Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
• • 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
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • 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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
• • 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 suitable for a vertical alignment material for vertically aligning liquid crystal molecules.
• the present invention provides a liquid crystal display such as an IPS liquid crystal display (In-plane Switching LCD) filled with a liquid crystal having positive dielectric anisotropy ( ⁇ > 0).
• IPS liquid crystal display In-plane Switching LCD
• ⁇ > 0 positive dielectric anisotropy
• the present invention relates to a cured film forming composition, an alignment material, and a retardation material.
• IPS-LCD is characterized by little change in brightness / color due to viewing angle because no vertical tilt of liquid crystal molecules occurs. However, it is difficult to increase contrast ratio, brightness, and response speed. It is done.
• a viewing angle compensation film is not used in the early IPS-LCD, and an IPS-LCD not using such a viewing angle compensation film has a tilt angle of Due to the relatively large light leakage in the dark state, there is a disadvantage of showing a low contrast ratio value.
• Patent Document 2 discloses an IPS-LCD compensation film using a + C plate and a + A plate (positive A plate).
• This document shows the following configuration of the liquid crystal display element described therein. 1) A liquid crystal layer having a horizontal alignment is sandwiched between both substrates supplied by electrodes capable of applying an electric field parallel to the surface of the liquid crystal layer. 2) One or more + A plates and + C plates are sandwiched between both polarizing plates. 3) The main optical axis of the + A plate is perpendicular to the main optical axis of the liquid crystal layer. 4) of the liquid crystal layer retardation value R LC, + C plate retardation value R + C, + A retardation value R + A plate is determined so as to satisfy the following equation.
• the + A plate is intended to provide an IPS-LCD having high contrast characteristics at the front and tilt angles and low color shift by minimizing dark light leakage at the tilt angle.
• an IPS-LCD having a + C plate is disclosed (Patent Document 3).
• JP-A-2-256603 Japanese Patent Laid-Open No. 11-133408 JP 2009-122715 A JP 2001-281669 A Japanese Patent Laying-Open No. 2015-79256
• the + C plate can compensate for light leakage where the viewing angle of the polarizing plate is large, so that the circular polarizing plate used as an anti-reflection film for IPS-LCD and organic EL displays can be used. It is very useful as an optical compensation film. However, it is difficult to develop the vertical alignment (positive C plate) property by a conventionally known stretching method.
• a conventionally proposed vertical alignment film using polyimide needs to use a polyimide solvent such as N-methyl-2-pyrrolidone for film formation. For this reason, although it does not become a problem in a glass base material, when a base material is a film, there exists a problem of giving a damage to a base material at the time of alignment film formation.
• the vertical alignment film using polyimide requires firing at a high temperature, and there is a problem that the film substrate cannot withstand the high temperature.
• An object of the present invention is to provide a cured film forming composition for providing an alignment material capable of stably aligning a polymerizable liquid crystal vertically under low-temperature and short-time firing conditions even on a resin film.
• Another object of the present invention is obtained from the cured film-forming composition, having excellent vertical orientation, solvent resistance, and stable polymerization on a resin film under low-temperature and short-time firing conditions.
• Another object of the present invention is to provide a phase difference material useful for an alignment material capable of vertically aligning a crystalline liquid crystal and a + C plate formed using the alignment material.
• a cured film based on a polymer having a vertically aligning group and a compound having two or more polymerizable groups containing a C ⁇ C double bond It has been found that a cured film having excellent vertical alignment can be formed by selecting a forming material, and the present invention has been completed.
• the present invention as a first aspect, (A) a polymer having a group represented by the following formula [1] as a vertical alignment group; (B) a cured film-forming composition containing a compound having two or more polymerizable groups containing a C ⁇ C double bond, and (C) a radical polymerization initiator,
• the present invention relates to a cured film-forming composition characterized in that substantially only component (B) has a polymerizable group containing a C ⁇ C double bond.
• Y 1 represents a single bond or consists of —O—, —CH 2 O—, —COO—, —OCO—, —NHCO—, —NH—CO—O— and —NH—CO—NH—.
• Y 2 represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms (the alkylene group may be interrupted by 1 to 3 bonding groups A provided that the bonding groups A are bonded to each other).
