1 to 2 and 19 were applied on a TAC film at a wet film thickness of 4 ⁇ m using a bar coater. Each was heated and dried in a thermal circulation oven at a temperature of 90 ° C. for 60 seconds to form a cured film on the TAC film.
  • the linearly polarized light of 313nm in the cured film was irradiated perpendicularly with an exposure amount of 5 mJ / cm 2 or 20 mJ / cm 2, to form an alignment material.
  • a polymerizable liquid crystal solution (RM-1) was applied with a wet film thickness of 6 ⁇ m using a bar coater. 60 seconds after drying this coating temperature 90 ° C. on a hot plate, exposed with 300 mJ / cm 2, to produce a phase difference member.
  • the phase difference material on the prepared substrate is sandwiched between a pair of polarizing plates, the state of the phase difference characteristic in the phase difference material is observed, ⁇ if the phase difference is expressed without defects, and no phase difference is expressed The thing was described as "x" in the column of "orientation”. The evaluation results are summarized in Table 3 later.
  • the cured film forming composition according to the present invention is very useful as a material for forming a liquid crystal alignment film of a liquid crystal display element and an alignment material for forming an optically anisotropic film provided inside or outside the liquid crystal display element.
  • it is suitable as a material for a phase difference material of a circularly polarizing plate used as an antireflection film for an IPS-LCD or an organic EL display.

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Abstract

Le problème décrit par la présente invention est de fournir une composition filmogène durcie pour la formation d'un film durci qui présente d'excellentes propriétés en matière d'alignement des cristaux liquides et de transmissivité de la lumière lorsqu'il est utilisé comme matériau d'alignement avec une couche d'un cristal liquide polymérisable disposé à sa surface. La solution selon l'invention consiste en une composition filmogène durcie contenant (A) un polymère obtenu à l'aide d'un monomère, le monomère étant un produit de réaction d'un monomère comportant un groupe époxy et d'un dérivé d'acide cinnamique représenté par la formule (1), et (B) un agent de réticulation ; un matériau d'alignement caractérisé en ce qu'il est obtenu à l'aide de la composition ; et un matériau à différence de phase caractérisé en ce qu'il est obtenu à l'aide de la composition. (Dans la formule (1) : A1 et A2 représentent un atome d'hydrogène ou un groupe méthyle ; R1 représente un atome d'hydrogène, un atome d'halogène ou similaire ; R2 représente un groupe aromatique divalent, un groupe alicyclique divalent, un groupe hétérocyclique divalent ou un groupe cyclique fusionné divalent ; R3 représente une simple liaison, un atome d'oxygène ou similaire ; R4 à R7 représentent chacun indépendamment un atome d'hydrogène, un atome d'halogène ou similaire ; et n est un nombre entier de 0 à 3.)
PCT/JP2018/012488 2017-03-27 2018-03-27 Composition filmogène durcie, matériau d'alignement et matériau à différence de phase Ceased WO2018181350A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021166619A1 (fr) * 2020-02-20 2021-08-26
US11312907B2 (en) * 2018-04-23 2022-04-26 Merck Patent Gmbh Liquid crystal mixture and liquid crystal display
US11352560B2 (en) * 2018-04-23 2022-06-07 Merck Patent Gmbh Liquid crystal mixture and liquid crystal display
WO2025203678A1 (fr) * 2024-03-29 2025-10-02 大阪有機化学工業株式会社 Composé, composition pour un film de photo-alignement, film de photo-alignement, produit stratifié et film de différence de phase

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009236958A (ja) * 2008-03-25 2009-10-15 Jsr Corp 液晶配向剤、液晶配向膜の形成方法および液晶表示素子
JP2012037868A (ja) * 2010-07-15 2012-02-23 Jsr Corp 位相差フィルム用液晶配向剤、位相差フィルム用液晶配向膜、位相差フィルム及びその製造方法
JP2015031823A (ja) * 2013-08-02 2015-02-16 大阪有機化学工業株式会社 光配向膜用組成物および新規重合体
WO2016143865A1 (fr) * 2015-03-11 2016-09-15 日産化学工業株式会社 Composition formant un film durci, matériau d'alignement et matériau de différence de phase
WO2016147987A1 (fr) * 2015-03-13 2016-09-22 日産化学工業株式会社 Composition de formation de film durci, matériau d'alignement et matériau de différence de phase
WO2017094490A1 (fr) * 2015-12-01 2017-06-08 富士フイルム株式会社 Appareil d'affichage à cristaux liquides et procédé de fabrication d'appareil d'affichage à cristaux liquides
WO2018034342A1 (fr) * 2016-08-19 2018-02-22 大阪有機化学工業株式会社 Composition de résine durcissable pour formation de film facilement pelable, et procédé de fabrication de celle-ci

