WO2006118094A1 - Composition traitable thermiquement, produit traité thermiquement, et dispositif d’affichage à cristaux liquides les utilisant - Google Patents

Composition traitable thermiquement, produit traité thermiquement, et dispositif d’affichage à cristaux liquides les utilisant Download PDF

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WO2006118094A1
WO2006118094A1 PCT/JP2006/308604 JP2006308604W WO2006118094A1 WO 2006118094 A1 WO2006118094 A1 WO 2006118094A1 JP 2006308604 W JP2006308604 W JP 2006308604W WO 2006118094 A1 WO2006118094 A1 WO 2006118094A1
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group
meth
curable composition
acid
compound
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PCT/JP2006/308604
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English (en)
Japanese (ja)
Inventor
Yuji Mizuho
Makoto Fukui
Toshiyuki Tanaka
Junji Mizukami
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Mitsubishi Chemical Corporation
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Priority claimed from JP2005282408A external-priority patent/JP5597905B2/ja
Priority claimed from JP2005291817A external-priority patent/JP5109246B2/ja
Application filed by Mitsubishi Chemical Corporation filed Critical Mitsubishi Chemical Corporation
Priority to KR1020077017257A priority Critical patent/KR101325949B1/ko
Priority to CN2006800053214A priority patent/CN101120029B/zh
Publication of WO2006118094A1 publication Critical patent/WO2006118094A1/fr

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    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to a curable composition, a cured product, and a liquid crystal display device. Specifically, for example, in a color filter such as a liquid crystal display, a curable composition used for image formation, overcoat, ribs and spacers, and a cured product formed from the curable composition; The present invention relates to a liquid crystal display device having the cured product.
  • a curable composition containing a resin, a photopolymerizable monomer, a photopolymerization initiator, etc. Things have been used.
  • Various compositions have been proposed for this curable composition from the standpoint of developability, pattern accuracy, adhesion, etc. As one of them, the efficiency of the formation process (shortening the curing time) and the yield are improved.
  • an unsaturated resin obtained by further reacting a reaction product of an epoxy resin and an unsaturated group-containing carboxylic acid with a polybasic carboxylic acid or its anhydride.
  • a technique using a group-containing coagulant is disclosed (Japanese Patent Laid-Open No. 2001-174621).
  • a curable composition for a color filter may be required to have high curability and excellent mechanical properties.
  • a spacer in the present specification, “spacer” is formed of a curable composition, and indicates a so-called columnar spacer, photospacer, etc.).
  • the force used to keep the distance between two substrates cell gap
  • a process of pressing the color filter and the substrate under high pressure and high pressure is required.
  • the physical properties are required to maintain the function of the spacer without being deformed by the high-temperature and high-pressure conditions at the time of crimping.
  • the mechanical properties of the curable composition for color filters such as the recovery rate and elastic recovery rate, return to the original shape when the external pressure is removed even when the external pressure is deformed. It is required as a characteristic.
  • a curable composition and the like in which the content of the polyfunctional acrylate monomer is specified has been proposed (Japanese Patent Laid-Open No. 2002-174812). Publication).
  • An object of the present invention is a curable composition used for a liquid crystal display or the like, and is capable of absorbing pressure nonuniformity at the time of producing a substrate with a large amount of deformation when subjected to external pressure. It aims at providing the curable composition which can form a thing. Another object of the present invention is to provide a curable composition capable of forming a cured product in which the restoration rate is not significantly reduced even under high pressure and the restoration rate is less dependent on pressure.
  • the curable composition of the present invention is characterized in that a cured product satisfying the following index formulas (1) and (2) can be formed in a load unloading test using a micro hardness tester.
  • R and R are the upper cross-sectional area forces 0 ⁇ 5 m 2 spacer
  • the elastic recovery rate (%) is shown.
  • the cured product of the present invention is formed from this curable composition.
  • the liquid crystal display device of the present invention has this cured product.
  • FIG. 1 is a schematic diagram showing a profile position when a spacer pattern is viewed from above.
  • FIG. 2 is a schematic diagram showing a profile of a vertical cross section of a spacer pattern.
  • FIG. 3 is a schematic diagram showing a load-displacement curve in a loader unloading test of a spacer. Detailed description
  • the present inventors have found that a curable composition capable of forming a cured product having specific mechanical properties can achieve the above-described object, and has completed the present invention.
  • the curable composition of the present invention can form a cured product satisfying the index formulas (1) and (2) in a load unloading test using a microhardness meter.
  • This curable composition should contain an ethylenically unsaturated compound having a double bond equivalent force of not more than 00.
  • This ethylenically unsaturated compound is obtained from an epoxy group-containing compound.
  • the ethylenically unsaturated compound may contain a carboxyl group.
  • This curable composition is at least one selected from the group consisting of a carboxyl group-containing bur resin, a copolymer containing a carboxyl group and an epoxy group, and acid-modified epoxy (meth) acrylates.
  • One compound may be contained.
  • the cured product of the present invention is formed of this curable composition.
  • the liquid crystal display device of the present invention has this cured product.
  • the amount of deformation when subjected to external pressure is large (that is, it is possible to absorb non-uniformity of pressure bonding during substrate production), and the recovery rate is also high under high pressure.
  • (meth) acryl means “acryl” and Z or “methacryl”.
  • total solid content means all components except the solvent in the curable composition.
  • the curable composition of the present invention is preferably characterized in that it can form a cured product satisfying the following index formulas (1) and (2) in a load unloading test using a micro hardness tester. Contains an ethylenically unsaturated compound having a double bond equivalent force of 00 or less. In addition, it contains other resins, polymerizable monomers, heat and Z or a photopolymerization initiator as required.
  • 1 2 indicates the elastic recovery rate (%) of the spacer with the upper cross-sectional area forces of 0 ⁇ 5 ⁇ 2 and 150 ⁇ 5 / ⁇ m 2 , respectively.
  • the curable composition of the present invention is usually used in a state where each component is dissolved or dispersed in a solvent in order to form a layer of the curable composition on the substrate by means such as coating and drying.
  • the curable composition in the present invention is a state in which the curable composition is dissolved or dispersed in a solvent, a state in which the solvent component is volatilized and removed, and then cured by heat, Z, light, or the like. Any of the states described above shall be included.
  • the ethylenically unsaturated compound is a polymerization initiation system containing a photopolymerization initiator and Z or a thermal polymerization initiator described later.
  • a radically polymerizable polymer that undergoes addition polymerization by action and, in some cases, crosslinks and cures. It is a compound having at least one tyrenically unsaturated bond in the molecule.
  • the curable composition of the present invention comprises an ethylenically unsaturated compound having a double bond equivalent force of 00 or less (hereinafter referred to as “hardened product”) in order to achieve the mechanical properties described in [16] below. It may be referred to as “specific ethylenically unsaturated compound (A)”.
  • the specific ethylenically unsaturated compound (A) according to the present invention has a smaller double bond equivalent, and the more double bonds per unit weight, the greater the elastic recovery rate and recovery rate of the resulting cured product. Therefore, the double bond equivalent of the specific ethylenically unsaturated compound (A) according to the present invention is 400 or less, preferably 350 or less, more preferably 300 or less. The lower limit of the double bond equivalent of the specific ethylenically unsaturated compound (A) is usually 100 or more.
  • double bond equivalent is the weight per mole of the double bond of the compound, and is calculated by the following formula. The larger the double bond per unit weight, the smaller the value of the double bond equivalent.
  • Double bond equivalent Compound weight (g) Number of moles of double bond in Z compound
  • the curable composition of the present invention containing the specific ethylenically unsaturated compound (A) is sometimes dissolved or dispersed in a solvent (hereinafter, referred to as "cured composition solution").
  • cured composition solution a solvent
  • the elastic recovery rate and recovery rate of the cured product increase as the reasoning force similar to the double bond equivalent of the specific ethylenically unsaturated compound (A) decreases. Therefore, it is preferably 300 or less, more preferably 250 or less.
  • the lower limit of the double bond equivalent as the whole solid content of the curable composition solution is usually 100 or more.
  • the double bond equivalent of the entire solid content in the curable composition solution is calculated by the above formula in the preparation capacity of the compound having an ethylenic double bond when preparing the curable composition.
  • the solid content concentration of the curable composition is measured by a known method and calculated by the following formula. You can also.
  • the specific ethylenically unsaturated compound (A) preferably has an acid group.
  • “Having an acid group” means having a group that gives a value greater than 0 as an acid value determined by titration with KOH. Specifically, it has a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group, etc. Among them, it is particularly preferable to have a carboxyl group.
  • the specific ethylenically unsaturated compound (A) is preferably obtained from an epoxy compound as described below.