• —CH 2 —CH (OH) —CH 2 — or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring
• the divalent cyclic group is Arbitrary hydrogen atoms on the cyclic group are linear or branched alkyl groups having 1 to 3 carbon atoms, linear or branched alkoxy groups having 1 to 3 carbon atoms, linear or branched
• Y 3 represents a single bond or an alkylene group having 1 to 15 carbon atoms (the alkylene group may be linear, branched, cyclic, or a combination thereof, and 1 to 3 bonding groups) Which can be interrupted at A, provided that the linking groups A are not bonded together).
• Y 4 represents a single bond, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring (in the divalent cyclic group, any hydrogen atom on the cyclic group is linear or branched)
• Y 5 is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring (the
• the bond between Y 2 and Y 3 may be a single bond or a bond group A
• the bond between Y 3 and Y 4 may be a single bond, it may also be made via the linking group A
• the bond between Y 4 and Y 5 may be a single bond, it may also be made via the linking group A
• Y 5 and Y 6 represents a group other than a single bond
• the bond between Y 5 and Y 6 may be a single bond, it may also be made via the linking group A
• n is 2 or more, the bond between one Y 5 and the adjacent Y 5 may be a single bond or a bond A,
• the polymerizable group containing a C ⁇ C double bond as the component (B) is at least one selected from an acryl group, a methacryl group, a vinyl group, an allyl group, and a maleimide group.
• the present invention relates to a cured film forming composition.
• the present invention relates to the cured film forming composition according to the first aspect or the second aspect, which contains 10 parts by mass to 2000 parts by mass of the component (B) based on 100 parts by mass of the component (A).
• the cured film formation composition in any one of the 1st viewpoint thru
• the present invention relates to an alignment material obtained by curing the cured film forming composition according to any one of the first to fourth 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 to fourth aspects.
• the first aspect of the present invention in order to provide an alignment material that has excellent vertical alignment and can stably align a polymerizable liquid crystal vertically under low-temperature and short-time firing conditions even on a resin film.
• Useful cured film forming compositions can be provided.
• the second aspect of the present invention it is possible to provide an alignment material that has excellent vertical alignment and can stably align the polymerizable liquid crystal vertically under low-temperature and short-time firing conditions.
• the third aspect of the present invention it is possible to provide a retardation material that can be formed on a resin film with high efficiency, is highly transparent, and has high solvent resistance.
• the cured film forming composition of the present invention comprises (A) a polymer having a vertical alignment group as a component, (B) a compound having two or more polymerizable groups containing a C ⁇ C double bond, and ( And a radical polymerization initiator as component C), and only component (B) has a polymerizable group containing a C ⁇ C double bond. And as long as the effect of this invention is not impaired, another additive can be contained.
• A a polymer having a vertical alignment group as a component
• B a compound having two or more polymerizable groups containing a C ⁇ C double bond
• a radical polymerization initiator as component C
• the component (A) contained in the cured film forming composition of the present invention is a polymer having a vertical alignment group.
• the vertical alignment group is a group represented by the following formula [1].
• the formula [1] represents a single bond, or —O—, —CH 2 O—, —COO—, —OCO—, —NHCO—, —NH—CO—O— and —NH—CO—.
• a linking group which is a group selected from the group consisting of NH— is represented.
• Y 2 represents a single bond or a linear or branched alkylene group having 1 to 15 carbon atoms, and the alkylene group can be interrupted by 1 to 3 bonding groups A. However, the bonding groups A are not bonded to each other.
• Y 2 also includes —CH 2 —CH (OH) —CH 2 —.
• Y 2 includes a divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on the cyclic group is a linear or branched carbon atom having 1 to 3 carbon atoms.
• Alkyl group, linear or branched alkoxyl group having 1 to 3 carbon atoms, linear or branched fluorine-containing alkyl group having 1 to 3 carbon atoms, linear or branched carbon atom number 1 May be substituted with 1 to 3 fluorine-containing alkoxyl groups or fluorine atoms.
• heterocyclic ring examples include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, Triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring and the like are more preferable.
• Examples of the alkyl group exemplified as the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a cyclopropyl group.
• examples of the alkyl group include oxygen groups. And a group to which an atom —O— is bonded.
• Examples of the fluorine-containing alkyl group and fluorine-containing alkoxyl group include groups in which any hydrogen atom of the alkyl group and alkoxyl group is substituted with a fluorine atom.
• Y 2 is preferably a benzene ring or a cyclohexane ring from the viewpoint of ease of synthesis.