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55165858A (en) 1979-06-13 1980-12-24 Toppan Printing Co Ltd Center-bound bookbinding folding pagination and its processing method
JPH1068816A (ja) 1996-08-29 1998-03-10 Sharp Corp 位相差板及び円偏光板
EP1021479B1 (fr) 1997-09-25 2002-07-17 Rolic AG Polyimides photo-reticulables
JP4207430B2 (ja) 2002-01-31 2009-01-14 Ｊｓｒ株式会社 液晶配向剤、液晶配向膜の形成方法および液晶表示素子
JP2005049865A (ja) 2003-07-17 2005-02-24 Arisawa Mfg Co Ltd 光学位相差素子の製造方法
US7425394B2 (en) * 2004-02-10 2008-09-16 Dai Nippon Printing Co., Ltd. Liquid crystal display
JP5316740B2 (ja) 2007-08-30 2013-10-16 Ｊｓｒ株式会社 液晶配向膜の形成方法
JP5373293B2 (ja) 2008-01-29 2013-12-18 富士フイルム株式会社 化合物、液晶組成物及び異方性材料
JP5413555B2 (ja) * 2008-05-23 2014-02-12 Ｊｓｒ株式会社 液晶配向剤、液晶配向膜の形成方法および液晶表示素子
KR101724107B1 (ko) * 2009-06-23 2017-04-06 닛산 가가쿠 고교 가부시키 가이샤 광배향성을 갖는 열경화막 형성 조성물
JPWO2014065327A1 (ja) * 2012-10-24 2016-09-08 日産化学工業株式会社 ヒドロキシル基を有するアクリルまたはメタクリル化合物及びその製造方法
JP6458949B2 (ja) * 2013-04-16 2019-01-30 日産化学株式会社 硬化膜形成組成物、配向材および位相差材
CN106062009B (zh) * 2014-02-28 2018-03-27 日产化学工业株式会社 固化膜形成用组合物、取向材料及相位差材料
KR102318651B1 (ko) * 2014-06-30 2021-10-28 닛산 가가쿠 가부시키가이샤 경화막 형성 조성물, 배향재 및 위상차재

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009236958A (ja) * 2008-03-25 2009-10-15 Jsr Corp 液晶配向剤、液晶配向膜の形成方法および液晶表示素子
JP2012037868A (ja) * 2010-07-15 2012-02-23 Jsr Corp 位相差フィルム用液晶配向剤、位相差フィルム用液晶配向膜、位相差フィルム及びその製造方法
JP2015031823A (ja) * 2013-08-02 2015-02-16 大阪有機化学工業株式会社 光配向膜用組成物および新規重合体
WO2016143865A1 (fr) * 2015-03-11 2016-09-15 日産化学工業株式会社 Composition formant un film durci, matériau d'alignement et matériau de différence de phase
WO2016147987A1 (fr) * 2015-03-13 2016-09-22 日産化学工業株式会社 Composition de formation de film durci, matériau d'alignement et matériau de différence de phase
WO2017094490A1 (fr) * 2015-12-01 2017-06-08 富士フイルム株式会社 Appareil d'affichage à cristaux liquides et procédé de fabrication d'appareil d'affichage à cristaux liquides
WO2018034342A1 (fr) * 2016-08-19 2018-02-22 大阪有機化学工業株式会社 Composition de résine durcissable pour formation de film facilement pelable, et procédé de fabrication de celle-ci

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11312907B2 (en) * 2018-04-23 2022-04-26 Merck Patent Gmbh Liquid crystal mixture and liquid crystal display
US11352560B2 (en) * 2018-04-23 2022-06-07 Merck Patent Gmbh Liquid crystal mixture and liquid crystal display
JPWO2021166619A1 (fr) * 2020-02-20 2021-08-26
WO2021166619A1 (fr) * 2020-02-20 2021-08-26 富士フイルム株式会社 Stratifié optique, plaque de polarisation et dispositif d'affichage d'image
CN115104050A (zh) * 2020-02-20 2022-09-23 富士胶片株式会社 光学层叠体、偏振片及图像显示装置
CN115104050B (zh) * 2020-02-20 2023-11-14 富士胶片株式会社 光学层叠体、偏振片及图像显示装置
JP7385729B2 (ja) 2020-02-20 2023-11-22 富士フイルム株式会社 光学積層体、偏光板および画像表示装置
WO2025203678A1 (fr) * 2024-03-29 2025-10-02 大阪有機化学工業株式会社 Composé, composition pour un film de photo-alignement, film de photo-alignement, produit stratifié et film de différence de phase

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