  • the specific ethylenically unsaturated compound (A) preferably has a weight average molecular weight of 1,000 or more, more preferably 1,500 or more, and particularly preferably 2,000 or more. Further, the weight average molecular weight of the specific ethylenically unsaturated compound (A) is usually 100,000 or less, preferably 10,000 or less. If the weight average molecular weight of the specific ethylenically unsaturated compound (A) is too small, the amount of displacement tends to be small, and if it is too large, poor development tends to occur.
  • the weight average molecular weight is measured in terms of polystyrene by GPC (gel permeation chromatography).
  • the specific ethylenically unsaturated compound (A) according to the present invention is not particularly limited as long as the double bond equivalent is 400 or less, but can be obtained from an epoxy group-containing compound as described below. It is preferable that it contains a carboxyl group.
  • Examples of the specific ethylenically unsaturated compound (A) include compounds represented by the following general formula (AI).
  • R 11 may have an alkylene group which may have a substituent or a substituent, and represents an arylene group.
  • R 12 has a substituent! / May be an ethylenically unsaturated group-containing carbonyloxy group.
  • R 13 and R ′′ each independently represents an arbitrary substituent. Show. n is an integer of 0-10. m is an integer of 1 or more.
  • X represents an arbitrary organic group which may have a substituent.
  • alkylene group for R 11 those having 1 to 5 carbon atoms are preferred, and a methylene group, an ethylene group, a propylene group, and a butylene group are more preferred.
  • the arylene group is more preferably a fullerene group having 6 to 10 carbon atoms. Of these, an alkylene group is preferred in the present invention.
  • Examples of the substituent that the alkylene group or arylene group of R 11 may have include, for example, a halogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and 2 carbon atoms.
  • ⁇ Alkenyl group, phenol group, carboxyl group, sulfur group, phosphino group, amino group, nitro group and the like of LO.
  • n is an integer of 0 to 0, preferably 0 to 5, and more preferably 0 to 3. If n exceeds the above range, when the resulting curable composition is a cured product, film loss or the like occurs in the image area during development, or heat resistance decreases.
  • the carbon number of the ethylenically unsaturated group-containing carbonyloxy group which may have a substituent of R 12 in the general formula (AI) is usually 3, and preferably 5 and more preferably the lower limit. Ten.
  • the upper limit is not particularly limited, but is preferably 50, more preferably 40, and particularly preferably 35. If the carbon number is too large or too small, the mechanical properties of the cured product formed by the curable composition of the present invention may not be obtained.
  • R 12 is more preferably a group represented by the following general formula (A-II).
  • R lb , R lb and R 1 ′ each independently represent a hydrogen atom or a methyl group, and Q represents an arbitrary divalent group.
  • Q may preferably have a substituent, and may be an alkylene group, Z, or a substituent.
  • R 21 and R 22 each have an alkyl group which may have a substituent, a substituent, an alkyl group, It may have a substituent! /, May be !, a cycloalkyl group, may have a substituent, may have a cycloalkyl group, or may have a substituent. Show.
  • alkyl group of R 21 and R 22 those having 1 to 20 carbon atoms are preferable, and as the alkenyl group, those having 2 to 20 carbon atoms are preferable! /.
  • Preferred is a cycloalkyl group having 3 to 20 carbon atoms.
  • the cycloalkyl group is preferably one having 3 to 20 carbon atoms, and the aryl group is preferably one having 6 to 20 carbon atoms.
  • R 21 and R 22 may have include, for example, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, a alkenyl group having 2 to 10 carbon atoms, and a phenol. -L group, carboxy group, carbol group, sulphur group, phosphino group, amino group, nitro group and the like.
  • R 21 preferably has a carboxyl group as a substituent.
  • the substituents represented by R 14 in the general formula (A- I) is Do particularly limited, but, for example, there are substituents represented by the following general formula (A- IV).
  • R u , R 12 , R 13 and n are as defined in the general formula (AI).
  • X in the general formula (AI) represents an arbitrary organic group which may have a substituent.
  • This X functions as a base for bonding a double bond-containing group, and does not increase the double bond equivalent as a whole. Therefore, this X is a functional group serving as a site for bonding an appropriate molecular weight and an appropriate number of substituents. There is a function to provide.
  • the molecular weight of X is usually 14 or more, preferably 28 or more, and usually 1000 or less, preferably 800 or less.
  • organic group that can be used as X include a linear or cyclic organic group.
  • linear chain examples include alkane, alkene, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, butyl acetate, and salt.
  • examples include organic groups derived from homo- or copolymers such as vinylidene and maleimide, acid-modified epoxyphthalates, polyolefins, polyamides, polyesters, polyethers, polyurethanes, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, and acetyl cellulose. .
  • Examples of the cyclic ring include an alicyclic ring, an aromatic ring, an alicyclic heterocyclic ring, a heterocyclic ring, and the like, or those condensed by these rings or bonded via a linking group.
  • the organic group derived from it is mentioned.
  • cyclopentane ring, cyclohexane ring, cyclohexene ring, tricyclodecane ring and the like are alicyclic rings
  • aromatic rings are benzene ring, naphthalene ring, and ant ring.
  • Helene ring, phenanthrene ring, azulene ring, fluorene ring, acenaphthylene ring, biphenylene ring, indene ring, etc. are alicyclic heterocycles, as heterocycles furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole Ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and the like.
  • Examples of the linking group via the bond of the cyclic organic group include a direct bond or a divalent or higher valent linking group.
  • Examples of the organic group for X include an alkylene group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, and 2 to 50 carbon atoms, preferably 2 carbon atoms.
  • Examples include residues obtained by removing hydroxyl groups of polyethers of ⁇ 30, bisphenols such as bisphenol A and bisphenol F shown below, and polyols such as trisphenol and novolak.
  • z represents an integer of 0 or more.
  • the bond as the linking group X takes at least two of them.
  • examples of the substituent linked to the remaining one or more bonds include an arbitrary substituent, and a group represented by the general formula (A-IV) is preferable.
  • examples of the substituent on the benzene ring include an alkyl group having 1 to 15 carbon atoms and a carbon number. 1-15 alkoxy group, C2-C15 acyl group, C6-C14 aryl group, carboxy group, hydroxyl group, C1-C16 alkoxycarbonyl group, carboxyl group, halogen An atom etc. are mentioned, A C1-C5 alkyl group, a phenol group, and a halogen atom are still more preferable.
  • the compound represented by the general formula (A-I) is not particularly limited as long as it has the structure, but for example, the following general formula (A-V)
  • A-V the following general formula
  • a compound represented by the following general formula (A-V) is used as a raw material, and this is an ethylenically unsaturated group-containing carbohydrate.
  • R u , X and n are as defined in the general formula (A—I).
  • R 1S has the same meaning as R 11 in formula (A—I).
  • Examples of the epoxy group-containing compound represented by the above general formula (A—V) include epoxy compounds described in [1 5 6] below, and bis (hydroxyphenol) fluorene type ester. Examples thereof include a poxy compound.
  • Examples of the bis (hydroxyphenol) fluorene that forms the bis (hydroxyphenol) fluorene type epoxy compound include 9, 9bis (4 'hydroxyphenol) fluorene, 9, 9-bis (4' —Hydroxy-1 3′-methylphenol) fluorene, 9, 9-bis (4′—hydroxy-1 3 ′, 5′-dimethylphenol) fluorene, 9, 9 —bis (4′-hydroxy-1-3′— Methoxyphenol) fluorene, 9, 9-bis (4'-hydroxyl 3'-funoleo-olefin) phenololene, 9, 9-bis (4'-hydroxy-l 3'-black-o-alkyl) fluorene 9, 9-bis (4'-hydroxy-1 3 ', 5'-dichlorophenol) fluorene, 9,
  • the epoxy group-containing compound represented by the general formula (AV) may be used alone or in combination of two or more.
  • the lower limit of the number of carbon atoms of the ethylenically unsaturated group-containing carbonyloxy group formed in the epoxy group-containing compound represented by the general formula (AV) is usually 3, preferably 5, More preferably, 10.
  • the upper limit is not particularly limited, but is preferably 50, more preferably 40, and particularly preferably 35. If the carbon number is less than the above range, when the curable composition is a cured product, the flexibility is insufficient and the adhesion to the substrate is inferior. On the other hand, if the carbon number is too large, the heat resistance is reduced. .
  • These ethylenically unsaturated group-containing carbo-oxy groups are preferably groups represented by the general formula (A-II).
