WO2006016467A1 - Photosensitive resin composition, color filter and liquid crystal display device - Google Patents

Photosensitive resin composition, color filter and liquid crystal display device Download PDF

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Publication number
WO2006016467A1
WO2006016467A1 PCT/JP2005/013284 JP2005013284W WO2006016467A1 WO 2006016467 A1 WO2006016467 A1 WO 2006016467A1 JP 2005013284 W JP2005013284 W JP 2005013284W WO 2006016467 A1 WO2006016467 A1 WO 2006016467A1
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Prior art keywords
resin composition
photosensitive resin
compound
group
general formula
Prior art date
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PCT/JP2005/013284
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French (fr)
Japanese (ja)
Inventor
Junji Mizukami
Yuuji Mizuho
Toshiyuki Tanaka
Makoto Fukui
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Mitsubishi Chemical Corporation
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Publication of WO2006016467A1 publication Critical patent/WO2006016467A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/58—Epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Definitions

  • Photosensitive resin composition Color filter, and liquid crystal display device
  • the present invention relates to a photosensitive resin composition suitable for image formation, black matrix use, overcoat use, rib use, and spacer use for color filters used in liquid crystal panels such as liquid crystal displays. And a color filter and a liquid crystal display device using the photosensitive resin composition.
  • Unsaturated groups obtained by further reacting a reaction product of epoxy resin with unsaturated group-containing carboxylic acid or its anhydride with polybasic carboxylic acid or its anhydride as sallow contained in the fat composition Techniques using the contained rosin have been disclosed (Japanese Patent Laid-Open No. 2001-174621, Japanese Patent No. 2878486, Japanese Patent Laid-Open No. 10-168 033).
  • the above-described resist used in conventional liquid crystal panels and the like is polybasic in a structural unit composed of a reaction product of epoxy resin and unsaturated group-containing carboxylic acid or anhydride thereof.
  • the ester moiety is cleaved during storage because it is crosslinked with a reactive carboxylic acid or its anhydride, the viscosity and development may occur due to changes in molecular weight due to the ester crosslinking. It causes significant changes in speed and other properties of the resin, and in turn the resist properties. As a result, troubles in the coating process and the image forming process are caused.
  • a photosensitive resin composition containing a component that can be polymerized by light, a photopolymerization initiator, and a binder resin, including the above-described photosensitive colored resin composition is generally coated. It is subjected to the process of photolithography through a process of drying 'exposure' and development. Therefore, in this process,
  • the removed portion has sufficient solubility
  • Residual stains occur on the unexposed substrate in the development process
  • the edge shape of the pixel is inferior in shape due to, for example, good solubility in unexposed areas;
  • the sensitivity of the pixels formed in the exposed area is not sufficient and the surface smoothness is poor;
  • the present invention has good adhesion to a substrate, and a coloring material such as pigment or carbon black is highly concentrated. Even if it is contained at a high degree, or for photospacer ribs that do not require pigments, etc., it has an excellent balance of sensitivity and solubility, and further, sharpness of pixel edge shape and taper shape
  • An object of the present invention is to provide a photosensitive resin composition that has excellent properties, adhesion, surface smoothness, anti-stain properties, heat resistance, and storage stability.
  • Another object of the present invention is to provide a high-quality color filter and further a high-quality liquid crystal display device using such a photosensitive resin composition.
  • the photosensitive resin composition of the first aspect is a photosensitive resin composition containing an organic binder, and the organic binder has at least two epoxy groups in the molecule. It contains an alkali-soluble unsaturated resin obtained by reacting a reaction product of a polyoxy compound (a) with an unsaturated group-containing carboxylic acid (b) with a compound (c) having an isocyanate group. .
  • the photosensitive resin composition of the second aspect is a photosensitive resin composition containing an organic binder, and the organic binder has at least two or more phenolic hydroxyl groups in the molecule.
  • An alkaline soluble unsaturated resin obtained by reacting a reaction product of the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g) with a compound (c) further having an isocyanate group. Containing.
  • FIG. 1 is a schematic diagram showing a maximum displacement H [max] and a final displacement H [Last] of a load unloading test in a photospacer formation evaluation.
  • the photosensitive resin composition of the first aspect is a photosensitive resin composition containing an organic binder, and the organic binder has at least two epoxy groups in the molecule. It contains an alkali-soluble unsaturated resin obtained by reacting a reaction product of a polyoxy compound (a) with an unsaturated group-containing carboxylic acid (b) with a compound (c) having an isocyanate group. .
  • the epoxy compound (a) may include a compound represented by the following general formula (I-a).
  • the photosensitive resin composition of the second aspect is a photosensitive resin composition containing an organic binder, and the organic binder has at least two or more phenolic hydroxyl groups in the molecule.
  • An alkaline soluble unsaturated resin obtained by reacting a reaction product of the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g) with a compound (c) further having an isocyanate group. Containing.
  • the phenolic hydroxyl group-containing compound (f) may include a compound represented by the following general formula (I f).
  • the compound may have two or more isocyanate groups in the molecule.
  • X in the general formula (I a) and the general formula (I f) represents the following general formula ( ⁇ ), ( ⁇ ), (II
  • I ⁇ R 16 and n have the same meaning as in the general formula (II).
  • the general formula ( ⁇ ) may be the following general formula (IIAa) or (IIAb).
  • R 1 and R 2 have the same meaning as in the general formula (II).
  • the photosensitive resin compositions of the first and second aspects may further contain a photopolymerization initiator.
  • the photosensitive resin compositions of the first and second aspects may further contain a coloring material.
  • a color filter may be formed using the photosensitive resin composition of the present invention.
  • the photosensitive resin composition of the present invention has good adhesion to the substrate.
  • This photosensitive resin composition is sensitive and soluble even when it contains pigments and color materials such as carbon black at a high concentration, and even when it is used for a photospacer rib that does not require a pigment.
  • it has excellent pixel edge shape and taper shape sharpness, adhesion, surface smoothness, antifouling property, heat resistance, and storage stability.
  • Alkali-soluble unsaturation as an organic binder contained in the photosensitive resin composition of the present invention As long as the resin has a chemical structure similar to that of the compound described in the claims of the present application, the purpose and effect of the present invention are achieved, so the production method is not particularly limited.
  • the following [A-1] or [A-2] can be mentioned.
  • [0026] Compound having an isocyanate group further obtained by reacting an epoxy compound (a) having at least two epoxy groups in the molecule with an unsaturated group-containing carboxylic acid (b)
  • C Alkali-soluble unsaturated rosin obtained by reacting with.
  • This alkali-soluble unsaturated resin is prepared by adding the compound (c) having an isocyanate group to the hydroxyl group of the reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b), and then adjusting the acid value. Therefore, it is preferable to further add a polybasic acid anhydride (d).
  • a reaction product of a phenolic hydroxyl group-containing compound (f) having at least two phenolic hydroxyl groups in the molecule and an unsaturated group-containing epoxy compound (g), and further an isocyanate group An alkali-soluble unsaturated resin obtained by reacting with the compound (c). This alkali-soluble unsaturated resin adds a compound (c) having an isocyanate group to the hydroxyl group of the reaction product of the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g). After that, it is preferable to further add a polybasic acid anhydride (d) for adjusting the acid value.
  • the photosensitive resin composition of the present invention is an organic binder, as long as it contains at least one alkali-soluble unsaturated resin of [A-1] or [A-2]. 2 or more types of [A-1] alkaline soluble unsaturated resin, 2 or more types of [A-2] alkali soluble unsaturated resin, or [A-1] alkali soluble unsaturated resin It may contain at least one type of fat and at least one type of [A-2] resoluble unsaturated fatty acid.
  • epoxy compound having at least two epoxy groups in the molecule (a) is not particularly limited as long as it has at least two epoxy groups in the molecule, and examples thereof include an epoxy compound represented by the following general formula (Ia).
  • the molecular weight of the X site is preferably 200 or more, more preferably 220 or more, still more preferably 280 or more, particularly preferably 300 or more, particularly preferably 330 or more, preferably 430 or less, more preferably 410 or less, More preferably, it is 380 or less.
  • epoxy compound (a-1) the epoxy compound represented by the above general formula (Ia) and having a molecular weight of 200 to 430 may be referred to as “epoxy compound (a-1)”.
  • X in the general formula (Ia) is preferably represented by the following general formula ( ⁇ ), ( ⁇ ) or (IIC).
  • R1 to R16 and n have the same meaning as in the general formula (II).
  • the general formula ( ⁇ ) is also preferably represented by the following general formula (IIAa) or (Ilab).
  • R 1 and R 2 have the same meaning as in the general formula (II).
  • ( 41. R 42 each independently represents an alkylene group which may have a substituent or an arylene group which may have a substituent
  • j.k each independently represents 0 to 10 (X—1) to (X—12), (X—40) to (X—43) in the above exemplary structures are the same as those in the general formula (I a). Forces that are specific examples of those represented by the general formula (IIAa) or (IIAb), among these, in particular (X—1), (X-2), (X—40), and (X—41) A structure represented by is preferable.
  • the epoxy compound (a) used in the present invention is an epoxy compound represented by the general formula (I-a), and an epoxy compound (hereinafter referred to as “epoxy compound”) in which the molecular weight of X is less than 200 or more than 480.
  • Compound (a-2) may be used, and such an epoxy compound (a2) may be used in combination with the epoxy compound (a-1).
  • Examples of the epoxy compound (a-2) include compounds in which, in the general formula (Ia), X is represented by the following general formula (IID) or ( ⁇ ).
  • R 1 and R 2 have the same meaning as in the general formula (II), and R ′′ to R 24 each independently have a hydrogen atom or a substituent.
  • R ′′ to R 24 each independently have a hydrogen atom or a substituent.
  • a good alkyl group having 1 to 3 carbon atoms is shown.
  • epoxy compounds (a-2) compounds in which X is represented by the following general formula (IIDa) are particularly preferable.
  • R 1 and R 2 have the same meaning as in the general formula (II), R 21 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent.
  • the epoxy compound (a-2) and the epoxy compound (a-1) are used in combination, the epoxy compound (a-2) is usually added to the epoxy compound (a-1). It is preferable to use in combination of not more than wt%, preferably not more than 15 wt%.
  • the epoxy compound represented by the general formula (Ia) includes, for example, a compound represented by the following general formula (IV) and an epihalohydrin such as epichlorohydrin and epipibrohydrin. It can be obtained by reacting at a temperature of 20 to 120 ° C. for 1 to L0 hours in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.
  • an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.
  • the alkali metal hydroxide may be used as an aqueous solution. Is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or atmospheric pressure, followed by liquid separation, removing water, and epino and lohydrin continuously in the reaction system. The method of returning can be good.
  • a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium chloride bromide, trimethylbenzyl ammonium chloride is added to a mixture of the compound represented by the above general formula (IV) and ⁇ pino and rhohydrin.
  • a method of reacting again at a temperature of 20 to 120 ° C. for 1 to 10 hours to dehalogenate hydrogen (ring closure) may be used.
  • the amount of epino and rhohydrin used in such a reaction is usually 1 mol or more, preferably 2 mol or more, and usually 30 mol, per 1 equivalent of the hydroxyl group of the compound represented by the general formula (IV). Below, preferably 20 mol or less.
  • the amount of the alkali metal hydroxide used is usually 0.8 mol or more, preferably 0.9 mol or more, usually 15 mol or less, preferably 1 mol per 1 equivalent of the hydroxyl group of the compound represented by the general formula (IV). 11 moles or less.
  • alcohols such as methanol and ethanol are used.
  • the reaction may be carried out by adding an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide.
  • an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide.
  • the amount used is usually 2% by weight or more, preferably 4% by weight or more, and usually 20% by weight or less, preferably 15% by weight or less, based on the amount of epino and rhohydrin.
  • an aprotic polar solvent is used, the amount used is usually 5% by weight or more, preferably 10% by weight or more, and usually 100% by weight or less, preferably 90% by weight or less, based on the amount of epino and rhohydrin. .
  • the amount of the alkali metal hydroxide used is preferably 0.01 mol or more, particularly preferably 0.05 mol, relative to 1 equivalent of the hydroxyl group of the compound represented by the general formula (IV) used for the epoxy.
  • the amount is preferably 0.3 mol or less, particularly preferably 0.2 mol or less.
  • the reaction temperature is 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
  • the produced salt is removed by filtration, washing with water, and the like, and further, a solvent such as toluene and methylisobutyl ketone is distilled off under reduced pressure by heating, whereby the compound represented by the above general formula (Ia) is obtained.
  • An epoxy compound is obtained.
  • the epoxy compound (a) used in the present invention is not limited to the epoxy compound represented by the general formula (Ia), and specific examples thereof include bisphenol A type epoxy compounds.
  • Fatty alcohol for example, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004”, etc.
  • alcoholic hydroxyl group and epoxy of bisphenol A type epoxy resin Epoxy resin obtained by the reaction of chlorohydrin for example, “NER 1302” (epoxy equivalent 323, soft soft point 76 ° C) manufactured by Nippon Shakuyaku Co., Ltd.
  • bisphenol F type resin for example, “Epicoat 807”, “EP-4001,” “EP-4002,” “EP-4004, etc.” manufactured by Yuka Shell Epoxy Co., Ltd.
  • the alcoholic hydroxyl group of bisphenol F-type epoxy resin and epichlorohydrin Epoxy resin obtained by reaction for example, “NER” manufactured by Nippon Kay
  • ESF-300 Powered epoxy resin "ESF-300”), Cyclic epoxy resin (“Celoxide 2021PJ”, “Celoxide® E” manufactured by Daicel Chemical Industries, Ltd.), dicyclopentagen type epoxy resin obtained by glycidylation of phenol resin by reaction of dicyclopentagen and phenol, Nippon Kayaku “XD-1000”, Dainippon Inkine “EXA-7200”, Nippon Kayaku “NC-3000”, “NC-7300”).
  • Another example of the epoxy compound (a) is a copolymer type epoxy resin.
  • the copolymer type epoxy resin include glycidyl (meth) attalylate, (meth) atalyloyl methylcyclohexene oxide, burcyclohexene oxide and the like (hereinafter referred to as “first component of copolymer type epoxy resin”).
  • second component of copolymer type epoxy resin for example, methyl (meth) acrylate, ethyl (meth) acrylate , Butyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoloxyl (meth) acrylate, benzyl (meth) acrylate, a- Methylstyrene, glycerin mono (meth) acrylate, and compound strength represented by the following general formula (IA) are also selected 1 Or a copolymer obtained by reacting two or more species with each other (in this specification, “(meth) acrylate”, “(meth) acryl”), etc. “Rate or methacrylate”, “acrylic or methacrylic”, etc., for example, “(meth) at
  • R 21 represents hydrogen or an ethyl group
  • R 22 represents hydrogen or an alkyl group having 1 to 6 carbon atoms
  • r is an integer of 2 to 10.
  • Examples of the compound represented by the general formula (IA) include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene dallicol mono (meth) acrylate. ) Alkoxypolyethylene glycol (meth) acrylate, such as acrylate, methoxydiethylene glycol mono (meth) acrylate, methoxy triethylene glycol mono (meth) acrylate, methoxy tetraethylene glycol mono (meth) acrylate, etc. It is done.
  • polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene dallicol mono (meth) acrylate.
  • Alkoxypolyethylene glycol (meth) acrylate such as acrylate, methoxydiethylene glycol mono (meth) acrylate,
  • the molecular weight of the copolymerized epoxy resin is preferably about 1000-200000.
  • the amount of the first component of the copolymerization type epoxy resin used is the same as that of the copolymerization type epoxy resin.
  • It is preferably 10% by weight or more, particularly preferably 20% by weight or more, preferably 70% by weight or less, particularly preferably 50% by weight or less, based on the two components.
  • the diglycidyl ethers of bisphenols represented by the general formula (Ia) are particularly preferred, especially the epoxy compound (a 1) is preferred.
  • the epoxy compound (a) may be used alone or in combination of two or more. When two or more types are used in combination, an epoxy compound containing two epoxy groups and an epoxy compound containing three or more epoxy groups are preferred. Specific combinations of epoxy compounds include compounds represented by the general formula (I a), Nippon Kayaku “XD-1000”, Dainippon Ink ⁇ -720 0 ”, trisphenol methane A combination with a type epoxy compound may be mentioned. [0059] [Unsaturated carboxylic acid (b)]
  • Examples of the unsaturated group-containing carboxylic acid (b) include unsaturated carboxylic acids having an ethylenically unsaturated double bond. Specific examples thereof include (meth) acrylic acid, crotonic acid, o-, m-, p-Buylbenzoic acid, monocarboxylic acids such as ⁇ -position haloalkyls, alkoxyls, halogens, nitros, and cyano substitutions of (meth) acrylic acid, 2— (meth) atariloy cough succinic acid, 2— (meth) atariloyloxche Tiladipic acid, 2- (meth) atariloy oral chechetilfalic acid, 2- (meth) atariloy oral chechetilhexahydrophthalic acid, 2- (meth) atariloy oral chetilmaleic acid, 2- (meth) aterylleuoxy Propyl succinic acid, 2— (meth) atari leu
  • (meth) acrylic acid are particularly preferred. These can be used alone or in combination of two or more.
  • a known method can be used as a method for reacting the epoxy group in the epoxy compound (a) with the unsaturated group-containing carboxylic acid (b).
  • the above epoxy compound (a) and unsaturated group-containing carboxylic acid (b) are combined with tertiary amines such as triethylamine, benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride.
  • Quaternary ammonium salts such as benzyltriethylammonium chloride, pyridine, triphenylphosphine, etc. as a catalyst, in an organic solvent at a reaction temperature of 50 to 150 ° C for several to several tens of hours.
  • the amount of the catalyst used is preferably 0.01% by weight or more, particularly preferably based on the reaction raw material mixture (the total of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b)). Is not less than 0.3% by weight, preferably not more than 10% by weight, particularly preferably not more than 5% by weight.
  • a polymerization inhibitor for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine.
  • the amount is preferably 0.01% by weight or more, particularly preferably 0.1% by weight or more, preferably 10% by weight or less, particularly preferably 5% by weight, based on the reaction raw material mixture.
  • the ratio of adding the unsaturated group-containing carboxylic acid (b) to the epoxy group of the epoxy compound (a) is usually 90 to L00 mol%. Since residual epoxy groups adversely affect storage stability, unsaturated group-containing carboxylic acids (b) are usually at least 0.8 equivalents, especially 0.9 equivalents, relative to 1 equivalent of epoxy groups in epoxy compound (a). It is preferable to carry out the reaction at a ratio of not less than the equivalent, usually not more than 1.5 equivalent, particularly not more than 1.1 equivalent.
  • the compound (c) having an isocyanate group to be added to the hydroxyl group of the reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b) known compounds can be used.
  • This compound (c) may have one isocyanate group in the molecule or may be a polyisocyanate compound having a plurality of isocyanate groups.
  • a polyisocyanate compound is preferably used.
  • the compounds having one isocyanate group in the molecule include butane isocyanate, 3-chlorobenzene benzene isocyanate, 4-chlorobenzene benzene isocyanate, cyclohexane isocyanate, benzene isocyanate, 3- Examples include isopropenoyl ⁇ , a-dimethylbenzyl isocyanate and m-toluene isocyanate.
  • polyisocyanate compounds include para-phenolic diisocyanate, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate.
  • Aromatic diisocyanates such as cyanate, naphthalene 1,5 diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexylisocyanate), ⁇ , ⁇ '--Diisocyanate Dicyclohexane, alicyclic diisocyanate, xylylene diisocyanate,, a, a', ⁇ '-tetramethylxylylene diisocyanate.
  • dimers and trimers of organic diisocyanates are preferred, and most preferred are products of tolylene diisocyanate with trimethylolpropane, tolylene diisocyanate trimer, isophorone dimer. Isocyanate trimer.
  • the compound (c) having an isocyanate group one type may be used alone, or two or more types may be used in combination.
  • the polyisocyanate is converted to an appropriate trimer catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acids. Perform a partial trimerization of the isocyanate group using salts, etc., stop the trimer by adding a catalyst poison, then extract the unreacted polyisocyanate by solvent extraction and thin-film distillation. There is a method of removing the desired isocyanurate group-containing polyisocyanate.
  • an appropriate trimer catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acids.
  • the addition ratio of the compound (c) having an isocyanate group is usually 10 mol% or more, preferably 20 mol, of the hydroxyl group produced when the unsaturated group-containing carboxylic acid (b) is added to the epoxy compound (a). % Or more, particularly preferably 30 mol% or more, usually 95 mol% or less, preferably 90 mol% or less. If this addition rate is too small, the film physical properties may decrease when it is formed into a coating film. If it is too large, the viscosity of the resulting resin solution will increase, and handling may be difficult.
  • the reaction temperature is usually 40 ° C or higher, preferably 50 ° C or higher, usually 150 ° C or lower, preferably 100 ° C or lower, and the reaction time is usually 1 to 100 hours, preferably 24 hours or less. . If the reaction temperature exceeds 130 ° C, polymerization of unsaturated groups will occur in part, leading to a rapid increase in molecular weight, and if it is less than 80 ° C, the reaction may not proceed smoothly.
  • an ordinary urethanization reaction catalyst is used as a catalyst that may be used as a catalyst.
  • a catalyst for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diatoate, stannous octoate and other tin systems, iron acetyl cetate, ferrous salts such as ferric iron, triethylamine, triethylene diamine Examples include tertiary amines such as amines.
  • the alkali-soluble unsaturated resin according to the present invention is obtained by adding the compound (c) having an isocyanate group to the hydroxyl group of the reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b). It is preferable that a polybasic acid anhydride (d) is further added to adjust the value.
  • polybasic acid anhydride (d) known ones can be used. Maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl Dicarboxylic anhydrides such as endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic acid Examples thereof include dianhydrides and tetracarboxylic dianhydrides such as biether ether tetracarboxylic dianhydrides.
  • a dicarboxylic anhydride such as tetrahydrophthalic anhydride or succinic anhydride may be used in combination with a tetracarboxylic dianhydride such as benzophenone tetracarboxylic dianhydride or biphenyltetracarboxylic acid.
  • a tetracarboxylic dianhydride such as benzophenone tetracarboxylic dianhydride or biphenyltetracarboxylic acid.
  • the acid value may be adjusted or an unsaturated group may be introduced by adding a compound having an active hydrogen group in the molecule to one acid anhydride part. .
  • Active hydrogen group in the above molecule those having an active hydrogen group and an organic acid group such as citrate, malic acid, and hydroxypivalic acid can be used as acid value adjusting applications, and as an application for introducing an unsaturated group.
  • those having an unsaturated group and an active hydrogen group such as hydroxyethyl (meth) acrylic acid, hydroxybutyl (meth) acrylic acid, 2-hydroxymethylacrylic acid methyl ester, 2-hydroxymethylacrylic acid ethyl ester, and the like. It is done.
  • the addition rate of the polybasic acid anhydride (d) is determined based on the unsaturated compound-containing carboxylic acid added to the epoxy compound (a).
  • the amount of the hydroxyl group produced when (b) is added is usually 5 to 90 mol%, preferably 5 to 80 mol%, more preferably 5 to 70 mol%. If the addition rate is too small, the solubility may be insufficient or the adhesion to the substrate may be insufficient.
  • a known method can be used as a method of adding the polybasic acid anhydride (d) to the isocyanate compound (c) addition product of the reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b).
  • the reaction temperature is usually 80 ° C or higher, preferably 90 ° C or higher, usually 130 ° C or lower, preferably 125 ° C or lower.
  • the reaction temperature exceeds 130 ° C, polymerization of unsaturated groups occurs in part, leading to a rapid increase in molecular weight.
  • the reaction does not proceed smoothly, and the polybasic acid anhydride (d) May remain.
  • the alkali-soluble unsaturated resin according to the present invention includes an isocyanate compound (c) adduct of a reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b) with a polybasic acid-free water. After addition of the product (d), an epoxy group-containing compound (e) may be further added to a part of the generated carboxyl group.
  • epoxy group-containing compound (e) glycidyl (meth) acrylate, 3, 4-epoxy cyclohexyl (meth) acrylate, or polymerizable non-polymerizable compounds for improving photosensitivity are used.
  • a glycidyl ether compound having a saturated group or a glycidyl ether compound having no polymerizable unsaturated group for improving developability can be used. Also good.
  • Specific examples of glycidyl ether compounds having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group (“Denacol EX—111” manufactured by Nagase Chemical Industries Co., Ltd.).
  • the phenolic hydroxyl group-containing compound (f) is not particularly limited as long as it has at least two phenolic hydroxyl groups in the molecule.
  • X has the same meaning as X in the general formula (I a), and it is preferable to explain the general formula (I a) described above, depending on its structure and the like. As described above.
  • the unsaturated group-containing epoxy compound (g) is not particularly limited as long as it has an ethylenically unsaturated double bond and has an epoxy group in the molecule.
  • an acrylate having an epoxy group is preferred. Specific examples include glycidyl (meth) acrylate and 3, 4 epoxy hexyl (meth) acrylate.
  • the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g) are mixed with a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, Quaternary ammonium salts such as tetraethylammonium chloride, benzyltriethylammonium chloride, pyridine, triphenylphosphine, etc. as a catalyst in an organic solvent at a reaction temperature of 50 to 150 ° C for several to several tens of hours
  • an unsaturated group-containing epoxy compound (g) can be added to the phenolic hydroxyl group-containing compound (f).
  • the amount of the catalyst used is preferably 0.01% by weight or more based on the reaction raw material mixture (the total of the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g)). Particularly preferably, it is 0.3% by weight or more, preferably 10% by weight or less, particularly preferably 5% by weight or less.
  • a polymerization inhibitor for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butyl catechol, phenothiazine. Is preferably 0.01% by weight or more, particularly preferably 0.1% by weight or more, preferably 10% by weight or less, particularly preferably 5% by weight, based on the reaction raw material mixture.
  • the ratio of the unsaturated group-containing epoxy compound (g) to be reacted with the phenolic hydroxyl group-containing compound (f) is usually 90 to 120 mol%. Since the residual epoxy group adversely affects storage stability, the phenolic hydroxyl group-containing compound (f) is usually at least 0.8 equivalent, especially 0, relative to 1 equivalent of the epoxy group of the unsaturated group-containing epoxy compound (g). It is preferable to carry out the reaction at a ratio of 9 equivalents or more, usually 1.5 equivalents or less, particularly 1.2 equivalents or less.
  • the addition of the group-containing compound (e) is performed by adding an isocyanate group to the reaction product of the epoxy compound ( a ) having at least two epoxy groups in the molecule and the unsaturated group-containing carboxylic acid (b).
  • Addition of compound (c), polybasic acid anhydride (d) Caro and an epoxy group-containing compound (e) can be added in the same manner.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by GPC of the alkali-soluble unsaturated resin according to the present invention obtained as described above is usually 700 or more, preferably 1000 or more, and usually 50000 or less, preferably 30000 or less. It is. If the weight average molecular weight of the alkali-soluble unsaturated resin is too small, the heat resistance and the film strength are inferior, and if it is too large, the solubility in the developer is insufficient.
  • the acid value (mg-KOH / g) of the alkali-soluble unsaturated coconut resin according to the present invention is usually 10 or more, preferably 30 or more, and usually 200 or less, preferably 150 or less. Al force If the acid value of the re-soluble unsaturated resin is too low, sufficient solubility cannot be obtained, and if the acid value is too high, the curability is insufficient and the surface properties deteriorate.
  • the photosensitive resin composition of the present invention may further contain a photopolymerization initiator.
  • the photopolymerization initiator used in the present invention is not particularly limited as long as it is a compound that polymerizes an ethylenically unsaturated group with actinic rays, but the photosensitive resin composition of the present invention has a polymerizable group.
  • the photopolymerization initiator has a function of generating a polymerization active radical by directly absorbing or photosensitizing light and causing a decomposition reaction or a hydrogen abstraction reaction. Is preferably used.
  • photopolymerization initiator that can be used in the present invention are listed below.
  • 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. No. 61-151197, JP-B 45-37377, JP-A 58-40302, and JP-A 10-39503.
  • the photosensitive resin composition of the present invention may be a photosensitive colored resin composition further containing a coloring material.
  • pigments are also preferred in terms of heat resistance, light resistance, and the like.
  • pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used.
  • organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene and perylene
  • organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene and perylene
  • organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene and perylene
  • various inorganic pigments are also used. Is possible. Specific examples of pigments that can be used are shown below
  • red pigments examples include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37. , 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53 : 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81 : 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144 , 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190,
  • CI CI Pigment Red 48 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably ⁇ CI Pigment Red 177, 209, 224, 254 are preferably used. I can list them.
  • Blue pigments include C. I. Pigment Bnole 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15:
  • C.I. pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. pigment blue 15: 6 can be mentioned.
  • Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 1 8, 19, 26, 36, 45, 48, 50, 51, 54, You can raise 55 and have the power S. Among these, CI Pigment Green 7 and 36 are preferable.
  • C.I. pigment yellow 83, 117, 129, 138, 139, 150, 154, 15 is preferable.
  • CI range pigment range 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 Among these, preferably Can mention CI Pigment Orange 38, 71.
  • Purple pigments include C.I. pigment violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5,
  • C.I. pigment violet 19, 23 is preferable, and C.I. pigment violet 23 is more preferable.
  • the photosensitive resin composition of the present invention is a photosensitive colored resin composition for a black filter matrix of a color filter
  • a black color material can be used as the color material.
  • the black color material may be a single black color material or a mixture of red, green, blue and the like.
  • These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable that the average particle size is 1 ⁇ m or less, preferably 0.5 ⁇ m or less.
  • Color materials that can be mixed to prepare black color materials include Victoria Pure Blue (42595), Auramin 0 (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 (50240), Ellioglaucin X (42080), No.
  • pigments that can be used in combination are represented by CI numbers.
  • black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, iron black, cyanine black, and titanium black.
  • carbon black and titanium black are particularly preferable from the viewpoints of light shielding rate and image characteristics.
  • examples of carbon black include the following carbon black.
  • Cabot Monarchl20, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, MonarchlOOO, MonarchllOO, Monarchl300, Monarchl400, Monarch4630, REGAL99, REGAL99R, REGAL415, RE GAL415R ⁇ ALAL250, REGAL250R REG 250, REGAL250R REG 250 REGAL660R, BLACK PEARLS480, PEARLS 130, VULCAN XC72R ⁇ ELFTEX-8
  • Colombian Carbon RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420 RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RA VEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN 1080U, RAVEN1170, RAVEN 1190U, RAVEN 1250, RAVEN 1500, RAVEN20 00, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, VEN 5
  • a method for producing titanium black a mixture of titanium dioxide and metallic titanium is heated and reduced in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432).
  • the ultrafine titanium dioxide obtained in step 1 is reduced in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), and titanium dioxide dihydrate or titanium dioxide hydroxide is reduced at high temperature in the presence of ammonia.
  • Method JP-A-60-65069, JP-A-61-201610, a method in which a vanadium compound is attached to titanium dioxide dihydrate or titanium oxide hydroxide and reduced at high temperature in the presence of ammonia (special Kaisho 61—201610)) is not limited to these.
  • titanium black examples include Titanium Black 10S, 12 manufactured by Mitsubishi Materials Corporation.
  • titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.
  • pigment barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, and the like can also be used.
  • These various pigments can be used in combination.
  • a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.
  • the average particle diameter of these pigments is usually 1 ⁇ m, preferably 0.5 ⁇ m or less, and more preferably 0.25 m or less.
  • the dye that can be used as the coloring material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinonimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
  • Examples of azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Benolet 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Tart Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Day Sparse Orange 5, CI Day Spur Red 58, CI Day Sparse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7, etc.
  • anthraquinone dyes include CI Bat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Bull 1 49, CI Disperse Red 60, CI Disperse Blue 56 , CI Disperse Blue 60 etc.
  • phthalocyanine dyes for example, CI pad blue 5 isotropic quinone imine dyes, for example, CI basic blue 3, CI basic blue 9, etc.
  • quinoline dyes for example, CI solvent yellow 33 CI Acid Yellow 3
  • CI Disperse Yellow 64 Isotropic Nitro dyes include, for example, CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42, and the like.
  • the photosensitive resin composition of the present invention is a photosensitive colored resin composition containing a coloring material
  • the photosensitive colored resin composition may further contain a dispersant.
  • the dispersant used in the present invention is preferably a nitrogen atom-containing dispersant.
  • the nitrogen atom-containing dispersant surfactants, polymer dispersants and the like are usually used, and polymer dispersants are particularly suitable.
  • polymer dispersant As a polymer dispersant,
  • One dispersant can be used alone It may be used, or two or more types may be mixed and used.
  • photosensitive colored resin can be maintained while maintaining dispersion stability. It is possible to achieve high adhesion during development between the coating film formed from the composition and the substrate, and to suppress residual undissolved substances.
  • the form of the nitrogen atom in the nitrogen atom-containing dispersant is preferably an amino group, a quaternary ammonium salt, or the like. This is because these functional groups usually have basicity so that they can easily coordinate with acidic groups such as pigments and pigment derivatives, thereby contributing to dispersion stabilization.
  • the amine value of the dispersant is usually 2 mg-KOHZg or more, preferably 3 mg-KOHZg or more, and usually 10 mg-KOHZg or less, preferably 80 mg-KOHZg or less. If the amine value is too low, the basicity is insufficient and the dispersion stability is poor. If the amine value is too high, the voltage holding ratio of the liquid crystal is lowered when used in a liquid crystal display device, resulting in display failure. It becomes easy and is not preferable.
  • Urethane dispersants include (1) polyisocyanate compounds, (2) compounds having one or two hydroxyl groups in the same molecule, and (3) active hydrogen and tertiary in the same molecule. It is preferably a dispersed resin obtained by reacting with a compound having an amino group.
  • polyisocyanate compounds include para-phenolic diisocyanate, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 4,4'-diphenyl-nomethane diisocyanate, naphthalene 1, 5 Aromatic diisocyanates such as diisocyanate and tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2, 4, 4 Trimethylhexamethylene diisocyanate, aliphatic such as dimer acid diisocyanate Diisocyanate, isophorone diisocyanate, 4, 4'-methylenbis (cyclohexyl isocyanate), ⁇ , ⁇ '— diisocyanate dimethylcyclohexane, alicyclic diisocyanate, xylylene diisocyanate, a , a, a ', ⁇ ' tetramethylxylylene diisocyanate
  • the preferred polyisocyanate is an organic diisocyanate trimer, the most preferred is a tolylene diisocyanate trimer and an isophorone diisocyanate trimer, which can be used alone. Two or more types may be used in combination.
  • the polyisocyanate is used as a suitable trimer catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acids.
  • a suitable trimer catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acids.
  • Examples of compounds having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, and polyolefin glycol.
  • polyether glycol examples include polyether diol, polyether ester diol, and mixtures of two or more of these.
  • polyether diols are those obtained by homo- or copolymerization of alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, and polyoxyoctamethylendaline. And mixtures of two or more thereof.
  • Polyether ester diols include those obtained by reacting a mixture of an ether group-containing diol or other darlicol with a dicarboxylic acid or an anhydride thereof, or by reacting polyester glycol with an alkylene oxide.
  • Polyoxytetrame Tylene) adipate and the like are preferred as the polyether glycol.
  • polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
  • Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol).
  • polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene Z-propylene adipate, etc., or the above diols or monohydric alcohols having 1 to 25 carbon atoms are used as initiators.
  • Obtained polylatathonediol or polylatatatone monool Such as poly force Purorata tons glycol, Po trimethyl valeronitrile rata tons and mixtures of two or more thereof.
  • the most preferred polyester dallicol is polystrength prolataton glycol or polystrength prolatatone with 1 to 25 carbons as an initiator. It is a compound obtained by doing.
  • polycarbonate glycol examples include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, and the like.
  • Polyolefin glycol examples thereof include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Of the compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferred.
  • the number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 or more, preferably 500 or more, more preferably 1,000 or more, and usually 10,000 or less, preferably 6 , 000 or less, more preferably 4,000 or less.
  • Active hydrogen that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a thio atom includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Preference is given to hydrogen atoms of primary amino groups.
  • the tertiary amino group is not particularly limited.