• Y 3 represents a single bond or an alkylene group having 1 to 15 carbon atoms, and the alkylene group is linear, branched, cyclic, or a combination thereof. Alternatively, it may be interrupted by 1 to 3 linking groups A, provided that the linking groups A are not bonded together.
• Y 4 represents a single bond or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is linear or A branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxyl group having 1 to 3 carbon atoms, a linear or branched alkyl group having 1 to 3 carbon atoms, It may be substituted with a linear or branched fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom.
• alkyl group and the like mentioned as the heterocyclic ring and the substituent can be the same as those mentioned for Y 2 above.
• Y 4 may be a divalent organic group selected from organic groups having 17 to 30 carbon atoms having a steroid skeleton.
• Preferred examples thereof include cholesteryl, androsteryl, ⁇ -cholesteryl, epiandrosteryl, erygosteryl, estril, 11 ⁇ -hydroxymethylsteryl, 11 ⁇ -progesteryl, lanosteryl, melatranyl, methyltestosteryl, noretisteryl, pregnenoyl, ⁇ -sitosteryl, It is a divalent group having a structure in which two hydrogen atoms are removed from a structure selected from stigmasteryl, testosteryl, acetic acid cholesterol ester, and the like. More specifically, for example, as follows. (In the formula, * represents a bonding position.)
• Y 4 is preferably a divalent organic group having 17 to 30 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton from the viewpoint of ease of synthesis.
• Y 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is a linear or branched carbon atom number.
• the alkyl group and the like mentioned as the heterocyclic ring and the substituent can be the same as those mentioned above for Y 4 .
• Y 5 is preferably a benzene ring or a cyclohexane ring.
• n represents an integer of 0 to 4, and when n is 2 or more, Y 5 may be the same group or different groups. Among these, n is preferably 0 to 3 from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 0-2.
• Y 6 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or 1 to 18 carbon atoms.
• the group may be linear, branched, cyclic, or a combination thereof, and may be interrupted by 1 to 3 bonding groups A provided that the bonding groups A are bonded to each other. Absent.
• Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms.
• Y 6 is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms.
• Y 6 is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
• Y 6 is preferably a hydrogen atom.
• the alkyl group having 1 to 18 carbon atoms is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group.
• Examples of the alkylene group having 1 to 15 carbon atoms include a divalent group obtained by removing one arbitrary hydrogen atom from the alkyl group.
• Examples of the alkoxyl group having 1 to 18 carbon atoms include groups in which an oxygen atom —O— is bonded to the groups listed as specific examples of the alkyl group.
• the fluorine-containing alkyl group having 1 to 18 carbon atoms and the fluorine-containing alkoxyl group having 1 to 18 carbon atoms include the alkyl group having 1 to 18 carbon atoms and the alkoxyl group having 1 to 18 carbon atoms.
• a group in which any hydrogen atom is substituted with a fluorine atom can be exemplified.
• the bond between Y 2 and Y 3 may be a single bond, may also be made via the linking group A, Y 3 and Y
• the bond between Y 3 and Y 4 may be a single bond or may be made through a bonding group A
• Y 4 and Y 5 may be other than a single bond.
• the bond between Y 4 and Y 5 may be a single bond or may be made through a bonding group A.
• Y 5 and Y 6 represent a group other than a single bond
• Y The bond between 5 and Y 6 may be a single bond or via a bonding group A.
• n is 2 or more, one Y 5 and Y 5 adjacent thereto are The bond may be a single bond or may be made through the bonding group A.
• the linking group A includes —O—, —CH 2 O—, —CO—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—CO—O—, —O—CO—.
• the total number of carbon atoms contained in the group represented by the formula [1] is 6 to 30, for example 6 to 20.
• the vertical alignment group represented by the formula [1] is a group containing an alkyl group having 7 to 18 carbon atoms, particularly 8 to 15 carbon atoms. It is preferably an alkyl group having 7 to 18 carbon atoms, particularly 8 to 15 carbon atoms.
• the method for obtaining the polymer of the component (A) of the present invention is not particularly limited.
• the polymer of the component (A) can be obtained by reacting a monomer having a vertical alignment group and an arbitrary monomer by a polymerization method such as radical polymerization.
• Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl).
• Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene and 1,7. -Octadiene monoepoxide.