  • the ethylenically unsaturated group-containing carbo-oxy group represented by the general formula (A-II) is obtained by a reaction using the compound represented by the general formula (A-V) as a raw material. If it is formed as a result, the formation method is not limited. Specific examples of the formation method include a method in which the compound represented by the general formula (A-V) is reacted with an ethylenically unsaturated group-containing rubonic acid (a), or an ethylenically unsaturated group.
  • the compound (c) having a functional group that reacts with the generated hydroxyl group or carboxyl group is reacted to produce an ethylenically unsaturated group-containing carbohydrate.
  • -Luxoxy group formation method can be mentioned.
  • Examples of the ethylenically unsaturated group-containing carboxylic acids (a) include acrylic acid, Crylic acid, Crotonic acid, ⁇ -, m—, p Bull benzoic acid, Monocarboxylic acids such as ⁇ -position haloalkyl, alkoxyl, halogen, nitro, and cyano substitution of (meth) acrylic acid; Or reaction products with polylatatatone; succinic anhydride, adipic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, methyltetrahydrohydrophthalic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Saturated or unsaturated dicarboxylic anhydrides such as methylmethylenetetrahydrophthalic anhydride and phthalic anhydride, and hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate
  • These ethylenically unsaturated group-containing carboxylic acids (a) may be used alone or in combination of two or more.
  • the carboxylic acids (b) that do not contain the ethylenically unsaturated group include hydroxyl group-containing carboxylic acids such as lactic acid and dihydroxypropionic acid and anhydrides thereof, oxalic acid, maleic acid, tetrahydro Examples thereof include saturated or unsaturated dicarboxylic acids such as phthalic acid, phthalic acid, and tartaric acid, and anhydrides thereof.
  • hydroxyl group or carboxyl group used when the compound (c) having a functional group that reacts with the generated hydroxyl group or carboxyl group is reacted to form an ethylenically unsaturated group-containing carboxy group.
  • the compound (c) having a functional group that reacts with the compound specifically, a compound having an epoxy group, a carboxyl group, or an isocyanate group is preferred.
  • a compound having an epoxy group, a carboxyl group, or an isocyanate group is preferred.
  • the ethylenically unsaturated group-containing carboxylic acids (a) include, but are not limited to, ethylenically unsaturated group-containing compounds such as unsaturated group-containing glycidyl compounds.
  • Each of the compounds (b) and (c) may be used alone or in combination of two or more.
  • the epoxy group-containing compound represented by the general formula (A-V) is used as a raw material, and an ethylenically unsaturated group-containing carbonyloxy group is formed thereon, followed by further reaction.
  • rubonic acid or its anhydride include oxalic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, phthalate Saturated or unsaturated dicarboxylic acids such as acid and chlorendic acid and their anhydrides, trimellitic acid and its anhydride, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, biphenyl ether Tetracarboxylic acids, tetracarboxylic acids such as 1,2,3,4-butanetetrac
  • dicarboxylic acids such as oxalic acid, tetrahydrophthalic acid and phthalic acid, and their acid anhydrides, trimellitic acid and Among these acid anhydrides, pyromellitic acid, biphenyltetracarboxylic acid, tetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, and acid dianhydrides
  • the acid dissociation constant More preferred are acid anhydrides of polyvalent carboxylic acids having a first dissociation constant of 3.5 or more.
  • the acid dissociation constant is more preferably 3.8 or more, particularly 4.0 or more.
  • Such acid anhydrides include succinic acid and acid anhydrides of tetrahydrophthalic acid, and acid dianhydrides of 1,2,3,4-butanetetracarboxylic acid, such as succinic acid and tetrahydrophthalic acid. Acid anhydrides of acids are particularly preferred.
  • the acid dissociation constant can be referred to Determination of Organic Structures by Physical Methods, Academic Press, New York, 1955 (Brown, HC et al.).
  • dicarboxylic acids such as succinic acid, tetrahydrophthalic acid, and phthalic acid, their acid anhydrides, trimellitic acid, and their acid anhydrides should be used. Is preferred.
  • these polyvalent carboxylic acids and acid anhydrides thereof may be used alone or in combination of two or more.
  • the epoxy group-containing compound represented by the general formula (AV) has an isocyanate group to be further reacted after forming an ethylenically unsaturated group-containing carbonyloxy group.
  • Compounds such as butane isocyanate, 3-chlorobenzene benzene isocyanate, cyclohexane isocyanate, 3-isopropenoyl at, a-dimethylbenzyl isocyanate, and other organic monoisocyanates, -Diisocyanate, 2) 4 Tolylene diisocyanate, 2, 6 Tolylene diisocyanate, 4, 4 'Diphenylenomethane diisocyanate, Naphthalene 1,5 Diisocyanate, Tolidine diisocyanate, etc.
  • Aliphatic diisocyanates such as benzoate, isophorone diisocyanate, 4, 4 '—methylenebis (cyclohexenoylisocyanate), ⁇ , ⁇ ' —diisocyanate dimethylcyclohexane, xylylene diisocyanate
  • An aliphatic diisocyanate having an aromatic ring such as a, a, a ′, ⁇ ′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1, 6, 11-undecantriisocyanate, 1, 8 Diisocyanate 1 4-Isocyanate methyloctane, 1, 3, 6-hexamethylene triisocyanate, bicycloheptane triisocyanate, Tris (isocyanate phenol methan
  • dimers and trimers of organic diisocyanates are dimers and trimers of organic diisocyanates, most preferred are trimethylolpropane products of tolylene diisocyanate, trimers of tolylene diisocyanate, trimers of isophorone diisocyanate. Is the body.
  • the above compounds may be used alone or in combination of two or more.
  • the compound represented by the general formula (AI) preferably has an acid value of 30 to 150 mg-KOHZg, and more preferably 40 to 1 OOmg-KOHZg. Good.
  • the force S in which the weight average molecular weight in terms of polystyrene by GPC is 1,000 to 100,000 S is preferable ⁇ , the force S is 1,500 to 100,000, and S is more preferable ⁇ 2,000 to 100,000. Particularly preferred is 000.
  • the bis (hydroxyphenol) fluorene type epoxy compound is converted into an organic compound such as methyl ethyl ketone, ethyl cellosolve acetate, butyl acetate sorb acetate by a conventionally known method described in JP-A-4-355450.
  • tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine, or tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetraptylammonium chloride, Hydroquinone, hydroquinone in the presence of a quaternary ammonium salt such as trimethylbenzyl ammonium chloride, a phosphorus compound such as triphenylphosphine, or a stibine such as triphenylsulfin.
  • a quaternary ammonium salt such as trimethylbenzyl ammonium chloride
  • a phosphorus compound such as triphenylphosphine
  • a stibine such as triphenylsulfin.
  • the ethylenically unsaturated group-containing carboxylic acid is usually 0.8 to 1.5 chemical equivalents, preferably 1 chemical equivalent to 1 chemical equivalent of the epoxy group of the epoxy compound. Is added in an amount of 0.9 to 1.1 chemical equivalent, and is usually subjected to an addition reaction at a temperature of 60 to 150 ° C, preferably 80 to 120 ° C, and then the polyvalent carboxylic acid or anhydride thereof is added.
  • the compound of interest is usually added in an amount of 0.05 chemical equivalent, preferably 0.5 chemical equivalent, preferably 0.5 chemical equivalent to 1 chemical equivalent of the hydroxyl group generated in the reaction, and the reaction is continued under the above conditions. Get.
  • the specific ethylenically unsaturated compound (A) is represented by, for example, the following general formula (A-VI) in addition to the compound represented by the general formula (AI). Can be mentioned. [Chemical 8]
  • the production method is not particularly limited.
  • diglycidyl ether is used as a raw material.
  • an ethylenically unsaturated group-containing carbonyloxy group is formed thereon, and further has a polyvalent carboxylic acid, its anhydride, and an isocyanate group.
  • Examples include compounds obtained by reacting one or more compounds selected from compounds.
  • the specific ethylenically unsaturated compound having a double bond equivalent strength of 00 or less can be used singly or as a mixture of two or more.
  • the content of the specific ethylenically unsaturated compound (A) in the curable composition of the present invention is usually 25% by weight or more, preferably 35% by weight or more, based on the total solid content in the curable composition. More preferably, it is 45% by weight or more.
  • the curable composition of the present invention may contain rosin in addition to or in place of the ethylenically unsaturated compound of [11].
  • resin to be blended one or more kinds of resins used in known resin composition for color filters can be used. Examples of such resins include (meth) acrylic acid, (meth) acrylic ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, butyl acetate, vinyl chloride.
  • Examples thereof include homo- or copolymers such as den and maleimides, acid-modified epoxy acrylates, polyamides, polyesters, polyethers, polyurethanes, polybutyrals, polybutal alcohols, polybutyropyrrolidones, and acetylyl celluloses.