  • a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, and the dialkylamino group are linked.
  • a group forming a heterocyclic structure more specifically, an imidazole ring or a triazole ring.
  • Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule are N, N dimethyl-1,3 propanediamine, N, N jetyl-1,3 propanediamine, N, N dipropinole 1 , 3 Propanadamine, N, N-Dibutinole 1,3 Propanadamine, N, N Dimethylethylenediamine, N, N Jetylethylenediamine, N, N Dipropylethylenediamine, N, N Dibutylethylenedi N, N Dimethyl-1,4-butanediamine, N, N Jetinoley 1,4 Butanediamine, N, N Dipropyl-1,4 Butanediamine, N, N Dibutyl-1,4 Butanediamine, and the like.
  • the tertiary amino group is a nitrogen-containing hetero ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, force rubazole ring, indazole ring, benzimidazole ring, benzotriazole ring N-containing hetero ring such as benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc.Nitrogen containing 5-membered ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, atalidine ring, isoquinoline ring Hetero 6-membered ring.
  • nitrogen-containing heterocycles are preferred, A dazole ring or a triazole ring.
  • Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3 aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2 aminoethyl) imidazole, and the like. .
  • specific examples of the compound having a triazole ring and a primary amino group include 3 amino-1, 2, 4 triazole, 5- (2 amino 5 black mouth phenol) 1 3 phenol 1 H —1, 2, 4 Triazonole, 4 Amino 4 H- 1, 2, 4 Triazole 3,5 Diol, 3 Amino 5 Phenol 1H— 1, 3, 4, 4 Tria: / 1 Norre, 5 Amino 1, 4 Diphenyl Nore 1, 2, 3 Tria: / Nore, 3 amino- 1-benzyl- 1H- 2, 4 triazole and the like.
  • N, N-dimethylol 1,3 propanediamine, N, N jetino 1,3-propane diamine, 1- (3-aminopropyl) imidazole, and 3-amino 1,2,4 triazole are preferable.
  • the preferred blending ratio of the urethane-based dispersed resin raw material is usually 10 parts by weight or more for a compound having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. 20 parts by weight or more, more preferably 30 parts by weight or more, usually 200 parts by weight or less, preferably 190 parts by weight or less, more preferably 180 parts by weight or less, and active hydrogen and tertiary amino acids in the same molecule.
  • the compound having a group is usually 0.2 parts by weight or more, preferably 0.3 parts by weight or more, and usually 25 parts by weight or less, preferably 24 parts by weight or less.
  • the weight average molecular weight in terms of polystyrene measured by GPC of the urethane-based dispersion resin according to the present invention is usually 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, and usually 200,000. In the following, preferred ⁇ is in the range of 100,000 or less, more preferred ⁇ is in the range of 50,000 or less. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered, and the dispersibility is poor and at the same time it becomes difficult to control the reaction.
  • urethane-based dispersion resin is performed according to a known method for producing polyurethane resin.
  • Solvents used for the production are usually ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve acetate, benzene , Hydrocarbons such as toluene, xylene and hexane, some alcohols such as diacetone alcohol, isopropanol, secondary butanol and tertiary butanol, and salts such as methylene chloride and black mouth form And aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide are used.
  • a usual urethanization reaction catalyst is used.
  • tertiary amines such as diamine.
  • the introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is 1 mg-KOHZg or more, especially 5 mg-KOHZg or more, 100 mg-KO HZg or less, especially in terms of amine value of the dispersed resin after the reaction. It is preferable to control within the range of 95 mg—KOHZg or less. If the amine value is less than the above range, the dispersing ability tends to be lowered, and if it exceeds the above range, developability tends to be lowered. In the case where the isocyanate group remains in the dispersion resin by the above reaction, it is preferable to further crush the isocyanate group with an alcohol amide compound since the stability of the dispersion resin with time increases.
  • the graft copolymer containing a nitrogen atom one having a repeating unit containing a nitrogen atom in the main chain is preferred. Among them, it is preferable to have a repeating unit represented by the following general formula (Ia) or a repeating unit represented by Z and the following general formula (ii) U.
  • R 31 represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms.
  • A is a hydrogen atom or the following general formula (iii)-(v)! Represents a deviation, preferably the following general formula (m).
  • w 1 represents a linear or branched alkylene group having 2 to ⁇ ⁇ , and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, hexylene, etc. is preferable.
  • . p represents an integer of 1 to 20, preferably an integer of 5 to 10.
  • G 1 represents a divalent linking group, and in particular, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene, and an alkylene group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy.
  • W 2 represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene or butylene, and among them, an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene is preferable.
  • G 2 represents a hydrogen atom or —CO—R 32 (R 32 represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc., among which ethyl, propyl, butyl, pentyl, etc. An alkyl group having 2 to 5 carbon atoms is preferred).
  • q represents an integer of 1 to 20, preferably an integer of 5 to 10.
  • W 3 represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 50 carbon atoms having 1 to 5 hydroxyl groups, and in particular, an alkyl having 10 to 20 carbon atoms such as stearyl.
  • Preferred is a hydroxy group having 1 to 2 hydroxyl groups having 1 to 2 hydroxyl groups such as monohydroxystearyl, etc.! / ⁇ .
  • the content of the repeating unit represented by the general formula (I-a) or (ii) in the graft copolymer according to the present invention is preferably 50 mol% or more in total, which is preferably higher. Preferably it is 70 mol% or more.
  • the total number of repeating units represented by general formula (Ia) or general formula (ii) in the graft copolymer is 1 or more, preferably 10 or more, more preferably 20 or more, and usually 100 or less, preferably Is 70 or less, more preferably 50 or less.
  • examples of other repeating units that may contain a repeating unit other than the general formula (Ia) and the general formula (ii) in the graft copolymer include an alkylene group and an alkyleneoxy group. Can be illustrated.
  • the terminal is —NH and —R 31 —NH (R 31 is the same as in the general formulas (I—a) and (ii)
  • the main chain may be linear or branched.
  • the weight-average molecular weight of the graft copolymer measured by GPC is preferably 3,000 or more, particularly 5,000 or more, preferably 100,000 or less, particularly 50,000 or less. If the weight average molecular weight is less than 3,000, the color material cannot be agglomerated and the viscosity may not increase or gelation may occur. Viscosity is preferable and solubility in organic solvents is insufficient.
  • the A block constituting the block copolymer of the dispersant is a quaternary ammonium base, preferably — N + R la R 2a R 3a 'Y_ (where R la , R 2a and R 3a are each independently Represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group, or two or more of R la , R 2a and R 3a are bonded to each other to form a cyclic structure. It has a quaternary ammonia base represented by: This quaternary ammonium base may be bonded directly to the main chain, or may be bonded to the main chain via a divalent linking group.
  • a cyclic structure formed by combining two or more of R la , R 2a and R 3a with each other includes, for example, a 5- to 7-membered nitrogen-containing heterocyclic ring Examples thereof include a single ring or a condensed ring obtained by condensing two of these.
  • the nitrogen-containing heterocycle is more preferably a saturated ring that is preferably non-aromatic. Specific examples include the following.
  • R represents any group of R la to R 3a .
  • R la to R 3a in the [0150] -N + R la R 2 3a more preferred, have a substituent good V, having an alkyl group, or a substituent having 1 to 3 carbon atoms Te! /, Even!
  • a block those containing a partial structure represented by the following general formula (1) are particularly preferable.
  • R la and R z R each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, two or more of R la , R 2a and R 3a may be bonded to each other to form a cyclic structure.
  • R 4a represents a hydrogen atom or a methyl group.
  • Q represents a divalent linking group, and represents an anion.
  • examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, CONH—R 5a —, —COO—R 6a — (provided that R 5a and R 6a are a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (one R 7a -0-R 8a- : R 7a and R are each independently an alkylene group ) And the like, preferably COO—R 6a —.
  • the partial structure containing the specific quaternary ammonium base as described above may be contained in one or more A blocks. In that case, two or more kinds of quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization.
  • examples of the partial structure that may be contained in the partial structural force A block that does not contain the quaternary ammonium base include a partial structure derived from a (meth) acrylate ester monomer described later. Etc.
  • the content of the partial structure containing no strong quaternary ammonium salt group in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. It is most preferable that the partial structure containing no ammonia base is not contained in the A block.
  • the B block constituting the block copolymer of the dispersant for example, styrene, a-Styrene monomers such as methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) (Meth) acrylic acid ester monomers such as acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, N, N-dimethylaminoethyl (meth) acrylate, and (meth) acrylic acid (Meth) acrylate monomers such as chloride; (meth) acrylamide monomers such as (meth) acrylamide, N-methylolacrylamide, N, N-dimethyl
  • the B block is preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (2).
  • R 9a represents a hydrogen atom or a methyl group.
  • R 1Qa may be a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent, which may represent an aralkyl group.
  • Two or more types of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block.
  • the B block may further contain a partial structure other than these.
  • Partial structural strength derived from two or more types of monomers Does not contain quaternary ammonia salt groups.
  • each partial structure is random or block copolymerized in the B block. It may be contained in any of the embodiments.
  • the B block contains a partial structure other than the partial structure derived from the (meth) acrylic acid ester monomer
  • the content of the partial structure other than the (meth) acrylic acid ester monomer in the B block Is preferably 0-50% by weight, more preferably 0-20% by weight, Most preferably, a partial structure other than the (meth) acrylic acid ester monomer is not contained in the B block.
  • the dispersant used in the present invention is an A-B block or B-A-B block copolymerization type polymer compound composed of such an A block and a B block.
  • Such a block copolymer The body is prepared, for example, by the living polymerization method shown below.
  • Living polymerization methods include a living living polymerization method, a cationic living polymerization method, and a radical living polymerization method.
  • the polymerization active species is eron, and for example, it is shown in the following scheme.
  • the radical living polymerization method is a polymerization active species power radical, and is represented by the following scheme, for example.
  • H 2 C CH monomer—2:
  • the A block ZB block ratio (weight) Ratio) is It is usually in the range of 1Z99 or more, especially 5Z95 or more, and usually 80Z20 or less, especially 60/40 or less. Outside this range, it may not be possible to combine good heat resistance and dispersibility.
  • the AB block copolymer and 8-block copolymer used in the present invention The amount of quaternary ammonium base in ⁇ is usually 0.1 to: LOmmol outside this range, it may not be possible to combine good heat resistance and dispersibility.
  • Such a block copolymer usually contains an amino group produced in the production process. Its amine value is about 1 to: LOOmg-KOHZg. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of the basic amino group with an acid.
  • the acid value of this block copolymer is generally 10 mg-KOHZg or less, which is generally preferred to be lower, although it depends on the presence and type of acidic groups that form the acid value. Is preferably in the range of not less than 1000 and not more than 100,000 in terms of weight average in terms of polystyrene. When the molecular weight of the block copolymer is less than 1000, the dispersion stability decreases, and when it exceeds 1000, the developability and resolution tend to decrease.
  • a phosphate ester type dispersant in addition to the block copolymer. This improves the solubility during development.
  • the phosphoric ester may be any of primary to tertiary esters, but primary ester is preferred from the viewpoint of dispersion performance.
  • Examples of the structure of the portion that binds to phosphoric acid include structures having a hydroxyl group at the terminal, as typified by polyesters such as poly-force prolatatone and polyethers such as polyethylene glycol. These may be a copolymer of polyester and polyether.
  • a double bond such as (meth) acrylate may be formed at one end of the polyester chain and Z or polyether chain, and a copolymer may be formed with another radical polymerizable compound.
  • the phosphate ester preferably has a partial structure represented by the following structural formula (3).
  • Such a phosphate ester can be produced, for example, by the method described in JP-B-50-22536 and JP-A-58-128393.
  • the molecular weight Mw of the phosphate ester type dispersant is usually 200 or more, and usually 5000 or less, preferably 1000 or less. Since this phosphate ester type dispersant is originally added for the purpose of imparting development solubility, it is not preferable to have a high molecular weight.
  • a photopolymerizable monomer (photopolymerizable compound) in addition to the photopolymerization initiator in view of sensitivity and the like.
  • the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group.
  • Specific examples of the compound having an ethylenically unsaturated group in the molecule include (meth) acrylic acid, alkyl ester of (meth) acrylic acid, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond and many ( And monoesters of monohydric alcohols.
  • the photopolymerizable monomer it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule.
  • Examples of powerful polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Examples thereof include esters obtained by esterification of polyvalent hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.
  • ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid examples include ethylene glycol diatalylate, triethylene glycol diatalylate, trimethylol propane triatrate, trimethylol ethane triatariate.
  • pentaerythritol diatarire Acrylates of aliphatic polyhydroxy compounds such as benzoate, pentaerythritol triatalylate, pentaerythritol tetraatalylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaatalylate, glycerol acrylate Acid esters, methacrylic acid esters in which the acrylates of these exemplified compounds are replaced with metatalylate, itaconate esters in place of itaconate, crotonic acid esters in place of clonate or maleates in place of maleate, etc.
  • aliphatic polyhydroxy compounds such as benzoate, pentaerythritol triatalylate, pentaerythritol tetraatalylate, dipentaerythritol tetraacryl
  • ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid examples include: Hyde Mouth Quinone Diatalylate, Hyde Mouth Quinone Dimetatalylate, Resorcin Diatalylate, Resorcin Dimetatalylate, Pyrogallol Tritalylate And aromatic polyhydroxy compounds such as acrylates and methacrylates.
  • the ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, Condensates of phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin, etc. is there.
  • polyfunctional ethylenic monomers used in the present invention include polyisocyanate compounds and hydroxyl group-containing (meth) acrylic acid esters or polyisocyanate compounds, polyols and hydroxyl group-containing (meta ) Urethane (meth) acrylates as obtained by reacting acrylic esters; epoxy acrylates such as addition reaction products of polyhydric epoxy compounds with hydroxy (meth) acrylates or (meth) acrylic acids Rates; acrylamides such as ethylene bisacrylamide; allylic esters such as diaryl phthalate; and bull group-containing compounds such as dibule phthalate are useful.
  • an organic solvent for the photosensitive resin composition of the present invention, an organic solvent, an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, a silane coupling agent and the like are suitable in addition to the above-described components. It can mix
  • organic solvent examples include diisopropyl ether, mineral spirits, n pentane, aminoleethenore, ethinorecaprylate, n-hexane, jetinore etherole, isoprene, ethinoreisobutinore Tenole, Butinorestearate, n-Octane, Parsol # 2, Apco # 18 Solvent, Diisobutylene, Amyl Acetate, Butyl Butylate, Apcocinner, Butyl Ether, Diisoptyl Ketone, Methyl Cyclohexene, Methyl Norketone, Propyl Ether, Dodecane, Socal solvent No.
  • the solvent is preferably one that can dissolve or disperse each component and has a boiling point in the range of 100 to 250 ° C. More preferably, it has a boiling point of 120 to 170 ° C. These may be used alone or as a mixture of two or more.
  • silane coupling agent In order to improve the adhesion to the substrate, it is possible to add a silane coupling agent.
  • silane coupling agent epoxy-based, methacryl-based, amino-based and other materials can be used. Epoxy-based silane coupling agents are particularly preferred.
  • the photosensitive resin composition of the present invention is produced according to a conventional method.
  • a photosensitive colored resin composition containing a color material first, a predetermined amount of each of the color material, the solvent, and the dispersant is weighed, and in the dispersion treatment step, the color material is dispersed to form a liquid.
  • the coloring composition (ink-like liquid).
  • a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, and the like can be used.
  • the color material is made into fine particles, so that the coating characteristics of the photosensitive colored resin composition are improved and the transmittance of the product color filter substrate is improved.
  • the alkali-soluble unsaturated resin may be used in combination.
  • the dispersion treatment when the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads having a diameter of 0.1 mm or zirconia beads.
  • the temperature during the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. Note that the dispersion time varies depending on the composition of the ink-like liquid (coloring material, solvent, dispersant), the size of the sand grinder, and the like, so it is necessary to adjust it appropriately.
  • the ink-like liquid obtained by the above dispersion treatment is mixed with a solvent, an alkali-soluble unsaturated resin, a photopolymerization initiator, and, in some cases, other components other than the above, to obtain a uniform dispersion solution.
  • fine dust may be mixed. Therefore, the obtained photosensitive colored resin composition is filtered with a filter or the like. It is preferable to over-process.
  • the photosensitive resin composition is produced by mixing the respective components without carrying out the dispersion treatment of the coloring material in the method for producing a photosensitive colored resin composition. be able to.
  • the blending amount of the alkali-soluble unsaturated coffin is usually 10% by weight or more, preferably 20% by weight or more, and usually 80% by weight or less, based on the total solid content of the photosensitive resin composition of the present invention. Preferably it is 70 weight% or less.
  • the ratio of the alkali-soluble unsaturated resin to the color material is usually 5% by weight or more, The range is preferably 10% by weight or more, usually 500% by weight or less, preferably 200% by weight or less. If the content of the alkali-soluble unsaturated resin is too small, the solubility of the unexposed part in the developer will be reduced, and if it is too high, it will be difficult to obtain the desired pixel thickness. Become.
  • total solid content means all components other than the solvent, and the total solid content in the photosensitive resin composition of the present invention is usually 10% by weight or more and 90% by weight. % Or less.
  • the content thereof is usually 0.1% by weight or more, preferably 0.5% by weight or more, based on the total solid content of the photosensitive resin composition of the present invention. More preferably, it is 0.7% or more, usually 30% by weight or less, preferably 20% by weight or less. If the content of the photopolymerization initiator is too small, the sensitivity may be lowered. On the other hand, if the content is too large, the solubility of the unexposed light part in the developing solution is lowered, and development defects are likely to be induced.
  • the content thereof can be selected in the range of usually 1 to 70% by weight with respect to the total solid content in the photosensitive colored resin composition of the present invention. Within this range, 10 to 70% by weight is more preferable, but 20% to 60% by weight is particularly preferable. If the content of the coloring material is too small, the film thickness with respect to the color density becomes too large, which adversely affects the gap control when forming a liquid crystal cell. On the other hand, if the content of the color material is too large, sufficient image formability may not be obtained.
  • the above-mentioned [1] urethane-based dispersed resin is used as the content with respect to the color material component in the photosensitive colored resin composition.
  • it is at least 10% by weight, preferably at least 20% by weight, particularly preferably at least 30% by weight, usually at most 300% by weight, preferably at most 100% by weight, particularly preferably at most 80% by weight.
  • the amount of the nitrogen atom-containing dispersant is too small, adsorption to the coloring material is insufficient and aggregation cannot be prevented, resulting in increased viscosity or gelling.
  • the amount is too large, the film thickness is increased. Both of them are not preferable because a cell gap control defect may occur in the liquid crystal cell process after the color filter is formed.
  • the content relative to the color material component in the photosensitive colored resin composition is usually 10% by weight or more, preferably 20% by weight or more. Particularly preferably, it is at least 30% by weight, usually at most 300% by weight, preferably at most 100% by weight, particularly preferably at most 80% by weight. If the amount of the dispersant component is too small, the adsorption to the coloring material is insufficient and aggregation cannot be prevented, and the viscosity or gelation may occur. On the other hand, if the amount is too large, the film thickness becomes too thick. In this case, after the color filter is formed, cell gap control failure may occur in the liquid crystal cell forming process.
  • the content relative to the color material component in the photosensitive colored resin composition is usually 10% by weight or more, preferably 20% by weight or more. Particularly preferably, it is at least 30% by weight, usually at most 300% by weight, preferably at most 100% by weight, particularly preferably at most 80% by weight. If the amount of the dispersant component is too small, the adsorption to the coloring material is insufficient and aggregation cannot be prevented, and the viscosity or gelation may occur. On the other hand, if the amount is too large, the film thickness becomes too thick. In this case, after the color filter is formed, cell gap control failure may occur in the liquid crystal cell forming process.
  • the phosphate ester type dispersant is usually 5 parts by weight or more, preferably 10 parts by weight or more, and usually 100 parts by weight or less based on 100 parts by weight of the [3] block copolymer. It is preferable to use 80 parts by weight or less. If the proportion of the phosphate ester type dispersant is too small, sufficient development solubility may not be exhibited. On the other hand, if the proportion of the ester phosphate dispersant is too large, the effect is saturated and the dispersibility may be lowered.
  • a photopolymerizable monomer When a photopolymerizable monomer is used, its content is usually 90% by weight or less, preferably 80% by weight or less, based on the total solid content of the photosensitive resin composition of the present invention.
  • Photopolymerizable module If the content of the nomer is too large, the permeability of the developing solution to the exposed area becomes high, and it becomes difficult to obtain a good image.
  • the lower limit of the content of the photopolymerizable monomer is usually 0% by weight or more, preferably 5% by weight or more.
  • the photosensitive resin composition of the present invention is a photosensitive resin composition for image formation, black matrix use, overcoat use, rib use, and spacer use for power filters used in liquid crystal panels such as liquid crystal displays. Useful as. Further, the photosensitive resin composition of the present invention can be used not only for color filters, but also for solder resists for flexible printed wiring boards, plating resists, correlation insulating films for multilayer printed wiring boards, photosensitive optical waveguides, and photocurable liquid crystals. It is useful as a seal material, photo-curing EL seal material, photo-curing adhesive and so on.
  • the color filter of the present invention can be produced by providing a black matrix on a transparent substrate and forming pixel images of red, green, and blue, and the photosensitive coloring layer of the present invention containing a coloring material.
  • the fat composition is used as a resist-forming coating solution of at least one of black, red, green, and blue.
  • Black resist is formed on the glass substrate surface on the transparent substrate, red, green, and blue are formed on the resin black matrix forming surface formed on the transparent substrate, or using a chromium compound or other light shielding metal material.
  • a pixel image of each color is formed on the metal black matrix forming surface by performing coating, heat drying, image exposure, development and thermosetting.
  • the photosensitive resin composition of the present invention that does not contain a coloring material is used as a photosensitive resin composition for overcoats, ribs, and spacers.
  • the transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength.
  • the material include polyester resin such as polyethylene terephthalate, polyolefin resin such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone thermoplastic resin sheet, epoxy resin, and unsaturated resin.
  • thermosetting resin sheets such as polyester resin and poly (meth) acrylic resin, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.
  • transparent substrates and black matrix-formed substrates may contain various resins such as corona discharge treatment, ozone treatment, silane coupling agents, and urethane-based resins. A thin film forming process or the like may be performed.
  • the thickness of the transparent substrate is usually in the range of 0.05 to: LOmm, preferably 0.1 to 7 mm.
  • the film thickness is usually in the range of 0.01 to 10 m, preferably 0.05 to 5 m.
  • the black matrix is formed on a transparent substrate using a light-shielding metal thin film or a photosensitive colored resin composition for resin black matrix.
  • a light-shielding metal thin film or a photosensitive colored resin composition for resin black matrix As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide, and chromium nitride, nickel and tungsten alloy, etc. are used, and these may be laminated in a plurality of layers.
  • These metal light-shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape by a positive type photoresist, cerium nitrate ammonium and perchlorine are applied to chromium. Etching solution mixed with acid and Z or nitric acid is used. For other materials, etching is performed using an etching solution according to the material, and finally the positive photoresist is removed with a special release agent. A black matrix can be formed.
  • a thin film of these metals or metal 'metal oxide is formed on the transparent substrate by vapor deposition or sputtering.
  • the coating film was exposed and developed using a photomask having a repetitive pattern such as stripes, mosaics and triangles to form a resist image. To do. Thereafter, this coating film can be etched to form a black matrix.
  • the photosensitive colored rosin composition of the present invention containing a black colorant is used to form a black matrix.
  • a black colorant such as carbon black, graphite, iron black, vanillin black, cyanine black, and titanium black, or red, green, and the like appropriately selected from inorganic or organic pigments and dyes
  • a method for forming the following red, green, and blue pixel images using a photosensitive colored resin composition containing a black color material mixed with blue or the like, and Similarly, a black matrix can be formed.
  • a photosensitive colored resin composition containing a color material of one color of red, green and blue is applied and dried, and then a photomask is superimposed on the coating film, Through this photomask, a pixel image is formed by image exposure, development, and if necessary, heat curing or photocuring to create a colored layer.
  • a color filter image can be formed by performing this operation for each of the three colored photosensitive colored resin compositions of red, green, and blue.
  • the photosensitive colored resin composition for the color filter can be applied by 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.
  • the die coating method significantly reduces the amount of coating solution used and suppresses the generation of foreign substances that are completely free from the effects of mist adhering to the spin coating method.
  • the film thickness after drying is usually preferably in the range of 0.2 to 20 m, more preferably in the range of 0.5 to 10 / ⁇ ⁇ , and even more preferably 0. Range of 8-5 m.
  • the coating film after the photosensitive colored resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a competition oven. 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 15 seconds to 5 minutes at a temperature of 40 to 200 ° C, preferably 50 to 130 ° C, depending on the type of solvent component and the performance of the dryer used.
  • the temperature is selected from 30 seconds to 3 minutes.
  • this The drying process of the coating film may be a reduced-pressure drying method in which drying is performed in the reduced-pressure chamber without increasing the temperature.
  • Image exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive colored resin composition and irradiating a UV or visible light source through this mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyhydric alcohol layer is formed on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. .
  • the light source used for the image exposure is not particularly limited. Examples of light sources include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal lamps, ride lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, and argon ion lasers. Laser light sources such as YAG laser, excimer laser, nitrogen laser, helium-powered dominum laser, and semiconductor laser. When irradiating light of a specific wavelength, use an optical filter.
  • the color filter according to the present invention comprises an organic solvent or an aqueous solution containing a surfactant and an alkaline compound after image-exposing a coating film made of a photosensitive colored resin composition with the above-mentioned light source. An image can be formed on the substrate by development to be used.
  • This aqueous solution may further contain 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, Ethylenedimine, tetramethylammonium hydroxide (TMAH), choline Organic alkaline compounds such as These alkaline compounds may be a mixture of two or more.
  • TMAH tetramethylammonium hydroxide
  • surfactant examples 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, alkyl betaines, amino acids, etc. Agents.
  • organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butylcetosolve, phenylsolvesolve, propylene glycol, diacetone alcohol and the like.
  • the organic solvent may be used alone or in combination with an aqueous solution.
  • the development processing conditions are not particularly limited.
  • the development temperature is in the range of 10 to 50 ° C, especially 15 to 45 ° C, particularly preferably 20 to 40 ° C. , Spray developing method, brush developing method, ultrasonic developing method and the like.
  • thermosetting treatment The color filter substrate after development is subjected to thermosetting treatment.
  • the temperature of the thermosetting treatment is selected in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes.
  • the formation of one-color pattern image is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter.
  • the order of the four-color patterning is not limited to the order described above.
  • Color filters are used as part of parts such as color displays and liquid crystal display devices by forming transparent electrodes such as ITO on the image as they are.
  • transparent electrodes such as ITO
  • a top coat layer such as polyamide or polyimide can be provided on the image.
  • the transparent electrode may not be formed.
  • a photosensitive resin composition dissolved or dispersed in a solvent is supplied into a film or pattern by a method such as coating on a substrate on which a spacer is to be provided, the solvent is dried.
  • a pattern is formed by a method such as photolithography in which exposure and development are performed if necessary.
  • a spacer is formed on the substrate by performing a thermosetting treatment if necessary.
  • the photosensitive resin 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 barber method, a flow coating method, a die coating method, a roll coating method, a spray coating method or the like can be used. Further, it may be supplied in a pattern by an inkjet method or a printing method.
  • 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. I also like a strong viewpoint.
  • 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 Is 8 ⁇ m or less, particularly preferably 5 m or less.
  • the drying after supplying the photosensitive resin composition on the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a competition 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 15 seconds to 5 minutes at a temperature of 40 to 100 ° C, preferably 50 to 90 ° C, depending on the type of solvent component and the performance of the dryer used. At temperature 30 It is selected in the range of seconds to 3 minutes.
  • the exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive resin composition and irradiating an ultraviolet or visible light source through this mask pattern. Further, a scanning exposure method using a laser beam may be used. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen.
  • the light source used for the exposure is not particularly limited.
  • Examples of light sources include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, and fluorescent lamps, as well as argon ion lasers and YAG lasers.
  • Laser light sources such as excimer laser, nitrogen laser, helium-powered Dominium laser, blue-violet semiconductor laser, and near-infrared semiconductor laser.
  • An optical filter can also be used when irradiating with a specific wavelength of light.
  • an image pattern can be formed on the substrate by development using an aqueous solution containing an alkaline compound and a surfactant or an organic solvent.
  • This aqueous solution can further contain organic solvents, buffering agents, complexing agents, dyes or pigments.
  • 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 alkaline compounds. These alkaline compounds may be a mixture of two or more.
  • the surfactant 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.
  • organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butylcetosolve, phencelesolve, propylene glycol, diaceton alcohol and the like.
  • the organic solvent can be used alone or in combination with a good aqueous solution.
  • the substrate after development is preferably subjected to a 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.
  • a rib (liquid crystal split alignment protrusion) is a protrusion formed on a transparent electrode in order to improve the viewing angle of a liquid crystal display device. By using the slope of the protrusion, the liquid crystal is locally tilted. The liquid crystal is divided in multiple directions. Hereinafter, a method for forming the rib will be described in detail.
  • the photosensitive resin composition of the present invention is spinnered on a transparent substrate having a thickness of 0.1 to 2 mm, on which a black matrix and color filters of red, blue and green are further deposited, and further, ITO having a thickness of 150 nm is deposited thereon.
  • a coating device such as wire bar, flow coater, die coater, roll coater or spray.
  • the coating thickness of the composition is usually 0.5 to 5 m.
  • a photomask is placed on the dried coating film, and image exposure is performed through the photomask. After exposure, pixels are formed by removing unexposed uncured portions by development.
  • the image obtained after development has a width of 5-20 / ⁇ ⁇ Thin line reproducibility is required, and there is a tendency for higher fine line reproducibility to be demanded due to the demand for high-quality displays.
  • the cross-sectional shape of the fine line image after development is a rectangular shape with clear contrast between the non-image and the image area, such as development time, developer aging, physical stimulation of the development shower, etc. A wide development margin is preferred.
  • the developed image has a cross-sectional shape close to a rectangular shape.
  • the arched shape necessary for the rib shape it is usually 150 ° C or higher, preferably 180 ° C or higher, more preferably 200 ° C or higher, usually 400 ° C or lower, preferably 300 ° C or lower, further
  • the heat treatment is performed at 280 ° C. or lower and usually 10 minutes or longer, preferably 15 minutes or longer, more preferably 20 minutes or longer, usually 120 minutes or shorter, preferably 60 minutes or shorter, more preferably 40 minutes or shorter.
  • the rectangular cross-sectional shape is transformed into an arch shape to form ribs having a width of 0.5 to 20 / ⁇ ⁇ and a height of 0.2 to 5 / ⁇ ⁇ .
  • the photosensitive resin composition and heating conditions are adjusted as appropriate, and the contact angle (W1) formed from the side surface of the thin line image (rectangular image cross-sectional shape) before heating and the substrate plane is
  • W1ZW2 is 1.2 or more, preferably 1.3 or more, more preferably 1.5 or more, usually 10 or less. , Preferably 8 or less.
  • the higher the heating temperature or the longer the heating time the larger the deformation rate. Conversely, the lower the heating temperature or the shorter the heating time, the lower the deformation rate.
  • an alignment film is usually formed on a color filter, a spacer is spread on the alignment film, and a liquid crystal cell is formed by bonding to a counter substrate, and a liquid crystal cell is formed on the formed liquid crystal cell. And is connected to the counter electrode to complete.
  • a resin film such as polyimide is suitable.
  • a gravure printing method and a wrinkle or flexographic printing method are usually employed, and the thickness of the alignment film is set to several lOnm.
  • the surface treatment is performed by treatment with a rubbing cloth, which is irradiated with ultraviolet rays, so that the surface state is adjusted so that the inclination of the liquid crystal can be adjusted.
  • the spacer a spacer having a size corresponding to the gap (gap) with the counter substrate is used, and a spacer of 2 to 8 m is usually preferable.
  • the photo A photospacer (PS) with a transparent resin film can be formed by sography, and this can be used in place of the spacer.
  • An array substrate is usually used as the counter substrate.
  • a TFT (thin film transistor) substrate is suitable.
  • the gap for bonding to the counter substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 to 8 m.
  • the portions other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin.
  • the sealing material is cured by UV irradiation and Z or heating, and the periphery of the liquid crystal cell is sealed.
  • the liquid crystal cell whose periphery is sealed is cut into panels, and then the pressure is reduced in the vacuum chamber. After the liquid crystal inlet is immersed in the liquid crystal, the inside of the chamber leaks. Liquid crystal is injected into the liquid crystal cell. Decompression degree in the liquid crystal cell is usually a 1 X 10- 2 ⁇ 1 X 1 0- 7 Pa, preferably 1 X 10- 3 ⁇ 1 X 10- 6 Pa. In addition, it is preferable that the liquid crystal cell is heated at the time of depressurization. The heating temperature is usually 30 to 100 ° C, more preferably 50 to 90 ° C. Heating during decompression is usually in the range of 10 to 60 minutes and then immersed in the liquid crystal. A liquid crystal cell filled with liquid crystal is completed by sealing the liquid crystal injection port with a UV curable resin, thereby completing the liquid crystal display (panel).
  • Liquid crystal types that are conventionally known, such as aromatic, aliphatic, and polycyclic compounds that are not particularly limited, may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like.
  • Nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known as thermo-mouth pick liquid crystals, but they may be misaligned.
  • Bisphenol A-type epoxy compound (following formula (3), epoxy equivalent 186 gZeq) 100 parts, acrylic acid 40 parts, p-methoxyphenol 0.06 parts, polypropylene phosphine 2.4 parts, propylene glycol monomethyl
  • the reaction vessel was charged with 126 parts of ether acetate and stirred at 95 ° C until the acid value was 5 mg-KOHZg or less. It took 10 hours for the acid value to reach the target (acid value 1.0).
  • 40 parts of propylene glycol monomethyl ether acetate was added to the resulting reaction solution, 19.5 parts of isophorone diisocyanate was added, and the mixture was reacted at 90 ° C for 3 hours, and trimellitic anhydride 39.
  • Bisphenol A type epoxy compound (formula (3) above, epoxy equivalent 186 g / eq) 100 parts, acrylic acid 40 parts, p-methoxyphenol 0.06 parts, phenylphenolphosphine 2.4 parts, propylene
  • the reaction vessel was charged with 126 parts of glycol monomethyl ether acetate and stirred at 95 ° C until the acid value was 5 mg-KOHZg or less. It took 10 hours for the acid value to reach the target (acid value 1.0).
  • 40 parts of propylene glycol monomethyl ether acetate was added to the resulting reaction solution, 17.5 parts of isophorone diisocyanate was added, and 90 ° C was added.
  • trimellitic anhydride For 4 hours, and then add 46.8 parts of trimellitic anhydride, react at 90 ° C for 3 hours, acid value 136, alkali-soluble unsaturated with polystyrene equivalent weight average molecular weight of 2840 measured by GPC A rosin (A-IV) solution was obtained.
  • Fluorene bisphenol type epoxy compound (following formula (4), epoxy equivalent 231gZeq) 100 parts, reaction mixture of succinic anhydride and tris (atariloy oxymethyl) ethanol (acid value 90.5) 273.2 parts, p-methoxyphenol 0.19 parts, 7.4 parts of triphenylphosphine, and 368 parts of propylene glycol monomethyl ether acetate were charged in a reaction vessel and stirred at 90 ° C. until the acid value was 5 mg-KOH / g or less. It took 10 hours for the acid value to reach the target (acid value 1.0).
  • Fluorene bisphenol type epoxy compound (formula (4), epoxy equivalent 231g / eq) 100 parts, reaction mixture of succinic anhydride and tris (atariloy oxymethyl) ethanol (acid value 90.5) 273.2 parts, p— Methoxyphenol 0.19 parts, Triphenylphosphine 7.4 parts, 368 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel and stirred at 90 ° C. until the acid value was 5 mg-KOHZg or less. It took 10 hours for the acid value to reach the target (acid value 1.0).