• Examples of the monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3- Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (Ethylene glycol) ethyl ether methacrylate, 5-acryloyl Carboxymethyl-6-hydroxy-norbornene-2-carboxylic-6-lactone and 5-methacryloyloxy such acryloyloxy-6-hydroxy-norbornene-2-carboxylic
• Examples of the monomer having an amino group include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.
• Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide and N- (hydroxyphenyl) maleimide.
• Examples of the monomer having an isocyanate group include acryloylethyl isocyanate, methacryloylethyl isocyanate, and m-tetramethylxylene isocyanate.
• acrylic ester compounds include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate.
• methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate.
• vinyl compound examples include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene, And 1,7-octadiene monoepoxide.
• styrene compound examples include styrene, methyl styrene, chlorostyrene, bromostyrene, and the like.
• maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
• the polymer of component (A) preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 2,000 to 150,000, and more preferably 3,000 to 100,000. Even more preferred. If the weight average molecular weight is over 200,000, the solubility in the solvent may be lowered and the handling property may be lowered. If the weight average molecular weight is less than 1,000, the solvent is too small. Resistance and heat resistance may decrease.
• the proportion of the vertically aligning group is preferably 3 mol% to 90 mol%, more preferably 5 mol% to 80 mol%, per 100 mol of all repeating units of the polymer. .
• the amount is less than 3 mol%, the vertical alignment property may be insufficient, and when it is more than 90 mol%, the liquid crystal coating property may be adversely affected.
• polymer having a vertical alignment group commercially available products can be suitably used, and examples thereof include ARUFUON UF-5041, UF-5080, and UF-5022 [all are manufactured by Toagosei Co., Ltd.].
• the component (B) in the cured film-forming composition of the present invention is a compound having two or more polymerizable groups containing a C ⁇ C double bond.
• 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 polymerizable group containing a C ⁇ C double bond as the component (B) preferably has 3 to 16 carbon atoms and has an unsaturated bond at the terminal, as shown in the formula (b2)
• the particular side chain represented is particularly preferred.
• R 51 has 1 to 14 carbon atoms and is an organic group selected from the group consisting of an aliphatic group, an aliphatic group containing a cyclic structure, and an aromatic group, or from this group An organic group comprising a combination of a plurality of organic groups selected.
• R 51 may contain an ester bond, an ether bond, an amide bond, a urethane bond, or the like.
• R 52 is a hydrogen atom or a methyl group, and a specific side chain in which R 52 is a hydrogen atom is preferable, and more preferably a specific side chain in which the terminal is an acryloyl group, a methacryloyl group, or a styryl group. is there.
• the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound.
• (meth) acrylic acid refers to acrylic acid and methacrylic acid.
• the (meth) acryloyl group represents CH 2 ⁇ CHCO— and CH (CH 3 ) ⁇ CHCO—.
• Examples of the compound having two (meth) acryloyl groups include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and neopentyl glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate Pentaerythritol di (meth) acrylate
• the compound having two or more (meth) acryloyl groups commercially available products can be suitably used.
• Examples of the compound having three (meth) acryloyl groups include, for example, ethylene oxide-modified 1,1,1-trimethylolethane tri (meth) acrylate [ethylene oxide addition mole number 3 to 30], ethylene oxide-modified trimethylol.
• Propane tri (meth) acrylate [ethylene oxide addition moles 3 to 30], propylene oxide modified trimethylolpropane tri (meth) acrylate [propylene oxide addition moles 3 to 30], ethylene oxide modified glycerin tri (meth) acrylate [ethylene oxide addition moles] 3-30], propylene oxide-modified glycerin tri (meth) acrylate [propylene oxide addition mole number 3-30], tris (2- (acryloyloxy) ethyl) isocyanurate, ⁇ -ca Lolactone-modified tris (2- (acryloyloxy) ethyl) isocyanurate [ ⁇ -caprolactone addition mole number 1-30], 1,1,1-trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Examples include ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and
• Examples of the compound having four (meth) acryloyl groups include ethylene oxide-modified ditrimethylolpropane tetra (meth) acrylate [ethylene oxide addition mole number 4 to 40], ethylene oxide-modified pentaerythritol tetra (meth) acrylate [ Ethylene oxide addition mole number 4 to 40], ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like.
• NK ester ATM-4E, ATM-35E [above, both manufactured by Shin-Nakamura Chemical Co., Ltd.]
• EBECRYL (registered trademark) 40 [Daicel Ornex] Biscoat # 300 [Osaka Organic Chemical Co., Ltd.]