  • homo- or copolymers such as den and maleimides, acid-modified epoxy acrylates, polyamides, polyesters, polyethers, polyurethanes, polybutyrals, polybutal alcohols, polybutyropyrrolidones, and acetylyl celluloses.
  • carboxyl group-containing vinyl-based resins are preferred.
  • (E) component epoxy group-containing (meth) acrylate” 5 to 90 mol%
  • Other radical polymerizable compounds that can be copolymerized with the component ”10 to 95 mol% are copolymerized, and 10 to the LOO mol% of the epoxy group contained in the resulting copolymer is“ (N) component: It is obtained by adding ⁇ unsaturated monobasic acid '' and adding ⁇ (T) component: polybasic acid anhydride '' to 10 to 100 mol% of the hydroxyl group formed when the above (N) component is added.
  • the resin hereinafter sometimes referred to as “E—R—N—T resin” is preferred.
  • carboxyl group-containing vinyl resin examples include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and the like, styrene, ⁇ -Methylolstyrene, hydroxystyrene, methinole (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate , Dodecyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, dicyclopental (meth) acrylate, adamantyl (meth) acrylate, isobol (meth) acrylate, hydroxymethyl ( (Meta) attalylate, hydroxyethyl (meth) acrylate
  • (meth) acrylate (meth) acrylic acid copolymers and styrene (meth) acrylate mono (meth) acrylic acid copolymers are preferred.
  • (meth) acrylate / (meth) acrylate copolymer 5 to 80 mol% of (meth) acrylate and 20 to (meth) acrylic acid Copolymers having a strength of 10 to 90 mol% of (meth) acrylate and 10 to 90 mol% of (meth) acrylic acid, which are more preferred to have a strength of 95 mol%, are particularly preferred.
  • styrene one (meth) Atari Rate (meth) acrylic acid copolymer, styrene 3-30 mol 0/0, and (meth) Atari rate from 10 to 70 mole 0/0, (meth) acrylic acid 10 and 60 mole 0/0 co polymer is further preferably made of a Metropolitan instrument styrene 25 mol 0/0, (meth) and Atari rate 20-60 mole 0/0, (meth) acrylic acid 15 to 55 moles A copolymer having a strength of% is particularly preferred. Further, these carboxy group-containing burresins preferably have an acid value of S30 to 250 mg-KOHZg and a polystyrene-converted weight average molecular weight of 1,000 to 300,000.
  • the carboxyl group-containing vinyl resin those having an ethylenically unsaturated bond in the side chain are preferable.
  • the carboxyl group-containing vinyl resin includes allyl glycidyl ether, glycidyl ether.
  • Decy 2 An alicyclic epoxy group-containing unsaturated compound such as oxymethyl (meth) acrylate is reacted with 5 to 90 mol%, preferably about 30 to 70 mol%, of the carboxyl group of the carboxyl group-containing bur resin.
  • the proportion of the compound and unsaturated carboxylic acid such as (meth) acrylic acid, or further unsaturated carboxylic acid ester in the whole compound having an unsaturated group is 10 to 90 mol%, preferably 30 Examples thereof include reaction products obtained by copolymerization so as to be about ⁇ 80 mol%. [0090] [1— 2— 1— 1] E— R— N— T
  • the curable composition of the present invention has 5 to 90 mol% of “( ⁇ ) component: epoxy group-containing (meth) acrylate”, “(R) component: ( E) Other radical polymerizable compounds that can be copolymerized with component ”10 to 95 mol% are copolymerized, and 10 to the epoxy group contained in the obtained copolymer: LOO mol% is added to“ (N) component: “Unsaturated monobasic acid” is added, and “(T) component: polybasic acid anhydride” is added to 10 to L00 mol% of the hydroxyl group produced when the (N) component is added. It is preferable to contain the obtained E—R—N—T resin.
  • the component (E) that is, the epoxy group-containing (meth) acrylate, for example, glycidyl (meth) acrylate, 3, 4 epoxy butyl (meth) acrylate, (3,4 epoxy group)
  • the epoxy group-containing (meth) acrylate for example, glycidyl (meth) acrylate, 3, 4 epoxy butyl (meth) acrylate, (3,4 epoxy group)
  • glycidyl (meth) acrylate is preferred.
  • These (E) components may be used alone or in combination of two or more in any combination and ratio.
  • Copolymerization ratio of component (E) (copolymerization ratio when producing a copolymer by copolymerizing component (E) and component (R).
  • copolymerization ratio Is usually 5 to 90 mol%, as described above, preferably 20 mol% or more, more preferably 30 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less. It is. If this ratio is too large, the (R) component may decrease, resulting in a decrease in heat resistance and strength, and if it is too small, the amount of the polymerizable component and alkali-soluble component added will be insufficient.
  • the copolymerization ratio of the component (R) is 10 to 95 mol% as described above, preferably 20 mol% or more, more preferably 30 mol% or more, and usually 80 mol% or less. More preferably, it is 70 mol% or less. If this ratio is too high, the component (E) is reduced, so that the addition amount of the polymerizable component and the alkali-soluble component may be insufficient, and if it is too low, the heat resistance and strength may be reduced.
  • Examples of the component (R) include mono (meta) having a partial structure represented by the following formula (13).
  • R ld to R bd each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, or propyl
  • R 7d and R 8d are Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group.
  • R 7d and R 8d may be linked to form a ring.
  • the ring formed by connecting R 7d and R 8d is preferably an aliphatic ring, and may be either saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
  • mono (meth) acrylate having a structure represented by the following formula (14), formula (15), or formula (16) is preferable. By introducing these partial structures, it is possible to increase heat resistance and strength.
  • These mono (meth) acrylates may be used alone or in combination of two or more in any combination and ratio.
  • R 9d represents a hydrogen atom or a methyl group
  • R 1M represents the above formula (13).
  • the content of the mono (meth) acrylate having the partial structure of the above formula (13) in the copolymerization monomer is usually 5 mole 0/0 or more, preferably 10 mol% or more, more preferably 15 mol% or more, and usually 90 mol% or less, preferably 70 mole 0/0 or less, more preferably 50 mol 0/0 or less It is. If the content of the mono (meth) acrylate is too small, the residue may not be sufficiently suppressed, and if it is too large, the dispersion stability may be lowered.
  • the radical polymerizable compound other than the above is not particularly limited, and examples thereof include the following.
  • (Meth) acrylic acid amide (meth) acrylic acid N, N dimethylamide, (meth) acrylic acid N, N jetylamide, (meth) acrylic acid N, N dipropylamide, (meth) acrylic acid N, N —di — (Meth) acrylic acid amides such as isopropylamide, (meth) acrylic acid anthraceramide;
  • Vinyls such as (meth) acrylic acid chloride, (meth) acryloyl-tolyl, acrolein, butyl chloride, vinyl chloride, butyl fluoride, vinyl fluoride, N butyl pyrrolidone, pyridine, vinyl acetate Compound;
  • Unsaturated dicarboxylic acid diesters such as cetyl citrate, cetyl maleate, cetyl fumarate, itaconate;
  • Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N— (4-hydroxyphenyl) maleimide;
  • the copolymerization ratio selected from styrene, benzyl (meth) acrylate and monomerimide is usually 1 mol% or more, preferably 3 mol% or more, and usually 70 mol% or less, preferably 50 It is less than mol%.
  • the (N) component added to the epoxy group contained in the copolymer of the (E) component and the (R) component is an unsaturated monobasic acid.
  • the component (N) a known component can be used.
  • the unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.
  • Specific examples thereof include the ethylenically unsaturated group-containing carboxylic acids (a) described in the above-mentioned specific ethylenically unsaturated compound (A). Of these, acrylic acid and Z or methacrylic acid are preferred.
  • These (N) components may be used alone or in combination of two or more in any combination and ratio.
  • the component (N) is a force to be added to 10 to LOO mol% of the epoxy groups contained in the copolymer obtained by the copolymerization reaction of the components (E) and (R). Is added to 30 mol% or more, more preferably 50 mol% or more. This is because if the addition ratio of the component (N) is too small, there are concerns about adverse effects due to residual epoxy groups such as stability over time.
  • the (T) component that is, the polybasic acid anhydride added to the hydroxyl group produced when the (N) component is added to the copolymer of the (E) component and the (R) component
  • a well-known thing can be used.
  • Specific examples thereof include “a polyvalent carboxylic acid to be reacted further after formation of an ethylenically unsaturated group-containing carbonyloxy group” described in the above-mentioned specific ethylenically unsaturated compound (A) ”.