  • a photosensitive black resin composition was obtained in the same manner as in Example 1 except that the alkali-soluble unsaturated resin (AI) was changed to the alkali-soluble unsaturated resin (A-III), and a black pixel was formed. It was.
  • a photosensitive black resin composition was obtained in the same manner as in Example 1 except that the alkali-soluble unsaturated resin (A-I) was changed to the alkali-soluble unsaturated resin (A-VII), and further black pixels were formed.
  • a photosensitive black resin composition was obtained in the same manner as in Example 1 except that the alkali-soluble unsaturated resin (A-I) was changed to the alkali-soluble unsaturated resin (A-VIII), and further black pixels were formed.
  • a photosensitive black resin composition was obtained in the same manner as in Example 1 except that the alkali-soluble unsaturated resin (AI) was changed to the alkali-soluble unsaturated resin (A-II), and a black pixel was formed. It was.
  • the minimum resist pattern size that can be resolved at an exposure that faithfully reproduces a 20 ⁇ m mask pattern was observed with a microscope at a magnification of 200 times.
  • the minimum pattern dimension of 10 m or less was defined as good adhesion, and the pattern exceeding 10 m was defined as adhesion inferior.
  • a pixel pattern with good linearity is defined as pixel sharpness
  • a resist pattern with protrusions or irregularities is defined as pixel sharpness inferior.
  • the photosensitive black coffin composition is stored for 2 weeks under two conditions of 35 ° C and 10 ° C.
  • the time required for development was compared. Those with a development time of 10% or more were designated as storage stability inferior, those with a change rate of less than 5% as good storage stability, and those with less than 1% as storage stability very good.
  • the minimum development time means a time during which the unexposed area is completely dissolved under the same image condition.
  • the recovery rate of the space server turn obtained in (2) above by load-unloading was evaluated by a load-unloading test using Shimadzu Dynamic Ultra Hardness Tester “DUH-W201 S”.
  • the obtained photosensitive resin composition was stored sealed at 70 ° C. for 72 hours, and the degree of change in viscosity when left at room temperature was determined from the following formula.
  • Degree of change (%) [(viscosity of products stored at 70 ° C for 72 hours) one (viscosity of products stored at room temperature)]
  • a photosensitive resin composition excellent in storage stability provides a spacer excellent in handleability after long-term storage. Can be formed.

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Abstract

A photosensitive resin composition comprising an alkali-soluble unsaturated resin as an organic binder produced by reacting an epoxy compound (a) having two or more epoxy groups in its molecule with an unsaturated group-containing carboxylic acid (b)and further reacting the reaction product with an isocyanate group-containing compound (c). A photosensitive resin composition comprising an alkali-soluble unsaturated resin produced by reacting a phenolic hydroxyl group-containing compound (f) having two or more phenolic hydroxyl groups in its molecule with an unsaturated group-containing epoxy compound (g) and further reacting the reaction product with an isocyanate group-containing compound (c).

Description

明 細 書  Specification
感光性樹脂組成物、カラーフィルタ及び液晶表示装置  Photosensitive resin composition, color filter, and liquid crystal display device
発明の分野  Field of Invention
[0001] 本発明は、液晶ディスプレイ等の液晶パネルに用いられるカラーフィルタの画像形 成用、ブラックマトリックス用、オーバーコート用、リブ用、及びスぺーサー用として好 適な感光性榭脂組成物と、この感光性榭脂組成物を用いたカラーフィルタ及び液晶 表示装置に関する。  The present invention relates to a photosensitive resin composition suitable for image formation, black matrix use, overcoat use, rib use, and spacer use for color filters used in liquid crystal panels such as liquid crystal displays. And a color filter and a liquid crystal display device using the photosensitive resin composition.
発明の背景  Background of the Invention
[0002] 従来、液晶ディスプレイ等の液晶パネルに用いられるカラーフィルタのカラー画素、 ブラックマトリックス、オーバーコート、リブ及びスぺーサ一等の形成には、榭脂、光重 合性モノマー及び光重合開始剤等からなる感光性樹脂組成物 (レジスト)が用いられ てきた。カラーフィルタ用レジストには、現像性、パターン精度、密着性等の観点から 種々の組成が提案されている力 その一つとして、形成プロセスにおける処理時間の 短縮、歩留まりの向上を目的として、上記榭脂組成物に含まれる榭脂として、ェポキ シ榭脂と不飽和基含有カルボン酸又はその無水物との反応物を更に多塩基性カル ボン酸又はその無水物と反応させて得られる不飽和基含有榭脂を用いた技術が開 示されている（特開 2001— 174621号公報、特許第 2878486号、特開平 10— 168 033号公報)。  [0002] Conventionally, for forming color pixels, black matrix, overcoat, ribs, spacers, etc. of color filters used in liquid crystal panels such as liquid crystal displays, resin, photopolymerizable monomers and photopolymerization are started. A photosensitive resin composition (resist) made of an agent or the like has been used. Various resist compositions have been proposed for color filter resists from the viewpoints of developability, pattern accuracy, adhesion, etc. As one of them, for the purpose of shortening the processing time in the forming process and improving the yield, Unsaturated groups obtained by further reacting a reaction product of epoxy resin with unsaturated group-containing carboxylic acid or its anhydride with polybasic carboxylic acid or its anhydride as sallow contained in the fat composition Techniques using the contained rosin have been disclosed (Japanese Patent Laid-Open No. 2001-174621, Japanese Patent No. 2878486, Japanese Patent Laid-Open No. 10-168 033).
[0003] 一方、塗料分野にお 、ても多様な榭脂組成物は開示されており、例えば、ペンダン ト基と 2価の反応基とを有する化合物分子中に 2個のイソシァネート基を有する化合 物との反応生成物力もなる榭脂を用いた組成物にっ 、て開示されて 、る (USP510 9097)。しカゝしながら、このような塗料としての榭脂組成物を、現像等の操作を必要と し、その際の微細加工精度等が期待されるレジストに転用することは、その目的が異 なる上、適用性や効果が当業者によって予測できるものではないため、このような塗 料用榭脂組成物をカラーフィルタ用レジスト等に供することはなされて 、な 、。  [0003] On the other hand, various resin compositions have been disclosed in the paint field. For example, compounds having two isocyanate groups in a compound molecule having a pendant group and a divalent reactive group are disclosed. US Pat. No. 5,010,977 discloses a composition using a resin that also has a reaction product with a product. However, the purpose of diverting the resin composition as such a paint to a resist that requires an operation such as development and is expected to have fine processing accuracy at that time is different. In addition, since applicability and effects cannot be predicted by those skilled in the art, such a resinous resin composition is not used for color filter resists.
[0004] し力しながら、従来の液晶パネル等に用いられる上述のレジストは、エポキシ榭脂と 不飽和基含有カルボン酸又はその無水物との反応物からなる構成単位に、多塩基 性カルボン酸又はその無水物を反応させて形成されるエステルで架橋しているため 、保存中にエステル部分の解裂が起こる場合、エステル架橋であるがために分子量 の変化等により、粘度、現像速度等の榭脂特性、ひいてはレジスト特性に大幅な変 化を生じる。この結果、塗布プロセスや、画像形成プロセスでのトラブル等が引き起こ される。 [0004] However, the above-described resist used in conventional liquid crystal panels and the like is polybasic in a structural unit composed of a reaction product of epoxy resin and unsaturated group-containing carboxylic acid or anhydride thereof. When the ester moiety is cleaved during storage because it is crosslinked with a reactive carboxylic acid or its anhydride, the viscosity and development may occur due to changes in molecular weight due to the ester crosslinking. It causes significant changes in speed and other properties of the resin, and in turn the resist properties. As a result, troubles in the coating process and the image forming process are caused.
[0005] また、上記感光性着色榭脂組成物を包含する、光によって重合し得る成分と光重 合開始剤とバインダー榭脂とを含有する感光性榭脂組成物においては、一般に塗 布'乾燥 '露光'現像の工程を経る光リソグラフイエ程に供される。そのため、かかるェ 程において、  [0005] In addition, a photosensitive resin composition containing a component that can be polymerized by light, a photopolymerization initiator, and a binder resin, including the above-described photosensitive colored resin composition, is generally coated. It is subjected to the process of photolithography through a process of drying 'exposure' and development. Therefore, in this process,
現像工程での除去部分に残渣ゃ地汚れが生じな 、こと；  Residual stains will not occur on the removed parts in the development process;
除去部分が十分な溶解性を有すること;及び  The removed portion has sufficient solubility; and
パターンエッジのシャープさなどの画素形成性を上げること；  Increase pixel formation such as sharpness of pattern edges;
力 常に求められている。し力しながら、上記のような色材の含量が高い感光性着色 榭脂組成物を用いて画素を形成した場合、  Power is always required. However, when a pixel is formed using a photosensitive colored resin composition having a high colorant content as described above,
現像工程で未露光部の基板上に残渣ゃ地汚れが生じる；  Residual stains occur on the unexposed substrate in the development process;
未露光部に良好な溶解性が得られな 、などのために、画素のエッジ形状のシヤー プ性に劣る；及び  The edge shape of the pixel is inferior in shape due to, for example, good solubility in unexposed areas; and
露光部に形成された画素の感度が十分ではなく表面平滑性が悪い；  The sensitivity of the pixels formed in the exposed area is not sufficient and the surface smoothness is poor;
t 、う現象が顕著に生じやす 、。  t.
[0006] 榭脂ブラックマトリックスのように光の全波長領域において遮光能力が要求される場 合では、 [0006] When a light blocking capability is required in the entire wavelength region of light, such as a rosin black matrix,
露光部分と未露光部分における架橋密度の差をつけることが著しく困難なこと； 露光された部分でも膜厚方向に対する架橋密度の差が発生すること、つまり、光照 射面側では十分に硬化しても、基底面側では硬化しな!、こと;及び  It is extremely difficult to make a difference in the crosslink density between the exposed and unexposed areas; a difference in the crosslink density in the film thickness direction occurs even in the exposed areas, that is, it is sufficiently cured on the light-exposed surface side. However, it will not harden on the base side!
現像液に不溶な多量な黒色色材を配合するため、現像性の低下が著しいこと； 等が、良好な感光特性を付与する上で障害となって 、る。  Since a large amount of black color material that is insoluble in the developer is blended, there is a significant decrease in developability; and the like is an obstacle to imparting good photosensitive properties.
発明の概要  Summary of the Invention
[0007] 本発明は、基板との密着性が良好で、顔料やカーボンブラックなどの色材を高い濃 度で含有する場合であっても、顔料等を必要としないフォトスぺーサーゃリブ用の場 合であっても、感度及び溶解性のバランスに優れ、更には画素エッジ形状やテーパ 一形状のシャープ性、密着性、表面平滑性、地汚れ防止性、耐熱性、更には保存安 定性に優れる感光性榭脂組成物を提供することを目的とする。 [0007] The present invention has good adhesion to a substrate, and a coloring material such as pigment or carbon black is highly concentrated. Even if it is contained at a high degree, or for photospacer ribs that do not require pigments, etc., it has an excellent balance of sensitivity and solubility, and further, sharpness of pixel edge shape and taper shape An object of the present invention is to provide a photosensitive resin composition that has excellent properties, adhesion, surface smoothness, anti-stain properties, heat resistance, and storage stability.
[0008] 本発明はまた、このような感光性榭脂組成物を使用して、高品質なカラーフィルタ、 更には高品質な液晶表示装置を提供することを目的とする。  [0008] Another object of the present invention is to provide a high-quality color filter and further a high-quality liquid crystal display device using such a photosensitive resin composition.
[0009] 第 1アスペクトの感光性榭脂組成物は、有機結合材を含有する感光性榭脂組成物 であって、該有機結合材が、分子内に少なくとも 2個以上のエポキシ基を有するェポ キシィ匕合物（a)と、不飽和基含有カルボン酸 (b)との反応物を、更にイソシァネート基 を有する化合物 (c)と反応させることにより得られるアルカリ可溶性不飽和榭脂を含 有する。  [0009] The photosensitive resin composition of the first aspect is a photosensitive resin composition containing an organic binder, and the organic binder has at least two epoxy groups in the molecule. It contains an alkali-soluble unsaturated resin obtained by reacting a reaction product of a polyoxy compound (a) with an unsaturated group-containing carboxylic acid (b) with a compound (c) having an isocyanate group. .
[0010] 第 2アスペクトの感光性榭脂組成物は、有機結合材を含有する感光性榭脂組成物 であって、該有機結合材が、分子内に少なくとも 2個以上のフ ノール性水酸基を有 するフエノール性水酸基含有化合物 (f)と、不飽和基含有エポキシ化合物 (g)との反 応物を、更にイソシァネート基を有する化合物（c)と反応させることにより得られるァ ルカリ可溶性不飽和榭脂を含有する。  [0010] The photosensitive resin composition of the second aspect is a photosensitive resin composition containing an organic binder, and the organic binder has at least two or more phenolic hydroxyl groups in the molecule. An alkaline soluble unsaturated resin obtained by reacting a reaction product of the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g) with a compound (c) further having an isocyanate group. Containing.
図面の簡単な説明  Brief Description of Drawings
[0011] [図 1]フォトスぺーサ一形成評価における負荷 除荷試験の最大変位 H [max]及び 最終変位 H [Last]を示す模式図である。  FIG. 1 is a schematic diagram showing a maximum displacement H [max] and a final displacement H [Last] of a load unloading test in a photospacer formation evaluation.
発明の好ましレ、形態の詳細な説明  Detailed description of preferred embodiments and forms of the invention
[0012] 第 1アスペクトの感光性榭脂組成物は、有機結合材を含有する感光性榭脂組成物 であって、該有機結合材が、分子内に少なくとも 2個以上のエポキシ基を有するェポ キシィ匕合物（a)と、不飽和基含有カルボン酸 (b)との反応物を、更にイソシァネート基 を有する化合物 (c)と反応させることにより得られるアルカリ可溶性不飽和榭脂を含 有する。 [0012] The photosensitive resin composition of the first aspect is a photosensitive resin composition containing an organic binder, and the organic binder has at least two epoxy groups in the molecule. It contains an alkali-soluble unsaturated resin obtained by reacting a reaction product of a polyoxy compound (a) with an unsaturated group-containing carboxylic acid (b) with a compound (c) having an isocyanate group. .
[0013] エポキシィ匕合物（a)は、下記一般式 (I— a)で表される化合物を含んでもよい。  [0013] The epoxy compound (a) may include a compound represented by the following general formula (I-a).
[化 1] CH2_CH _CH2— O— X O— CH2— CH— CH2 ■( I ~ a) \ / \ / [Chemical 1] CH 2 _CH _CH 2 — O— XO— CH 2 — CH— CH 2 ■ (I ~ a) \ / \ /
o o  o o
Figure imgf000006_0001
ノ
Figure imgf000006_0001
No
[0014] 第 2アスペクトの感光性榭脂組成物は、有機結合材を含有する感光性榭脂組成物 であって、該有機結合材が、分子内に少なくとも 2個以上のフ ノール性水酸基を有 するフエノール性水酸基含有化合物 (f)と、不飽和基含有エポキシ化合物 (g)との反 応物を、更にイソシァネート基を有する化合物（c)と反応させることにより得られるァ ルカリ可溶性不飽和榭脂を含有する。 [0014] The photosensitive resin composition of the second aspect is a photosensitive resin composition containing an organic binder, and the organic binder has at least two or more phenolic hydroxyl groups in the molecule. An alkaline soluble unsaturated resin obtained by reacting a reaction product of the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g) with a compound (c) further having an isocyanate group. Containing.
[0015] フエノール性水酸基含有化合物 (f)は、下記一般式 (I f)で表される化合物を含 んでもよい。  [0015] The phenolic hydroxyl group-containing compound (f) may include a compound represented by the following general formula (I f).
[化 2] [Chemical 2]
HO— X— OH --- ( I -f) HO— X— OH --- (I -f)
Figure imgf000007_0001
ノ
Figure imgf000007_0001
No
[0016] 化合物 ）は、イソシァネート基を分子内に 2個以上有してもよい。 [0016] The compound) may have two or more isocyanate groups in the molecule.
[0017] 一般式 (I a)及び前記一般式 (I f)における Xは、下記一般式 (ΠΑ)、（ΠΒ)、 (II [0017] X in the general formula (I a) and the general formula (I f) represents the following general formula (式), (ΠΒ), (II
C)の!、ずれかであってもよ!/、。 C)!
[化 3] [Chemical 3]
Figure imgf000008_0001
Figure imgf000008_0001
Figure imgf000008_0002
上記一般式 (ΠΑ)、 (ΙΙΒ)、 (IIC)中、 I^ R16及び nは前記一般式 (II)におけると同 義である。
Figure imgf000008_0002
In the general formulas (ΠΑ), (ΙΙΒ), and (IIC), I ^ R 16 and n have the same meaning as in the general formula (II).
一般式 (ΠΑ)は、下記一般式 (IIAa)又は（IIAb)であってもよ 、。  The general formula (ΠΑ) may be the following general formula (IIAa) or (IIAb).
[化 4] [Chemical 4]
Figure imgf000009_0001
上記一般式 (IIAa)、 （IIAb)中、 R1, R2は前記一般式 (II)におけると同義である。
Figure imgf000009_0001
In the general formulas (IIAa) and (IIAb), R 1 and R 2 have the same meaning as in the general formula (II).
[0019] 第 1、第 2アスペクトの感光性榭脂組成物は、更に光重合開始剤を含有してもよい。 [0019] The photosensitive resin compositions of the first and second aspects may further contain a photopolymerization initiator.
[0020] 第 1、第 2アスペクトの感光性榭脂組成物は、更に色材を含有してもよい。 [0020] The photosensitive resin compositions of the first and second aspects may further contain a coloring material.
[0021] 本発明の感光性榭脂組成物を用いてカラーフィルタが形成されてもよい。 A color filter may be formed using the photosensitive resin composition of the present invention.
[0022] 本発明の感光性榭脂組成物を用いて形成された部材、例えばカラーフィルタ、スぺ ーサ一、リブ材等は、液晶表示装置に用いられ得る。 [0022] Members formed using the photosensitive resin composition of the present invention, such as color filters, spacers, rib materials, and the like, can be used in liquid crystal display devices.
[0023] 本発明の感光性榭脂組成物は、基板との密着性が良好である。この感光性榭脂組 成物は、顔料やカーボンブラックなどの色材を高い濃度で含有する場合でも、また顔 料等を必要としな 、フォトスぺーサーゃリブ用の場合でも、感度及び溶解性のバラン スに優れ、更には画素エッジ形状やテーパー形状のシャープ性、密着性、表面平滑 性、地汚れ防止性、耐熱性、更には保存安定性に優れる。この感光性榭脂組成物を 使用して、高品質なカラーフィルタ、更には高品質な液晶表示装置を提供することが できる。 [0023] The photosensitive resin composition of the present invention has good adhesion to the substrate. This photosensitive resin composition is sensitive and soluble even when it contains pigments and color materials such as carbon black at a high concentration, and even when it is used for a photospacer rib that does not require a pigment. In addition, it has excellent pixel edge shape and taper shape sharpness, adhesion, surface smoothness, antifouling property, heat resistance, and storage stability. By using this photosensitive resin composition, it is possible to provide a high-quality color filter and further a high-quality liquid crystal display device.
[0024] 以下に本発明の好ましい形態をさらに詳細に説明する。  [0024] Preferred embodiments of the present invention are described in more detail below.
[0025] <アルカリ可溶性不飽和榭脂 > [0025] <Alkali-soluble unsaturated rosin>
本発明の感光性榭脂組成物に含まれる有機結合材としてのアルカリ可溶性不飽和 榭脂は、結果的に本願請求項に記載される化合物と同様の化学構造を持っているも のであれば、本願発明の目的及び効果を達するので、その製造方法については特 に限定されないが、例えば、下記の [A—1]又は [A— 2]を挙げることができる。 Alkali-soluble unsaturation as an organic binder contained in the photosensitive resin composition of the present invention As long as the resin has a chemical structure similar to that of the compound described in the claims of the present application, the purpose and effect of the present invention are achieved, so the production method is not particularly limited. For example, the following [A-1] or [A-2] can be mentioned.
[0026] [A— 1]分子内に少なくとも 2個以上のエポキシ基を有するエポキシィ匕合物（a)と、不 飽和基含有カルボン酸 (b)との反応物を、更にイソシァネート基を有する化合物（c) と反応させることにより得られるアルカリ可溶性不飽和榭脂。このアルカリ可溶性不飽 和榭脂は、エポキシ化合物 (a)と不飽和基含有カルボン酸 (b)との反応物の水酸基 にイソシァネート基を有する化合物（c)を付加させた後、酸価の調整のために更に多 塩基酸無水物（d)を付加させたものであることが好ましい。また、エポキシ化合物（a) と不飽和基含有カルボン酸 (b)との反応物のイソシァネートイ匕合物（c)付加物に、多 塩基酸無水物（d)を付加させた後、更に、生成したカルボキシル基の一部にェポキ シ基含有化合物 (e)を付加させたものであっても良!、。 [0026] [A-1] Compound having an isocyanate group further obtained by reacting an epoxy compound (a) having at least two epoxy groups in the molecule with an unsaturated group-containing carboxylic acid (b) (C) Alkali-soluble unsaturated rosin obtained by reacting with. This alkali-soluble unsaturated resin is prepared by adding the compound (c) having an isocyanate group to the hydroxyl group of the reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b), and then adjusting the acid value. Therefore, it is preferable to further add a polybasic acid anhydride (d). Further, after adding the polybasic acid anhydride (d) to the isocyanate compound (c) addition product of the reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b), the product is further formed. An epoxy group-containing compound (e) may be added to a part of the carboxyl group!
[ A— 2]分子内に少なくとも 2個以上のフエノール性水酸基を有するフエノール性水 酸基含有化合物 (f)と、不飽和基含有エポキシ化合物 (g)との反応物を、更にイソシ ァネート基を有する化合物（c)と反応させることにより得られるアルカリ可溶性不飽和 榭脂。このアルカリ可溶性不飽和榭脂は、フエノール性水酸基含有ィ匕合物 (f)と不飽 和基含有エポキシ化合物 (g)との反応物の水酸基にイソシァネート基を有する化合 物（c)を付加させた後、酸価の調整のために更に多塩基酸無水物（d)を付加させた ものであることが好ましい。また、フエノール性水酸基含有化合物 (f)と不飽和基含有 エポキシ化合物 (g)との反応物のイソシァネートイ匕合物（c)付加物に、多塩基酸無水 物（d)を付加させた後、更に、生成したカルボキシル基の一部にエポキシ基含有ィ匕 合物（e)を付加させたものであっても良!、。  [A-2] A reaction product of a phenolic hydroxyl group-containing compound (f) having at least two phenolic hydroxyl groups in the molecule and an unsaturated group-containing epoxy compound (g), and further an isocyanate group An alkali-soluble unsaturated resin obtained by reacting with the compound (c). This alkali-soluble unsaturated resin adds a compound (c) having an isocyanate group to the hydroxyl group of the reaction product of the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g). After that, it is preferable to further add a polybasic acid anhydride (d) for adjusting the acid value. Further, after adding the polybasic acid anhydride (d) to the isocyanate compound (c) adduct of the reaction product of the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g), Further, a part of the generated carboxyl group may be added with an epoxy group-containing compound (e)!
[0027] 本発明の感光性榭脂組成物は、有機結合材として、上記 [A— 1]又は [A— 2]のァ ルカリ可溶性不飽和榭脂の少なくとも 1種を含有するものであれば良ぐ [A— 1]のァ ルカリ可溶性不飽和榭脂の 2種以上、 [A— 2]のアルカリ可溶性不飽和榭脂の 2種 以上、或いは、 [A—1]のアルカリ可溶性不飽和榭脂の 1種以上と [A— 2]のアル力 リ可溶性不飽和榭脂の 1種以上とを含有するものであっても良 、。  [0027] The photosensitive resin composition of the present invention is an organic binder, as long as it contains at least one alkali-soluble unsaturated resin of [A-1] or [A-2]. 2 or more types of [A-1] alkaline soluble unsaturated resin, 2 or more types of [A-2] alkali soluble unsaturated resin, or [A-1] alkali soluble unsaturated resin It may contain at least one type of fat and at least one type of [A-2] resoluble unsaturated fatty acid.
[0028] [分子内に少なくとも 2個以上のエポキシ基を有するエポキシィ匕合物（a) ] エポキシ化合物 (a)は分子内に少なくとも 2個以上のエポキシ基を有するものであ れば特に限定はないが、例えば下記一般式 (I a)で表されるエポキシィ匕合物が挙 げられる。 [0028] [Epoxy compound having at least two epoxy groups in the molecule (a)] The epoxy compound (a) is not particularly limited as long as it has at least two epoxy groups in the molecule, and examples thereof include an epoxy compound represented by the following general formula (Ia).
[化 5]  [Chemical 5]
CH2-CH-CH -0-X-0-CH2-CH -CH, ( I -a) \ / \ / CH 2 -CH-CH -0-X-0-CH 2 -CH -CH, (I -a) \ / \ /
o o  o o
Figure imgf000011_0001
Figure imgf000011_0001
[0029] 上記一般式 (I a)において、 X部位の分子量が小さすぎると、アルカリ現像液への 溶解性が速すぎるため、特に榭脂ブラックマトリックスにおいては、露光部においても 現像液の浸透が生じ、密着性が悪化する。また、 X部位の分子量が大きすぎると、ァ ルカリ現像液への溶解性が遅すぎるため、タクトタイムの延長等で生産性が悪ィ匕する 。 X部分の分子量は、好ましくは 200以上、より好ましくは 220以上、更に好ましくは 2 80以上、特に好ましくは 300以上、とりわけ好ましくは 330以上であり、好ましくは 43 0以下、より好ましくは 410以下、更に好ましくは 380以下である。以下において、上 記一般式（I a)で表されるエポキシ化合物であって、分子量 200〜430のエポキシ 化合物を「エポキシィ匕合物 (a— 1)」と称す場合がある。 [0029] In the general formula (Ia), if the molecular weight of the X site is too small, the solubility in an alkaline developer is too fast. And adhesion is deteriorated. On the other hand, if the molecular weight of the X site is too large, the solubility in the alkaline developer is too slow, resulting in poor productivity due to an extension of the tact time. The molecular weight of the X moiety is preferably 200 or more, more preferably 220 or more, still more preferably 280 or more, particularly preferably 300 or more, particularly preferably 330 or more, preferably 430 or less, more preferably 410 or less, More preferably, it is 380 or less. Hereinafter, the epoxy compound represented by the above general formula (Ia) and having a molecular weight of 200 to 430 may be referred to as “epoxy compound (a-1)”.
[0030] なお、上記一般式 (I— a)にお!/、て、 ^〜 6のアルキル基は、直鎖アルキル基、分 岐アルキル基、シクロアルキル基のいずれであっても良ぐアルキル基が直鎖又は分 岐の場合、好ましい炭素数は 1〜10であり、シクロアルキル基の場合、好ましい炭素 数は 5〜 10である。 [0031] また、 R1と R2、 R3と R4とが連結して形成する環としては、炭素数 5〜15のシクロアル カン環、或いはァダマンタン環が挙げられる。なお、 R1と R2、 R3と R4とが連結して形 成される環は、任意の箇所に任意の数の置換基を有しても良ぐその置換基としては 炭素数 1〜5のアルキル基が挙げられる。 [0030] The above formula (I- a) your! /, Te, ^ alkyl group having to 6, straight-chain alkyl groups, branch alkyl group, good tool alkyl be any of the cycloalkyl groups When the group is linear or branched, the preferred carbon number is 1-10, and when the group is a cycloalkyl group, the preferred carbon number is 5-10. [0031] Examples of the ring formed by connecting R 1 and R 2 , R 3 and R 4 include a cycloalkane ring having 5 to 15 carbon atoms or an adamantane ring. The ring formed by linking R 1 and R 2 and R 3 and R 4 may have any number of substituents at any position. ˜5 alkyl groups.
[0032] 前記一般式 (I a)における Xは、好ましくは下記一般式 (ΠΑ)、（ΠΒ)又は (IIC)で 表される。  [0032] X in the general formula (Ia) is preferably represented by the following general formula (ΠΑ), (ΠΒ) or (IIC).
[化 6]  [Chemical 6]
Figure imgf000012_0001
上記一般式（IIA)〜（IIC)において、 R1〜R16及び nは前記一般式（II)におけると 同義である。
Figure imgf000012_0001
In the general formulas (IIA) to (IIC), R1 to R16 and n have the same meaning as in the general formula (II).
前記一般式 (ΠΑ)はまた、好ましくは下記一般式 (IIAa)又は（Ilab)で表される。  The general formula (ΠΑ) is also preferably represented by the following general formula (IIAa) or (Ilab).
[化 7] …（！ I Aa) [Chemical 7] … (! I Aa)
…（！ I Ab)… (! I Ab)
Figure imgf000013_0001
Figure imgf000013_0001
式中、 R1, R2は前記一般式 (II)におけると同義である。 In the formula, R 1 and R 2 have the same meaning as in the general formula (II).
[0034] 上記条件を満たす、 X部位の具体例としては、下記構造が挙げられる力 何ら以下 のものに限定されるものではない。 [0034] Specific examples of the X site that satisfy the above conditions are not limited to those having any of the following forces.
[0035] [化 8] [0035] [Chemical 8]
Figure imgf000014_0001
Figure imgf000014_0001
[6^ ] [9S00] 8Z£lO/SOOZd /13d £1 .9^9Ϊ0/900Ζ OAV
Figure imgf000016_0001
Figure imgf000016_0002
Figure imgf000016_0003
Figure imgf000016_0004
Figure imgf000016_0005
[0037] [化 10] [6 ^] [9S00] 8Z £ lO / SOOZd / 13d £ 1 .9 ^ 9Ϊ0 / 900Ζ OAV
Figure imgf000016_0001
Figure imgf000016_0002
Figure imgf000016_0003
Figure imgf000016_0004
Figure imgf000016_0005
[0037] [Chemical 10]
(X-21)
Figure imgf000017_0001
(X-21)
Figure imgf000017_0001
(X-25)
Figure imgf000017_0002
(X-25)
Figure imgf000017_0002
[0038] [化 11] (X-28) (X-29)
Figure imgf000018_0001
[0038] [Chemical 11] (X-28) (X-29)
Figure imgf000018_0001
(X-32)
Figure imgf000018_0002
(X-32)
Figure imgf000018_0002
Figure imgf000018_0003
(X 37) (X— 38)
Figure imgf000018_0003
(X 37) (X— 38)
Figure imgf000019_0001
Figure imgf000019_0001
(X-43) (X-43)
R41OtO
Figure imgf000019_0002
R 41 OtO
Figure imgf000019_0002
( 41. R42はそれぞれ独立に、置換基を有していても良いアルキレン基又は、置換基を 有していても良いァリ一レン基を示し、 j. kはそれぞれ独立に 0~ 10の整数を示す。） なお、上記例示構造のうち、（X— 1)〜（X— 12) , (X— 40)〜（X— 43)は、前記一 般式 (I a)における Xが前記一般式 (IIAa)又は（IIAb)で表されるものの具体例で ある力、これらのうち、特に (X— 1), (X-2), (X— 40),及び (X— 41)で表される 構造のものが好ましい。 本発明で用いるエポキシィ匕合物（a)は、前記一般式 (I— a)で表されるエポキシ化 合物で、 Xの分子量が 200未満、又は 480を超えるエポキシィ匕合物（以下「エポキシ 化合物（a— 2)」と称す場合がある。）であっても良ぐまた、このようなエポキシ化合物 (a 2)をエポキシィ匕合物（a— 1)と併用しても良 、。このエポキシ化合物（a— 2)とし ては、特に前記一般式 (I— a)において、 Xが下記一般式 (IID)又は（ΠΕ)で表される 化合物が挙げられる。 ( 41. R 42 each independently represents an alkylene group which may have a substituent or an arylene group which may have a substituent, and j.k each independently represents 0 to 10 (X—1) to (X—12), (X—40) to (X—43) in the above exemplary structures are the same as those in the general formula (I a). Forces that are specific examples of those represented by the general formula (IIAa) or (IIAb), among these, in particular (X—1), (X-2), (X—40), and (X—41) A structure represented by is preferable. The epoxy compound (a) used in the present invention is an epoxy compound represented by the general formula (I-a), and an epoxy compound (hereinafter referred to as “epoxy compound”) in which the molecular weight of X is less than 200 or more than 480. Compound (a-2) ”may be used, and such an epoxy compound (a2) may be used in combination with the epoxy compound (a-1). Examples of the epoxy compound (a-2) include compounds in which, in the general formula (Ia), X is represented by the following general formula (IID) or (ΠΕ).
[化 13] [Chemical 13]
…（！ I D)
Figure imgf000020_0001
… (! ID)
Figure imgf000020_0001
Figure imgf000020_0002
上記一般式 (IID) , (HE)において、 R1, R2は前記一般式 (II)におけると同義であり R"〜R24はそれぞれ独立に、水素原子又は置換基を有していても良い炭素数 1〜 3のアルキル基を示す。
Figure imgf000020_0002
In the above general formulas (IID) and (HE), R 1 and R 2 have the same meaning as in the general formula (II), and R ″ to R 24 each independently have a hydrogen atom or a substituent. A good alkyl group having 1 to 3 carbon atoms is shown.
また、上記エポキシィ匕合物（a— 2)の中では、 Xが下記一般式 (IIDa)で表される化 合物が特に好ましい。  Among the epoxy compounds (a-2), compounds in which X is represented by the following general formula (IIDa) are particularly preferable.
[化 14] [Chemical 14]
Figure imgf000020_0003
上記一般式 (IIDa)において、 R1, R2は前記一般式 (II)におけると同義であり、 R21はそれぞれ独立に、水素原子又は置換基を有していても良い炭素数 1〜3のアル キル基を示す。
Figure imgf000020_0003
In the general formula (IIDa), R 1 and R 2 have the same meaning as in the general formula (II), R 21 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent.
[0043] 上記エポキシ化合物（a— 2)とエポキシィ匕合物（a— 1)とを併用する場合、エポキシ 化合物（a— 1)に対して、エポキシィ匕合物（a— 2)を通常 20重量％以下、好ましくは 1 5重量％以下併用することが好ましい。  [0043] When the epoxy compound (a-2) and the epoxy compound (a-1) are used in combination, the epoxy compound (a-2) is usually added to the epoxy compound (a-1). It is preferable to use in combination of not more than wt%, preferably not more than 15 wt%.
[0044] 前記一般式 (I a)で表されるエポキシィヒ合物は、例えば下記一般式 (IV)で表され る化合物と、ェピクロルヒドリン、ェピブロムヒドリン等のェピハロヒドリンとを、水酸化ナ トリウム、水酸化カリウム等のアルカリ金属水酸化物の存在下に 20〜120°Cの温度で 1〜： L0時間反応させることにより得ることができる。  [0044] The epoxy compound represented by the general formula (Ia) includes, for example, a compound represented by the following general formula (IV) and an epihalohydrin such as epichlorohydrin and epipibrohydrin. It can be obtained by reacting at a temperature of 20 to 120 ° C. for 1 to L0 hours in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.
HO-X-OH "- (IV)  HO-X-OH "-(IV)
一般式 (IV)中、 Xは一般式 (I a)におけるものと同じ意味を表す。  In general formula (IV), X represents the same meaning as in general formula (Ia).
[0045] 前記一般式 (I a)で表されるエポキシィ匕合物を得る反応において、アルカリ金属 水酸化物はその水溶液を使用しても良ぐその場合に該アルカリ金属水酸化物の水 溶液を連続的に反応系内に添加すると共に減圧下、又は常圧下連続的に水及びェ ピハロヒドリンを留出させ、更に分液し、水は除去しェピノ、ロヒドリンは反応系内に連 続的に戻す方法であっても良 、。  [0045] In the reaction for obtaining the epoxy compound represented by the general formula (Ia), the alkali metal hydroxide may be used as an aqueous solution. Is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or atmospheric pressure, followed by liquid separation, removing water, and epino and lohydrin continuously in the reaction system. The method of returning can be good.