• light acrylate PE-4A [manufactured by Kyoeisha Chemical Co., Ltd.]
• NK ester AD-TMP, A-TMMT [above, both Shin-Nakamura Chemical Co., Ltd.]
• EBECRYL registered trademark
• Examples of the compound having 5 or more (meth) acryloyl groups include ethylene oxide-modified dipentaerythritol hexa (meth) acrylate [ethylene oxide addition mole number 6 to 60], ethylene oxide-modified tripentaerythritol octa ( Examples thereof include (meth) acrylate [ethylene oxide addition mole number 6 to 60], dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate and the like.
• NK ester A-DPH-12E [manufactured by Shin-Nakamura Chemical Co., Ltd.], biscort # 802 [manufactured by Osaka Organic Chemical Co., Ltd.]; Acrylate DPE-6A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester A-9550, A-DPH [all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.]; DPHA [manufactured by Daicel Ornex Co., Ltd.] Can be mentioned.
• bifunctional urethane (meth) acrylate examples include urethanized product of phenylglycidyl ether (meth) acrylic acid adduct and hexamethylene diisocyanate, phenylglycidyl ether (meth) acrylic acid adduct and toluene diisocyanate. Etc.
• bifunctional urethane (meth) acrylate for example, AH-600, AT-600 [above, both manufactured by Kyoeisha Chemical Co., Ltd.]; NK Oligo U-2PPA, U-200PA, UA-160TM, UA-290TM, UA-4200, UA-4400, UA-122P, UA-W2A [all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 210 215, 230, 244, 245, 270, 280 / 15IB, 284, 285, 4858, 8307, 8402, 8411, 8804, 8807, 9227EA, 9270 , KRM (registered trademark) 7735 [above, both manufactured by Daicel Ornex Co., Ltd.]; Murasaki (registered trademark) UV-6630B, 7000 7461TE, 2000B, 2750B, 3
• polyfunctional urethane (meth) acrylate compounds having three (meth) acryloyl groups include NK Oligo UA-7100 (manufactured by Shin-Nakamura Chemical Co., Ltd.); EBECRYL (registered trademark) 204, 205, 264, 265, 294 / 25HD, 1259, 4820, 8311, 8465, 8701, 9260, KRM (Registered Trademark) 8296, 8667 [above, Daicel Ornex Co., Ltd. ); Murasaki (registered trademark) UV-7550B, 7000B, 7510B, 7461TE, 2750B [all of which are manufactured by Nippon Synthetic Chemical Industry Co., Ltd.].
• polyfunctional urethane (meth) acrylate compounds having four (meth) acryloyl groups include EBECRYL (Registered Trademark) 8210, 8405, KRM (Registered Trademark) 8528 [above, both are Daicel Ornex Manufactured by Co., Ltd.]; Shikko (registered trademark) UV-7650B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd.].
• Examples of the polyfunctional urethane (meth) acrylate compound having 5 or more (meth) acryloyl groups are urethanized products of pentaerythritol tri (meth) acrylate and hexamethylene diisocyanate, Urethanes of pentaerythritol tri (meth) acrylate and toluene diisocyanate, urethanates of pentaerythritol tri (meth) acrylate and isophorone diisocyanate, urethanates of dipentaerythritol penta (meth) acrylate and hexamethylene diisocyanate, etc. .
• urethane (meth) acrylates having 5 or more functional groups can be suitably used.
• UA-306H, UA-306T, UA-306I, UA-510H [above, all manufactured by Kyoeisha Chemical Co., Ltd.]
• the component (B) of the present invention may be a polymer compound having a side chain in which one or more terminals are polymerizable unsaturated bonds in the molecule.
• a polymer compound having a side chain whose terminal is a polymerizable unsaturated bond a polymer compound having a (meth) acryloyl group in two or more side chains in the molecule is preferable.
• polymer compound examples include polymer compounds containing one or more (meth) acryloyl groups such as urethane acrylic, epoxy acrylic, and various (meth) acrylates.
• the weight average molecular weight of the polymer compound (B) is preferably 1,000 to 200,000, more preferably 5,000 to 50,000. When the molecular weight is less than 1,000, the effect of the present invention is not achieved. On the other hand, if the molecular weight exceeds 100,000, it may not dissolve in the composition.