  • the component (T) one type may be used alone, or two or more types may be used in any combination and in any ratio. By adding such components, the non-nitrogen-containing resin can be made alkaline soluble.
  • the component (T) is added to 10 to LOO mol% of the hydroxyl group produced when the component (N) is added, preferably 20 mol% or more, more preferably 30 mol% or more, Further, it is preferably added to 90 mol% or less, more preferably 80 mol% or less. If this addition ratio is too large, the remaining film ratio during development may decrease, and if it is too small, the solubility may be insufficient.
  • E-R-N-T resin has added glycidyl (meth) acrylate and polymerizable unsaturated groups to some of the carboxyl groups that have been formed after addition of the (T) component.
  • glycidyl ether compound or to improve developability, after adding (T) component, a glycidyl ether compound that does not have a polymerizable unsaturated group in a part of the generated carboxyl group is added. These can be added, or both of them may be added.
  • Examples of the resin include those described in JP-A-8-297366 and JP-A-2001-89533.
  • the weight average molecular weight of the resin is not limited, but for example, the polystyrene equivalent weight average molecular weight (Mw) measured by GPC is usually 3000 or more, preferably 5000 or more, and usually 100000 or less. Preferably, it is 50000 or less. If the weight average molecular weight is less than 3000, heat resistance and film strength may be inferior. If it exceeds 100000, solubility in a developer may be insufficient.
  • the molecular weight distribution (weight average molecular weight (Mw) Z number average molecular weight (Mn)) is preferably 2.0 to 5.0.
  • Examples of the copolymer containing a carboxyl group and an epoxy group include an unsaturated carboxylic acid, an unsaturated compound having an epoxy group, and a copolymer with other compounds as required.
  • JP-A-11-133600 And alkali-soluble rosin used in the composition described in 1. above.
  • Examples of the acid-modified epoxy (meth) acrylates are those obtained from an epoxy group-containing compound among those having the same structure as the specific ethylenically unsaturated compound (A) described in [1 1-1]. And a double bond equivalent force exceeding 00.
  • the content of the resin described in [1-2] is usually 20% by weight or more, preferably 25% by weight or more, and usually 70% by weight based on the total solid content of the curable composition of the present invention. % By weight or less, preferably 60% by weight or less. If the content of these rosins is too much or too little, it is not preferable because they tend to lower the developability, curability and mechanical properties of the cured product.
  • the curable composition of the present invention preferably contains a polymerizable monomer in addition to the ethylenically unsaturated compound described in [1 1] and Z or the resin described in [1 2].
  • the term “monomer” in the present invention means a concept relative to a so-called polymer substance, and in addition to “monomer” in a narrow sense, “dimer”, “trimer”, “oligomer”. ”Means a concept that also includes“
  • Examples of the polymerizable monomer include compounds having at least one ethylenically unsaturated group in the molecule.
  • Specific examples of compounds having an ethylenically unsaturated group in the molecule include (meth) acrylic acid, alkyl esters of (meth) acrylic acid, acrylonitrile, styrene, carboxylic acids having one ethylenically unsaturated bond and many ( And monoesters of monohydric alcohols.
  • a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule examples include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Examples include esters obtained by an esterification reaction of a polyhydric hydroxy compound such as a hydroxy compound or an aromatic polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.
  • ester of the aliphatic polyhydroxyl compound and the unsaturated carboxylic acid examples include ethylene glycol ditalylate, triethylene glycol ditalylate, trimethylolpropantritalate, pentaerythritol tritalylate, Acrylates of aliphatic polyhydroxy compounds such as pentaerythritol tetraatalylate, dipentaerythritol tetraatalylate, dipentaerythritol pentaatalylate, dipentaerythritol hexaatalylate, and acrylates of these exemplified compounds are used. Examples thereof include methacrylic acid esters substituted for metatalylate, itaconate esters substituted for itaconate, crotonic acid esters substituted for clonate or maleates substituted for maleate, and the like.
  • Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include, for example, hydrated quinone diatalylate, hydrated quinone dimetatalylate, resorcin ditalitalate, resorcin dimetatalylate, pyrogallol tritalylate. And aromatic polyhydroxy compounds such as acrylates and methacrylates.
  • esters of polyhydroxy compounds with polybasic carboxylic acids and unsaturated carboxylic acids are not necessarily a single substance, but typical examples include condensates of acrylic acid, phthalic acid, and ethylene glycol, and condensation of acrylic acid, maleic acid, and diethylene glycol. Products, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.
  • polyfunctional ethylenic monomer used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester or polyisocyanate compound, a polyol and a hydroxyl group ( ) Urethane (meth) acrylates obtained by reacting acrylic esters; acrylamides such as ethylenebisacrylamide; aryl esters such as diaryl phthalate; vinyl group-containing compounds such as divinyl phthalate, etc. Is useful.
  • One of these polymerizable monomers may be contained alone in the curable composition, or two or more thereof may be contained.
  • the content of the polymerizable monomer in the curable composition of the present invention is usually less than 80% by weight, preferably less than 70% by weight, preferably 10% by weight or more, based on the total solid content. is there
  • the curable composition of the present invention may contain a polymerizable monomer having a secondary hydroxyl group for the purpose of providing adhesion to the substrate and imparting alkali resistance.
  • the polymerizable monomer having a secondary hydroxyl group is not particularly limited as long as it is a compound having at least one secondary hydroxyl group and one ethylenically unsaturated group in the molecule. Examples of the compound include at least one of the partial structures i) to (iii).
  • R bl represents a hydrogen atom or a methyl group
  • * represents a bond with another site in the polymerizable monomer
  • the compound includes at least one partial structure represented by the following formulas (iv) and (v), or a compound represented by the following formula (vi): I can list.
  • R ′′ represents a hydrogen atom or a methyl group
  • * represents a bonding position with another site in the polymerizable monomer
  • G represents an arbitrary divalent group.
  • examples of the divalent group represented by G include an alkylene group, an alkylene group, an alkylene group, an arylene group and the like, which may have a substituent. It is done.
  • examples of the substituent which may have include a halogen atom, a hydroxyl group, an alkyl group, and an aryl group.
  • polymerizable monomer having a secondary hydroxyl group a commercially available product can be used.
  • examples of commercially available products include the following.
  • the above-mentioned polymerizable monomers having a secondary hydroxyl group may be used alone or in combination of two or more. It can be used as a mixture.
  • the content of the polymerizable monomer having a secondary hydroxyl group in the curable composition of the present invention is usually 0.5 to 20% by weight, preferably based on the total solid content in the curable composition. Is 0.5 to 15% by weight, more preferably 0.5 to L: 0% by weight.
  • Polymerizable mono having a secondary hydroxyl group If the content of the mer is too small, the effect of improving adhesion with the substrate and imparting alkali resistance cannot be obtained. On the other hand, if the content of the polymerizable monomer having a secondary hydroxyl group is too large, the hardenability is impaired. For example, when used for a spacer, the necessary mechanical properties cannot be obtained. It is not preferable.
  • the curable composition of the present invention may contain a photopolymerization initiator and / or a thermal polymerization initiator depending on the method of curing the curable composition.
  • the photopolymerization initiator and Z or thermal polymerization initiator according to the present invention are not particularly limited as long as they are compounds capable of polymerizing ethylenically unsaturated groups with actinic rays and Z or heat, and are not particularly limited.
  • Z or a thermal polymerization initiator A polymerization initiator can be used.
  • Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethyl anthraquinone, 2-t butyl anthraquinone, and 1-mouth anthraquinone;
  • Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methinolebenzophenone, 2-clobenbenzophenone, 4-bromobenzophenone, 2-force ruboxybenzophenone; 2, 2 dimethoxy-2-phenylacetophenone, 2, 2 diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, ⁇ -hydroxy 2-methylphenylpropanone, 1-hydroxy-1- 1-methylethyl ( ⁇ —Isopropylphenyl) ketone, 1-hydroxy — 1 ( ⁇ dodecylphenyl) ketone, 2 benzyl-2-dimethylamino 1- (4-morpholinophyl) butane 1-one, 2-methyl- [4 (methylthio) phenol- 2] Morpholinone 1 Propanone, 1, 1, 1 Acetophenone derivatives such as trichloromethyl- ( ⁇ -butyl
  • Thioxanthone derivatives such as thixanthone, 2-ethylthioxanthone, 2-isopropylthixanthone, 2-cyclothioxanthone, 2,4 dimethylthioxanthone, 2,4 jetylthioxanthone, 2,4-diisopropylthioxanthone;
  • ⁇ benzoic acid ester derivatives such as dimethylamino benzoate, ⁇ decylamino benzoate, etc .