[0046] また、前記一般式 (IV)で表される化合物とヱピノ、ロヒドリンの溶解混合物にテトラメ チルアンモ -ゥムクロライド、テトラメチルアンモ -ゥムブロマイド、トリメチルベンジル アンモ-ゥムクロライド等の 4級アンモ-ゥム塩を触媒として添カ卩し、 50〜150でで1 〜5時間反応させて得られる、一般式 (IV)で表される化合物のハロヒドリンエーテル 化物に、アルカリ金属水酸化物の固体又は水溶液を加え、再び 20〜120°Cの温度 で 1〜10時間反応させて脱ハロゲンィ匕水素（閉環）させる方法でも良い。  [0046] Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium chloride bromide, trimethylbenzyl ammonium chloride is added to a mixture of the compound represented by the above general formula (IV) and ヱ pino and rhohydrin. Add the catalyst as a catalyst, and react with the halohydrin etherified compound of the formula (IV) obtained by reacting at 50 to 150 for 1 to 5 hours with a solid or aqueous solution of an alkali metal hydroxide. In addition, a method of reacting again at a temperature of 20 to 120 ° C. for 1 to 10 hours to dehalogenate hydrogen (ring closure) may be used.
[0047] このような反応において使用されるェピノ、ロヒドリンの量は一般式 (IV)で表される化 合物の水酸基 1当量に対し通常 1モル以上、好ましくは 2モル以上で、通常 30モル 以下、好ましくは 20モル以下である。また、アルカリ金属水酸化物の使用量は一般 式 (IV)で表される化合物の水酸基 1当量に対し通常 0. 8モル以上、好ましくは 0. 9 モル以上で、通常 15モル以下、好ましくは 11モル以下である。  [0047] The amount of epino and rhohydrin used in such a reaction is usually 1 mol or more, preferably 2 mol or more, and usually 30 mol, per 1 equivalent of the hydroxyl group of the compound represented by the general formula (IV). Below, preferably 20 mol or less. The amount of the alkali metal hydroxide used is usually 0.8 mol or more, preferably 0.9 mol or more, usually 15 mol or less, preferably 1 mol per 1 equivalent of the hydroxyl group of the compound represented by the general formula (IV). 11 moles or less.
[0048] 更に、反応を円滑に進行させるためにメタノール、エタノールなどのアルコール類の 他、ジメチルスルホン、ジメチルスルホキシド等の非プロトン性極性溶媒などを添カロし て反応を行っても良い。アルコール類を使用する場合、その使用量はェピノ、ロヒドリ ンの量に対し、通常 2重量％以上、好ましくは 4重量％以上で、通常 20重量％以下、 好ましくは 15重量％以下である。また、非プロトン性極性溶媒を用いる場合、その使 用量はェピノ、ロヒドリンの量に対し通常 5重量％以上、好ましくは 10重量％以上で、 通常 100重量％以下、好ましくは 90重量％以下である。 [0048] Further, in order to facilitate the reaction, alcohols such as methanol and ethanol are used. Alternatively, the reaction may be carried out by adding an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide. When alcohols are used, the amount used is usually 2% by weight or more, preferably 4% by weight or more, and usually 20% by weight or less, preferably 15% by weight or less, based on the amount of epino and rhohydrin. When an aprotic polar solvent is used, the amount used is usually 5% by weight or more, preferably 10% by weight or more, and usually 100% by weight or less, preferably 90% by weight or less, based on the amount of epino and rhohydrin. .
[0049] これらのエポキシ化反応の反応物を水洗後、又は水洗無しに加熱減圧下、 110〜 250°C、圧力 1. 3kPa (10mmHg)以下でェピハロヒドリンや他の添加溶媒などを除 去する。また、更に加水分解性ハロゲンの少ないエポキシ榭脂とするために、得られ たエポキシ榭脂を再びトルエン、メチルイソプチルケトンなどの溶剤に溶解し、水酸ィ匕 ナトリウム、水酸ィ匕カリウムなどのアルカリ金属水酸ィ匕物の水溶液をカ卩えて反応を行 い、閉環を確実なものにすることもできる。この場合、アルカリ金属水酸化物の使用量 はエポキシィ匕に使用した一般式 (IV)で表される化合物の水酸基 1当量に対して好ま しくは 0. 01モル以上、特に好ましくは 0. 05モル以上で、好ましくは 0. 3モル以下、 特に好ましくは 0. 2モル以下である。反応温度は 50〜120°C、反応時間は通常 0. 5 〜2時間である。 [0049] After the reaction product of these epoxidation reactions is washed with water or without washing with water, epihalohydrin and other added solvents are removed at 110 to 250 ° C under a pressure of 1.3 kPa (10 mmHg) or less. In addition, in order to obtain an epoxy resin having less hydrolyzable halogen, the obtained epoxy resin is dissolved again in a solvent such as toluene or methylisobutyl ketone, and then sodium hydroxide, potassium hydroxide, etc. It is also possible to carry out the reaction with an aqueous solution of an alkali metal hydroxide to ensure ring closure. In this case, the amount of the alkali metal hydroxide used is preferably 0.01 mol or more, particularly preferably 0.05 mol, relative to 1 equivalent of the hydroxyl group of the compound represented by the general formula (IV) used for the epoxy. The amount is preferably 0.3 mol or less, particularly preferably 0.2 mol or less. The reaction temperature is 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
[0050] 反応終了後、生成した塩を濾過、水洗などにより除去し、更に、加熱減圧下トルェ ン、メチルイソプチルケトンなどの溶剤を留去することにより、前記一般式 (I a)で表 されるエポキシィ匕合物が得られる。  [0050] After the completion of the reaction, the produced salt is removed by filtration, washing with water, and the like, and further, a solvent such as toluene and methylisobutyl ketone is distilled off under reduced pressure by heating, whereby the compound represented by the above general formula (Ia) is obtained. An epoxy compound is obtained.
[0051] 本発明において用いるエポキシィ匕合物（a)は、前記一般式 (I— a)で表されるェポ キシ化合物に何ら限定されず、その具体例としては、ビスフエノール A型エポキシ榭 脂（例えば、油化シェルエポキシ (株)製「ェピコート 828」、「ェピコート 1001」、「ェピ コート 1002」、「ェピコート 1004」等）、ビスフエノール A型エポキシ榭脂のアルコール 性水酸基とェピクロルヒドリンの反応により得られるエポキシ榭脂（例えば、 日本ィ匕薬（ 株)製「NER— 1302」（エポキシ当量 323,軟ィ匕点 76°C) )、ビスフエノール F型榭脂 (例えば、油化シェルエポキシ（株）製「ェピコート 807」、「EP— 4001」、「EP— 400 2」、「EP— 4004等」）、ビスフエノール F型エポキシ榭脂のアルコール性水酸基とェ ピクロルヒドリンの反応により得られるエポキシ榭脂（例えば、 日本化薬 (株)製「NER 7406」（エポキシ当量 350,軟化点 66°C) )、ビスフエノール S型エポキシ榭脂、ビ フエ-ルグリシジルエーテル（例えば、油化シェルエポキシ（株）製「YX 4000」）、 フエノールノボラック型エポキシ榭脂（例えば、 日本ィ匕薬 (株)製「ΕΡΡΝ— 201」、油 化シェルエポキシ (株）製「ΕΡ— 152」、「ΕΡ—154」、ダウケミカル (株）製「DEN—4 38」）、クレゾ一ルノボラック型エポキシ榭脂（例えば、 日本ィ匕薬 (株)製「EOCN— 10 2S」、「EOCN— 1020」、「EOCN— 104S」）、トリグリシジルイソシァヌレート（例え ば、 日産化学 (株)製「TEPIC」 )、トリスフェノールメタン型エポキシ榭脂（例えば、 日 本化薬（株）製「EPPN— 501」、「EPN— 502」、「EPPN— 503」）、フルオレンェポ キシ榭脂 (例えば、新日鐡ィ匕学 (株)製力ルドエポキシ榭脂「ESF— 300」）、脂環式 エポキシ榭脂 (ダイセルィ匕学工業 (株)製「セロキサイド 2021PJ、「セロキサイド ΈΗΡ E」）、ジシクロペンタジェンとフエノールの反応によるフエノール榭脂をグリシジル化し たジシクロペンタジェン型エポキシ榭脂、 日本化薬社製「XD— 1000」、大日本イン キネ土製「EXA— 7200」、 日本化薬社製「NC— 3000」、「NC— 7300」）等が挙げら れる。 [0051] The epoxy compound (a) used in the present invention is not limited to the epoxy compound represented by the general formula (Ia), and specific examples thereof include bisphenol A type epoxy compounds. Fatty alcohol (for example, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004”, etc.) manufactured by Yuka Shell Epoxy Co., Ltd., alcoholic hydroxyl group and epoxy of bisphenol A type epoxy resin Epoxy resin obtained by the reaction of chlorohydrin (for example, “NER 1302” (epoxy equivalent 323, soft soft point 76 ° C) manufactured by Nippon Shakuyaku Co., Ltd.), bisphenol F type resin (for example, , “Epicoat 807”, “EP-4001,” “EP-4002,” “EP-4004, etc.” manufactured by Yuka Shell Epoxy Co., Ltd.), the alcoholic hydroxyl group of bisphenol F-type epoxy resin and epichlorohydrin Epoxy resin obtained by reaction (For example, “NER” manufactured by Nippon Kayaku Co., Ltd. 7406 "(epoxy equivalent 350, softening point 66 ° C)), bisphenol S type epoxy resin, bi-glycidyl ether (for example," YX 4000 "manufactured by Yuka Shell Epoxy Co., Ltd.), phenol novolac type epoxy Oils (for example, “ΕΡΡΝ-201” manufactured by Nippon Gyaku Co., Ltd., “ΕΡ-152”, “ΕΡ-154” manufactured by Yuka Shell Epoxy Co., Ltd., “DEN—4 38” manufactured by Dow Chemical Co., Ltd.) )), Cresol novolac type epoxy resin (for example, “EOCN-10 2S”, “EOCN-1020”, “EOCN—104S” manufactured by Nippon Gaiyaku Co., Ltd.), triglycidyl isocyanurate (for example, "TEPIC" manufactured by Nissan Chemical Co., Ltd.), trisphenolmethane type epoxy resin (for example, "EPPN-501", "EPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), fluorene epoxy Oil (for example, Nippon Steel Chemical Co., Ltd. Powered epoxy resin "ESF-300"), Cyclic epoxy resin (“Celoxide 2021PJ”, “Celoxide® E” manufactured by Daicel Chemical Industries, Ltd.), dicyclopentagen type epoxy resin obtained by glycidylation of phenol resin by reaction of dicyclopentagen and phenol, Nippon Kayaku “XD-1000”, Dainippon Inkine “EXA-7200”, Nippon Kayaku “NC-3000”, “NC-7300”).
[0052] エポキシィ匕合物（a)の他の例としては共重合型エポキシ榭脂が挙げられる。共重合 型エポキシ榭脂としては、例えばグリシジル (メタ）アタリレート、（メタ)アタリロイルメチ ルシクロへキセンオキサイド、ビュルシクロへキセンオキサイドなど（以下「共重合型ェ ポキシ榭脂の第 1成分」と称す。 )とこれら以外の 1官能エチレン性不飽和基含有ィ匕 合物（以下、「共重合型エポキシ榭脂の第 2成分」と称す。 )、例えば、メチル (メタ)ァ タリレート、ェチル (メタ）アタリレート、ブチル (メタ）アタリレート、 2—ヒドロキシェチル アタリレート、 2—ヒドロキシプロピル (メタ）アタリレート、（メタ）アクリル酸、スチレン、フ エノキシェチル（メタ）アタリレート、ベンジル（メタ）アタリレート、 aーメチルスチレン、 グリセリンモノ (メタ)アタリレート、下記一般式 (IA)で表される化合物力も選ばれる 1 種又は 2種以上、とを反応させて得られた共重合体が挙げられる (なお、本明細書に おいて、「(メタ)アタリレート」、「(メタ)アクリル〜」等は、「アタリレート又はメタタリレー ト」、「アクリル〜又はメタクリル〜」等を意味するものとし、例えば後述の「(メタ)アタリ ル酸」は「アクリル酸又はメタクリル酸」を意味するものとする）。 [0052] Another example of the epoxy compound (a) is a copolymer type epoxy resin. Examples of the copolymer type epoxy resin include glycidyl (meth) attalylate, (meth) atalyloyl methylcyclohexene oxide, burcyclohexene oxide and the like (hereinafter referred to as “first component of copolymer type epoxy resin”). And other monofunctional ethylenically unsaturated group-containing compounds (hereinafter referred to as “second component of copolymer type epoxy resin”), for example, methyl (meth) acrylate, ethyl (meth) acrylate , Butyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoloxyl (meth) acrylate, benzyl (meth) acrylate, a- Methylstyrene, glycerin mono (meth) acrylate, and compound strength represented by the following general formula (IA) are also selected 1 Or a copolymer obtained by reacting two or more species with each other (in this specification, “(meth) acrylate”, “(meth) acryl”), etc. “Rate or methacrylate”, “acrylic or methacrylic”, etc., for example, “(meth) atallylic acid” described later means “acrylic acid or methacrylic acid”).
[0053] [化 15]
Figure imgf000024_0001
式中、 R21は水素又はェチル基、 R22は水素又は炭素数 1〜6のアルキル基を示し、 rは 2〜 10の整数である。 [0053] [Chemical 15]
Figure imgf000024_0001
In the formula, R 21 represents hydrogen or an ethyl group, R 22 represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and r is an integer of 2 to 10.
[0054] 上記一般式 (IA)の化合物としては例えばジエチレングリコールモノ (メタ）アタリレ ート、トリエチレングリコールモノ (メタ）アタリレート、テトラエチレンダリコールモノ（メタ )アタリレート等のポリエチレングリコールモノ (メタ）アタリレート、メトキシジエチレング リコールモノ（メタ）アタリレート、メトキシトリエチレングリコールモノ（メタ）アタリレート、 メトキシテトラエチレングリコールモノ (メタ）アタリレート、等のアルコキシポリエチレン グリコール (メタ）アタリレート等が挙げられる。 [0054] Examples of the compound represented by the general formula (IA) include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene dallicol mono (meth) acrylate. ) Alkoxypolyethylene glycol (meth) acrylate, such as acrylate, methoxydiethylene glycol mono (meth) acrylate, methoxy triethylene glycol mono (meth) acrylate, methoxy tetraethylene glycol mono (meth) acrylate, etc. It is done.
[0055] 上記共重合型エポキシ榭脂の分子量は約 1000〜200000が好ましい。また、上 記共重合型エポキシ榭脂の第 1成分の使用量は、上記共重合型エポキシ榭脂の第 [0055] The molecular weight of the copolymerized epoxy resin is preferably about 1000-200000. The amount of the first component of the copolymerization type epoxy resin used is the same as that of the copolymerization type epoxy resin.
2成分に対して好ましくは 10重量％以上、特に好ましくは 20重量％以上で、好ましく は 70重量％以下、特に好ましくは 50重量％以下である。 It is preferably 10% by weight or more, particularly preferably 20% by weight or more, preferably 70% by weight or less, particularly preferably 50% by weight or less, based on the two components.
[0056] このような共重合型エポキシ榭脂としては、具体的には日本油脂 (株)製「CP— 15」[0056] As such a copolymer type epoxy resin, specifically, "CP-15" manufactured by Nippon Oil & Fats Co., Ltd.
、 「CP— 30」、 「CP— 50」、 「CP— 20SA」、 「CP— 510SA」、 「CP— 50S」、 「CP—, “CP-30”, “CP-50”, “CP-20SA”, “CP—510SA”, “CP-50S”, “CP—
50M」、 「CP— 20MA」等が例示される。 “50M”, “CP-20MA” and the like.
[0057] 上述したようなエポキシィ匕合物（a)のうち、特に、前記一般式 (I— a)で表されるビス フエノール類のジグリシジルエーテル類が好ましぐとりわけ、前記エポキシ化合物（a 1)が好ましい。 Among the epoxy compounds (a) as described above, the diglycidyl ethers of bisphenols represented by the general formula (Ia) are particularly preferred, especially the epoxy compound (a 1) is preferred.
[0058] なお、エポキシ化合物 (a)は、 1種を単独で用いても良ぐ 2種以上を併用しても良 い。 2種以上を併用する場合のエポキシィ匕合物の組合せとしては、エポキシ基を 2個 含有するエポキシ化合物と、エポキシ基を 3個以上含有するエポキシィ匕合物の組合 せが好ましぐこのようなエポキシィ匕合物の組合せとしては、具体的には一般式 (I a )で表される化合物と日本化薬社製「XD— 1000」、大日本インキ社製 ΓΕΧΑ- 720 0」、トリスフェノールメタン型エポキシィ匕合物との組合せ等が挙げられる。 [0059] [不飽和基含有カルボン酸 (b) ] [0058] The epoxy compound (a) may be used alone or in combination of two or more. When two or more types are used in combination, an epoxy compound containing two epoxy groups and an epoxy compound containing three or more epoxy groups are preferred. Specific combinations of epoxy compounds include compounds represented by the general formula (I a), Nippon Kayaku “XD-1000”, Dainippon Ink ΓΕΧΑ-720 0 ”, trisphenol methane A combination with a type epoxy compound may be mentioned. [0059] [Unsaturated carboxylic acid (b)]
不飽和基含有カルボン酸 (b)としては、エチレン性不飽和二重結合を有する不飽 和カルボン酸が挙げられ、具体例としては、（メタ）アクリル酸、クロトン酸、 o—、 m—、 p—ビュル安息香酸、（メタ）アクリル酸の α位ハロアルキル、アルコキシル、ハロゲン 、ニトロ、シァノ置換体などのモノカルボン酸、 2— (メタ）アタリロイ口キシェチルコハク 酸、 2— (メタ）アタリロイロキシェチルアジピン酸、 2— (メタ）アタリロイ口キシェチルフ タル酸、 2— (メタ）アタリロイ口キシェチルへキサヒドロフタル酸、 2— (メタ）アタリロイ口 キシェチルマレイン酸、 2—（メタ）アタリロイロキシプロピルコハク酸、 2—（メタ）アタリ ロイロキシプロピルアジピン酸、 2— (メタ）アタリロイロキシプロピルテトラヒドロフタル酸 、 2 - (メタ）アタリロイロキシプロピルフタル酸、 2— (メタ）アタリロイロキシプロピルマレ イン酸、 2— (メタ）アタリロイ口キシブチルコハク酸、 2— (メタ）アタリロイロキシブチル アジピン酸、 2 - (メタ）アタリロイ口キシブチルヒドロフタル酸、 2— (メタ）アタリロイロキ シブチルフタル酸、 2— (メタ）アタリロイロキシブチルマレイン酸 (メタ）、アクリル酸に ε—力プロラタトン、 β—プロピオラタトン、 y—ブチ口ラタトン、 δ—バレロラタトン等 のラタトン類を付加させたものである単量体、（メタ）アクリル酸ダイマー、ペンタエリス リトールトリ (メタ)アタリレートと無水コハク酸との反応で生成する化合物、或いは、ぺ ンタエリスリトールトリ (メタ)アタリレートと無水フタル酸との反応で生成する化合物な どが挙げられる。  Examples of the unsaturated group-containing carboxylic acid (b) include unsaturated carboxylic acids having an ethylenically unsaturated double bond. Specific examples thereof include (meth) acrylic acid, crotonic acid, o-, m-, p-Buylbenzoic acid, monocarboxylic acids such as α-position haloalkyls, alkoxyls, halogens, nitros, and cyano substitutions of (meth) acrylic acid, 2— (meth) atariloy cough succinic acid, 2— (meth) atariloyloxche Tiladipic acid, 2- (meth) atariloy oral chechetilfalic acid, 2- (meth) atariloy oral chechetilhexahydrophthalic acid, 2- (meth) atariloy oral chechetilmaleic acid, 2- (meth) aterylleuoxy Propyl succinic acid, 2— (meth) atari leuoxypropyl adipic acid, 2— (meth) attayl leuoxypropyl tetrahydrophthalic acid, 2- ) Atalylyloxypropyl phthalic acid, 2— (Meth) Atalylyloxypropyl maleic acid, 2 — (Meth) Atalloy xybutyl succinic acid, 2 — (Meth) Atalylyloxybutyl adipic acid, 2- (meth) Atariloy oral hydroxybutyl hydrophthalic acid, 2— (meth) ataliroyoxybutyl phthalic acid, 2— (meth) atalyloxybutylmaleic acid (meth), acrylic acid with ε—force prolatatatone, β—propiolatathone, y—buty oral ratataton, δ-Monomers to which latatones such as valerolatataton are added, (meth) acrylic acid dimer, pentaerythritol tri (meth) atalylate, a compound formed by the reaction of succinic anhydride, or pentaerythritol tri And compounds formed by the reaction of (meth) acrylate and phthalic anhydride. .
[0060] 特に好ましいものは、（メタ）アクリル酸である。これらは 1種を単独で用いても良ぐ 2 種以上を混合して用いても良 、。  [0060] Particularly preferred is (meth) acrylic acid. These can be used alone or in combination of two or more.
[0061] [エポキシィ匕合物（a)と不飽和基含有カルボン酸 (b)との反応]  [0061] [Reaction of epoxy compound (a) with unsaturated group-containing carboxylic acid (b)]
エポキシ化合物 (a)中のエポキシ基と不飽和基含有カルボン酸 (b)とを反応させる 方法としては公知の手法を用いることができる。例えば、上記エポキシ化合物（a)と不 飽和基含有カルボン酸 (b)とを、トリェチルァミン、ベンジルメチルァミン等の 3級アミ ン、ドデシルトリメチルアンモ -ゥムクロライド、テトラメチルアンモ -ゥムクロライド、テト ラエチルアンモ -ゥムクロライド、ベンジルトリェチルアンモ -ゥムクロライド等の 4級ァ ンモ -ゥム塩、ピリジン、トリフエ-ルホスフィン等を触媒として、有機溶剤中、反応温 度 50〜 150°Cで数〜数十時間反応させることにより、エポキシ化合物にカルボン酸 を付加することができる。 As a method for reacting the epoxy group in the epoxy compound (a) with the unsaturated group-containing carboxylic acid (b), a known method can be used. For example, the above epoxy compound (a) and unsaturated group-containing carboxylic acid (b) are combined with tertiary amines such as triethylamine, benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride. , Quaternary ammonium salts such as benzyltriethylammonium chloride, pyridine, triphenylphosphine, etc. as a catalyst, in an organic solvent at a reaction temperature of 50 to 150 ° C for several to several tens of hours. By the carboxylic acid to the epoxy compound Can be added.
[0062] 該触媒の使用量は、反応原料混合物 (エポキシィ匕合物 (a)と不飽和基含有カルボ ン酸 (b)との合計）に対して好ましくは 0. 01重量％以上、特に好ましくは 0. 3重量％ 以上で、好ましくは 10重量％以下、特に好ましくは 5重量％以下である。また反応中 の重合を防止するために、重合防止剤（例えばメトキノン、ハイドロキノン、メチルノヽィ ドロキノン、 p—メトキシフエノール、ピロガロール、 tert—ブチルカテコール、フエノチ アジン等)を使用することが好ましぐその使用量は、反応原料混合物に対して好まし くは 0. 01重量％以上、特に好ましくは 0. 1重量％以上で、好ましくは 10重量％以下 、特に好ましくは 5重量％である。  [0062] The amount of the catalyst used is preferably 0.01% by weight or more, particularly preferably based on the reaction raw material mixture (the total of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b)). Is not less than 0.3% by weight, preferably not more than 10% by weight, particularly preferably not more than 5% by weight. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine). The amount is preferably 0.01% by weight or more, particularly preferably 0.1% by weight or more, preferably 10% by weight or less, particularly preferably 5% by weight, based on the reaction raw material mixture.
[0063] エポキシ化合物 (a)のエポキシ基に不飽和基含有カルボン酸 (b)を付加させる割 合は、通常 90〜： L00モル％である。エポキシ基の残存は保存安定性に悪影響を与 えるため、不飽和基含有カルボン酸 (b)はエポキシ化合物 (a)のエポキシ基 1当量に 対して、通常 0. 8当量以上、特に 0. 9当量以上で、通常 1. 5当量以下、特に 1. 1当 量以下の割合で反応を行うことが好まし 、。  [0063] The ratio of adding the unsaturated group-containing carboxylic acid (b) to the epoxy group of the epoxy compound (a) is usually 90 to L00 mol%. Since residual epoxy groups adversely affect storage stability, unsaturated group-containing carboxylic acids (b) are usually at least 0.8 equivalents, especially 0.9 equivalents, relative to 1 equivalent of epoxy groups in epoxy compound (a). It is preferable to carry out the reaction at a ratio of not less than the equivalent, usually not more than 1.5 equivalent, particularly not more than 1.1 equivalent.
[0064] [イソシァネート基を有する化合物（c) ]  [0064] [Compound having isocyanate group (c)]
エポキシ化合物（a)と不飽和基含有カルボン酸 (b)との反応物の水酸基に付加さ せるイソシァネート基を有する化合物（c)としては、公知のものが使用できる。この化 合物（c)は、イソシァネート基を分子中に 1つ有するものでも良いし、イソシァネート基 を複数有するポリイソシァネートイ匕合物であっても良 、。架橋して分子量の大きな榭 脂を得るためには好ましくはポリイソシァネートイ匕合物を用いるのが良 、。  As the compound (c) having an isocyanate group to be added to the hydroxyl group of the reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b), known compounds can be used. This compound (c) may have one isocyanate group in the molecule or may be a polyisocyanate compound having a plurality of isocyanate groups. In order to obtain a resin having a large molecular weight by crosslinking, a polyisocyanate compound is preferably used.
[0065] イソシァネート基を分子中に 1つ有する化合物としては、ブタンイソシァネート、 3— クロ口ベンゼンイソシァネート、 4 クロ口ベンゼンイソシァネート、シクロへキサンイソ シァネート、ベンゼンイソシァネート、 3—イソプロぺノィルー α , aージメチルベンジ ルイソシァネート、 m—トルエンイソシァネートなどが挙げられる。  [0065] The compounds having one isocyanate group in the molecule include butane isocyanate, 3-chlorobenzene benzene isocyanate, 4-chlorobenzene benzene isocyanate, cyclohexane isocyanate, benzene isocyanate, 3- Examples include isopropenoyl α, a-dimethylbenzyl isocyanate and m-toluene isocyanate.
[0066] ポリイソシァネートイ匕合物の例としてはパラフエ-レンジイソシァネート、 2, 4 トリレ ンジイソシァネート、 2, 6 トリレンジイソシァネート、 4, 4' ージフエニルメタンジイソ シァネート、ナフタレン 1, 5 ジイソシァネート、トリジンジイソシァネート、等の芳香 族ジイソシァネート、へキサメチレンジイソシァネート、リジンメチルエステルジイソシァ ネート、 2, 4, 4—トリメチルへキサメチレンジイソシァネート、ダイマー酸ジイソシァネ ート等の脂肪族ジイソシァネート、イソホロンジイソシァネート、 4, 4' ーメチレンビス（ シクロへキシルイソシァネート）、 ω , ω ' —ジイソシネートジメチルシクロへキサン等 の脂環族ジイソシァネート、キシリレンジイソシァネート、 , a , a ' , α ' ーテトラメ チルキシリレンジイソシァネート等の芳香環を有する脂肪族ジイソシァネート、リジン エステルトリイソシァネート、 1, 6, 11—ゥンデカントリイソシァネート、 1, 8—ジィソシ ァネート一 4—イソシァネートメチルオクタン、 1 , 3, 6—へキサメチレントリイソシァネ ート、ビシクロヘプタントリイソシァネート、トリス (イソシァネートフエ-ルメタン）、トリス（ イソシァネートフエ-ル）チォホスフェート等のトリイソシァネート、及びこれらの 3量体 、水付加物、及びこれらのポリオール付加物等が挙げられる。 [0066] Examples of polyisocyanate compounds include para-phenolic diisocyanate, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate. Aromatic diisocyanates such as cyanate, naphthalene 1,5 diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexylisocyanate), ω , ω '--Diisocyanate Dicyclohexane, alicyclic diisocyanate, xylylene diisocyanate,, a, a', α '-tetramethylxylylene diisocyanate, etc., aliphatic diisocyanate, lysine ester Triisocyanate, 1,6,11-undecane triisocyanate, 1,8-disiocyanate 1-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, Bicycloheptane triisocyanate, Tris (isocyanate phenol), Tris (isocyanate phenol) Triisobutyl Xia sulfonates such Chiohosufeto, and these trimers, water adducts, and the like of these polyol adducts.
[0067] これらのうち、好ましいのは有機ジイソシァネートの二、三量体で、最も好ましいのは トリレンジイソシァネートのトリメチロールプロパン付カ卩物、トリレンジイソシァネートの 三量体、イソホロンジイソシァネートの三量体である。  [0067] Of these, preferred are dimers and trimers of organic diisocyanates, and most preferred are products of tolylene diisocyanate with trimethylolpropane, tolylene diisocyanate trimer, isophorone dimer. Isocyanate trimer.
[0068] イソシァネート基を有する化合物（c)は 1種を単独で用いても、 2種以上を併用して も良い。  [0068] As the compound (c) having an isocyanate group, one type may be used alone, or two or more types may be used in combination.
[0069] 有機ジイソシァネートの三量体の製造方法としては、前記ポリイソシァネート類を適 当な三量ィ匕触媒、例えば第 3級ァミン類、ホスフィン類、アルコキシド類、金属酸化物 、カルボン酸塩類等を用いてイソシァネート基の部分的な三量ィ匕を行い、触媒毒の 添カ卩により三量ィ匕を停止させた後、未反応のポリイソシァネートを溶剤抽出、薄膜蒸 留により除去して目的のイソシァヌレート基含有ポリイソシァネートを得る方法が挙げ られる。  [0069] As a method for producing a trimer of an organic diisocyanate, the polyisocyanate is converted to an appropriate trimer catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acids. Perform a partial trimerization of the isocyanate group using salts, etc., stop the trimer by adding a catalyst poison, then extract the unreacted polyisocyanate by solvent extraction and thin-film distillation. There is a method of removing the desired isocyanurate group-containing polyisocyanate.
[0070] [イソシァネート基を有する化合物（c)の付加]  [0070] [Addition of compound (c) having isocyanate group]
イソシァネート基を有する化合物（c)の付加率は、エポキシ化合物 (a)に不飽和基 含有カルボン酸 (b)を付加させたときに生成される水酸基の、通常 10モル％以上、 好ましくは 20モル％以上、特に好ましくは 30モル％以上で、通常 95モル％以下、好 ましくは 90モル％以下である。この付加率が少なすぎると、塗膜にした場合の膜物性 が低下するおそれがあり、多いと、得られる榭脂溶液の粘度が増大し、取り扱いが困 難となることがある。 [0071] 上記のエポキシ化合物（a)に、不飽和基含有カルボン酸 (b)を付加させた後、イソ シァネート基を有する化合物（c)を付加させる方法としては、公知の方法を用いること ができる。その反応温度は通常 40°C以上、好ましくは 50°C以上で、通常 150°C以下 、好ましくは 100°C以下であり、反応時間は通常 1〜100時間、好ましくは 24時間以 内である。反応温度が 130°Cを超えると、不飽和基の重合が一部起こり、分子量の急 激な増大につながり、 80°C未満では反応がスムーズに進まないおそれがある。 The addition ratio of the compound (c) having an isocyanate group is usually 10 mol% or more, preferably 20 mol, of the hydroxyl group produced when the unsaturated group-containing carboxylic acid (b) is added to the epoxy compound (a). % Or more, particularly preferably 30 mol% or more, usually 95 mol% or less, preferably 90 mol% or less. If this addition rate is too small, the film physical properties may decrease when it is formed into a coating film. If it is too large, the viscosity of the resulting resin solution will increase, and handling may be difficult. [0071] As a method of adding the unsaturated group-containing carboxylic acid (b) to the epoxy compound (a) and then adding the compound (c) having an isocyanate group, a known method may be used. it can. The reaction temperature is usually 40 ° C or higher, preferably 50 ° C or higher, usually 150 ° C or lower, preferably 100 ° C or lower, and the reaction time is usually 1 to 100 hours, preferably 24 hours or less. . If the reaction temperature exceeds 130 ° C, polymerization of unsaturated groups will occur in part, leading to a rapid increase in molecular weight, and if it is less than 80 ° C, the reaction may not proceed smoothly.
[0072] この付加反応では、触媒を用いても良ぐ触媒としては通常のウレタン化反応触媒 が用いられる。例えばジブチルチンジラウレート、ジォクチルチンジラウレート、ジブチ ルチンジォタトエート、スタナスォクトエート等の錫系、鉄ァセチルァセトナート、塩ィ匕 第二鉄等の鉄系、トリェチルァミン、トリエチレンジァミン等の 3級ァミン系等が挙げら れる。  [0072] In this addition reaction, an ordinary urethanization reaction catalyst is used as a catalyst that may be used as a catalyst. For example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diatoate, stannous octoate and other tin systems, iron acetyl cetate, ferrous salts such as ferric iron, triethylamine, triethylene diamine Examples include tertiary amines such as amines.
[0073] [多塩基酸無水物（d)の付加]  [0073] [Addition of polybasic acid anhydride (d)]
本発明に係るアルカリ可溶性不飽和榭脂は、エポキシ化合物 (a)と不飽和基含有 カルボン酸 (b)との反応物の水酸基にイソシァネート基を有する化合物（c)を付加さ せた後、酸価の調整のために更に多塩基酸無水物（d)を付加させたものであること が好ましい。  The alkali-soluble unsaturated resin according to the present invention is obtained by adding the compound (c) having an isocyanate group to the hydroxyl group of the reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b). It is preferable that a polybasic acid anhydride (d) is further added to adjust the value.
[0074] 多塩基酸無水物（d)としては、公知のものが使用でき、無水マレイン酸、無水コハク 酸、無水ィタコン酸、無水フタル酸、テトラヒドロ無水フタル酸、へキサヒドロ無水フタ ル酸、メチルエンドメチレンテトラヒドロ無水フタル酸、無水クロレンド酸、メチルテトラヒ ドロ無水フタル酸等のジカルボン酸無水物；無水トリメリット酸、無水ピロメリット酸、ベ ンゾフエノンテトラカルボン酸二無水物、ビフエ-ルテトラカルボン酸二無水物、ビフエ -ルエーテルテトラカルボン酸二無水物等のテトラカルボン酸二無水物等が挙げら れる。特に、テトラヒドロ無水フタル酸又は無水コハク酸などのジカルボン酸無水物と 、ベンゾフエノンテトラカルボン酸二無水物、ビフエ-ルテトラカルボン酸などのテトラ カルボン酸二無水物を併用して使用することが、得られる感光性榭脂組成物を成膜 した場合に、良好な膜特性を示すため好ましい。テトラカルボン酸二無水物を用いる 場合、更に一方の酸無水物部に分子中に活性水素基を有する化合物を付加させて 、酸価を調整したり、不飽和基を導入したりしても良い。上述の分子中に活性水素基 を有する化合物のうち、酸価調整用途としてはクェン酸、マリック酸、ヒドロキシピバリ ック酸等の活性水素基と有機酸基を有するものが挙げられ、また、不飽和基を導入 する用途としては、ヒドロキシェチル (メタ)アクリル酸、ヒドロキシブチル (メタ)アクリル 酸、 2—ヒドロキシメチルアクリル酸メチルエステル、 2—ヒドロキシメチルアクリル酸ェ チルエステル等の不飽和基と活性水素基を有するものが挙げられる。 [0074] As the polybasic acid anhydride (d), known ones can be used. Maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl Dicarboxylic anhydrides such as endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic acid Examples thereof include dianhydrides and tetracarboxylic dianhydrides such as biether ether tetracarboxylic dianhydrides. In particular, a dicarboxylic anhydride such as tetrahydrophthalic anhydride or succinic anhydride may be used in combination with a tetracarboxylic dianhydride such as benzophenone tetracarboxylic dianhydride or biphenyltetracarboxylic acid. In the case where the resulting photosensitive resin composition is formed into a film, it is preferable because it exhibits good film characteristics. When tetracarboxylic dianhydride is used, the acid value may be adjusted or an unsaturated group may be introduced by adding a compound having an active hydrogen group in the molecule to one acid anhydride part. . Active hydrogen group in the above molecule Among the compounds having an acid value, those having an active hydrogen group and an organic acid group such as citrate, malic acid, and hydroxypivalic acid can be used as acid value adjusting applications, and as an application for introducing an unsaturated group. Are those having an unsaturated group and an active hydrogen group, such as hydroxyethyl (meth) acrylic acid, hydroxybutyl (meth) acrylic acid, 2-hydroxymethylacrylic acid methyl ester, 2-hydroxymethylacrylic acid ethyl ester, and the like. It is done.