• Examples of such a compound as the component (B) include Acryt 8BR-930M, 8UH-1006, 8KQ-2001, 8KX-078, 1SX-1055 [above, Taisei Fine Chemical Co., Ltd.], SMP -250A, SMP-360A, SMP-550A [above, manufactured by Kyoeisha Chemical Co., Ltd.] and the like.
• the content is 10 parts by mass to 2000 parts by mass, preferably 15 parts by mass to 500 parts by mass, per 100 parts by mass of the component (A).
• Component (C) in the cured film forming composition of the present invention is a radical polymerization initiator.
• the radical polymerization initiator known ones can be used. For example, alkylphenones, benzophenones, acylphosphine oxides, Michler's benzoylbenzoates, oxime esters, tetramethylthiuram monosulfides, Examples include thioxanthones.
• radical polymerization initiator used in the present invention examples include ⁇ -diketones such as diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2, Benzophenones such as 4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; acetophenone, p-dimethylaminoacetophenone, ⁇ , ⁇ -Dimethoxy- ⁇ -acetoxyacetophenone, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone, p-methoxyacetophenone, 1- [2-methyl-4-methylthiophenyl] -2
• Acetophenones such as ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone, phenacyl chloride, tribromomethylphenyl sulfone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1,2′-bisimidazoles and 4
• a combination of 4′-diethylaminobenzophenone and mercaptobenzothiazole, Lucillin TPO (trade name), Irgacure 651 (trade name), and Irgacure 369 (trade name) are preferred.
• the above radical polymerization initiators may be used alone or in combination of two or more.
• the radical polymerization initiator is preferably used in an amount of 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 2 to 30 parts by mass with respect to 100 parts by mass of the component (A). Can do. If the amount of radical polymerization initiator used is less than the above range, it is easily affected by radical deactivation by oxygen (decrease in sensitivity), and if it exceeds the above range, compatibility is deteriorated and storage stability is lowered. There is a tendency to do.
• 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 should just dissolve (A) component, (B) component, (C) component, and the other additive mentioned later as needed, and the kind and structure are not specifically 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
• methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable from the viewpoint that the resin film is a resistant solvent.
• These solvents can be used singly or in combination of two or more.
• the cured film forming composition of the present invention is a sensitizer, an adhesion improver, a silane coupling agent, a surfactant, a rheology modifier, a pigment, as necessary, as long as the effects of the present invention are not impaired.
• Dyes, storage stabilizers, antifoaming agents, antioxidants and the like can be contained.
• the cured film forming composition of the present invention comprises (A) a polymer having a vertically-alignable group, (B) a compound having two or more polymerizable groups containing a C ⁇ C double bond, and (C) component.
• the polymerization initiator may further contain 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]: Based on 100 parts by mass of component (A) and component (A), 0.1 part by mass to 100 parts by mass of the polymer as component (B) and 10 parts by mass to 2000 parts by mass of component (A). A cured film-forming composition containing from about 50 to 50 parts by mass of component (C). [2]: Based on 100 parts by mass of component (A) and component (A), 10 parts by mass to 2000 parts by mass of component (B), 0.1 parts per 100 parts by mass of polymer as component (A) A cured film forming composition containing from 50 parts by weight to 50 parts by weight of component (C) and a solvent.
• 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 method of mixing the component (B), further the component (C), etc. in a predetermined ratio with a solution of the component (A) dissolved in a solvent to obtain a uniform solution, or this preparation method In an appropriate stage, there may be mentioned a method in which other additives are further added and mixed as necessary.
• 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.
• DPHA Dipentaerythritol hexaacrylate 8KX: 8KX-078 manufactured by Taisei Fine Chemical Co., Ltd. (solid content concentration 40% by mass) 8KQ: Taisei Fine Chemical Co., Ltd. 8KQ-2001 (solid content concentration 39% by mass) 8UH: Taisei Fine Chemical Co., Ltd.
• Mn number average molecular weight
• Mw number average molecular weight
• ⁇ Polymerization example 2> LAA 1.0 g, MAA 0.8 g, and AIBN 0.1 g as a polymerization catalyst were dissolved in 7.8 g of PM, and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 25% by mass) ( P2) was obtained. Mn of the obtained acrylic copolymer was 13,700 and Mw was 24,000.
• the alignment materials obtained using the cured film forming compositions of the examples exhibited good vertical alignment properties.
• 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 an optical compensation film of a circularly polarizing plate used as an antireflection film for an IPS-LCD or an organic EL display.

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