  • 9-phenolacridine, 9- ( ⁇ -methoxyphenol) ataridine derivatives such as 9; dimethylbenzphenazine and other phenazine derivatives;
  • Anthrone derivatives such as benzanthrone
  • Dicyclopentagenyl Ti dichloride dicyclopentagenil Ti bisphenyl, dicyclopentadiene Ti-bis 1, 3, 4, 5, 6 pentafluorophenyl 1 yl, dicyclopentadi Nitrous Ti—Bis 2, 3, 5, 6—Tetrafluorophenyl — 1—yl, dicyclopentadiene Nitrous Ti— 2, 6 Difluoro 3— (pill 1—yl) —Hue-1 Titanocene derivatives such as
  • Oxyester compounds such as — (o benzoyloxime)], 1 [9 ethyl 6- (2 benzoyl) 9H force rubazole 3 yl] ethanone 11 (o acetyloxime).
  • photopolymerization initiators that can be used in the present invention include fine chemicals, March 1, 1991, Vol. 20, No. 4, P. 16 to P26, and JP-A-59-152396, JP-A 61-151197, JP-B 45-37377, JP-A 58-40302, JP It is also described in Kaihei 10-39503.
  • One of these photopolymerization initiators may be included alone in the curable composition, or two or more thereof may be included.
  • thermal polymerization initiator used in the present invention include azo compounds, organic peroxides, hydrogen peroxide and the like. Of these, azo compounds are preferably used.
  • Examples of the azo compounds include 2,2'-azobisisobutyric-tolyl, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexene-1-1-carbodi). Tolyl), 2,2'-azobis (2,4-dimethylvale-tolyl), 1-[(1-cyan-1-methylethyl) azo] formamide (2- (force ruba molyazo) isobutylo-tolyl), 2,2-azobis [2-methyl- ⁇ - [1, 1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2'-azobis [N- (2-probe) -2-methylpropionamide], 2,2'-azobis [N- (2-probe) -2-ethylpropionamide], 2,2'-azobis [N-butyl-2-methylpropion Amido], 2, 2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis (d
  • organic peroxide examples include benzoyl peroxide, peroxide t-butyl, and tamennodropoxide.
  • thermal polymerization initiators may be contained alone or two or more thereof may be contained in the curable composition. Further, a photopolymerization initiator and a thermal polymerization initiator may be used in combination.
  • the content of these photopolymerization initiator and Z or thermal polymerization initiator is usually 0.01% by weight or more, preferably 0.1%, based on the total solid content of the curable composition of the present invention. % By weight or more It is preferably 0.5% by weight or more, usually 30% by weight or less, preferably 20% by weight or less. If the content is too low, the sensitivity may be lowered. On the other hand, if the content is too high, the solubility of the unexposed portion in the developer is lowered, and development defects are likely to be induced.
  • the curable composition of the present invention includes a solvent, a colorant, an adhesion improver, a coating improver, a development improver, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, and a silane coupling.
  • a solvent a colorant
  • an adhesion improver a coating improver
  • a development improver an ultraviolet absorber
  • a polymerization inhibitor a polymerization inhibitor
  • an antioxidant a silane coupling.
  • silane coupling silane coupling.
  • An agent, an epoxy compound, an amino compound, a polymerization accelerator and the like can be appropriately blended.
  • the solvent used in the curable composition of the present invention is not particularly limited, and examples thereof include water, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, jetinoreethenole, Isoprene, ethinoreisobutinoleate, butyl stearate, n-octane, Parsol # 2, Apco # 18 solvent, disobutylene, amyl acetate, butyl butyrate, apcocinner, butyl ether, disobutyl ketone, methylcyclohexene, Methyl nonyl ketone, propyl ether, dodecane, Socal solvent No.
  • the solvent can dissolve or disperse each component, and is selected according to the method of using the curable composition of the present invention, but a solvent having a boiling point in the range of 60 to 280 ° C is selected. It is preferable. More preferably, it has a boiling point of 70 to 260 ° C. These solvents can be used alone or in admixture of two or more.
  • colorant used in the curable composition of the present invention known colorants such as pigments and dyes can be used.
  • a pigment when used, a known dispersant or dispersion aid may be used in combination so that the pigment does not aggregate and can be stably present in the curable composition.
  • the content of the colorant is not particularly limited, but is usually 70% by weight or less based on the total solid content of the curable composition.
  • coatability improver or development improver used in the curable composition of the present invention For example, known cationic, ionic, nonionic, fluorine-based, and silicon-based surfactants can be used.
  • development improver known ones such as organic carboxylic acids and Z or water-free products thereof can be used. The content thereof is usually 20% by weight or less, preferably 10% by weight or less, based on the total solid content of the curable composition.
  • polymerization inhibitors such as hydroquinone and methoxyphenol, and hindered phenols such as 2,6-di-tert-butyl-4-talesol (BHT) are used.
  • BHT 2,6-di-tert-butyl-4-talesol
  • the content thereof is usually in the range of 5 ppm or more, preferably 10 ppm or more, usually 10 ppm or less, preferably 600 ppm or less, based on the total solid content of the curable composition. If the content is small, the stability tends to deteriorate. If the content is too large, for example, curing with heat and Z or light may cause insufficient curing, which is not preferable. In particular, when used in a normal photolithography method, it is necessary to set the optimum amount in view of both storage stability and sensitivity of the curable composition.
  • the curable composition of the present invention may contain a silane coupling agent in order to improve adhesion to the substrate.
  • a silane coupling agent in order to improve adhesion to the substrate.
  • epoxy, (meth) acrylic, amino, etc. can be used alone or in combination of two or more.
  • epoxy silane coupling agents Is preferred.
  • the content thereof is usually 20% by weight or less, preferably 15% by weight or less, based on the total solid content in the curable composition.
  • This curable composition is improved by an epoxy compound to improve curability and adhesion to the substrate! It may be.
  • epoxy compound a polyglycidyl ether compound, a polycarboxylic acid compound, which is obtained by reacting a polyhydric oxyxy compound and epichlorohydrin constituting a repeating unit of a so-called epoxy resin.
  • Polyglycidyl ester compounds obtained by reacting a compound with epichlorohydrin, and polyglycidylamine compounds obtained by reacting a polyamine compound with epichlorohydrin, etc. Compounds ranging from low molecular weight to high molecular weight It is.
  • Examples of the polyglycidyl ether compound include diglycidyl ethers of alkylene glycols having 1 to 20 carbon atoms such as ethylene glycol, propylene glycol, butanediol, and hexanediol, and carbon numbers such as polyethylene glycol and polypropylene glycol.
  • Examples of the polyglycidyl ether compound include diglycidyl ethers of alkylene glycols having 1 to 20 carbon atoms such as ethylene glycol, propylene glycol, butanediol, and hexanediol, and carbon numbers such as polyethylene glycol and polypropylene glycol.
  • -50 diglycidyl ethers of polyalkylene glycols polyglycidyl ethers of polyols such as glycerol and pentaerythritol
  • diglycidyl ethers of aromatic diols polyglycidyl ethers of aromatic polyols
  • polyethylene glycol diglycidyl ether type epoxy bis (4-hydroxyphenyl) diglycidyl ether type epoxy, bis (3,5-dimethyl-4-hydroxyphenyl) diglycidyl ether type epoxy, Diglycidyl ether of bisphenol F, diglycidyl ether epoxy of bisphenol A, diglycidyl ether epoxy of tetramethylbisphenol A, diglycidyl ether epoxy of bisphenol A with ethylene oxide, fluorene type bis Examples include phenol diglycidyl ether type epoxy, phenol novolac type epoxy, cresol novolac type epoxy, and the like. These polyglycidyl ether compounds include acid anhydrides and divalent acid groups on the remaining hydroxy groups. A compound or the like may be reacted to introduce a carboxyl group.
  • the polyglycidyl ester compounds include, for example, diglycidino lesenore type epoxy of hexahydrophthalic acid, diglycidino lesenore type epoxy of phthalenoic acid, and the polyglycidyl amine compound.
  • Examples of the compound include bis (4-aminophenol) methan diglycidinoleamine type epoxy, isocyanurenoic acid triglycidinoleamine type epoxy, and the like.
  • Such epoxy compound may be contained alone or in combination of two or more in the curable composition.
  • the content of the epoxy compound in the curable composition is usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content. When the content of the epoxy compound is too large, the storage stability of the curable composition may be deteriorated.
  • the curable composition of the present invention has one or more amino compounds in order to improve its curability (curing speed of the curable composition, mechanical properties of the cured product) and adhesion to the substrate. It is also preferable to add.