[0075] 多塩基酸無水物（d)の付加率は、エポキシ化合物 (a)に不飽和基含有カルボン酸  [0075] The addition rate of the polybasic acid anhydride (d) is determined based on the unsaturated compound-containing carboxylic acid added to the epoxy compound (a).
(b)を付加させたときに生成される水酸基の、通常 5〜90モル％、好ましくは 5〜80 モル％、より好ましくは 5〜70モル％である。この付加率が少なすぎると溶解性が不 足したり、基板への密着性が不足することがある。  The amount of the hydroxyl group produced when (b) is added is usually 5 to 90 mol%, preferably 5 to 80 mol%, more preferably 5 to 70 mol%. If the addition rate is too small, the solubility may be insufficient or the adhesion to the substrate may be insufficient.
[0076] 上記のエポキシ化合物（a)と不飽和基含有カルボン酸 (b)との反応物のイソシァネ ート化合物（c)付加物に、多塩基酸無水物（d)を付加させる方法としては、公知の方 法を用いることができる。その反応温度は通常 80°C以上、好ましくは 90°C以上で、 通常 130°C以下、好ましくは 125°C以下である。反応温度が 130°Cを超えると、不飽 和基の重合が一部起こり、分子量の急激な増大につながり、 80°C未満では反応がス ムーズに進まず、多塩基酸無水物（d)が残存するおそれがある。  [0076] As a method of adding the polybasic acid anhydride (d) to the isocyanate compound (c) addition product of the reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b), A known method can be used. The reaction temperature is usually 80 ° C or higher, preferably 90 ° C or higher, usually 130 ° C or lower, preferably 125 ° C or lower. When the reaction temperature exceeds 130 ° C, polymerization of unsaturated groups occurs in part, leading to a rapid increase in molecular weight. At temperatures below 80 ° C, the reaction does not proceed smoothly, and the polybasic acid anhydride (d) May remain.
[0077] [エポキシ基含有化合物 (e)の付加]  [0077] [Addition of epoxy group-containing compound (e)]
本発明に係るアルカリ可溶性不飽和榭脂は、上記のエポキシ化合物（a)と不飽和 基含有カルボン酸 (b)との反応物のイソシァネートイ匕合物（c)付加物に、多塩基酸無 水物（d)を付加させた後、更に、生成したカルボキシル基の一部にエポキシ基含有 化合物（e)を付加させたものであっても良!、。  The alkali-soluble unsaturated resin according to the present invention includes an isocyanate compound (c) adduct of a reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b) with a polybasic acid-free water. After addition of the product (d), an epoxy group-containing compound (e) may be further added to a part of the generated carboxyl group.
[0078] この場合、エポキシ基含有化合物（e)としては、光感度を向上させるための、グリシ ジル (メタ）アタリレート、 3, 4—エポキシシクロへキシル (メタ）アタリレートや、重合性 不飽和基を有するグリシジルエーテルィ匕合物などや、現像性を向上させるための、 重合性不飽和基を有さな 、グリシジルエーテルィ匕合物などを用いることができ、この 両者を併用しても良 ヽ。重合性不飽和基を有さな ヽグリシジルエーテルィ匕合物の具 体例としてはフエ-ル基ゃアルキル基を有するグリシジルエーテルィ匕合物（ナガセ化 成工業 (株）製「デナコール EX— 111」、「デナコール EX— 121」、「デナコール EX — 141」、「デナコール EX— 145」、「デナコール EX— 146」、「デナコール EX— 17 1」、「デナコール EX— 192」）等がある。 [0078] In this case, as the epoxy group-containing compound (e), glycidyl (meth) acrylate, 3, 4-epoxy cyclohexyl (meth) acrylate, or polymerizable non-polymerizable compounds for improving photosensitivity are used. A glycidyl ether compound having a saturated group or a glycidyl ether compound having no polymerizable unsaturated group for improving developability can be used. Also good. Specific examples of glycidyl ether compounds having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group (“Denacol EX—111” manufactured by Nagase Chemical Industries Co., Ltd.). ”,“ Denacol EX—121 ”,“ Denacol EX—141 ”,“ Denacol EX—145 ”,“ Denacol EX—146 ”,“ Denacol EX—17 ” 1 ”,“ Denacol EX—192 ”).
[0079] [分子内に少なくとも 2個以上のフ ノール性水酸基を有するフ ノール性水酸基 含有化合物 (f) ] [0079] [A phenolic hydroxyl group-containing compound having at least two phenolic hydroxyl groups in the molecule (f)]
フエノール性水酸基含有化合物 (f)は分子内に少なくとも 2個以上のフ ノール性 水酸基を有するものであれば特に限定はないが、例えば下記一般式 (I f)で表され るフエノール性水酸基含有化合物が挙げられる。  The phenolic hydroxyl group-containing compound (f) is not particularly limited as long as it has at least two phenolic hydroxyl groups in the molecule. For example, the phenolic hydroxyl group-containing compound represented by the following general formula (I f) Is mentioned.
[化 16]  [Chemical 16]
HO-X-OH ( I -0 HO-X-OH (I -0
、 ,
Figure imgf000030_0001
Figure imgf000030_0001
[0080] 上記一般式 (I f)において、 Xは、前記一般式 (I a)における Xと同義であり、そ の好ま 、構造等にっ 、ても前述の一般式 (I a)の説明にお 、て記載した通りであ る。 [0080] In the above general formula (I f), X has the same meaning as X in the general formula (I a), and it is preferable to explain the general formula (I a) described above, depending on its structure and the like. As described above.
[0081] [不飽和基含有エポキシ化合物 (g) ]  [0081] [Unsaturated epoxy compound (g)]
不飽和基含有エポキシ化合物 (g)はエチレン性不飽和二重結合を有し、分子内に エポキシ基を有するものであれば特に限定はな 、が、エポキシ基を有するアタリレー ト類が好ましぐ具体的には例えばグリシジル (メタ）アタリレート、 3, 4 エポキシシク 口へキシル (メタ）アタリレート等が挙げられる。  The unsaturated group-containing epoxy compound (g) is not particularly limited as long as it has an ethylenically unsaturated double bond and has an epoxy group in the molecule. However, an acrylate having an epoxy group is preferred. Specific examples include glycidyl (meth) acrylate and 3, 4 epoxy hexyl (meth) acrylate.
[0082] [フエノール性水酸基含有化合物 (f)と不飽和基含有エポキシ化合物 (g)との反応] フエノール性水酸基含有化合物 (f)と不飽和基含有エポキシ化合物 (g)とを反応さ せる方法としては公知の手法を用いることができる。例えば、上記のフエノール性水 酸基含有化合物 (f)と不飽和基含有エポキシ化合物 (g)とをトリエチルァミン、ベンジ ルメチルァミン等の 3級ァミン、ドデシルトリメチルアンモ -ゥムクロライド、テトラメチル アンモ-ゥムクロライド、テトラエチルアンモ -ゥムクロライド、ベンジルトリェチルアン モ -ゥムクロライド等の 4級アンモ-ゥム塩、ピリジン、トリフエ-ルホスフィン等を触媒 として、有機溶剤中、反応温度 50〜150°Cで数〜数十時間反応させることにより、フ ェノール性水酸基含有化合物 (f)に不飽和基含有エポキシ化合物 (g)を付加するこ とがでさる。 [Reaction of phenolic hydroxyl group-containing compound (f) and unsaturated group-containing epoxy compound (g)] The phenolic hydroxyl group-containing compound (f) and unsaturated group-containing epoxy compound (g) are reacted. A known method can be used as a method for the above. For example, the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g) are mixed with a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, Quaternary ammonium salts such as tetraethylammonium chloride, benzyltriethylammonium chloride, pyridine, triphenylphosphine, etc. as a catalyst in an organic solvent at a reaction temperature of 50 to 150 ° C for several to several tens of hours By reacting, an unsaturated group-containing epoxy compound (g) can be added to the phenolic hydroxyl group-containing compound (f).
[0083] 該触媒の使用量は、反応原料混合物 (フエノール性水酸基含有化合物 (f)と不飽 和基含有エポキシィ匕合物 (g)との合計）に対して好ましくは 0. 01重量％以上、特に 好ましくは 0. 3重量％以上で、好ましくは 10重量％以下、特に好ましくは 5重量％以 下である。また反応中の重合を防止するために、重合防止剤（例えばメトキノン、ハイ ドロキノン、メチルハイドロキノン、 p—メトキシフエノール、ピロガロール、 tert—ブチル カテコール、フエノチアジン等）を使用することが好ましぐその使用量は、反応原料 混合物に対して好ましくは 0. 01重量％以上、特に好ましくは 0. 1重量％以上で、好 ましくは 10重量％以下、特に好ましくは 5重量％である。  [0083] The amount of the catalyst used is preferably 0.01% by weight or more based on the reaction raw material mixture (the total of the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g)). Particularly preferably, it is 0.3% by weight or more, preferably 10% by weight or less, particularly preferably 5% by weight or less. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butyl catechol, phenothiazine). Is preferably 0.01% by weight or more, particularly preferably 0.1% by weight or more, preferably 10% by weight or less, particularly preferably 5% by weight, based on the reaction raw material mixture.
[0084] フエノール性水酸基含有化合物 (f)に対して反応させる不飽和基含有エポキシィ匕 合物 (g)の割合は、通常 90〜120モル％である。エポキシ基の残存は保存安定性に 悪影響を与えるため、フエノール性水酸基含有化合物 (f)は不飽和基含有エポキシ 化合物 (g)のエポキシ基 1当量に対して、通常 0. 8当量以上、特に 0. 9当量以上で 、通常 1. 5当量以下、特に 1. 2当量以下の割合で反応を行うことが好ましい。  [0084] The ratio of the unsaturated group-containing epoxy compound (g) to be reacted with the phenolic hydroxyl group-containing compound (f) is usually 90 to 120 mol%. Since the residual epoxy group adversely affects storage stability, the phenolic hydroxyl group-containing compound (f) is usually at least 0.8 equivalent, especially 0, relative to 1 equivalent of the epoxy group of the unsaturated group-containing epoxy compound (g). It is preferable to carry out the reaction at a ratio of 9 equivalents or more, usually 1.5 equivalents or less, particularly 1.2 equivalents or less.
[0085] [イソシァネート基を有する化合物（c)の付加、多塩基酸無水物（d)の付加、ェポキ シ基含有化合物 (e)の付加]  [0085] [Addition of compound (c) having isocyanate group, addition of polybasic acid anhydride (d), addition of epoxy group-containing compound (e)]
フエノール性水酸基含有化合物 (f)と不飽和基含有エポキシ化合物 (g)との反応物 へのイソシァネート基を有する化合物（c)の付加、更には多塩基酸無水物（d)の付 カロ、エポキシ基含有化合物 (e)の付加はそれぞれ、前記の、分子内に少なくとも 2個 以上のエポキシ基を有するエポキシ化合物（a)と不飽和基含有カルボン酸 (b)との 反応物へのイソシァネート基を有する化合物（c)の付加、多塩基酸無水物（d)の付 カロ、エポキシ基含有化合物 (e)の付加と同様の方法で行うことができる。 Addition of a compound (c) having an isocyanate group to a reaction product of a phenolic hydroxyl group-containing compound (f) and an unsaturated group-containing epoxy compound (g), and addition of a polybasic acid anhydride (d) The addition of the group-containing compound (e) is performed by adding an isocyanate group to the reaction product of the epoxy compound ( a ) having at least two epoxy groups in the molecule and the unsaturated group-containing carboxylic acid (b). Addition of compound (c), polybasic acid anhydride (d) Caro and an epoxy group-containing compound (e) can be added in the same manner.
[0086] [アルカリ可溶性不飽和榭脂の物性]  [0086] [Physical properties of alkali-soluble unsaturated rosin]
上述のようにして得られる本発明に係るアルカリ可溶性不飽和榭脂の GPCで測定 したポリスチレン換算重量平均分子量 (Mw)は通常 700以上、好ましくは 1000以上 であり、通常 50000以下、好ましくは 30000以下である。このアルカリ可溶性不飽和 榭脂の重量平均分子量が小さすぎると、耐熱性、膜強度に劣り、大きすぎると現像液 に対する溶解性が不足するため好ましくな 、。  The weight average molecular weight (Mw) in terms of polystyrene measured by GPC of the alkali-soluble unsaturated resin according to the present invention obtained as described above is usually 700 or more, preferably 1000 or more, and usually 50000 or less, preferably 30000 or less. It is. If the weight average molecular weight of the alkali-soluble unsaturated resin is too small, the heat resistance and the film strength are inferior, and if it is too large, the solubility in the developer is insufficient.
[0087] また、本発明に係るアルカリ可溶性不飽和榭脂の酸価 (mg-KOH/g)は、通常 1 0以上、好ましくは 30以上であり、通常 200以下、好ましくは 150以下である。アル力 リ可溶性不飽和榭脂の酸価が低すぎると十分な溶解性が得られず、酸価が高すぎる と硬化性が不足し、表面性が悪化する。  [0087] The acid value (mg-KOH / g) of the alkali-soluble unsaturated coconut resin according to the present invention is usually 10 or more, preferably 30 or more, and usually 200 or less, preferably 150 or less. Al force If the acid value of the re-soluble unsaturated resin is too low, sufficient solubility cannot be obtained, and if the acid value is too high, the curability is insufficient and the surface properties deteriorate.
[0088] <光重合開始剤 >  [0088] <Photopolymerization initiator>
本発明の感光性榭脂組成物は、更に光重合開始剤を含有していても良い。  The photosensitive resin composition of the present invention may further contain a photopolymerization initiator.
[0089] 本発明に用いられる光重合開始剤は、活性光線によりエチレン性不飽和基を重合 させる化合物であれば特に限定されないが、本発明の感光性榭脂組成物が、重合 可能な基を有する化合物としてエチレン性ィ匕合物を含む場合には、光を直接吸収す るか光増感されて、分解反応又は水素引き抜き反応を起こし、重合活性ラジカルを 発生する機能を有する光重合開始剤を使用するのが好ましい。  [0089] The photopolymerization initiator used in the present invention is not particularly limited as long as it is a compound that polymerizes an ethylenically unsaturated group with actinic rays, but the photosensitive resin composition of the present invention has a polymerizable group. In the case where the compound having an ethylenic compound is included, the photopolymerization initiator has a function of generating a polymerization active radical by directly absorbing or photosensitizing light and causing a decomposition reaction or a hydrogen abstraction reaction. Is preferably used.
[0090] 本発明で用いることができる光重合開始剤の具体的な例を以下に列挙する。 2 - (4 —メトキシフエ-ル） 4, 6—ビス（トリクロロメチル） s トリァジン、 2— (4—メトキシ ナフチル）—4, 6—ビス（トリクロロメチル）—s トリァジン、 2— (4—エトキシナフチル） —4, 6—ビス（トリクロロメチル）—s トリァジン、 2— (4—エトキシカルボ-ルナフチル )—4, 6 ビス（トリクロロメチル） s トリァジン等のハロメチルイ匕トリァジン誘導体; 2 —トリクロロメチル一 5— (2'—ベンゾフリル）一 1, 3, 4—ォキサジァゾール、 2 トリクロ ロメチル— 5—〔 β - (2'—ベンゾフリル）ビュル〕— 1, 3, 4—ォキサジァゾール、—トリ クロロメチル一 5—〔 — (2'— (6"—ベンゾフリル）ビュル）〕一 1, 3, 4—ォキサジァゾ ール、 2 トリクロロメチル— 5—フリル— 1, 3, 4—ォキサジァゾール等のハロメチル化 ォキサジァゾール誘導体； 2—（2 '—クロ口フエ-ル） -4, 5 ジフエ-ルイミダソール 2 量体、 2— (2'—クロ口フエ-ル） -4, 5 ビス（3'—メトキシフエ-ル）イミダゾール 2量 体、 2— (2'—フルオロフェ -ル）—4, 5 ジフエ-ルイミダゾール 2量体、 2— (2'—メト キシフエ-ル）一 4, 5 ジフエ-ルイミダゾール 2量体、（4'—メトキシフエ-ル）一 4, 5 ジフエ-ルイミダゾール 2量体等のイミダゾール誘導体；ベンゾインメチルエーテル 、ベンゾインフエ-ルエーテル、ベンゾインイソブチルエーテル、ベンゾインイソプロピ ルエーテル等のベンゾインアルキルエーテル類； 2—メチルアントラキノン、 2 -ェチル アントラキノン、 2—t—ブチルアントラキノン、 1 クロ口アントラキノン等のアントラキノ ン誘導体；ベンゾフエノン、ミヒラーズケトン、 2 メチルベンゾフエノン、 3 メチルベン ゾフエノン、 4—メチノレべンゾフエノン、 2 クロ口べンゾフエノン、 4—ブロモベンゾフエ ノン、 2—力ノレボキシベンゾフエノン等のベンゾフエノン誘導体； 2, 2—ジメトキシー 2— フエニルァセトフエノン、 2, 2 ジエトキシァセトフエノン、 1ーヒドロキシシクロへキシル フエ二ルケトン、 α ヒドロキシ一 2—メチルフエニルプロパノン、 1—ヒドロキシ一 1—メ チルェチル一（ρ—イソプロピルフエ-ル）ケトン、 1—ヒドロキシ一 1— (ρ ドデシルフ ェ -ル）ケトン、 2—メチルー（4，一（メチルチオ）フエ-ル）ー2 モルホリノー1 プロ ノ《ノン、 1, 1, 1—トリクロロメチル一（ρ ブチルフエ-ル）ケトン等のァセトフエノン誘 導体；チォキサントン、 2—ェチルチオキサントン、 2—イソプロピルチォキサントン、 2 クロ口チォキサントン、 2, 4 ジメチルチオキサントン、 2, 4 ジェチルチオキサント ン、 2, 4ージイソプロピルチオキサントン等のチォキサントン誘導体; ρ ジメチルアミ ノ安息香酸ェチル、 Ρ ジェチルァミノ安息香酸ェチル等の安息香酸エステル誘導 体； 9-フエ-ルァクリジン、 9- (Ρ-メトキシフエ-ル）アタリジン等のアタリジン誘導体； 9, 10-ジメチルベンズフエナジン等のフエナジン誘導体；ベンズアンスロン等のアンス口 ン誘導体；ジシクロペンタジェ-ル Ti ジクロライド、ジシクロペンタジェ-ル Ti— ビスフエ二ノレ、ジシクロペンタジェニノレー Ti—ビス 2, 3, 4, 5, 6—ペンタフノレオロフ ェニルー 1 ィル、ジシクロペンタジェ二ルー Ti—ビス 2, 3, 5, 6—テトラフルオロフ ェニルー 1 ィル、ジシクロペンタジェ二ルー Ti—ビス 2, 4, 6 トリフルオロフェニ 1 ィル、ジシクロペンタジェ二ルー Ti— 2, 6 ジプルオロフェニー 1 ィル、ジシク 口ペンタジェ二ルー Ti— 2, 4—ジフルオロフェニー 1 ィル、ジメチルシクロペンタジ ェ-ル Ti—ビス一 2, 3, 4, 5, 6 ペンタフルォロフエ- 1—ィル、ジメチルシクロ ペンタジェ二ルー Ti—ビス 2, 6 ジフルオロフェニー 1 ィル、ジシクロペンタジェ -ル一 Ti— 2, 6 ジフルォロ一 3— (ピル一 1—ィル）一フエ- 1—ィル等のチタノセ ン誘導体。更には、特開 2000— 80068号公報に記載されているォキシム系開始剤 も特に好適に使用できる。 [0090] Specific examples of the photopolymerization initiator that can be used in the present invention are listed below. 2- (4-Methoxyphenyl) 4,6-Bis (trichloromethyl) s triazine, 2- (4-Methoxynaphthyl) -4,6-bis (trichloromethyl) -s triazine, 2- (4-ethoxynaphthyl) ) —4, 6-bis (trichloromethyl) —s triazine, 2— (4-ethoxycarbo-naphthalyl) —4, 6 bis (trichloromethyl) s triazine and other halomethyl iodotriazine derivatives; 2 — trichloromethyl mono 5— (2'-benzofuryl) -1,3,4-oxadiazole, 2 trichloromethyl-5- [β- (2'-benzofuryl) bulu]-1,3,4-oxadiazol, trichloromethyl-1-5- (2 '— (6 ”-benzofuryl) butyl)] 1, 1, 4- 4-oxadiazol, 2 halomethylated oxadiazole derivatives such as trichloromethyl-5-furyl-1, 3, 4-oxadiazole; 2- (2 '—Black mouth ferrule) -4, 5 Dimer, 2— (2′—Black-mouthed) -4, 5 Bis (3′-methoxyphenol) imidazole Dimer, 2 -— (2′-Fluorophenol) —4, 5 Diphenyl Imidazole dimer, imidazole such as 2- (2'-methoxyphenyl) -1,4,5 diphenylimidazole dimer, (4'-methoxyphenol) -1,4,5 diphenylimidazole dimer Derivatives; Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenol ether, benzoin isobutyl ether, and benzoin isopropyl ether; Anthraquinones such as 2-methylanthraquinone, 2-ethyl anthraquinone, 2-t-butylanthraquinone, and 1-mouth anthraquinone Derivatives: benzophenone, Michler's ketone, 2 methylbenzophenone, 3 methylbenzophenone, 4-methinolebenzophenone, 2 chloro Benzophenone derivatives such as oral benzophenone, 4-bromobenzophenone, 2-force noreboxybenzophenone, 2, 2-dimethoxy 2-phenylacetophenone, 2, 2 diethoxyacetophenone, 1-hydroxycyclohex Xylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methyl ether (ρ-isopropylphenol) ketone, 1-hydroxy-1- (ρ dodecyl phenyl) ketone, 2-methyl- (4,1 (methylthio) phenol) -2 morpholino 1pronone << non, 1, 1, 1-trichloromethyl mono (ρ-butylphenol) ketone and other acetophenone derivatives; thixanthone, 2- Tilthioxanthone, 2-Isopropylthixanthone, 2-clothioxanthone, 2,4 Dimethylthioxanthone, 2,4 Jettyl Thioxanthone derivatives such as xanthone and 2,4-diisopropylthioxanthone; ρ Derivatives of benzoic acid esters such as dimethylaminobenzoate, ェ ethylylbenzoate; 9-phenolacridine, 9- (Ρ-methoxyphenol) ataridin Phenazine derivatives such as 9, 10-dimethylbenzphenazine; anthrone derivatives such as benzanthrone; dicyclopentagel Ti dichloride, dicyclopentagel Ti-bisphenol, di Cyclopentageninore Ti-bis 2, 3, 4, 5, 6-pentafluororeophenyl 1 yl, dicyclopentadienyl Ti-bis 2, 3, 5, 6-tetrafluorophenyl 1 yl Dicyclopentadiene Ti-bis 2, 4, 6 trifluorophenyl 1 dicyclopentadiene Ti— 2, 6 diploro Phenol 1 il, Dicyclopentadiene Ti- 2, 4-Difluorophene 1 dimethylcyclopentadiyl Ti-bis 1, 3, 4, 5, 6 Pentafluorophe 1 And dimethylcyclo Titanocene such as Penta-Ji-Lu Ti—Bis 2,6 Difluoropheny 1-yl, Dicyclopenta-gel 1 Ti— 2, 6 Difluoro 1--Pil 1--il 1-F 1-il Derivative. Furthermore, the oxime initiators described in JP-A-2000-80068 can be particularly preferably used.
[0091] この他、本発明で用いることができる光重合開始剤は、ファインケミカル、 1991年 3 月 1日号、 Vol.20、 No.4, P.16〜P26や、特開昭 59— 152396号公報、特開昭 61— 151197号公報、特公昭 45— 37377号公報、特開昭 58— 40302号公報、特 開平 10— 39503号公報にも記載されて 、る。  [0091] In addition, 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. No. 61-151197, JP-B 45-37377, JP-A 58-40302, and JP-A 10-39503.
[0092] <色材>  [0092] <Coloring material>
本発明の感光性榭脂組成物は、更に色材を含有する感光性着色榭脂組成物であ つても良い。  The photosensitive resin composition of the present invention may be a photosensitive colored resin composition further containing a coloring material.
[0093] 色材としては、染顔料が使用できるが、耐熱性、耐光性等の点力も顔料が好ま 、 。顔料としては青色顔料、緑色顔料、赤色顔料、黄色顔料、紫色顔料、オレンジ顔料 、ブラウン顔料、黒色顔料等各種の色の顔料を使用することができる。また、その構 造としてはァゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、イソインド リノン系、ジォキサジン系、インダンスレン系、ペリレン系等の有機顔料の他に種々の 無機顔料等も利用可能である。以下に、使用できる顔料の具体例をビグメントナンパ 一で示す。なお、以下に挙げる「C. I.ビグメントレッド 2」等の用語は、カラーインデッ タス (C. I. )を意味する。  [0093] As the coloring material, dyes and pigments can be used, but pigments are also preferred in terms of heat resistance, light resistance, and the like. As the pigment, pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to its organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene and perylene, various inorganic pigments are also used. Is possible. Specific examples of pigments that can be used are shown below as pigment numbers. Terms such as “C.I. Pigment Red 2” mentioned below mean color index (C.I.).
[0094] 赤色顔料としては、 C. I.ピグメントレッド 1、 2、 3、 4、 5、 6、 7、 8、 9、 12、 14、 15、 16、 17、 21、 22、 23、 31、 32、 37、 38、 41、 47、 48、 48:1、 48:2、 48:3、 48:4 、 49、 49:1、 49:2、 50:1、 52:1、 52:2、 53、 53:1、 53:2、 53:3、 57、 57:1、 57 :2、 58:4、 60、 63、 63:1、 63:2、 64、 64:1、 68、 69、 81、 81:1、 81:2、 81:3、 81:4、 83、 88、 90:1、 101、 101:1、 104、 108、 108:1、 109、 112、 113、 114、 122、 123、 144、 146、 147、 149、 151、 166、 168、 169、 170、 172、 173、 174 、 175、 176、 177、 178、 179、 181、 184、 185、 187、 188、 190、 193、 194、 20 0、 202、 206、 207、 208、 209、 210、 214、 216、 220、 221、 224、 230、 231、 2 32、 233、 235、 236、 237、 238、 239、 242、 243、 245、 247、 249、 250、 251、 253、 254、 255、 256、 257、 258、 259、 260、 262、 263、 264、 265、 266、 267 、 268、 269、 270、 271、 272、 273、 274、 275、 276を挙げ、ること力 Sできる。この中 でも、好ましくは C. I.ビグメントレッド 48:1、 122、 168、 177、 202、 206、 207、 20 9、 224、 242、 254、更に好ましく ίま C. I.ピグメントレッド 177、 209、 224、 254を挙 げることができる。 [0094] Examples of red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37. , 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53 : 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81 : 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144 , 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 20 0, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247 , 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 Power S can be. Of these, CI CI Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably ί CI Pigment Red 177, 209, 224, 254 are preferably used. I can list them.
[0095] 青色顔料としては、 C. I.ピグメントブノレ一 1、 1:2、 9、 14、 15、 15:1、 15:2、 15:  [0095] Blue pigments include C. I. Pigment Bnole 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15:
3、 15:4、 15:6、 16、 17、 19、 25、 27、 28、 29、 33、 35、 36、 56、 56:1、 60、 61 、61:1、 62、 63、 66、 67、 68、 71、 72、 73、 74、 75、 76、 78、 79を挙げ、ること力 Sで きる。この中でも、好ましくは C. I.ピグメントブノレ一 15、 15:1、 15:2、 15:3、 15:4、 15:6、更に好ましくは C. I.ビグメントブルー 15 :6を挙げることができる。  3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among these, C.I. pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. pigment blue 15: 6 can be mentioned.
[0096] 緑色顔料としては、 C. I.ピグメントグリーン 1、 2、 4、 7、 8、 10、 13、 14、 15、 17、 1 8、 19、 26、 36、 45、 48、 50、 51、 54、 55を挙げ、ること力 Sできる。この中でも、好まし くは C. I.ビグメントグリーン 7、 36を挙げることができる。  [0096] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 1 8, 19, 26, 36, 45, 48, 50, 51, 54, You can raise 55 and have the power S. Among these, CI Pigment Green 7 and 36 are preferable.
[0097] 黄色顔料としては、 C. I.ピグメントイエロー 1、 1： 1、 2、 3、 4、 5、 6、 9、 10、 12、 13 、 14、 16、 17、 24、 31、 32、 34、 35、 35: 1、 36、 36: 1、 37、 37: 1、 40、 41、 42、 43、 48、 53、 55、 61、 62、 62:1、 63、 65、 73、 74、 75, 81、 83、 87、 93、 94、 95 、 97、 100、 101、 104、 105、 108、 109、 110、 111、 116、 117、 119、 120、 126 、 127、 127:1、 128、 129、 133、 134、 136、 138、 139、 142、 147、 148、 150、 151、 153、 154、 155、 157、 158、 159、 160、 161、 162、 163、 164、 165、 166 、 167、 168、 169、 170、 172、 173、 174、 175、 176、 180、 181、 182、 183、 18 [0097] CI pigment yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81 , 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133 , 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169 , 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 18
4、 185、 188、 189、 190、 191、 191:1、 192、 193、 194、 195、 196、 197、 198 、 199、 200、 202、 203、 204、 205、 206、 207、 208を挙げ、ること力 Sできる。この中 でも、好ましくは C. I.ビグメントイエロー 83、 117、 129, 138, 139, 150、 154, 154, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 Ability to do S. Among these, C.I. pigment yellow 83, 117, 129, 138, 139, 150, 154, 15 is preferable.
5、 180、 185、更に好ましくは C. I.ビグメントイエロー 83、 138、 139、 150、 180を 挙げることができる。 5, 180, 185, more preferably CI pigment yellow 83, 138, 139, 150, 180.
[0098] 才レンジ顔料としては、 C. I.ピグメント才レンジ 1、 2、 5、 13、 16、 17、 19、 20、 21 、 22、 23、 24、 34、 36、 38、 39、 43、 46、 48、 49、 61、 62、 64、 65、 67、 68、 69 、 70、 71、 72、 73、 74、 75、 77、 78、 79を挙げ、ること力 Sできる。この中でも、好ましく は、 C. I.ビグメントオレンジ 38、 71を挙げることができる。 [0098] CI range pigment range 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 Among these, preferably Can mention CI Pigment Orange 38, 71.
[0099] 紫色顔料としては、 C. I.ビグメントバイオレット 1、 1 : 1、 2、 2 : 2、 3、 3 : 1、 3 : 3、 5、  [0099] Purple pigments include C.I. pigment violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5,
5 : 1、 14、 15、 16、 19、 23、 25、 27、 29、 31、 32、 37、 39、 42、 44、 47、 49、 50 を挙げることができる。この中でも、好ましくは C. I.ビグメントバイオレット 19、 23、更 に好ましくは C. I.ビグメントバイオレット 23を挙げることができる。  5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among these, C.I. pigment violet 19, 23 is preferable, and C.I. pigment violet 23 is more preferable.
[0100] また、本発明の感光性榭脂組成物が、カラーフィルタの榭脂ブラックマトリックス用 感光性着色榭脂組成物である場合、色材としては、黒色の色材を用いることができる 。黒色色材は、黒色色材を単独でも良ぐ又は赤、緑、青等の混合によるものでも良 い。また、これら色材は無機又は有機の顔料、染料の中から適宜選択することができ る。無機、有機顔料の場合には平均粒径 1 μ m以下、好ましくは 0. 5 μ m以下に分 散して用いるのが好ましい。  [0100] When the photosensitive resin composition of the present invention is a photosensitive colored resin composition for a black filter matrix of a color filter, a black color material can be used as the color material. The black color material may be a single black color material or a mixture of red, green, blue and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable that the average particle size is 1 μm or less, preferably 0.5 μm or less.
[0101] 黒色色材を調製するために混合使用可能な色材としては、ビクトリアピュアブルー（ 42595)、オーラミン 0 (41000)、カチロンブリリアントフラビン（ベーシック 13)、ロー ダミン 6GCP (45160)、ローダミン B (45170)、サフラニン OK70 : 100 (50240)、ェ リオグラウシン X (42080)、 No. 120Zリオノールイェロー（21090)、リオノールイエ ロー GRO (21090)、シムラーファーストイェロー 8GF (21105)、ベンジジンイェロー 4T—564D (21095)、シムラーファーストレッド 4015 ( 12355)、リオノールレッド 7B 4401 ( 15850)、ファース卜ゲンブルー TGR—L (74160)、ジオノールブルー SM (2 6150)、リオノールブルー ES (ビグメントブルー 15 : 6)、リオノーゲンレッド GD (ビグメ ントレッド 168)、リオノールグリーン 2YS (ビグメントグリーン 36)等が挙げられる（なお 、上記の（ ）内の数字は、カラーインデックス (C. I. )を意味する）。  [0101] Color materials that can be mixed to prepare black color materials include Victoria Pure Blue (42595), Auramin 0 (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 (50240), Ellioglaucin X (42080), No. 120Z Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T—564D (21095), Shimla First Red 4015 (12355), Lionol Red 7B 4401 (15850), Firth Gen Blue TGR—L (74160), Dionol Blue SM (2 6150), Lionol Blue ES (Vigment Blue 15: 6), Lionogen Red GD (Vigment Red 168), Lionol Green 2YS (Vigment Green 36), etc. (The numbers in parentheses above are Color index (means C.I.)).
[0102] また、更に他の混合使用可能な顔料について C. I.ナンバーにて示すと、例えば、 C. I.黄色顔料 20、 24, 86, 93, 109、 110、 117, 125, 137, 138, 147, 148, 1 53、 154、 166、 C. I.オレンジ顔料 36、 43、 51、 55、 59、 61、 C. I.赤色顔料 9、 9 7、 122、 123、 149、 168、 177、 180、 192、 215、 216、 217、 220、 223、 224、 2 26、 227、 228、 240、 C. I.ノ ィォレツ卜顔料 19、 23、 29、 30、 37、 40、 50、 C. I. 青色顔料 15、 15 : 1、 15 : 4, 22、 60、 64, C. I.緑色顔料 7、 C. I.ブラウン顔料 23 、 25、 26等を挙げることができる。 [0103] また、単独使用可能な黒色色材としては、カーボンブラック、アセチレンブラック、ラ ンプブラック、ボーンブラック、黒鉛、鉄黒、ァ-リンブラック、シァニンブラック、チタン ブラック等が挙げられる。 [0102] Further, other pigments that can be used in combination are represented by CI numbers. For example, CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 1 53, 154, 166, CI orange pigment 36, 43, 51, 55, 59, 61, CI red pigment 9, 9 7, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 2 26, 227, 228, 240, CI Neolet Pigment 19, 23, 29, 30, 37, 40, 50, CI Blue Pigment 15, 15: 1, 15: 4, 22, 60 64, CI green pigment 7, CI brown pigment 23, 25, 26 and the like. [0103] Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, iron black, cyanine black, and titanium black.
[0104] これらの中で、特にカーボンブラック、チタンブラックが遮光率、画像特性の観点か ら好ましい。カーボンブラックの例としては、以下のようなカーボンブラックが挙げられ る。  Among these, carbon black and titanium black are particularly preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.
[0105] 三菱ィ匕学社製： MA7、 MA8、 MA11、 MA100、 MA100R、 MA220、 MA230、 MA600、 #5、 #10、 #20、 #25、 #30、 #32、 #33、 #40、 #44、 #45、 #4 7、 #50、 #52、 #55、 #650、 #750、 #850、 #950、 #960、 #970、 #980、 #990、 #1000、 #2200、 #2300、 #2350、 #2400、 #2600、 #3050、 #31 50、 #3250、 #3600、 #3750、 #3950、 #4000、 #4010、 OIL7B, OIL9B, OIL11Bゝ OIL30B、 OIL31B  [0105] Made by Mitsubishi Kaisha: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 4 7, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 31 50, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B ゝ OIL30B, OIL31B
[0106] デグサ社製： Printex3、 Printex30P、 Printex30、 Printex30OP、 Printex40、 Printex45、 Printex55、 Printex60、 Printex75、 Printex80、 Printex85、 Prin tex90、 Printex A、 Printex L、 Printex G、 Printex P、 Printex U、 Printe x V、 PrintexG、 SpecialBlack550、 SpecialBlack350、 SpecialBlack250、 Sp ecialBlackl00、 SpecialBlack6、 SpecialBlack5、 SpecialBlack4、 Color Blac k FW1、 Color Black FW2、 Color Black FW2V、 Color Black FW18、 C olor Black FW18、 Color Black FW200、 Color Black S 160、 Color Bla ck S170  [0106] Degussa: Printex3, Printex30P, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Prin tex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V , PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlackl00, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S 160, Color Bla ck S170
[0107] キャボット社製： Monarchl20、 Monarch280、 Monarch460、 Monarch800、 M onarch880、 Monarch900、 MonarchlOOO, MonarchllOO, Monarchl300、 Monarchl400、 Monarch4630、 REGAL99、 REGAL99R、 REGAL415、 RE GAL415Rゝ REGAL250、 REGAL250Rゝ REGAL330、 REGAL400Rゝ REG AL55R0, REGAL660R、 BLACK PEARLS480、 PEARLS 130, VULCAN XC72Rゝ ELFTEX-8  [0107] Cabot: Monarchl20, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, MonarchlOOO, MonarchllOO, Monarchl300, Monarchl400, Monarch4630, REGAL99, REGAL99R, REGAL415, RE GAL415R ゝ ALAL250, REGAL250R REG 250, REGAL250R REG 250 REGAL660R, BLACK PEARLS480, PEARLS 130, VULCAN XC72R ゝ ELFTEX-8
[0108] コロンビヤン カーボン社製： RAVEN11、RAVEN14、RAVEN15、RAVEN16、 RAVEN22RAVEN30, RAVEN35、 RAVEN40、 RAVEN410, RAVEN420 、 RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H、 RA VEN1000、 RAVEN1020, RAVEN1040、 RAVEN1060U、 RAVEN 1080U 、 RAVEN1170, RAVEN 1190U, RAVEN 1250, RAVEN 1500, RAVEN20 00、 RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN 5750、 RAVEN7000 [0108] Colombian Carbon: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420 RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RA VEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN 1080U, RAVEN1170, RAVEN 1190U, RAVEN 1250, RAVEN 1500, RAVEN20 00, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, VEN 5
[0109] チタンブラックの作製方法としては、二酸化チタンと金属チタンの混合体を還元雰 囲気下で加熱し還元させる方法 (特開昭 49— 5432号公報）、四塩ィ匕チタンの高温 加水分解で得られた超微細二酸化チタンを水素を含む還元雰囲気中で還元する方 法 (特開昭 57— 205322号公報）、二酸ィ匕チタン又は水酸ィ匕チタンをアンモニア存 在下で高温還元する方法 (特開昭 60— 65069号公報、特開昭 61— 201610号公 報）、二酸ィ匕チタン又は水酸ィ匕チタンにバナジウム化合物を付着させ、アンモニア存 在下で高温還元する方法 (特開昭 61— 201610号公報）、などがある力 これらに限 定されるものではない。  [0109] As a method for producing titanium black, a mixture of titanium dioxide and metallic titanium is heated and reduced in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432). The ultrafine titanium dioxide obtained in step 1 is reduced in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), and titanium dioxide dihydrate or titanium dioxide hydroxide is reduced at high temperature in the presence of ammonia. Method (JP-A-60-65069, JP-A-61-201610), a method in which a vanadium compound is attached to titanium dioxide dihydrate or titanium oxide hydroxide and reduced at high temperature in the presence of ammonia (special Kaisho 61—201610)) is not limited to these.
[0110] チタンブラックの市販品の例としては、三菱マテリアル社製チタンブラック 10S、 12 [0110] Examples of commercially available titanium black include Titanium Black 10S, 12 manufactured by Mitsubishi Materials Corporation.
Sゝ 13Rゝ 13Mゝ 13M— Cなど力挙げられる。 S ゝ 13R ゝ 13M ゝ 13M— C and so on.
[0111] 他の黒色顔料の例としては、チタンブラック、ァニリンブラック、酸化鉄系黒色顔料、 及び、赤色、緑色、青色の三色の有機顔料を混合して黒色顔料として用いることがで きる。 [0111] As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments. .
[0112] また、顔料として、硫酸バリウム、硫酸鉛、酸化チタン、黄色鉛、ベンガラ、酸化クロ ム等を用いることもできる。  [0112] Further, as the pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, and the like can also be used.
[0113] これら各種の顔料は、複数種を併用することもできる。例えば、色度の調整のため に、顔料として、緑色顔料と黄色顔料とを併用したり、青色顔料と紫色顔料とを併用し たりすることができる。 [0113] These various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.
[0114] なお、これらの顔料の平均粒径は通常 1 μ m、好ましくは 0. 5 μ m以下、更に好ま しくは 0. 25 m以下である。また、色材として使用できる染料としては、ァゾ系染料、 アントラキノン系染料、フタロシアニン系染料、キノンィミン系染料、キノリン系染料、二 トロ系染料、カルボニル系染料、メチン系染料等が挙げられる。  [0114] The average particle diameter of these pigments is usually 1 µm, preferably 0.5 µm or less, and more preferably 0.25 m or less. Examples of the dye that can be used as the coloring material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinonimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
[0115] ァゾ系染料としては、例えば、 C. I.アシッドイェロー 11, C. I.アシッドオレンジ 7, C. I.アシッドレッド 37, C. I.アシッドレッド 180, C. I.アシッドブノレー 29, C. I.ダ ィレクトレッド 28, C. I.ダイレクトレッド 83, C. I.ダイレクトイェロー 12, C. I.ダイレ タトオレンジ 26, C. I.ダイレクトグリーン 28, C. I.ダイレクトグリーン 59, C. I. リアク ティブイェロー 2, C. I.リアクティブレッド 17, C. I. リアクティブレッド 120, C. I.リア クティブブラック 5, C. I.デイスパースオレンジ 5, C. I.デイスパースレッド 58, C. I. デイスパースブルー 165, C. I.ベーシックブルー 41, C. I.ベーシックレッド 18, C. I.モルダントレッド 7, C. I.モルダントイエロー 5, C. I.モルダントブラック 7等が挙げ られる。 [0115] Examples of azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Benolet 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Tart Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Day Sparse Orange 5, CI Day Spur Red 58, CI Day Sparse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7, etc.
[0116] アントラキノン系染料としては、例えば、 C. I.バットブルー 4, C. I.アシッドブルー 40, C. I.アシッドグリーン 25, C. I.リアクティブブルー 19, C. I. リアクティブブル 一 49, C. I.デイスパースレッド 60, C. I.デイスパースブルー 56, C. I.デイスパー スブルー 60等が挙げられる。  [0116] Examples of anthraquinone dyes include CI Bat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Bull 1 49, CI Disperse Red 60, CI Disperse Blue 56 , CI Disperse Blue 60 etc.
[0117] この他、フタロシアニン系染料として、例えば、 C. I.パッドブルー 5等力 キノンイミ ン系染料として、例えば、 C. I.ベーシックブルー 3, C. I.ベーシックブルー 9等が、 キノリン系染料として、例えば、 C. I.ソルベントイェロー 33, C. I.アシッドイェロー 3 , C. I.デイスパースィエロー 64等力 ニトロ系染料として、例えば、 C. I.アシッドィ エロー 1, C. I.アシッドオレンジ 3, C. I.デイスパースィエロー 42等が挙げられる。  [0117] In addition, as phthalocyanine dyes, for example, CI pad blue 5 isotropic quinone imine dyes, for example, CI basic blue 3, CI basic blue 9, etc., as quinoline dyes, for example, CI solvent yellow 33 CI Acid Yellow 3, CI Disperse Yellow 64 Isotropic Nitro dyes include, for example, CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42, and the like.
[0118] <分散剤 >  [0118] <Dispersant>
本発明の感光性榭脂組成物が、色材を含有する感光性着色榭脂組成物である場 合、この感光性着色榭脂組成物は、更に分散剤を含有するものであっても良い。  When the photosensitive resin composition of the present invention is a photosensitive colored resin composition containing a coloring material, the photosensitive colored resin composition may further contain a dispersant. .
[0119] 本発明に用いられる分散剤としては、窒素原子含有分散剤が好ましい。窒素原子 含有分散剤としては、通常、界面活性剤、高分子分散剤などが使用されるが、特に 高分子分散剤が好適である。高分子分散剤としては、  [0119] The dispersant used in the present invention is preferably a nitrogen atom-containing dispersant. As the nitrogen atom-containing dispersant, surfactants, polymer dispersants and the like are usually used, and polymer dispersants are particularly suitable. As a polymer dispersant,
[1]ウレタン系分散剤  [1] Urethane dispersant
[2]窒素原子を含有するグラフト共重合体  [2] Graft copolymers containing nitrogen atoms
[3]側鎖に 4級アンモニゥム塩基を有する Aブロックと、 4級アンモニゥム塩基を有さ ない Bブロックとからなる、 A— Bブロック共重合体及び Z又は B— A— Bブロック共重 合体の少なくともいずれか一つを含有することが好ましい。分散剤は、 1種を単独で 使用しても、 2種類以上を混合しても用いても良い。 [3] An A—B block copolymer and a Z or B—A—B block copolymer consisting of an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base. It is preferable to contain at least one of them. One dispersant can be used alone It may be used, or two or more types may be mixed and used.
[0120] 本発明では、これらの窒素原子含有分散剤と、本発明に係る前記特定のアルカリ 可溶性不飽和榭脂とを組み合わせて使用することによって、分散安定性を保ちつつ 、感光性着色榭脂組成物により形成される塗膜と基板との現像時の高い密着性、及 び未溶解物の残存抑制を達成することができる。  [0120] In the present invention, by using a combination of these nitrogen atom-containing dispersant and the specific alkali-soluble unsaturated resin according to the present invention, photosensitive colored resin can be maintained while maintaining dispersion stability. It is possible to achieve high adhesion during development between the coating film formed from the composition and the substrate, and to suppress residual undissolved substances.
[0121] 窒素原子含有分散剤中の窒素原子の形態としては、アミノ基、 4級アンモ-ゥム塩 などが好ましい。これらの官能基は、通常、塩基性を有するため顔料及び顔料誘導 体などの酸性基と配位し易ぐその結果、分散安定化に寄与するためである。分散剤 のァミン価は、通常 2mg—KOHZg以上、好ましくは 3mg—KOHZg以上で、通常 lOOmg—KOHZg以下、好ましくは 80mg—KOHZg以下である。ァミン価が低す ぎる場合は塩基性が不十分で分散安定性に乏しぐァミン価が高すぎる場合は液晶 表示装置に用いた場合液晶の電圧保持率を低下させ、その結果、表示不良を起こし 易くなり好ましくない。  [0121] The form of the nitrogen atom in the nitrogen atom-containing dispersant is preferably an amino group, a quaternary ammonium salt, or the like. This is because these functional groups usually have basicity so that they can easily coordinate with acidic groups such as pigments and pigment derivatives, thereby contributing to dispersion stabilization. The amine value of the dispersant is usually 2 mg-KOHZg or more, preferably 3 mg-KOHZg or more, and usually 10 mg-KOHZg or less, preferably 80 mg-KOHZg or less. If the amine value is too low, the basicity is insufficient and the dispersion stability is poor. If the amine value is too high, the voltage holding ratio of the liquid crystal is lowered when used in a liquid crystal display device, resulting in display failure. It becomes easy and is not preferable.
[0122] 次に、好ましい分散剤について、詳細に説明する。  [0122] Next, preferred dispersants will be described in detail.
[1]ウレタン系分散剤  [1] Urethane dispersant
ウレタン系分散剤としては、（1)ポリイソシァネートイ匕合物、（2)同一分子内に水酸 基を 1個又は 2個有する化合物、（3)同一分子内に活性水素と 3級アミノ基を有する 化合物とを反応させることによって得られる分散榭脂であることが好ましい。  Urethane dispersants include (1) polyisocyanate compounds, (2) compounds having one or two hydroxyl groups in the same molecule, and (3) active hydrogen and tertiary in the same molecule. It is preferably a dispersed resin obtained by reacting with a compound having an amino group.
[0123] (1)ポリイソシァネートイ匕合物、  [0123] (1) Polyisocyanate compound,
上記ポリイソシァネートイ匕合物の例としてはパラフエ-レンジイソシァネート、 2, 4 トリレンジイソシァネート、 2, 6 トリレンジイソシァネート、 4, 4' ージフエ-ノレメタン ジイソシァネート、ナフタレン 1, 5 ジイソシァネート、トリジンジイソシァネート等の 芳香族ジイソシァネート、へキサメチレンジイソシァネート、リジンメチルエステルジィ ソシァネート、 2, 4, 4 トリメチルへキサメチレンジイソシァネート、ダイマー酸ジイソ シァネート等の脂肪族ジイソシァネート、イソホロンジイソシァネート、 4, 4' ーメチレ ンビス（シクロへキシルイソシァネート）、 ω , ω ' —ジイソシネートジメチルシクロへキ サン等の脂環族ジイソシァネート、キシリレンジイソシァネート、 a , a , a ' , α ' テトラメチルキシリレンジイソシァネート等の芳香環を有する脂肪族ジイソシァネート、 リジンエステルトリイソシァネート、 1, 6, 11—ゥンデカントリイソシァネート、 1, 8 ジ イソシァネート一 4—イソシァネートメチルオクタン、 1, 3, 6 へキサメチレントリイソシ ァネート、ビシクロヘプタントリイソシァネート、トリス（イソシァネートフエ-ノレメタン）、ト リス（イソシァネートフエ-ル）チォホスフェート等のトリイソシァネート、及びこれらの 3 量体、水付加物、及びこれらのポリオール付加物等が挙げられる。ポリイソシァネート として好まし ヽのは有機ジイソシァネートの三量体で、最も好まし ヽのはトリレンジイソ シァネートの三量体とイソホロンジイソシァネートの三量体であり、これらは単独で用 いても、 2種以上を併用しても良い。 Examples of the above polyisocyanate compounds include para-phenolic diisocyanate, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 4,4'-diphenyl-nomethane diisocyanate, naphthalene 1, 5 Aromatic diisocyanates such as diisocyanate and tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2, 4, 4 Trimethylhexamethylene diisocyanate, aliphatic such as dimer acid diisocyanate Diisocyanate, isophorone diisocyanate, 4, 4'-methylenbis (cyclohexyl isocyanate), ω, ω '— diisocyanate dimethylcyclohexane, alicyclic diisocyanate, xylylene diisocyanate, a , a, a ', α' tetramethylxylylene diisocyanate Aliphatic having an aromatic ring like Jiisoshianeto, Lysine ester triisocyanate, 1, 6, 11-undecane triisocyanate, 1,8 diisocyanate mono-4-isocyanate methyloctane, 1, 3, 6 hexamethylene triisocyanate, bicycloheptanetri Isocyanates, tris (isocyanate phenol-methane), triisocyanates such as tris (isocyanate phenol) thiophosphate, and their trimers, water adducts, and polyol adducts thereof Etc. The preferred polyisocyanate is an organic diisocyanate trimer, the most preferred is a tolylene diisocyanate trimer and an isophorone diisocyanate trimer, which can be used alone. Two or more types may be used in combination.
[0124] 有機ジイソシァネートの三量体の製造方法としては、前記ポリイソシァネート類を適 当な三量ィ匕触媒、例えば第 3級ァミン類、ホスフィン類、アルコキシド類、金属酸化物 、カルボン酸塩類等を用いてイソシァネート基の部分的な三量ィ匕を行い、触媒毒の 添カ卩により三量ィ匕を停止させた後、未反応のポリイソシァネートを溶剤抽出、薄膜蒸 留により除去して目的のイソシァヌレート基含有ポリイソシァネートを得る方法が挙げ られる。 [0124] As a method for producing a trimer of an organic diisocyanate, the polyisocyanate is used as a suitable trimer catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acids. Perform a partial trimerization of the isocyanate group using salts, etc., stop the trimer by adding a catalyst poison, then extract the unreacted polyisocyanate by solvent extraction and thin-film distillation. There is a method of removing the desired isocyanurate group-containing polyisocyanate.
[0125] (2)同一分子内に水酸基を 1個又は 2個有する化合物  [0125] (2) Compound having one or two hydroxyl groups in the same molecule
同一分子内に水酸基を 1個又は 2個有する化合物としては、ポリエーテルグリコー ル、ポリエステルグリコール、ポリカーボネートグリコール、ポリオレフイングリコール等 Examples of compounds having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, and polyolefin glycol.
、及びこれらの化合物の片末端水酸基が炭素数 1〜25のアルキル基でアルコキシィ匕 されたものが挙げられ、これらは単独で用いても、 2種以上を併用しても良い。 And those having one terminal hydroxyl group of these compounds alkoxylated with an alkyl group having 1 to 25 carbon atoms. These may be used alone or in combination of two or more.
[0126] ポリエーテルグリコールとしては、ポリエーテルジオール、ポリエーテルエステルジ オール、及びこれら 2種類以上の混合物が挙げられる。ポリエーテルジオールとして は、アルキレンォキシドを単独又は共重合させて得られるもの、例えばポリエチレング リコール、ポリプロピレングリコール、ポリエチレン プロピレングリコール、ポリオキシ テトラメチレングリコール、ポリオキシへキサメチレングリコール、ポリオキシォクタメチ レンダリコール及びそれらの 2種以上の混合物が挙げられる。ポリエーテルエステル ジオールとしては、エーテル基含有ジオールもしくは他のダリコールとの混合物をジ カルボン酸又はそれらの無水物と反応させる力、又はポリエステルグリコールにアル キレンォキシドを反応させることによって得られるもの、例えばポリ（ポリオキシテトラメ チレン)アジペート等が挙げられる。ポリエーテルグリコールとして最も好ましいのはポ リエチレングリコール、ポリプロピレングリコール、ポリオキシテトラメチレングリコール 又はこれらの化合物の片末端水酸基が炭素数 1〜25のアルキル基でアルコキシィ匕 された化合物である。 [0126] Examples of the polyether glycol include polyether diol, polyether ester diol, and mixtures of two or more of these. Examples of polyether diols are those obtained by homo- or copolymerization of alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, and polyoxyoctamethylendaline. And mixtures of two or more thereof. Polyether ester diols include those obtained by reacting a mixture of an ether group-containing diol or other darlicol with a dicarboxylic acid or an anhydride thereof, or by reacting polyester glycol with an alkylene oxide. Polyoxytetrame Tylene) adipate and the like. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
[0127] ポリエステルグリコールとしては、ジカルボン酸（コハク酸、グルタル酸、アジピン酸、 セバシン酸、フマル酸、マレイン酸、フタル酸等）又はそれらの無水物とグリコール（ェ チレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコー ル、ジプロピレングリコール、トリプロピレングリコール、 1, 2 ブタンジオール、 1, 3 ブタンジオール、 1, 4 ブタンジオール、 2, 3 ブタンジオール、 3—メチルー 1, 5 ペンタンジオール、ネオペンチルグリコール、 2—メチルー 1, 3 プロパンジォー ル、 2—メチルー 2 プロピル 1, 3 プロパンジオール、 2 ブチルー 2 ェチル - 1, 3 プロパンジーオル、 1, 5 ペンタンジオール、 1, 6 へキサンジオール、 2 ーメチルー 2, 4 ペンタンジオール、 2, 2, 4 トリメチルー 1, 3 ペンタンジオール 、 2 ェチルー 1, 3 へキサンジオール、 2, 5 ジメチルー 2, 5 へキサンジォー ル、 1, 8 オタタメチレングリコール、 2—メチルー 1, 8 オタタメチレングリコール、 1 , 9ーノナンジオール等の脂肪族グリコール、ビスヒドロキシメチルシクロへキサン等の 脂環族グリコール、キシリレングリコール、ビスヒドロキシエトキシベンゼン等の芳香族 グリコール、 N—メチルジェタノールァミン等の N アルキルジァルカノールアミン等） とを重縮合させて得られたもの、例えばポリエチレンアジペート、ポリブチレンアジべ ート、ポリへキサメチレンアジペート、ポリエチレン Zプロピレンアジペート等、又は前 記ジオール類又は炭素数 1〜25の 1価アルコールを開始剤として用いて得られるポ リラタトンジオール又はポリラタトンモノオール、例えばポリ力プロラタトングリコール、ポ リメチルバレロラタトン及びこれらの 2種以上の混合物が挙げられる。ポリエステルダリ コールとして最も好ましいのはポリ力プロラタトングリコール又は炭素数 1〜25のアル コールを開始剤としたポリ力プロラタトン、より具体的には、モノオールに ε一力プロラ タトンを開環付加重合して得られる化合物である。  [0127] Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol). , Propylene glycol, dipropylene glycol, tripropylene glycol, 1,2 butanediol, 1,3 butanediol, 1,4 butanediol, 2,3 butanediol, 3-methyl-1,5 pentanediol, neopentyl glycol, 2-methyl-1,3 propanediol, 2-methyl-2-propyl 1,3 propanediol, 2-butyl-2-ethyl-1,3 propanediol, 1,5 pentanediol, 1,6 hexanediol, 2-methyl-2, 4 Pentanediol, 2, 2, 4 trimethyl-1, 3 pentane Aliphatic glycols such as diols, 2-ethyl-1,3-hexanediol, 2,5 dimethyl-2,5-hexanediol, 1,8 otatamethylene glycol, 2-methyl-1,8 otatamethylene glycol, 1,9-nonanediol , Alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and N alkyldialkanolamines such as N-methyljetanolamine). For example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene Z-propylene adipate, etc., or the above diols or monohydric alcohols having 1 to 25 carbon atoms are used as initiators. Obtained polylatathonediol or polylatatatone monool Such as poly force Purorata tons glycol, Po trimethyl valeronitrile rata tons and mixtures of two or more thereof. The most preferred polyester dallicol is polystrength prolataton glycol or polystrength prolatatone with 1 to 25 carbons as an initiator. It is a compound obtained by doing.
[0128] ポリカーボネートグリコールとしては、ポリ（1, 6 へキシレン）カーボネート、ポリ（3 ーメチルー 1, 5 ペンチレン）カーボネート等が挙げられる。ポリオレフイングリコール としては、ポリブタジエングリコール、水素添加型ポリブタジエングリコール、水素添加 型ポリイソプレングリコール等が挙げられる。同一分子内に水酸基を 1個又は 2個有 する化合物のうち、特にポリエーテルグリコールとポリエステルグリコールが好ましい。 [0128] Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, and the like. Polyolefin glycol Examples thereof include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Of the compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferred.
[0129] 同一分子内に水酸基を 1個又は 2個有する化合物の数平均分子量は、通常 300以 上、好ましくは 500以上、より好ましくは 1, 000以上で、通常 10, 000以下、好ましく は 6, 000以下、より好ましくは 4, 000以下である。  [0129] The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 or more, preferably 500 or more, more preferably 1,000 or more, and usually 10,000 or less, preferably 6 , 000 or less, more preferably 4,000 or less.
[0130] (3)同一分子内に活性水素と 3級アミノ基を有する化合物  [0130] (3) Compound having active hydrogen and tertiary amino group in the same molecule
活性水素、即ち、酸素原子、窒素原子又はィォゥ原子に直接結合している水素原 子としては、水酸基、アミノ基、チオール基等の官能基中の水素原子が挙げられ、中 でもアミノ基、特に 1級のアミノ基の水素原子が好ま 、。  Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a thio atom includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Preference is given to hydrogen atoms of primary amino groups.
[0131] 3級アミノ基は特に限定されないが、例えば、メチル、ェチル、イソプロピル、 n—ブ チル等の炭素数 1〜4のアルキル基を有するジアルキルアミノ基や、該ジアルキルァ ミノ基が連結してヘテロ環構造を形成している基、より具体的には、イミダゾール環又 はトリアゾール環が挙げられる。  [0131] The tertiary amino group is not particularly limited. For example, a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, and the dialkylamino group are linked. A group forming a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
[0132] このような同一分子内に活性水素と 3級アミノ基を有する化合物を例示するならば、 N, N ジメチルー 1, 3 プロパンジァミン、 N, N ジェチルー 1, 3 プロパンジァ ミン、 N, N ジプロピノレー 1, 3 プロパンジァミン、 N, N—ジブチノレー 1, 3 プロ パンジァミン、 N, N ジメチルエチレンジァミン、 N, N ジェチルエチレンジァミン、 N, N ジプロピルエチレンジァミン、 N, N ジブチルエチレンジァミン、 N, N ジメ チノレー 1, 4 ブタンジァミン、 N, N ジェチノレー 1, 4 ブタンジァミン、 N, N ジ プロピル— 1, 4 ブタンジァミン、 N, N ジブチル— 1, 4 ブタンジァミン等か挙げ られる。  [0132] Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule are N, N dimethyl-1,3 propanediamine, N, N jetyl-1,3 propanediamine, N, N dipropinole 1 , 3 Propanadamine, N, N-Dibutinole 1,3 Propanadamine, N, N Dimethylethylenediamine, N, N Jetylethylenediamine, N, N Dipropylethylenediamine, N, N Dibutylethylenedi N, N Dimethyl-1,4-butanediamine, N, N Jetinoley 1,4 Butanediamine, N, N Dipropyl-1,4 Butanediamine, N, N Dibutyl-1,4 Butanediamine, and the like.
[0133] また、 3級ァミノ基が窒素含有へテロ環であるものとして、ピラゾール環、イミダゾー ル環、トリァゾール環、テトラゾール環、インドール環、力ルバゾール環、インダゾール 環、ベンズイミダゾール環、ベンゾトリアゾール環、ベンゾォキサゾール環、ベンゾチ ァゾール環、ベンゾチアジアゾール環等の N含有へテロ 5員環、ピリジン環、ピリダジ ン環、ピリミジン環、トリアジン環、キノリン環、アタリジン環、イソキノリン環、等の窒素 含有へテロ 6員環が挙げられる。これらの窒素含有へテロ環として好ま 、ものはイミ ダゾール環又はトリァゾール環である。 [0133] Further, as the tertiary amino group is a nitrogen-containing hetero ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, force rubazole ring, indazole ring, benzimidazole ring, benzotriazole ring N-containing hetero ring such as benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc.Nitrogen containing 5-membered ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, atalidine ring, isoquinoline ring Hetero 6-membered ring. These nitrogen-containing heterocycles are preferred, A dazole ring or a triazole ring.
[0134] これらのイミダゾール環と一級アミノ基を有する化合物を具体的に例示するならば、 1— (3 ァミノプロピル)イミダゾール、ヒスチジン、 2 ァミノイミダゾール、 1— (2 ァ ミノェチル)イミダゾール等が挙げられる。また、トリァゾール環と一級アミノ基を有する 化合物を具体的に例示するならば、 3 ァミノ— 1, 2, 4 トリァゾール、 5— (2 アミ ノー 5 クロ口フエ二ノレ）一 3 フエ二ノレ一 1H—1, 2, 4 トリァゾーノレ、 4 アミノー 4 H- 1, 2, 4 トリァゾールー 3, 5 ジオール、 3 アミノー 5 フエ二ルー 1H— 1, 3 , 4 トリア:/一ノレ、 5 アミノー 1, 4 ジフエ二ノレ一 1, 2, 3 トリア:/一ノレ、 3 ァミノ — 1—ベンジル— 1H— 2, 4 トリァゾール等が挙げられる。なかでも、 N, N ジメチ ノレ 1, 3 プロパンジァミン、 N, N ジェチノレ一 1, 3 プロパンジァミン、 1— (3— ァミノプロピル)イミダゾール、 3 ァミノ一 1, 2, 4 トリァゾールが好ましい。  [0134] Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3 aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2 aminoethyl) imidazole, and the like. . In addition, specific examples of the compound having a triazole ring and a primary amino group include 3 amino-1, 2, 4 triazole, 5- (2 amino 5 black mouth phenol) 1 3 phenol 1 H —1, 2, 4 Triazonole, 4 Amino 4 H- 1, 2, 4 Triazole 3,5 Diol, 3 Amino 5 Phenol 1H— 1, 3, 4, 4 Tria: / 1 Norre, 5 Amino 1, 4 Diphenyl Nore 1, 2, 3 Tria: / Nore, 3 amino- 1-benzyl- 1H- 2, 4 triazole and the like. Of these, N, N-dimethylol 1,3 propanediamine, N, N jetino 1,3-propane diamine, 1- (3-aminopropyl) imidazole, and 3-amino 1,2,4 triazole are preferable.
[0135] ウレタン系分散榭脂原料の好ましい配合比率は、ポリイソシァネートイ匕合物 100重 量部に対し、同一分子内に水酸基を 1個又は 2個有する化合物が通常 10重量部以 上、好ましくは 20重量部以上、更に好ましくは 30重量部以上で、通常 200重量部以 下、好ましくは 190重量部以下、更に好ましくは 180重量部以下、同一分子内に活 性水素と 3級アミノ基を有する化合物は通常 0. 2重量部以上、好ましくは 0. 3重量部 以上で、通常 25重量部以下、好ましくは 24重量部以下である。  [0135] The preferred blending ratio of the urethane-based dispersed resin raw material is usually 10 parts by weight or more for a compound having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. 20 parts by weight or more, more preferably 30 parts by weight or more, usually 200 parts by weight or less, preferably 190 parts by weight or less, more preferably 180 parts by weight or less, and active hydrogen and tertiary amino acids in the same molecule. The compound having a group is usually 0.2 parts by weight or more, preferably 0.3 parts by weight or more, and usually 25 parts by weight or less, preferably 24 parts by weight or less.
[0136] 本発明に係るウレタン系分散樹脂の GPCで測定されるポリスチレン換算重量平均 分子量は、通常 1, 000以上、好ましくは 2, 000以上、より好ましくは 3, 000以上で、 通常 200, 000以下、好まし <は 100, 000以下、より好まし <は 50, 000以下の範囲 である。この分子量が 1, 000未満では分散性及び分散安定性が劣り、 200, 000を 超えると溶解性が低下し、分散性が劣ると同時に反応の制御が困難となる。  [0136] The weight average molecular weight in terms of polystyrene measured by GPC of the urethane-based dispersion resin according to the present invention is usually 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, and usually 200,000. In the following, preferred <is in the range of 100,000 or less, more preferred <is in the range of 50,000 or less. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered, and the dispersibility is poor and at the same time it becomes difficult to control the reaction.
[0137] 本発明に係るウレタン系分散樹脂の製造は、ポリウレタン榭脂製造の公知の方法に 従って行われる。製造する際の溶媒としては、通常、アセトン、メチルェチルケトン、メ チルイソブチルケトン、シクロペンタノン、シクロへキサノン、イソホロン等のケトン類、 酢酸ェチル、酢酸ブチル、酢酸セロソルブ等のエステル類、ベンゼン、トルエン、キシ レン、へキサン等の炭化水素類、ダイアセトンアルコール、イソプロパノール、第二ブ タノール、第三ブタノール等一部のアルコール類、塩化メチレン、クロ口ホルム等の塩 化物、テトラヒドロフラン、ジェチルエーテル等のエーテル類、ジメチルホルムアミド、 N—メチルピロリドン、ジメチルスルホキサイド等の非プロトン性極性溶媒等が用いら れる。 [0137] Production of the urethane-based dispersion resin according to the present invention is performed according to a known method for producing polyurethane resin. Solvents used for the production are usually ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve acetate, benzene , Hydrocarbons such as toluene, xylene and hexane, some alcohols such as diacetone alcohol, isopropanol, secondary butanol and tertiary butanol, and salts such as methylene chloride and black mouth form And aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide are used.
[0138] また、製造する際の触媒としては通常のウレタン化反応触媒が用いられる。例えば ジブチノレチンジラウレート、ジォクチノレチンジラウレート、ジブチノレチンジォタトエート 、スタナスォクトエート等の錫系、鉄ァセチルァセトナート、塩化第二鉄等の鉄系、トリ ェチルァミン、トリエチレンジァミン等の 3級ァミン系等が挙げられる。  [0138] As the catalyst for production, a usual urethanization reaction catalyst is used. For example, dibutinoretin dilaurate, dioctinoretin dilaurate, dibutinoretin ditatoate, stannous octoate and other tin systems, iron acetyl cetate, ferric chloride and other iron systems, triethylamine, triethylene Examples include tertiary amines such as diamine.
[0139] 同一分子内に活性水素と 3級アミノ基を有する化合物の導入量は反応後の分散榭 脂のアミン価で lmg—KOHZg以上、特に 5mg—KOHZg以上で、 100mg—KO HZg以下、特に 95mg— KOHZg以下の範囲に制御することが好ましい。アミン価 が上記範囲未満であると分散能力が低下する傾向があり、また、上記範囲を超えると 現像性が低下しやすくなる。なお、以上の反応で分散樹脂にイソシァネート基が残存 する場合には更に、アルコールゃァミノ化合物でイソシァネート基を潰すと分散榭脂 の経時安定性が高くなるので好まし 、。  [0139] The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is 1 mg-KOHZg or more, especially 5 mg-KOHZg or more, 100 mg-KO HZg or less, especially in terms of amine value of the dispersed resin after the reaction. It is preferable to control within the range of 95 mg—KOHZg or less. If the amine value is less than the above range, the dispersing ability tends to be lowered, and if it exceeds the above range, developability tends to be lowered. In the case where the isocyanate group remains in the dispersion resin by the above reaction, it is preferable to further crush the isocyanate group with an alcohol amide compound since the stability of the dispersion resin with time increases.
[0140] [2]窒素原子を含有するグラフト共重合体  [0140] [2] Graft copolymer containing nitrogen atom
窒素原子を含有するグラフト共重合体としては、主鎖に窒素原子を含有する繰り返 し単位を有するものが好ましい。中でも、下記一般式 (I a)で表される繰り返し単位 又は Z及び下記一般式 (ii)で表される繰り返し単位を有することが好ま U、。  As the graft copolymer containing a nitrogen atom, one having a repeating unit containing a nitrogen atom in the main chain is preferred. Among them, it is preferable to have a repeating unit represented by the following general formula (Ia) or a repeating unit represented by Z and the following general formula (ii) U.
[0141] [化 17]  [0141] [Chemical 17]
A
Figure imgf000045_0001
A
Figure imgf000045_0001
A A
Figure imgf000045_0002
上記一般式 (I— a) , (ϋ)中、 R31は、メチレン、エチレン、プロピレン等の直鎖状又は 分岐状の炭素数 1〜5のアルキレン基を表し、好ましくは炭素数 2〜3のアルキレン基 であり、更に好ましくはエチレン基である。 Aは水素原子又は下記一般式 (iii)〜(v) の！、ずれかを表すが、好ましくは下記一般式 (m)である。
Figure imgf000045_0002
In the above general formulas (I-a) and (ϋ), R 31 represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms. An alkylene group, more preferably an ethylene group. A is a hydrogen atom or the following general formula (iii)-(v)! Represents a deviation, preferably the following general formula (m).
[化 18]  [Chemical 18]
Figure imgf000046_0001
上記一般式 (m)中、 w1は炭素数 2〜ιοの直鎖状又は分岐状のアルキレン基を表 し、中でもブチレン、ペンチレン、へキシレン等の炭素数 4〜7のアルキレン基が好ま しい。 pは 1〜20の整数を表し、好ましくは 5〜 10の整数である。
Figure imgf000046_0001
In the above general formula (m), w 1 represents a linear or branched alkylene group having 2 to ιο 炭素, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, hexylene, etc. is preferable. . p represents an integer of 1 to 20, preferably an integer of 5 to 10.