  • the content thereof is usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content in the curable composition. Further, it is usually 0.5% by weight or more, preferably 1% by weight or more. When the content is too large, the storage stability of the curable composition may be deteriorated. On the other hand, when the content is too small, the effect of improving the hardenability and adhesion to the substrate is lowered.
  • the content when the curing rate is expected, is usually 10% by weight or less, preferably 5% by weight or less. Further, it is usually 0.5% by weight or more, preferably 1% by weight or more. If this content is too large, there is a possibility that the pattern formability is deteriorated.
  • amino compound examples include an amino compound having a methylol group as a functional group and at least two alkoxymethyl groups obtained by condensing and modifying an alcohol having 1 to 8 carbon atoms.
  • melamine and formaldehyde are used.
  • Polycondensed melamine resin benzoguanamine and formaldehyde-condensed benzoguanamine resin, glycoluril and formaldehyde polycondensed glycoluril resin, urea and formaldehyde polycondensed urea
  • examples thereof include a resin, melamine, benzoguanamine, glycoluril, urea, and the like copolycondensed with two or more types of resin and modified resins obtained by alcohol condensation modification of methylol groups of these resins.
  • a modified resin having a modified ratio of methylol groups in which melamine resin and its modified resin are preferred are 70% or more, and a modified resin having a modified ratio of methylol groups that is more preferred in 80% or more. Is particularly preferred.
  • one or more polymerization accelerators may be added to accelerate polymerization and curing.
  • Examples of the polymerization accelerator include 2 mercaptobenzozoazole, 2 mercaptobenzimidazole, 2 mercaptobenzoxazole, 3 mercapto 1,2,4 triazole, 2-mercapto 1-4 (3H) -quinazoline, 13-Mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, mercapto group-containing compounds such as pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane tristhione Polyfunctional thiol compounds such as glycolate, pentaerythritol tetrakisthiopropionate, derivatives of N, N dialkylaminobenzoate, N-phenol glycine or its salt such as ammonium salt sodium salt, -Lualanin, also Its ammoxidation - Umuya salts such as sodium salts,
  • the content of these polymerization accelerators is usually 10% by weight or less, preferably 5% by weight or less, based on the total solid content in the curable composition. When the content is too large, there are problems such as poor developability and adhesion, which is not preferable.
  • the cured product formed by the curable composition of the present invention has preferable characteristics particularly when used in a spacer application.
  • a spacer used in a liquid crystal display device (hereinafter sometimes referred to as a "panel") of a large-sized liquid crystal screen television as described above is subjected to a load in the manufacturing process of the panel.
  • the total deformation of the spacer tends to increase soon. Also, especially on large screen panels, uneven load tends to occur at each part.
  • a spacer made of a cured product formed from the curable composition of the present invention has a large amount of deformation when subjected to external pressure (that is, it can absorb non-uniformity of pressure bonding during substrate production).
  • the elastic recovery rate does not decrease significantly even under high pressure (ie, the pressure dependency of the elastic recovery rate is small).
  • 1 2 1 2 I is 0.35 or more, preferably 0.4 or more, more preferably 0.5 or more. Usually, it is 1 or less.
  • the load unloading test with the microhardness tester was performed in the later section [2] and the spacer pattern formed by a known method, with an upper cross-sectional area of 40 ⁇ 10 ⁇ m 2 and 150 ⁇ 5 A pattern with a height of 3.5 ⁇ 0.1 m is carried out as follows using a micro hardness tester.
  • the space server turn is preferred because it can measure the force accurately even if the shape of the top surface is circular.
  • the upper cross-sectional area of the space server turn is the following area!
  • a longitudinal section passing through the center axis of the spacer pattern is profiled using an ultra-deep color 3D shape measurement microscope ⁇ -9500 manufactured by Keyence Corporation.
  • the spacer pattern profiling method will be described with reference to Figs.
  • Fig. 1 is a schematic diagram showing the profile position when the spacer turn is viewed from above
  • Fig. 2 is a schematic diagram showing the profile of the vertical pattern of the spacer pattern. In Figs.
  • 1 is the spacer pattern
  • 2 is the center axis of the spacer turn
  • 3 is the profile position
  • 4 is the profile of the spacer pattern longitudinal section
  • 5 is the board surface force
  • the height, 6 is the height of 95% of the height from the substrate surface to the highest position
  • 7 is the diameter ⁇ of the upper section circle.
  • the board surface in the figure of the spacer pattern at the height (6) of 95% of the height (5) from the board surface of the profiled figure (4) to the highest point Q A straight line parallel to Measure the length of ⁇ '(7).
  • the area of the circle whose diameter is AA is the upper cross-sectional area of the spacer pattern.
  • the height (6) of 95% of the point Q at the highest position of the pattern from the substrate surface is the spacer height.
  • test conditions were a flat indenter with a measurement temperature of 23 ° C and a diameter of 50 ⁇ m, and a constant speed (2 mN
  • the values of the index formulas (1) and (2) indicate the maximum displacement H [max] (mN) of the spacer having the upper area of 40 ⁇ 5 111 2 and 150 ⁇ 5 m 2 respectively.
  • the composition of the curable composition of the present invention is not limited.
  • Such mechanical properties include, for example, (0 addition of an ethylenically unsaturated compound in which the curable composition has a double bond equivalent force of 00 or less, addition of (iOE-R-N-T resin, (M) Addition of amino compound, Gv)
  • the double bond equivalent of the total solid content in the composition is usually 300 or less, preferably 250 or less, and usually 100 or more.
  • the curable composition of the present invention is a method similar to a known curable composition for a color filter. Although it is used, the case where it is used as a photosensitive composition for spacers will be described below.
  • a curable composition dissolved or dispersed in a solvent is supplied on a substrate on which a spacer is to be provided in a film or pattern by a method such as coating, the solvent is dried.
  • pattern formation is performed by a method such as photolithography in which exposure and development are performed if necessary.
  • a spacer is formed on the substrate by performing additional exposure or thermosetting treatment.
  • the curable composition of the present invention is usually supplied onto a substrate in a state dissolved or dispersed in a solvent.
  • a conventionally known method such as a spinner method, a wire-bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method or the like can be used.
  • the die coating method significantly reduces the amount of coating solution used, has no influence from mist adhering to the spin coating method, and suppresses the generation of foreign matter.
  • the viewpoint power is also preferable.
  • the coating amount varies depending on the application.
  • the dry film thickness is usually 0.5 m or more, preferably 1 ⁇ m or more, and usually 10 ⁇ m or less, preferably 9 ⁇ m or less. Particularly preferably, it is in the range of 7 ⁇ m or less.
  • it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. If the variation in the spacer height is large, uneven defects will occur in the liquid crystal panel.
  • the curable composition may be supplied in a pattern by an inkjet method or a printing method.
  • the drying after supplying the curable composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convex oven. Moreover, you may combine the reduced pressure drying method which does not raise temperature but performs drying in the reduced pressure chamber.
  • the drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like.
  • the drying time is usually selected in the range of 40 to 130 ° C for 15 seconds to 5 minutes, preferably 50 to 110 ° C, depending on the type of solvent component and the performance of the dryer used. Is selected in the range of 30 seconds to 3 minutes. [0181] [2-3] Exposure method
  • the exposure is performed by overlaying a negative mask pattern on the coating film of the curable composition and irradiating an ultraviolet or visible light source through this mask pattern. Further, a scanning exposure method using a laser beam without using a mask pattern may be used. In this case, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being reduced by oxygen, the reaction is performed in a deoxygenated atmosphere, or a polybulol alcohol layer or the like is formed on the photopolymerizable layer made of the curable composition of the present invention. Exposure may be performed after the oxygen blocking layer is formed.
  • the light source used for the exposure is not particularly limited.
  • Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, and argon ions.
  • Laser light sources such as lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-powered Dominium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers.
  • An optical filter can also be used when irradiating light of a specific wavelength.
  • an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent.
  • This aqueous solution may further contain a surfactant, an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
  • Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, metasilicate Inorganic alkaline compounds such as sodium, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, -Or triethanolamine, mono 'di- or trimethylamine, mono' di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethylenimine, Existence of ethylenedimine, tetramethylammonium hydroxide (TMAH), choline, etc.
  • TMAH tetramethylammonium hydroxide
  • alkaline I there may be a mixture of two or more.
  • surfactants include non-ionic interfaces such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters.
  • Amphoteric surfactants such as surfactants, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate esters, alkylbetaines, amino acids, etc. Agents. These may be used alone or in combination of two or more.
  • organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butylcetosolve, phenylsolvesolve, propylene glycol, diaceton alcohol and the like.
  • the organic solvent may be used alone or as a mixed solvent of two or more, or as an aqueous solution.
  • the substrate after development may be subjected to additional exposure by the same method as the exposure method described above, or may be subjected to thermosetting treatment.