[化 19] [Chemical 19]
Figure imgf000046_0002
上記一般式 (iv)中、 G1は 2価の連結基を表し、中でもエチレン、プロピレン等の炭 素数 1〜4のアルキレン基とエチレンォキシ、プロピレンォキシ等の炭素数 1〜4のァ ルキレンォキシ基が好ましい。 W2はエチレン、プロピレン、ブチレン等の直鎖状又は 分岐状の炭素数 2〜 10のアルキレン基を表し、中でもエチレン、プロピレン等の炭素 数 2〜3のアルキレン基が好ましい。 G2は水素原子又は— CO— R32 (R32はェチル、 プロピル、ブチル、ペンチル、へキシル等の炭素数 1〜10のアルキル基を表し、中で もェチル、プロピル、ブチル、ペンチル等の炭素数 2〜5のアルキル基が好ましい）を 表す。 qは、 1〜20の整数を表し、好ましくは 5〜10の整数である。
Figure imgf000046_0002
In the above general formula (iv), G 1 represents a divalent linking group, and in particular, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene, and an alkylene group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy. Is preferred. W 2 represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene or butylene, and among them, an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene is preferable. G 2 represents a hydrogen atom or —CO—R 32 (R 32 represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc., among which ethyl, propyl, butyl, pentyl, etc. An alkyl group having 2 to 5 carbon atoms is preferred). q represents an integer of 1 to 20, preferably an integer of 5 to 10.
[化 20] ■•■(v) [Chemical 20] (V)
上記一般式 (v)中、 W3は炭素数 1〜50のアルキル基又は水酸基を 1〜5有する炭 素数 1〜50のヒドロキシアルキル基を表し、中でもステアリル等の炭素数 10〜20のァ ルキル基、モノヒドロキシステアリル等の水酸基を 1〜2個有する炭素数 10〜20のヒド 口キシァノレキノレ基が好まし!/ヽ。 In the general formula (v), W 3 represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 50 carbon atoms having 1 to 5 hydroxyl groups, and in particular, an alkyl having 10 to 20 carbon atoms such as stearyl. Preferred is a hydroxy group having 1 to 2 hydroxyl groups having 1 to 2 hydroxyl groups such as monohydroxystearyl, etc.! / ヽ.
[0142] 本発明に係るグラフト共重合体における一般式 (I— a)又は (ii)で表される繰り返し 単位の含有率は、高い方が好ましぐ合計で通常 50モル％以上であり、好ましくは 7 0モル％以上である。一般式 (I a)で表される繰り返し単位と、一般式 (ii)で表される 繰り返し単位の、両方を併有しても良ぐその含有比率に特に制限は無いが、好まし くは一般式 (I - a)の繰り返し単位の方を多く含有して 、た方が好ま 、。グラフト共 重合体中の一般式 (I a)又は一般式 (ii)で表される繰り返し単位の合計数は、 1以 上、好ましくは 10以上、更に好ましくは 20以上で、通常 100以下、好ましくは 70以下 、更に好ましくは 50以下である。また、グラフト共重合体中には一般式 (I— a)及び一 般式 (ii)以外の繰り返し単位を含んでいても良ぐ他の繰り返し単位としては、例えば アルキレン基、アルキレンォキシ基などが例示できる。本発明に係るグラフト共重合 体は、その末端が— NH及び— R31— NH (R31は、一般式 (I— a) , (ii)におけると同 [0142] The content of the repeating unit represented by the general formula (I-a) or (ii) in the graft copolymer according to the present invention is preferably 50 mol% or more in total, which is preferably higher. Preferably it is 70 mol% or more. There is no particular limitation on the content ratio of the repeating unit represented by the general formula (Ia) and the repeating unit represented by the general formula (ii), but it is preferable. It contains more repeating units of the general formula (I-a) and is preferred. The total number of repeating units represented by general formula (Ia) or general formula (ii) in the graft copolymer is 1 or more, preferably 10 or more, more preferably 20 or more, and usually 100 or less, preferably Is 70 or less, more preferably 50 or less. In addition, examples of other repeating units that may contain a repeating unit other than the general formula (Ia) and the general formula (ii) in the graft copolymer include an alkylene group and an alkyleneoxy group. Can be illustrated. In the graft copolymer according to the present invention, the terminal is —NH and —R 31 —NH (R 31 is the same as in the general formulas (I—a) and (ii)
2 2  twenty two
義）のものが好ましい。  Right) is preferred.
[0143] なお、上述したようなグラフト共重合体であれば、主鎖が直鎖状であっても分岐して いても良い。  [0143] In the case of the graft copolymer as described above, the main chain may be linear or branched.
[0144] このグラフト共重合体の GPCで測定した重量平均分子量としては、 3, 000以上、 特に 5, 000以上力好ましく、 100, 000以下、特に 50, 000以下力 ^好まし 、。この重 量平均分子量が 3, 000未満であると、色材の凝集を防ぐことができず、高粘度化な いしはゲルイ匕してしまうことがあり、 100, 000を超えるとそれ自体が高粘度となり、ま た有機溶媒への溶解性が不足するため好ましくな 、。  [0144] The weight-average molecular weight of the graft copolymer measured by GPC is preferably 3,000 or more, particularly 5,000 or more, preferably 100,000 or less, particularly 50,000 or less. If the weight average molecular weight is less than 3,000, the color material cannot be agglomerated and the viscosity may not increase or gelation may occur. Viscosity is preferable and solubility in organic solvents is insufficient.
[0145] 上記分散剤の合成方法は、公知の方法が採用でき、例えば特公昭 63— 30057号 公報に記載の方法を用いることができる。 [0145] As a method for synthesizing the dispersant, a known method can be employed, for example, Japanese Patent Publication No. 63-30057 The method described in the publication can be used.
[0146] [3]側鎖に 4級アンモニゥム塩基を有する Aブロックと、 4級アンモニゥム塩基を有さ ない Bブロックとからなる、 A— Bブロック共重合体及び Z又は B— A— Bブロック共重 合体  [3] [3] An A-B block copolymer and a Z or B-A-B block consisting of an A block having a quaternary ammonium base in the side chain and a B block not having a quaternary ammonium base. Polymer
分散剤のブロック共重合体を構成する Aブロックは、 4級アンモ-ゥム塩基、好ましく は— N+RlaR2aR3a'Y_ (但し、 Rla、 R2a及び R3aは、各々独立に、水素原子、又は置換 されていても良い環状若しくは鎖状の炭化水素基を表す。或いは、 Rla、 R2a及び R3a のうち 2つ以上が互いに結合して、環状構造を形成していても良い。 ΥΊま、対ァ-ォ ンを表す。）で表わされる 4級アンモ-ゥム塩基を有する。この 4級アンモ-ゥム塩基 は、直接主鎖に結合していても良いが、 2価の連結基を介して主鎖に結合していても 良い。 The A block constituting the block copolymer of the dispersant is a quaternary ammonium base, preferably — N + R la R 2a R 3a 'Y_ (where R la , R 2a and R 3a are each independently Represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group, or two or more of R la , R 2a and R 3a are bonded to each other to form a cyclic structure. It has a quaternary ammonia base represented by: This quaternary ammonium base may be bonded directly to the main chain, or may be bonded to the main chain via a divalent linking group.
[0147] — N+RlaR2 3aにおいて、 Rla、 R2a及び R3aのうち 2つ以上が互いに結合して形成す る環状構造としては、例えば 5〜7員環の含窒素複素環単環又はこれらが 2個縮合し てなる縮合環が挙げられる。該含窒素複素環は芳香性を有さないものが好ましぐ飽 和環であればより好ましい。具体的には、例えば下記のものが挙げられる。 [0147] — In N + R la R 2 3a , a cyclic structure formed by combining two or more of R la , R 2a and R 3a with each other includes, for example, a 5- to 7-membered nitrogen-containing heterocyclic ring Examples thereof include a single ring or a condensed ring obtained by condensing two of these. The nitrogen-containing heterocycle is more preferably a saturated ring that is preferably non-aromatic. Specific examples include the following.
[0148] [化 21]  [0148] [Chemical 21]
Figure imgf000048_0001
上記式中、 Rは Rla〜R3aのうち何れかの基を表す。
Figure imgf000048_0001
In the above formula, R represents any group of R la to R 3a .
[0149] これらの環状構造は、更に置換基を有していても良い。 [0149] These cyclic structures may further have a substituent.
[0150] —N+RlaR2 3aにおける Rla〜R3aとして、より好ましいのは、置換基を有していても良 V、炭素数 1〜3のアルキル基、又は置換基を有して!/、ても良!、フエ-ル基である。 As R la to R 3a in the [0150] -N + R la R 2 3a, more preferred, have a substituent good V, having an alkyl group, or a substituent having 1 to 3 carbon atoms Te! /, Even!
[0151] Aブロックとしては、特に、下記一般式（1)で表わされる部分構造を含有するものが 好ましい。  [0151] As the A block, those containing a partial structure represented by the following general formula (1) are particularly preferable.
[0152] [化 22] 4a [0152] [Chemical 22] 4a
( 1 )
Figure imgf000049_0001
上記一般式（1)中、 Rla、 Rz R ま各々独立に、水素原子、又は置換されていても 良い環状若しくは鎖状の炭化水素基を表す。或いは、 Rla、 R2a及び R3aのうち 2っ以 上が互いに結合して、環状構造を形成していても良い。 R4aは、水素原子又はメチル 基を表す。 Qは、 2価の連結基を表し、 ΥΊま、対ァニオンを表す。 (1)
Figure imgf000049_0001
In the above general formula (1), R la and R z R each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, two or more of R la , R 2a and R 3a may be bonded to each other to form a cyclic structure. R 4a represents a hydrogen atom or a methyl group. Q represents a divalent linking group, and represents an anion.
[0153] 上記一般式（1)において、 2価の連結基 Xとしては、例えば、炭素数 1〜10のアル キレン基、ァリーレン基、 CONH— R5a―、— COO— R6a— (但し、 R5a及び R6aは、 直接結合、炭素数 1〜10のアルキレン基、又は炭素数 1〜10のエーテル基（一 R7a -0-R8a-： R7a及び R は、各々独立にアルキレン基)を表わす。）等が挙げられ、 好ましくは COO—R6a—である。 In the above general formula (1), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, CONH—R 5a —, —COO—R 6a — (provided that R 5a and R 6a are a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (one R 7a -0-R 8a- : R 7a and R are each independently an alkylene group ) And the like, preferably COO—R 6a —.
[0154] また、対ァ-オンの Y—としては、 C厂、 Br", Γ、 CIO―、 BF―、 CH COO", PF—等  [0154] Also, as Y- for counter-on, C 厂, Br ", Γ, CIO-, BF-, CH COO", PF-, etc.
4 4 3 6 が挙げられる。  4 4 3 6
[0155] 上記の如き特定の 4級アンモ-ゥム塩基を含有する部分構造は、 1つの Aブロック 中に 2種以上含有されていても良い。その場合、 2種以上の 4級アンモ-ゥム塩基含 有部分構造は、該 Aブロック中にぉ 、てランダム共重合又はブロック共重合の何れの 態様で含有されていても良い。また、該 4級アンモ -ゥム塩基を含有しない部分構造 力 Aブロック中に含まれていても良ぐ該部分構造の例としては、後述の (メタ）アタリ ル酸エステル系モノマー由来の部分構造等が挙げられる。力かる 4級アンモ-ゥム塩 基を含まない部分構造の、 Aブロック中の含有量は、好ましくは 0〜50重量％、より好 ましくは 0〜20重量％であるが、かかる 4級アンモ-ゥム塩基非含有部分構造は Aブ ロック中に含まれな 、ことが最も好ま 、。  [0155] The partial structure containing the specific quaternary ammonium base as described above may be contained in one or more A blocks. In that case, two or more kinds of quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. In addition, examples of the partial structure that may be contained in the partial structural force A block that does not contain the quaternary ammonium base include a partial structure derived from a (meth) acrylate ester monomer described later. Etc. The content of the partial structure containing no strong quaternary ammonium salt group in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. It is most preferable that the partial structure containing no ammonia base is not contained in the A block.
[0156] 一方、分散剤のブロック共重合体を構成する Bブロックとしては、例えば、スチレン、 a—メチルスチレンなどのスチレン系モノマー；（メタ）アクリル酸メチル、 （メタ）アタリ ル酸ェチル、 （メタ）アクリル酸プロピル、 （メタ）アクリル酸イソプロピル、 （メタ）アクリル 酸ブチル、グリシジル (メタ）アタリレート、ベンジル (メタ）アタリレート、ヒドロキシェチ ル (メタ）アタリレート、ェチルアクリル酸グリシジル、 N, N—ジメチルアミノエチル (メタ )アタリレートなどの（メタ）アクリル酸エステル系モノマー；（メタ）アクリル酸クロライドな どの（メタ）アクリル酸塩系モノマー；（メタ）アクリルアミド、 N—メチロールアクリルアミド 、 N, N—ジメチルアクリルアミド、 N, N—ジメチルアミノエチルアクリルアミドなどの（メ タ）アクリルアミド系モノマー；酢酸ビュル；アクリロニトリル；ァリルグリシジルエーテル、 クロトン酸グリシジルエーテル； N—メタクリロイルモルホリン、などのコモノマーを共重 合させたポリマー構造が挙げられる。 On the other hand, as the B block constituting the block copolymer of the dispersant, for example, styrene, a-Styrene monomers such as methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) (Meth) acrylic acid ester monomers such as acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, N, N-dimethylaminoethyl (meth) acrylate, and (meth) acrylic acid (Meth) acrylate monomers such as chloride; (meth) acrylamide monomers such as (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminoethylacrylamide; Acrylonitrile; Aril Glycidyl ether, crotonic acid glycidyl ether; N- methacryloyl morpholine, comonomer copolymerization engaged allowed polymer structures such as.
[0157] Bブロックは、特に下記一般式（2)で表される、（メタ）アクリル酸エステル系モノマー 由来の部分構造であることが好ましい。  [0157] The B block is preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (2).
[0158] [化 23]  [0158] [Chemical 23]
r
Figure imgf000050_0001
上記一般式 (2)中、 R9aは、水素原子又はメチル基を表す。 R1Qaは、置換基を有して いても良い環状又は鎖状のアルキル基、置換基を有していても良いァリル基、又は 置換基を有して 、ても良 、ァラルキル基を表す。 r
Figure imgf000050_0001
In the general formula (2), R 9a represents a hydrogen atom or a methyl group. R 1Qa may be a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent, which may represent an aralkyl group.
[0159] 上記 (メタ）アクリル酸エステル系モノマー由来の部分構造は、 1つの Bブロック中に 2種以上含有されていても良い。もちろん該 Bブロックは、更にこれら以外の部分構造 を含有していても良い。 2種以上のモノマー由来の部分構造力 4級アンモ-ゥム塩 基を含有しな ヽ Bブロック中に存在する場合、各部分構造は該 Bブロック中にお ヽて ランダム共重合又はブロック共重合の何れの態様で含有されて 、ても良 、。 Bブロッ ク中に上記 (メタ)アクリル酸エステル系モノマー由来の部分構造以外の部分構成を 含有する場合、当該 (メタ)アクリル酸エステル系モノマー以外の部分構造の、 Bプロ ック中の含有量は、好ましくは 0〜50重量％、より好ましくは 0〜20重量％であるが、 かかる (メタ）アクリル酸エステル系モノマー以外の部分構造は Bブロック中に含まれ ないことが最も好ましい。 [0159] Two or more types of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. Partial structural strength derived from two or more types of monomers Does not contain quaternary ammonia salt groups. When present in B block, each partial structure is random or block copolymerized in the B block. It may be contained in any of the embodiments. When the B block contains a partial structure other than the partial structure derived from the (meth) acrylic acid ester monomer, the content of the partial structure other than the (meth) acrylic acid ester monomer in the B block Is preferably 0-50% by weight, more preferably 0-20% by weight, Most preferably, a partial structure other than the (meth) acrylic acid ester monomer is not contained in the B block.
[0160] 本発明で用いる分散剤は、このような Aブロックと Bブロックとからなる、 A— Bブロッ ク又は B— A— Bブロック共重合型高分子化合物である力 このようなブロック共重合 体は、例えば以下に示すリビング重合法にて調製される。 [0160] The dispersant used in the present invention is an A-B block or B-A-B block copolymerization type polymer compound composed of such an A block and a B block. Such a block copolymer The body is prepared, for example, by the living polymerization method shown below.
[0161] リビング重合法にはァ-オンリビング重合法、カチオンリビング重合法、ラジカルリビ ング重合法がある。ァ-オンリビング重合法は、重合活性種がァ-オンであり、例え ば下記スキームで示される。 [0161] Living polymerization methods include a living living polymerization method, a cationic living polymerization method, and a radical living polymerization method. In the er-living polymerization method, the polymerization active species is eron, and for example, it is shown in the following scheme.
[0162] [化 24] [0162] [Chemical 24]
(ァニオンリビング重合法） (Anion living polymerization method)
モノマー①： H2C = CH— モノマ—②： H2C ^= CH の場合 Monomer ①: H 2 C = CH- monomer -②: H 2 C ^ = case of CH
Ar Ar  Ar Ar
+ 有機金属（M)化合物+ Organometallic (M) compounds
Figure imgf000052_0001
Figure imgf000052_0001
Figure imgf000052_0002
モノマー①
Figure imgf000052_0002
Monomer ①
-τ τυ- CH2— ® M®
Figure imgf000052_0003
-τ τυ- CH 2 — ® M®
Figure imgf000052_0003
モノマー②Monomer ②
® iiiniiiiii M®
Figure imgf000052_0004
® iiiniiiiii M®
Figure imgf000052_0004
Figure imgf000052_0005
Figure imgf000052_0005
[0163] ラジカルリビング重合法は重合活性種力ラジカルであり、例えば下記スキームで示 される。 [0163] The radical living polymerization method is a polymerization active species power radical, and is represented by the following scheme, for example.
[0164] [化 25] (ラジカルリビング重合法:ニトロキシル法） [0164] [Chemical 25] (Radical living polymerization method: Nitroxyl method)
モノマ一①： H2C = CH モノマ一②： H2C = CH の場合 Monomer (1): H 2 C = CH Monomer (2): H 2 C = CH
Ar1 Ar2 Ar 1 Ar 2
Figure imgf000053_0001
モノマ一②
Figure imgf000053_0002
化 26]
Figure imgf000053_0001
Mono one ②
Figure imgf000053_0002
26
(ラジカルリビング重合法: ATRP法) (Radical living polymerization method: ATRP method)
H2C = CH モノマ—②： H 2 C = CH monomer—②:
COORa COORb COOR a COOR b
+ 有機金属（Me)化合物+ Organometallic (Me) compounds
Figure imgf000054_0001
Figure imgf000054_0001
COOR Me :遷移金属  COOR Me: Transition metal
J TU ^ CH2— CH Me J TU ^ CH 2 — CH Me
COORa モノマー①
Figure imgf000054_0002
COOR a monomer (1)
Figure imgf000054_0002
モノマー② woL cH2- CH CH2— CH2— CH Me Monomer② woL cH 2 -CH CH 2 — CH 2 — CH Me
COOR J x+1 COORb COOR J x + 1 COOR b
Figure imgf000054_0003
Figure imgf000054_0003
[0166] このような分散剤を合成するに際しては、特開平 9— 62002号公報や、 P. Lutz, P . Masson et al, Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andr ews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Po lym. J. 17, 977 (1985), 18, 1037 (1986), 右手浩ー、畑田耕一、高分子加工、 36、 366 (1987) ,東村敏延、沢本光男、高分子論文集、 46、 189 (1989) , M. K uroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), 相田卓三、井上祥平、 有機合成ィ匕学、 43, 300 (1985) , D. Y. Sogoh, W. R. Hertler et al, Macrom olecules, 20, 1473 (1987)などに記載の公知の方法を採用することができる。 [0166] In the synthesis of such a dispersant, JP-A-9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), BC Anderson, GD Andr ews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Hiroshi Right-hand, Koichi Hatada, Takashi Molecular Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 ( 1987), Takuzo Aida, Shohei Inoue, Organic Synthesis Science, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macrom olecules, 20, 1473 (1987), etc. Can do.
[0167] 本発明で用いる分散剤が A—Bブロック共重合体であっても、 B—A—Bブロック共 重合体であっても、その共重合体を構成する Aブロック ZBブロック比（重量比）は、 通常 1Z99以上、中でも 5Z95以上、また、通常 80Z20以下、中でも 60/40以下 の範囲であることが好ましい。この範囲外では、良好な耐熱性と分散性を兼備するこ とができない場合がある。 [0167] Regardless of whether the dispersant used in the present invention is an A-B block copolymer or a B-A-B block copolymer, the A block ZB block ratio (weight) Ratio) is It is usually in the range of 1Z99 or more, especially 5Z95 or more, and usually 80Z20 or less, especially 60/40 or less. Outside this range, it may not be possible to combine good heat resistance and dispersibility.
[0168] また、本発明で用いる A—Bブロック共重合体、 ー八ー ブロック共重合体！^中の 4級アンモ-ゥム塩基の量は、通常 0. 1〜： LOmmolであることが好ましぐこの範囲外 では、良好な耐熱性と分散性を兼備することができない場合がある。なお、このような ブロック共重合体中には、通常、製造過程で生じたァミノ基が含有される場合がある 力 そのアミン価は 1〜： LOOmg— KOHZg程度である。なお、アミン価は、塩基性ァ ミノ基を酸により中和滴定し、酸価に対応させて KOHの mg数で表した値である。  [0168] Further, the AB block copolymer and 8-block copolymer used in the present invention! The amount of quaternary ammonium base in ^ is usually 0.1 to: LOmmol outside this range, it may not be possible to combine good heat resistance and dispersibility. Such a block copolymer usually contains an amino group produced in the production process. Its amine value is about 1 to: LOOmg-KOHZg. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of the basic amino group with an acid.
[0169] また、このブロック共重合体の酸価は、該酸価の元となる酸性基の有無及び種類に もよるが、一般に低い方が好ましぐ通常 10mg— KOHZg以下であり、その分子量 は、ポリスチレン換算の重量平均で、通常 1000以上、 100, 000以下の範囲が好ま しい。ブロック共重合体の分子量が 1000未満であると分散安定性が低下し、 100, 0 00を超えると現像性、解像性が低下する傾向にある。  [0169] In addition, the acid value of this block copolymer is generally 10 mg-KOHZg or less, which is generally preferred to be lower, although it depends on the presence and type of acidic groups that form the acid value. Is preferably in the range of not less than 1000 and not more than 100,000 in terms of weight average in terms of polystyrene. When the molecular weight of the block copolymer is less than 1000, the dispersion stability decreases, and when it exceeds 1000, the developability and resolution tend to decrease.
[0170] また、本発明にお 、ては、前記ブロック共重合体にカ卩えて、リン酸エステル型分散 剤を含有することが好ましい。これによつて、現像時の溶解性が良好になる。  [0170] In the present invention, it is preferable to contain a phosphate ester type dispersant in addition to the block copolymer. This improves the solubility during development.
[0171] リン酸エステルは、 1〜 3級エステルのどれでも良いが、分散性能の点から、 1級ェ ステルが好ましい。リン酸と結合する部分の構造は、例えばポリ力プロラタトンなどの ポリエステル、ポリエチレングリコールなどのポリエーテルに代表される、末端に水酸 基を持つ構造が挙げられる。これらは、ポリエステルとポリエーテルの共重合体でも 差し支えない。また、ポリエステル鎖及び Z又はポリエーテル鎖の片末端に (メタ)ァ タリレートなどの二重結合を有し、他のラジカル重合性化合物と共重合体を形成して も良い。  [0171] The phosphoric ester may be any of primary to tertiary esters, but primary ester is preferred from the viewpoint of dispersion performance. Examples of the structure of the portion that binds to phosphoric acid include structures having a hydroxyl group at the terminal, as typified by polyesters such as poly-force prolatatone and polyethers such as polyethylene glycol. These may be a copolymer of polyester and polyether. In addition, a double bond such as (meth) acrylate may be formed at one end of the polyester chain and Z or polyether chain, and a copolymer may be formed with another radical polymerizable compound.
[0172] 具体的に、リン酸エステルとしては、下記構造式（3)で表わされる部分構造を有す るものが好ましい。  [0172] Specifically, the phosphate ester preferably has a partial structure represented by the following structural formula (3).
[0173] [化 27]
Figure imgf000056_0001
[0173] [Chemical 27]
Figure imgf000056_0001
[0174] この様なリン酸エステルは、例えば特公昭 50— 22536号公報、特開昭 58— 1283 93号に記載の方法によって製造することができる。 Such a phosphate ester can be produced, for example, by the method described in JP-B-50-22536 and JP-A-58-128393.
[0175] 上記リン酸エステル型分散剤の分子量 Mwは、通常 200以上、また、通常 5000以 下、好ましくは 1000以下の範囲である。このリン酸エステル型分散剤は、元来、現像 溶解性を付与する目的で添加しているため、あまり高分子量にすることは好ましくな い。 [0175] The molecular weight Mw of the phosphate ester type dispersant is usually 200 or more, and usually 5000 or less, preferably 1000 or less. Since this phosphate ester type dispersant is originally added for the purpose of imparting development solubility, it is not preferable to have a high molecular weight.
[0176] <光重合性モノマー >  [0176] <Photopolymerizable monomer>
本発明の感光性榭脂組成物においては、光重合開始剤に加え、更に光重合性モ ノマー (光重合性ィ匕合物）を使用するのが感度等の点で好ましい。本発明に用いられ る光重合性モノマーとしては、エチレン性不飽和基を少なくとも 1個有する化合物を 挙げることができる。分子内にエチレン性不飽和基を有する化合物の具体例としては 、 （メタ）アクリル酸、 （メタ）アクリル酸のアルキルエステル、アクリロニトリル、スチレン、 エチレン性不飽和結合を 1個有するカルボン酸と多（単)価アルコールのモノエステ ル等が挙げられる。  In the photosensitive resin composition of the present invention, it is preferable to use a photopolymerizable monomer (photopolymerizable compound) in addition to the photopolymerization initiator in view of sensitivity and the like. Examples of the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group. Specific examples of the compound having an ethylenically unsaturated group in the molecule include (meth) acrylic acid, alkyl ester of (meth) acrylic acid, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond and many ( And monoesters of monohydric alcohols.
[0177] 光重合性モノマーとしては、特に、 1分子中にエチレン性不飽和基を 2個以上有す る多官能エチレン性単量体を使用することが望まし 、。力かる多官能エチレン性単量 体の例としては、例えば脂肪族ポリヒドロキシィ匕合物と不飽和カルボン酸とのエステ ル；芳香族ポリヒドロキシィ匕合物と不飽和カルボン酸とのエステル；脂肪族ポリヒドロキ シ化合物、芳香族ポリヒドロキシィ匕合物等の多価ヒドロキシ化合物と、不飽和カルボン 酸及び多塩基性カルボン酸とのエステル化反応により得られるエステルなどが挙げら れる。  [0177] As the photopolymerizable monomer, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. Examples of powerful polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Examples thereof include esters obtained by esterification of polyvalent hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.
[0178] 前記脂肪族ポリヒドロキシィ匕合物と不飽和カルボン酸とのエステルとしては、ェチレ ングリコールジアタリレート、トリエチレングリコールジアタリレート、トリメチロールプロパ ントリアタリレート、トリメチロールェタントリアタリレート、ペンタエリスリトールジアタリレ ート、ペンタエリスリトールトリアタリレート、ペンタエリスリトールテトラアタリレート、ジぺ ンタエリスリトールテトラアタリレート、ジペンタエリスリトールペンタアタリレート、ジペン タエリスリトールへキサアタリレート、グリセロールアタリレート等の脂肪族ポリヒドロキシ 化合物のアクリル酸エステル、これら例示化合物のアタリレートをメタタリレートに代え たメタクリル酸エステル、同様にイタコネートに代えたィタコン酸エステル、クロネート に代えたクロトン酸エステルもしくはマレエートに代えたマレイン酸エステル等が挙げ られる。 [0178] Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diatalylate, triethylene glycol diatalylate, trimethylol propane triatrate, trimethylol ethane triatariate. Rate, pentaerythritol diatarire Acrylates of aliphatic polyhydroxy compounds such as benzoate, pentaerythritol triatalylate, pentaerythritol tetraatalylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaatalylate, glycerol acrylate Acid esters, methacrylic acid esters in which the acrylates of these exemplified compounds are replaced with metatalylate, itaconate esters in place of itaconate, crotonic acid esters in place of clonate or maleates in place of maleate, etc.
[0179] 芳香族ポリヒドロキシィ匕合物と不飽和カルボン酸とのエステルとしては、ハイド口キノ ンジアタリレート、ハイド口キノンジメタタリレート、レゾルシンジアタリレート、レゾルシン ジメタタリレート、ピロガロールトリアタリレート等の芳香族ポリヒドロキシィ匕合物のアタリ ル酸エステル及びメタクリル酸エステル等が挙げられる。  [0179] Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include: Hyde Mouth Quinone Diatalylate, Hyde Mouth Quinone Dimetatalylate, Resorcin Diatalylate, Resorcin Dimetatalylate, Pyrogallol Tritalylate And aromatic polyhydroxy compounds such as acrylates and methacrylates.
[0180] 多塩基性カルボン酸及び不飽和カルボン酸と、多価ヒドロキシ化合物のエステル化 反応により得られるエステルとしては必ずしも単一物ではないが代表的な具体例を挙 げれば、アクリル酸、フタル酸、及びエチレングリコールの縮合物、アクリル酸、マレイ ン酸、及びジエチレングリコールの縮合物、メタクリル酸、テレフタル酸及びペンタエリ スリトールの縮合物、アクリル酸、アジピン酸、ブタンジオール及びグリセリンの縮合物 等がある。  [0180] The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, Condensates of phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin, etc. is there.
[0181] その他、本発明に用いられる多官能エチレン性単量体の例としては、ポリイソシァ ネート化合物と水酸基含有 (メタ)アクリル酸エステル又はポリイソシァネートイ匕合物と ポリオール及び水酸基含有 (メタ)アクリル酸エステルを反応させて得られるようなウレ タン (メタ)アタリレート類；多価エポキシィ匕合物とヒドロキシ (メタ)アタリレート又は (メタ )アクリル酸との付加反応物のようなエポキシアタリレート類;エチレンビスアクリルアミ ド等のアクリルアミド類；フタル酸ジァリル等のァリルエステル類；ジビュルフタレート等 のビュル基含有ィ匕合物等が有用である。  [0181] Other examples of polyfunctional ethylenic monomers used in the present invention include polyisocyanate compounds and hydroxyl group-containing (meth) acrylic acid esters or polyisocyanate compounds, polyols and hydroxyl group-containing (meta ) Urethane (meth) acrylates as obtained by reacting acrylic esters; epoxy acrylates such as addition reaction products of polyhydric epoxy compounds with hydroxy (meth) acrylates or (meth) acrylic acids Rates; acrylamides such as ethylene bisacrylamide; allylic esters such as diaryl phthalate; and bull group-containing compounds such as dibule phthalate are useful.
[0182] く感光性榭脂組成物のその他の配合成分 > [0182] Other ingredients of photosensitive resin composition>
本発明の感光性榭脂組成物には、上述の成分の他、有機溶剤、密着向上剤、塗 布性向上剤、現像改良剤、紫外線吸収剤、酸化防止剤、シランカップリング剤等を適 宜配合することができる。 (1) 有機溶剤 For the photosensitive resin composition of the present invention, an organic solvent, an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, a silane coupling agent and the like are suitable in addition to the above-described components. It can mix | blend suitably. (1) Organic solvent
有機溶剤としては特に制限は無いが、例えば、ジイソプロピルエーテル、ミネラルス ピリット、 n ペンタン、アミノレエーテノレ、ェチノレカプリレート、 n—へキサン、ジェチノレ エーテノレ、イソプレン、ェチノレイソブチノレエーテノレ、ブチノレステアレート、 n オクタン 、パルソル # 2、ァプコ # 18ソルベント、ジイソブチレン、ァミルアセテート、ブチルブ チレート、ァプコシンナー、ブチルエーテル、ジイソプチルケトン、メチルシクロへキセ ン、メチルノ-ルケトン、プロピルエーテル、ドデカン、 Socal solvent No. 1及び N o. 2、ァミルホルメート、ジへキシルエーテル、ジイソプロピルケトン、ソルべッソ # 15 0、酢酸ブチル（n、 sec、 t)、へキセン、シェル TS28 ソルベント、ブチルクロライド、 ェチルアミルケトン、ェチルベンゾネート、ァミルク口ライド、エチレングリコールジェチ ルエーテル、ェチルオルソホルメート、メトキシメチルペンタノン、メチルブチルケトン、 メチルへキシルケトン、メチルイソブチレート、ベンゾ-トリル、ェチルプロピオネート、 メチルセ口ソルブアセテート、メチルイソアミルケトン、メチルイソブチルケトン、プロピ ルアセテート、ァミルアセテート、ァミルホルメート、ビシクロへキシル、ジエチレングリ コールモノェチルエーテルアセテート、ジペンテン、メトキシメチルペンタノール、メチ ルアミルケトン、メチルイソプロピルケトン、プロピルプロピオネート、プロピレングリコー ルー t ブチルエーテル、メチルェチルケトン、メチルセ口ソルブ、ェチノレセロソノレブ、 ェチルセ口ソルブアセテート、カルビトール、シクロへキサノン、酢酸ェチル、プロピレ ングリコール、プロピレングリコーノレモノメチノレエーテル、プロピレングリコーノレモノメチ ノレエーテノレアセテート、プロピレングリコーノレモノェチノレエーテノレ、プロピレングリコー ノレモノェチノレエーテノレアセテート、ジプロピレングリコールモノェチルエーテル、ジプ ロピレングリコーノレモノメチノレエーテノレ、プロピレングリコーノレモノェチノレエーテノレア セテート、ジプロピレングリコールモノメチルエーテルアセテート、 3—メトキシプロピオ ン酸、 3—エトキシプロピオン酸、 3—エトキシプロピオン酸ェチル、 3—メトキシプロピ オン酸メチル、 3—メトキシプロピオン酸ェチル、 3—メトキシプロピオン酸プロピル、 3 ーメトキシプロピオン酸ブチル、ジグライム、ジプロピレングリコールモノメチルエーテ ル、エチレングリコールアセテート、ェチルカルビトール、ブチルカルビトール、ェチレ ングリコーノレモノブチノレエーテノレ、プロピレングリコーノレ tーブチノレエーテノレ、 3—メ チルー 3—メトキシブタノール、トリプロピレングリコールメチルエーテル、 3—メチルー 3—メトキシブチルアセテート等の有機溶剤を具体的に挙げることができる。 There are no particular restrictions on the organic solvent, but examples include diisopropyl ether, mineral spirits, n pentane, aminoleethenore, ethinorecaprylate, n-hexane, jetinore etherole, isoprene, ethinoreisobutinore Tenole, Butinorestearate, n-Octane, Parsol # 2, Apco # 18 Solvent, Diisobutylene, Amyl Acetate, Butyl Butylate, Apcocinner, Butyl Ether, Diisoptyl Ketone, Methyl Cyclohexene, Methyl Norketone, Propyl Ether, Dodecane, Socal solvent No. 1 and No. 2, Amylformate, Dihexyl ether, Diisopropyl ketone, Solvesso # 150, Butyl acetate (n, sec, t), Hexene, Shell TS28 Solvent, Butyl chloride , Ethyl amyl ketone, ethyl be Zonate, milk powder, ethylene glycol ethyl ether, ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzo-tolyl, ethyl propionate, methyl solvate sorb acetate , Methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methyl amyl ketone, methyl isopropyl ketone, propyl propionate , Propylene glycol t-butyl ether, methyl ethyl ketone, methyl cetorsolve, ethinorecero sonoleb, ethyl cereal sorb acetate, carbi , Cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethenoyl ether, propylene glycol monomethenoate acetate, propylene glycol monomethenoate acetate, propylene glycol monomethenoate Tenole acetate, Dipropylene glycol monoethyl ether, Dipropylene glycol monomethino ethenore, Propylene glycol mono methino thioateolate, Dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3- Ethoxypropionic acid, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Chill, diglyme, dipropylene glycol monomethyl ether, ethylene glycol acetate, E chill carbitol, butyl carbitol, Echire ring Ricoh Honoré monobutyl Honoré ether Honoré, propylene glycol Honoré t-butylate Honoré ether Honoré, 3- menu Specific examples thereof include organic solvents such as tylu-3-methoxybutanol, tripropylene glycol methyl ether, and 3-methyl-3-methoxybutyl acetate.