  • the thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes. It is particularly preferable to perform such a thermosetting treatment.
  • preferable conditions for forming the cured product having the mechanical properties described in [16] are, for example, 200 to 250 ° C, particularly 230 ° C, 15 A thermosetting treatment of up to 30 minutes can be mentioned.
  • Pentaerythritol Atari rate about 20 weight 0/0;
  • the solid content acid value was 54 mg-KOHZg, and the weight average molecular weight was 2,500.
  • reaction product of bisphenol A type epoxy compound dipentaerythritol bentatalylate with compound succinic acid half ester and 1, 2, 3, 6-tetrahydrophthalic anhydride compound (A2) % (The double bond equivalent of this component is 189); and
  • Kisa Atari rate about 59 weight to dipentaerythritol 0/0;
  • the mixture (mixture A2M containing an ethylenically unsaturated compound) as a whole had a solid content acid value of 19.9 mg—KOHZg and a weight average molecular weight of 2,500.
  • Epoxy compound represented by the following structural formula (epoxy equivalent 305) 45 parts by weight, (AA2) 300 parts by weight, tetramethylpiperidine 1-oxyl 0.17 parts by weight, triphenylphosphine 6.9 parts by weight, propylene
  • the reaction vessel was charged with 95 parts by weight of glycol monomethyl ether acetate and stirred at 90 ° C. until the acid value was 2.5 mg-KOHZg or less. It took 8 hours for the acid value to reach the target.
  • 13.5 parts by weight of 1,2,3,4-butanetetracarboxylic dianhydride was added and reacted at 90 ° C. for 4 hours.
  • Kisa Atari rate about 57 weight to dipentaerythritol 0/0;
  • the mixture (mixture A3M containing an ethylenically unsaturated compound) had a solid content acid value of 22.8 mg—KOHZg and a weight average molecular weight of 1,600.
  • the reaction vessel was then purged with air, and 0.05 parts by weight of paramethoxyphenol, 21.3 parts by weight of acrylic acid and 2.1 parts by weight of tetraethylammonium chloride were added, and the reaction was continued at 80 ° C for 8 hours. . Thereafter, 12.5 parts by weight of tetrahydrophthalic anhydride was added and reacted at 85 ° C for 4 hours. Propylene glycol monomethyl ether acetate was added to the resulting reaction solution to obtain a solution having a solid content of 50% by weight.
  • the obtained ethylenically unsaturated compound had a solid content acid value of 38 mg-KOHZg, a weight average molecular weight of 10,000, and a double bond equivalent of 409.
  • reaction vessel was purged with air, and 0.1 parts by weight of paramethoxyphenol, 103.8 parts by weight of glycidyl methacrylate and 4.2 parts by weight of tetraethylammonium chloride were charged, and the reaction was carried out at 85 ° C for 10 hours.
  • Propylene glycol monomethyl ether acetate was added to the resulting reaction solution to prepare a solution having a solid content of 50% by weight.
  • Solid content of the obtained ethylenically unsaturated compound Acid value is 22mg—KOHZg, weight average molecular weight is 16,000, double bond equivalent is 286 o
  • a flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2,1azobis (2,4 dimethylvale-tolyl) and 200 parts by weight of diethylene glycol dimethyl ether. Subsequently, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 45 parts by weight of glycidyl methacrylate and 25 parts by weight of dicyclopentamethacrylate were charged with nitrogen, and then gently agitated. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing acrylic resin (R1). The resulting acrylic resin had a solid acid value of 121 mg—KOH weight average molecular weight of 16,000.
  • the acrylic resin contains almost no ethylenically unsaturated group (that is, the double bond equivalent is infinite).
  • Ethylenically unsaturated compound, polymerization initiator, polymerizable monomer, surfactant, and other additives are mixed in the mixing ratio shown in Table 1, and propylene glycol monomethyl ether acetate is added to obtain a solid content concentration of 35 wt. % And stirred at room temperature for dissolution, followed by filtration with a Millipore filter (2 m) to obtain a curable composition.
  • a mixture containing an ethylenically unsaturated compound means the mixture obtained in Synthesis Examples 1 to 3 ((A1M), (A2M), and (A3M)), respectively.
  • the mixing ratio (parts by weight) of the total solid content of the mixture was shown. Details of each component other than the compounds (Al), (A2), (A3), (A4), (A5), and (R1) obtained in Synthesis Examples 1 to 6 are as follows.
  • Fluorosurfactant ⁇ FC430 '' manufactured by Sumitomo 3EM (Nl) Silane coupling agent: “SH6040” manufactured by Toray Dow Coung
  • the minimum development time means a time during which the unexposed area is completely dissolved under the same development conditions.
  • a load L is applied to the spacer pattern at a constant speed (2 mNZsec) with a 50 m square flat indenter at a measurement temperature of 23 ° C. Unloading was performed at the same speed.
  • the values of the index formulas (1) and (2) are obtained from the pressure P, the total deformation H, and the elastic recovery rate R.
  • Japanese Patent Application 2005-1 29193 Japanese patent applications (Japanese Patent Application 2005-129897), Japanese patent applications (Japanese Patent Application 2005-12). 9898), Japanese patent application filed on September 28, 2005 (Japanese Patent Application 2005-282408), Japanese Patent Application (Japanese Patent Application 2005-282409), and Japanese Patent Application filed on October 4, 2005 (Japanese Patent Application No. 2005-291817), which is incorporated by reference in its entirety.

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Abstract

La présente invention concerne une composition traitable thermiquement à utiliser, par exemple, dans des affichages à cristaux liquides, qui peut former un produit traité thermiquement qui peut être largement déformé si exposé à une pression externe (c’est-à-dire qu’une force non uniforme appliquée dans la préparation d'un substrat peut être absorbée) et n'engendre pas de diminution significative de récupération même sous haute pression (c’est-à-dire que la dépendance de la récupération à la pression est faible). La composition traitable thermiquement peut former un produit traité thermiquement satisfaisant à la formule d'indices ci-après dans un test de charge-décharge avec un testeur à microdureté : |H1 - H2|/|P1 - P2| ≥ 0,35 et |R1 - R2|/|P1 - P2| ≤ 15, H1 et H2 représentant le degré total de déformation des entretoises présentant respectivement des zones supérieures sectionnelles de 40 ± 5 µm2 et 150 ± 5 µm2, en µm ; P1 et P2 représentant les pressions appliquées aux entretoises présentant respectivement des zones supérieures sectionnelles de 40 ± 5 µm2 et 150 ± 5 µm2, en mN/µm2 ; et R1 et R2 représentant la récupération élastique des entretoises présentant des zones supérieures sectionnelles de 40 ± 5 µm2 et 150 ± 5 µm2, en %.
PCT/JP2006/308604 2005-04-27 2006-04-25 Composition traitable thermiquement, produit traité thermiquement, et dispositif d’affichage à cristaux liquides les utilisant WO2006118094A1 (fr)

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CN2006800053214A CN101120029B (zh) 2005-04-27 2006-04-25 固化性组合物、固化物以及使用该固化物的液晶显示装置

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JP2005-282408 2005-09-28
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JP2005282408A JP5597905B2 (ja) 2005-04-27 2005-09-28 硬化性組成物、硬化物及びこれを用いた液晶表示装置
JP2005-291817 2005-10-04
JP2005291817A JP5109246B2 (ja) 2004-12-09 2005-10-04 硬化性組成物、硬化物、カラーフィルタ及び液晶表示装置

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US9908991B2 (en) 2012-06-08 2018-03-06 Dic Corporation Organic pigment composition for color filters, method for producing the same, and color filter
CN111149058A (zh) * 2017-09-22 2020-05-12 东丽株式会社 透明感光性树脂组合物、光刻间隔物、液晶显示装置、光刻间隔物的制造方法、液晶显示装置的制造方法及透明感光性树脂组合物在透镜扫描曝光中的应用

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JP2007119718A (ja) * 2005-04-27 2007-05-17 Mitsubishi Chemicals Corp 硬化性組成物、硬化物及びこれを用いた液晶表示装置
CN102566271A (zh) * 2010-12-10 2012-07-11 住友化学株式会社 感光性树脂组合物
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CN111149058B (zh) * 2017-09-22 2024-03-08 东丽株式会社 透明感光性树脂组合物及其应用、光刻间隔物和液晶显示装置及其制造方法

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CN101120029B (zh) 2010-09-29
CN101921375A (zh) 2010-12-22
KR101325949B1 (ko) 2013-11-07
KR20080000556A (ko) 2008-01-02
CN101120029A (zh) 2008-02-06

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