[0184] 溶剤は各成分を溶解又は分散させることができるもので、沸点が 100〜250°Cの範 囲のものを選択するのが好ましい。より好ましくは 120〜170°Cの沸点をもつものであ る。これらは 1種を単独で用いても良ぐ 2種以上を混合して用いても良い。  [0184] The solvent is preferably one that can dissolve or disperse each component and has a boiling point in the range of 100 to 250 ° C. More preferably, it has a boiling point of 120 to 170 ° C. These may be used alone or as a mixture of two or more.
[0185] (2) シランカップリング剤  [0185] (2) Silane coupling agent
基板との密着性を改善するため、シランカップリング剤を添加することも可能である 。シランカップリング剤の種類としては、エポキシ系、メタクリル系、アミノ系等種々の 物が使用できる力 特にエポキシ系のシランカップリング剤が好まし 、。  In order to improve the adhesion to the substrate, it is possible to add a silane coupling agent. As the type of silane coupling agent, epoxy-based, methacryl-based, amino-based and other materials can be used. Epoxy-based silane coupling agents are particularly preferred.
[0186] <感光性榭脂組成物の製造方法 >  <Method for producing photosensitive resin composition>
本発明の感光性榭脂組成物は、常法に従って製造される。  The photosensitive resin composition of the present invention is produced according to a conventional method.
[0187] 例えば、色材を含有する感光性着色榭脂組成物であれば、まず、色材、溶剤、及 び分散剤を各所定量秤量し、分散処理工程において、色材を分散させて液状の着 色組成物 (インク状液体）とする。この分散処理工程では、ペイントコンディショナー、 サンドグラインダー、ボールミル、ロールミル、ストーンミル、ジェットミル、ホモジナイザ 一などを使用することができる。この分散処理を行うことによって色材が微粒子化され るため、感光性着色榭脂組成物の塗布特性が向上し、製品のカラーフィルタ基板の 透過率が向上する。  [0187] For example, in the case of a photosensitive colored resin composition containing a color material, first, a predetermined amount of each of the color material, the solvent, and the dispersant is weighed, and in the dispersion treatment step, the color material is dispersed to form a liquid. The coloring composition (ink-like liquid). In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, and the like can be used. By performing this dispersion treatment, the color material is made into fine particles, so that the coating characteristics of the photosensitive colored resin composition are improved and the transmittance of the product color filter substrate is improved.
[0188] 色材を分散処理する際に、前記のアルカリ可溶性不飽和榭脂を併用しても良い。  [0188] When the colorant is subjected to a dispersion treatment, the alkali-soluble unsaturated resin may be used in combination.
例えば、サンドグラインダーを用いて分散処理を行う場合は、 0. 1力も数 mm径のガ ラスビーズ、又は、ジルコユアビーズを用いるのが好ましい。分散処理する際の温度 は通常、 0°C〜100°Cの範囲、好ましくは室温〜 80°Cの範囲に設定する。なお、分 散時間は、インキ状液体の組成 (色材、溶剤、分散剤）、及びサンドグラインダーの装 置の大きさなどにより適正時間が異なるため、適宜調整する必要がある。  For example, when the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads having a diameter of 0.1 mm or zirconia beads. The temperature during the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. Note that the dispersion time varies depending on the composition of the ink-like liquid (coloring material, solvent, dispersant), the size of the sand grinder, and the like, so it is necessary to adjust it appropriately.
[0189] 上記分散処理によって得られたインキ状液体に、溶剤、アルカリ可溶性不飽和榭 脂、光重合開始剤、場合によっては上記以外の他の成分などを混合し、均一な分散 溶液とする。なお、分散処理工程及び混合の各工程においては、微細なゴミが混入 することがあるため、得られた感光性着色榭脂組成物をフィルターなどによって、濾 過処理することが好ましい。 [0189] The ink-like liquid obtained by the above dispersion treatment is mixed with a solvent, an alkali-soluble unsaturated resin, a photopolymerization initiator, and, in some cases, other components other than the above, to obtain a uniform dispersion solution. In each of the dispersion treatment step and the mixing step, fine dust may be mixed. Therefore, the obtained photosensitive colored resin composition is filtered with a filter or the like. It is preferable to over-process.
[0190] 色材を含有しな!ヽ感光性榭脂組成物は、上記感光性着色榭脂組成物の製造方法 における色材の分散処理を行わずに、各成分を混合することにより製造することがで きる。 [0190] No photosensitive material! The photosensitive resin composition is produced by mixing the respective components without carrying out the dispersion treatment of the coloring material in the method for producing a photosensitive colored resin composition. be able to.
[0191] <感光性榭脂組成物中の成分配合量 >  [0191] <Ingredient blending amount in photosensitive resin composition>
アルカリ可溶性不飽和榭脂の配合量は、本発明の感光性榭脂組成物の全固形分 に対して、通常 10重量％以上、好ましくは 20重量％以上であり、通常 80重量％以 下、好ましくは 70重量％以下である。また、本発明の感光性榭脂組成物が色材を含 有する感光性着色榭脂組成物である場合、アルカリ可溶性不飽和榭脂の色材に対 する比率としては、通常 5重量％以上、好ましくは 10重量％以上で、通常 500重量 %以下、好ましくは 200重量％以下の範囲である。アルカリ可溶性不飽和榭脂の含 有量が少なすぎると、未露光部分の現像液に対する溶解性が低下し、現像不良を誘 起させやすぐ逆に多いと、所望の画素膜厚が得られ難くなる。  The blending amount of the alkali-soluble unsaturated coffin is usually 10% by weight or more, preferably 20% by weight or more, and usually 80% by weight or less, based on the total solid content of the photosensitive resin composition of the present invention. Preferably it is 70 weight% or less. Further, when the photosensitive resin composition of the present invention is a photosensitive colored resin composition containing a color material, the ratio of the alkali-soluble unsaturated resin to the color material is usually 5% by weight or more, The range is preferably 10% by weight or more, usually 500% by weight or less, preferably 200% by weight or less. If the content of the alkali-soluble unsaturated resin is too small, the solubility of the unexposed part in the developer will be reduced, and if it is too high, it will be difficult to obtain the desired pixel thickness. Become.
[0192] なお、本発明において「全固形分」とは、溶剤以外の全ての成分を意味し、本発明 の感光性榭脂組成物中の全固形分は、通常 10重量％以上、 90重量％以下である。  In the present invention, “total solid content” means all components other than the solvent, and the total solid content in the photosensitive resin composition of the present invention is usually 10% by weight or more and 90% by weight. % Or less.
[0193] 光重合開始剤を配合する場合、その含有量は、本発明の感光性榭脂組成物の全 固形分に対して、通常 0. 1重量％以上、好ましくは 0. 5重量％以上、更に好ましくは 0. 7重量以上であり、通常 30重量％以下、好ましくは 20重量％以下である。光重合 開始剤の含有率が少なすぎると感度低下を起こすことがあり、反対に多すぎると未露 光部分の現像液に対する溶解性が低下し、現像不良を誘起させやす ヽ。  [0193] When the photopolymerization initiator is blended, the content thereof is usually 0.1% by weight or more, preferably 0.5% by weight or more, based on the total solid content of the photosensitive resin composition of the present invention. More preferably, it is 0.7% or more, usually 30% by weight or less, preferably 20% by weight or less. If the content of the photopolymerization initiator is too small, the sensitivity may be lowered. On the other hand, if the content is too large, the solubility of the unexposed light part in the developing solution is lowered, and development defects are likely to be induced.
[0194] 色材を配合する場合、その含有量は、本発明の感光性着色榭脂組成物中の全固 形分量に対して通常 1〜70重量％の範囲で選ぶことができる。この範囲の中では、 1 0〜70重量％がより好ましぐ中でも 20重量％以上 60重量％以下が特に好ましい。 色材の含有量が少なすぎると、色濃度に対する膜厚が大きくなりすぎて、液晶セル化 の際のギャップ制御などに悪影響を及ぼす。また、逆に色材の含有量が多すぎると、 十分な画像形成性が得られなくなることがある。  [0194] When a coloring material is blended, the content thereof can be selected in the range of usually 1 to 70% by weight with respect to the total solid content in the photosensitive colored resin composition of the present invention. Within this range, 10 to 70% by weight is more preferable, but 20% to 60% by weight is particularly preferable. If the content of the coloring material is too small, the film thickness with respect to the color density becomes too large, which adversely affects the gap control when forming a liquid crystal cell. On the other hand, if the content of the color material is too large, sufficient image formability may not be obtained.
[0195] 分散剤を配合する場合であって、窒素原子含有分散剤のうち、前記 [1]ウレタン系 分散榭脂を用いる場合、感光性着色榭脂組成物中の色材成分に対する含有量とし ては、通常 10重量％以上、好ましくは 20重量％以上、特に好ましくは 30重量％以 上であり、通常 300重量％以下、好ましくは 100重量％以下、特に好ましくは 80重量 %以下である。窒素原子含有分散剤が少なすぎると、色材への吸着が不足し、凝集 を防ぐことができず、高粘度化ないしゲルイ匕してしまうことがあり、逆に多すぎると、膜 厚が厚くなりすぎて、カラーフィルタにした後、液晶セルィ匕工程でのセルギャップ制御 不良が出ることがあるため、どちらも好ましくない。 [0195] In the case where a dispersant is blended, and among the nitrogen atom-containing dispersants, the above-mentioned [1] urethane-based dispersed resin is used as the content with respect to the color material component in the photosensitive colored resin composition. In general, it is at least 10% by weight, preferably at least 20% by weight, particularly preferably at least 30% by weight, usually at most 300% by weight, preferably at most 100% by weight, particularly preferably at most 80% by weight. If the amount of the nitrogen atom-containing dispersant is too small, adsorption to the coloring material is insufficient and aggregation cannot be prevented, resulting in increased viscosity or gelling. On the other hand, if the amount is too large, the film thickness is increased. Both of them are not preferable because a cell gap control defect may occur in the liquid crystal cell process after the color filter is formed.
[0196] また、分散剤として前記 [2]グラフト共重合体を用いる場合、感光性着色榭脂組成 物中の色材成分に対する含有量としては、通常 10重量％以上、好ましくは 20重量 %以上、特に好ましくは 30重量％以上であり、通常 300重量％以下、好ましくは 100 重量％以下、特に好ましくは 80重量％以下である。分散剤成分が少なすぎると、色 材への吸着が不足し、凝集を防ぐことができず、高粘度化ないしゲルイ匕してしまうこと があり、逆に多すぎると、膜厚が厚くなりすぎて、カラーフィルタにした後、液晶セル化 工程でのセルギャップ制御不良が出ることがあるため、どちらも好ましくない。  [0196] When the above-mentioned [2] graft copolymer is used as a dispersant, the content relative to the color material component in the photosensitive colored resin composition is usually 10% by weight or more, preferably 20% by weight or more. Particularly preferably, it is at least 30% by weight, usually at most 300% by weight, preferably at most 100% by weight, particularly preferably at most 80% by weight. If the amount of the dispersant component is too small, the adsorption to the coloring material is insufficient and aggregation cannot be prevented, and the viscosity or gelation may occur. On the other hand, if the amount is too large, the film thickness becomes too thick. In this case, after the color filter is formed, cell gap control failure may occur in the liquid crystal cell forming process.
[0197] また、分散剤として前記 [3]ブロック共重合体を用いる場合、感光性着色榭脂組成 物中の色材成分に対する含有量としては、通常 10重量％以上、好ましくは 20重量 %以上、特に好ましくは 30重量％以上であり、通常 300重量％以下、好ましくは 100 重量％以下、特に好ましくは 80重量％以下である。分散剤成分が少なすぎると、色 材への吸着が不足し、凝集を防ぐことができず、高粘度化ないしゲルイ匕してしまうこと があり、逆に多すぎると、膜厚が厚くなりすぎて、カラーフィルタにした後、液晶セル化 工程でのセルギャップ制御不良が出ることがあるため、どちらも好ましくない。  [0197] Further, when the above-mentioned [3] block copolymer is used as a dispersant, the content relative to the color material component in the photosensitive colored resin composition is usually 10% by weight or more, preferably 20% by weight or more. Particularly preferably, it is at least 30% by weight, usually at most 300% by weight, preferably at most 100% by weight, particularly preferably at most 80% by weight. If the amount of the dispersant component is too small, the adsorption to the coloring material is insufficient and aggregation cannot be prevented, and the viscosity or gelation may occur. On the other hand, if the amount is too large, the film thickness becomes too thick. In this case, after the color filter is formed, cell gap control failure may occur in the liquid crystal cell forming process.
[0198] また、前記リン酸エステル型分散剤は、前記 [3]ブロック共重合体 100重量部に対 して、通常 5重量部以上、好ましくは 10重量部以上、また、通常 100重量部以下、好 ましくは 80重量部以下で用いることが好ましい。リン酸エステル型分散剤の割合が少 な過ぎると、十分な現像溶解性が発現されないおそれがある。一方、逆にリン酸エス テル型分散剤の割合が多過ぎても、効果は飽和して、逆に分散性が低下するおそれ がある。  [0198] The phosphate ester type dispersant is usually 5 parts by weight or more, preferably 10 parts by weight or more, and usually 100 parts by weight or less based on 100 parts by weight of the [3] block copolymer. It is preferable to use 80 parts by weight or less. If the proportion of the phosphate ester type dispersant is too small, sufficient development solubility may not be exhibited. On the other hand, if the proportion of the ester phosphate dispersant is too large, the effect is saturated and the dispersibility may be lowered.
[0199] 光重合性モノマーを用いる場合、その含有量は、本発明の感光性榭脂組成物の全 固形分に対して、通常 90重量％以下、好ましくは 80重量％以下である。光重合性モ ノマーの含有量が多すぎると、露光部への現像液の浸透性が高くなり、良好な画像 を得ることが困難となる。なお、光重合性モノマーの含有量の下限は、通常 0重量％ 以上、好ましくは 5重量％以上である。 [0199] When a photopolymerizable monomer is used, its content is usually 90% by weight or less, preferably 80% by weight or less, based on the total solid content of the photosensitive resin composition of the present invention. Photopolymerizable module If the content of the nomer is too large, the permeability of the developing solution to the exposed area becomes high, and it becomes difficult to obtain a good image. The lower limit of the content of the photopolymerizable monomer is usually 0% by weight or more, preferably 5% by weight or more.
[0200] <感光性榭脂組成物の用途 > [0200] <Application of photosensitive resin composition>
本発明の感光性榭脂組成物は、液晶ディスプレイ等の液晶パネルに用いられる力 ラーフィルタの画像形成用、ブラックマトリックス用、オーバーコート用、リブ用、及びス ぺーサ一用感光性樹脂組成物として有用である。また、本発明の感光性榭脂組成物 は、カラーフィルタ用途以外にも、フレキシブルプリント配線板用ソルダーレジスト、メ ツキレジスト、多層プリント配線板用相関絶縁膜、感光性光導波路、光硬化型液晶シ 一ル材、光硬化型 ELシール材、光硬化性接着剤等として有用である。  The photosensitive resin composition of the present invention is a photosensitive resin composition for image formation, black matrix use, overcoat use, rib use, and spacer use for power filters used in liquid crystal panels such as liquid crystal displays. Useful as. Further, the photosensitive resin composition of the present invention can be used not only for color filters, but also for solder resists for flexible printed wiring boards, plating resists, correlation insulating films for multilayer printed wiring boards, photosensitive optical waveguides, and photocurable liquid crystals. It is useful as a seal material, photo-curing EL seal material, photo-curing adhesive and so on.
[0201] [カラーフィルタ] [0201] [Color filter]
透明基板上に、ブラックマトリックスを設け、通常、赤色、緑色、青色の画素画像を 形成することにより、本発明のカラーフィルタを製造することができ、色材を含む本発 明の感光性着色榭脂組成物は、黒色、赤色、緑色、青色のうち少なくとも一種のレジ スト形成用塗布液として使用される。ブラックレジストに関しては、透明基板上素ガラ ス面上、赤色、緑色、青色に関しては透明基板上に形成された榭脂ブラックマトリック ス形成面上、又は、クロム化合物その他の遮光金属材料を用いて形成した金属ブラ ックマトリックス形成面上に、塗布、加熱乾燥、画像露光、現像及び熱硬化の各処理 を行って各色の画素画像を形成する。また、色材を含まない本発明の感光性榭脂組 成物は、オーバーコート用、リブ用、及びスぺーサー用感光性榭脂組成物として用い られる。  The color filter of the present invention can be produced by providing a black matrix on a transparent substrate and forming pixel images of red, green, and blue, and the photosensitive coloring layer of the present invention containing a coloring material. The fat composition is used as a resist-forming coating solution of at least one of black, red, green, and blue. Black resist is formed on the glass substrate surface on the transparent substrate, red, green, and blue are formed on the resin black matrix forming surface formed on the transparent substrate, or using a chromium compound or other light shielding metal material. A pixel image of each color is formed on the metal black matrix forming surface by performing coating, heat drying, image exposure, development and thermosetting. In addition, the photosensitive resin composition of the present invention that does not contain a coloring material is used as a photosensitive resin composition for overcoats, ribs, and spacers.
[0202] カラーフィルタの透明基板としては、透明で適度の強度があれば、その材質は特に 限定されるものではない。材質としては、例えば、ポリエチレンテレフタレートなどのポ リエステル系榭脂、ポリプロピレン、ポリエチレンなどのポリオレフイン系榭脂、ポリカー ボネート、ポリメチルメタタリレート、ポリスルホンの熱可塑性榭脂製シート、エポキシ 榭脂、不飽和ポリエステル榭脂、ポリ (メタ)アクリル系榭脂などの熱硬化性榭脂シート 、又は各種ガラスなどが挙げられる。この中でも、耐熱'性の観点からガラス、耐熱性榭 脂が好ましい。 [0203] 透明基板及びブラックマトリックス形成基板には、接着性などの表面物性の改良の ため、必要に応じ、コロナ放電処理、オゾン処理、シランカップリング剤や、ウレタン系 榭脂などの各種樹脂の薄膜形成処理などを行っても良い。 [0202] The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resin such as polyethylene terephthalate, polyolefin resin such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone thermoplastic resin sheet, epoxy resin, and unsaturated resin. Examples thereof include thermosetting resin sheets such as polyester resin and poly (meth) acrylic resin, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance. [0203] In order to improve surface properties such as adhesiveness, transparent substrates and black matrix-formed substrates may contain various resins such as corona discharge treatment, ozone treatment, silane coupling agents, and urethane-based resins. A thin film forming process or the like may be performed.
[0204] 透明基板の厚さは、通常 0. 05〜： LOmm、好ましくは 0. l〜7mmの範囲とされる。  [0204] The thickness of the transparent substrate is usually in the range of 0.05 to: LOmm, preferably 0.1 to 7 mm.
また各種樹脂の薄膜形成処理を行う場合、その膜厚は、通常 0. 01〜10 m、好ま しくは 0. 05〜5 mの範囲である。  When thin film forming treatment of various resins is performed, the film thickness is usually in the range of 0.01 to 10 m, preferably 0.05 to 5 m.
[0205] [1]ブラックマトリックス  [0205] [1] Black matrix
ブラックマトリックスは、遮光金属薄膜又は榭脂ブラックマトリックス用感光性着色榭 脂組成物を利用して、透明基板上に形成される。遮光金属材料としては、金属クロム 、酸化クロム、窒化クロムなどのクロム化合物、ニッケルとタングステン合金などが用い られ、これらを複数層状に積層させたものであっても良い。  The black matrix is formed on a transparent substrate using a light-shielding metal thin film or a photosensitive colored resin composition for resin black matrix. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide, and chromium nitride, nickel and tungsten alloy, etc. are used, and these may be laminated in a plurality of layers.
[0206] これらの金属遮光膜は、一般にスパッタリング法によって形成され、ポジ型フオトレ ジストにより、膜状に所望のパターンを形成した後、クロムに対しては硝酸第二セリウ ムアンモ-ゥムと過塩素酸及び Z又は硝酸とを混合したエッチング液を用い、その他 の材料に対しては、材料に応じたエッチング液を用いて蝕刻され、最後にポジ型フォ トレジストを専用の剥離剤で剥離することによって、ブラックマトリックスを形成すること ができる。  [0206] These metal light-shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape by a positive type photoresist, cerium nitrate ammonium and perchlorine are applied to chromium. Etching solution mixed with acid and Z or nitric acid is used. For other materials, etching is performed using an etching solution according to the material, and finally the positive photoresist is removed with a special release agent. A black matrix can be formed.
[0207] この場合、まず、蒸着又はスパッタリング法などにより、透明基板上にこれら金属又 は金属'金属酸化物の薄膜を形成する。次いで、この薄膜上に感光性着色榭脂組成 物の塗膜を形成した後、ストライプ、モザイク、トライアングルなどの繰り返しパターン を有するフォトマスクを用いて、塗膜を露光'現像し、レジスト画像を形成する。その後 、この塗膜にエッチング処理を施してブラックマトリックスを形成することができる。  [0207] In this case, first, a thin film of these metals or metal 'metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the photosensitive colored resin composition on this thin film, the coating film was exposed and developed using a photomask having a repetitive pattern such as stripes, mosaics and triangles to form a resist image. To do. Thereafter, this coating film can be etched to form a black matrix.
[0208] 榭脂ブラックマトリックス用感光性着色榭脂組成物を利用する場合は、黒色の色材 を含有する本発明の感光性着色榭脂組成物を使用して、ブラックマトリックスを形成 する。例えば、カーボンブラック、黒鉛、鉄黒、ァニリンブラック、シァニンブラック、チ タンブラックなどの黒色色材単独又は複数、もしくは、無機又は有機の顔料、染料の 中から適宜選択される赤色、緑色、青色などの混合による黒色色材を含有する感光 性着色榭脂組成物を使用し、下記の赤色、緑色、青色の画素画像を形成する方法と 同様にして、ブラックマトリックスを形成することができる。 [0208] When the photosensitive colored rosin composition for rosin black matrix is used, the photosensitive colored rosin composition of the present invention containing a black colorant is used to form a black matrix. For example, one or more black color materials such as carbon black, graphite, iron black, vanillin black, cyanine black, and titanium black, or red, green, and the like appropriately selected from inorganic or organic pigments and dyes A method for forming the following red, green, and blue pixel images using a photosensitive colored resin composition containing a black color material mixed with blue or the like, and Similarly, a black matrix can be formed.
[0209] [2]画素  [0209] [2] Pixel
ブラックマトリックスを設けた透明基板上に、赤色、緑色、青色のうち一色の色材を 含有する感光性着色榭脂組成物を塗布し、乾燥した後、塗膜の上にフォトマスクを重 ね、このフォトマスクを介して画像露光、現像、必要に応じて熱硬化又は光硬化により 画素画像を形成させ、着色層を作成する。この操作を、赤色、緑色、青色の三色の 感光性着色榭脂組成物について各々行うことによって、カラーフィルタ画像を形成す ることがでさる。  On a transparent substrate provided with a black matrix, a photosensitive colored resin composition containing a color material of one color of red, green and blue is applied and dried, and then a photomask is superimposed on the coating film, Through this photomask, a pixel image is formed by image exposure, development, and if necessary, heat curing or photocuring to create a colored layer. A color filter image can be formed by performing this operation for each of the three colored photosensitive colored resin compositions of red, green, and blue.
[0210] (2— 1)塗布方法 [0210] (2-1) Application method
カラーフィルタ用の感光性着色榭脂組成物の塗布は、スピナ一法、ワイヤーバー法 、フローコート法、ダイコート法、ロールコート法、又はスプレーコート法などによって 行うことができる。中でも、ダイコート法によれば、塗布液使用量が大幅に削減され、 かつ、スピンコート法によった際に付着するミストなどの影響が全くなぐ異物発生が 抑制されるなど、総合的な観点力も好ま 、。  The photosensitive colored resin composition for the color filter can be applied by 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. In particular, the die coating method significantly reduces the amount of coating solution used and suppresses the generation of foreign substances that are completely free from the effects of mist adhering to the spin coating method. Favored ,.
[0211] 塗膜の厚さは、厚すぎると、ノターン現像が困難となるとともに、液晶セル化工程で のギャップ調整が困難となることがあり、薄すぎると顔料濃度を高めることが困難となり 所望の色発現が不可能となることがある。塗膜の厚さは、乾燥後の膜厚として、通常 0. 2〜20 mの範囲とするのが好ましぐより好ましいのは 0. 5〜10 /ζ πιの範囲、更 に好ましいのは 0. 8〜5 mの範囲である。  [0211] If the thickness of the coating film is too thick, it will be difficult to develop a no-turn development, and it may be difficult to adjust the gap in the liquid crystal cell forming process. May not be possible. The film thickness after drying is usually preferably in the range of 0.2 to 20 m, more preferably in the range of 0.5 to 10 / ζ πι, and even more preferably 0. Range of 8-5 m.
[0212] (2— 2)乾燥方法  [0212] (2-2) Drying method
基板に感光性着色榭脂組成物を塗布した後の塗膜の乾燥は、ホットプレート、 IRォ 一ブン、又はコンペクシヨンオーブンを使用した乾燥法によるのが好ましい。乾燥の 条件は、前記溶剤成分の種類、使用する乾燥機の性能などに応じて適宜選択するこ とができる。乾燥時間は、溶剤成分の種類、使用する乾燥機の性能などに応じて、通 常は、 40〜200°Cの温度で 15秒〜 5分間の範囲で選ばれ、好ましくは 50〜130°C の温度で 30秒〜 3分間の範囲で選ばれる。  The coating film after the photosensitive colored resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a competition oven. 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 15 seconds to 5 minutes at a temperature of 40 to 200 ° C, preferably 50 to 130 ° C, depending on the type of solvent component and the performance of the dryer used. The temperature is selected from 30 seconds to 3 minutes.
[0213] 乾燥温度は、高いほど透明基板に対する塗膜の接着性が向上するが、高すぎると ノインダー榭脂が分解し、熱重合を誘発して現像不良を生ずる場合がある。なお、こ の塗膜の乾燥工程は、温度を高めず、減圧チャンバ一内で乾燥を行う、減圧乾燥法 であっても良い。 [0213] The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, if the drying temperature is too high, the Noinda resin may be decomposed to induce thermal polymerization and cause poor development. In addition, this The drying process of the coating film may be a reduced-pressure drying method in which drying is performed in the reduced-pressure chamber without increasing the temperature.
[0214] (2— 3)露光方法  [0214] (2-3) Exposure method
画像露光は、感光性着色榭脂組成物の塗膜上に、ネガのマスクパターンを重ね、 このマスクパターンを介し、紫外線又は可視光線の光源を照射して行う。この際、必 要に応じ、酸素による光重合性層の感度の低下を防ぐため、光重合性の塗膜上にポ リビュルアルコール層などの酸素遮断層を形成した後に露光を行っても良い。上記 の画像露光に使用される光源は、特に限定されるものではない。光源としては、例え ば、キセノンランプ、ハロゲンランプ、タングステンランプ、高圧水銀灯、超高圧水銀 灯、メタルノ、ライドランプ、中圧水銀灯、低圧水銀灯、カーボンアーク、蛍光ランプな どのランプ光源や、アルゴンイオンレーザー、 YAGレーザー、エキシマレーザー、窒 素レーザー、ヘリウム力ドミニゥムレーザー、半導体レーザーなどのレーザー光源な どが挙げられる。特定の波長の光を照射して使用する場合には、光学フィルタを利用 することちでさる。  Image exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive colored resin composition and irradiating a UV or visible light source through this mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyhydric alcohol layer is formed on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. . The light source used for the image exposure is not particularly limited. Examples of light sources include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal lamps, ride lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, and argon ion lasers. Laser light sources such as YAG laser, excimer laser, nitrogen laser, helium-powered dominum laser, and semiconductor laser. When irradiating light of a specific wavelength, use an optical filter.
[0215] (2— 4)現像方法 [0215] (2-4) Development method
本発明に係るカラーフィルタは、感光性着色榭脂組成物による塗膜を、上記の光源 によって画像露光を行った後、有機溶剤、又は、界面活性剤とアルカリ性ィ匕合物とを 含む水溶液を用いる現像によって、基板上に画像を形成して作製することができる。 この水溶液には、更に有機溶剤、緩衝剤、錯化剤、染料又は顔料を含ませることが できる。  The color filter according to the present invention comprises an organic solvent or an aqueous solution containing a surfactant and an alkaline compound after image-exposing a coating film made of a photosensitive colored resin composition with the above-mentioned light source. An image can be formed on the substrate by development to be used. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
[0216] アルカリ性ィ匕合物としては、水酸化ナトリウム、水酸ィ匕カリウム、水酸化リチウム、炭 酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、ケィ酸ナトリウム、 ケィ酸カリウム、メタケイ酸ナトリウム、リン酸ナトリウム、リン酸カリウム、リン酸水素ナト リウム、リン酸水素カリウム、リン酸二水素ナトリウム、リン酸二水素カリウム、水酸化ァ ンモ -ゥムなどの無機アルカリ性化合物や、モノー'ジ—又はトリエタノールァミン、モ ノ 'ジ一又はトリメチルァミン、モノ一'ジ一又はトリェチルァミン、モノ一又はジイソ プロピルァミン、 n—ブチルァミン、モノ一'ジ一又はトリイソプロパノールァミン、ェチ レンィミン、エチレンジィミン、テトラメチルアンモ-ゥムヒドロキシド（TMAH)、コリン などの有機アルカリ性ィ匕合物が挙げられる。これらのアルカリ性ィ匕合物は、 2種以上 の混合物であっても良い。 [0216] 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, Ethylenedimine, tetramethylammonium hydroxide (TMAH), choline Organic alkaline compounds such as These alkaline compounds may be a mixture of two or more.
[0217] 界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシ エチレンアルキルァリールエーテル類、ポリオキシエチレンアルキルエステル類、ソル ビタンアルキルエステル類、モノグリセリドアルキルエステル類などのノ-オン系界面 活性剤、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、ァ ルキル硫酸塩類、アルキルスルホン酸塩類、スルホコハク酸エステル塩類などのァ- オン性界面活性剤、アルキルべタイン類、アミノ酸類などの両性界面活性剤が挙げら れる。 [0217] Examples of the surfactant 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, alkyl betaines, amino acids, etc. Agents.
[0218] 有機溶剤としては、例えば、イソプロピルアルコール、ベンジルアルコール、ェチル セロソルブ、ブチルセ口ソルブ、フエ二ルセ口ソルブ、プロピレングリコール、ジァセト ンアルコールなどが挙げられる。有機溶剤は、単独で用いても良ぐまた、水溶液と 混合して用いても良い。  [0218] Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butylcetosolve, phenylsolvesolve, propylene glycol, diacetone alcohol and the like. The organic solvent may be used alone or in combination with an aqueous solution.
[0219] 現像処理の条件は特に制限はなぐ通常、現像温度は 10〜50°Cの範囲、中でも 1 5〜45°C、特に好ましくは 20〜40°Cで、現像方法は、浸漬現像法、スプレー現像法 、ブラシ現像法、超音波現像法などのいずれかの方法によることができる。  [0219] The development processing conditions are not particularly limited. Usually, the development temperature is in the range of 10 to 50 ° C, especially 15 to 45 ° C, particularly preferably 20 to 40 ° C. , Spray developing method, brush developing method, ultrasonic developing method and the like.
[0220] (2— 5)熱硬化処理方法  [0220] (2-5) Thermosetting method
現像の後のカラーフィルタ基板には、熱硬化処理を施す。この際の熱硬化処理条 件は、温度は 100〜280°Cの範囲、好ましくは 150〜250°Cの範囲で選ばれ、時間 は 5〜60分間の範囲で選ばれる。これら一連の工程を経て、一色のパターユング画 像形成は終了する。この工程を順次繰り返し、ブラック、赤色、緑色、青色をパター- ングし、カラーフィルタを形成する。なお、 4色のパターユングの順番は、上記した順 番に限定されるものではない。  The color filter substrate after development is subjected to thermosetting treatment. In this case, the temperature of the thermosetting treatment is selected in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes. After a series of these steps, the formation of one-color pattern image is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. The order of the four-color patterning is not limited to the order described above.
[0221] (2— 6)透明電極の形成方法  [0221] (2-6) Method of forming transparent electrode
カラーフィルタは、このままの状態で画像上に ITOなどの透明電極を形成して、カラ 一ディスプレー、液晶表示装置などの部品の一部として使用されるが、表面平滑性 や耐久性を高めるため、必要に応じ、画像上にポリアミド、ポリイミドなどのトップコート 層を設けることもできる。また一部、平面配向型駆動方式 (IPSモード)などの用途に おいては、透明電極を形成しないこともある。 Color filters are used as part of parts such as color displays and liquid crystal display devices by forming transparent electrodes such as ITO on the image as they are. In order to improve surface smoothness and durability, If necessary, a top coat layer such as polyamide or polyimide can be provided on the image. Also, for some applications such as planar orientation drive (IPS mode) However, the transparent electrode may not be formed.
[0222] [3]スぺーサー  [0222] [3] Spacer
本発明の感光性榭脂組成物をスぺーサー用感光性榭脂組成物として用いる場合 When using the photosensitive resin composition of the present invention as a photosensitive resin composition for spacers
、通常、スぺーサ一が設けられるべき基板上に、溶剤に溶解或いは分散された感光 性榭脂組成物を、塗布等の方法により膜状或いはパターン状に供給し、溶剤を乾燥 させた後、膜状に供給された場合には、必要により露光一現像を行うフォトリソグラフ ィーなどの方法によりパターン形成を行う。その後、必要により熱硬化処理を行うこと により、該基板上にスぺーサ一が形成される。 Usually, after a photosensitive resin composition dissolved or dispersed in a solvent is supplied into a film or pattern by a method such as coating on a substrate on which a spacer is to be provided, the solvent is dried. When the film is supplied, a pattern is formed by a method such as photolithography in which exposure and development are performed if necessary. Thereafter, a spacer is formed on the substrate by performing a thermosetting treatment if necessary.
[0223] (3— 1)基板への供給方法  [0223] (3-1) Supplying method to substrate
本発明の感光性榭脂組成物は、通常溶剤に溶解或いは分散された状態で、基板 上へ供給される。その供給方法としては、従来公知の方法、例えば、スピナ一法、ヮ ィヤーバー法、フローコート法、ダイコート法、ロールコート法、スプレーコート法など によって行うことができる。また、インクジェット法や印刷法などにより、パターン状に供 給しても良い。中でも、ダイコート法によれば、塗布液使用量が大幅に削減され、か つ、スピンコート法によった際に付着するミストなどの影響が全くない、異物発生が抑 制されるなど、総合的な観点力も好ま 、。  The photosensitive resin composition of the present invention is usually supplied onto a substrate in a state dissolved or dispersed in a solvent. As the supply method, a conventionally known method such as a spinner method, a barber method, a flow coating method, a die coating method, a roll coating method, a spray coating method or the like can be used. Further, it may be supplied in a pattern by an inkjet method or a printing method. In particular, 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. I also like a strong viewpoint.
[0224] 塗布量は用途により異なるが、例えばスぺーサ一の場合には、乾燥膜厚として、通 常 0. 5 μ m以上、好ましくは 1 μ m以上で、通常 10 μ m以下、好ましくは 8 μ m以下、 特に好ましくは 5 m以下の範囲である。また、乾燥膜厚あるいは最終的に形成され たスぺーサ一の高さが、基板全域に渡って均一であることが重要である。ばらつきが 大き 、場合には、液晶パネルにムラ欠陥を生ずることとなる。  [0224] The coating amount varies depending on the application. For example, in the case of a spacer, the dry film thickness is usually 0.5 μm or more, preferably 1 μm or more, and usually 10 μm or less, preferably Is 8 μm or less, particularly preferably 5 m or less. In addition, 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 is large, uneven defects will occur in the liquid crystal panel.
[0225] (3— 2)乾燥方法  [0225] (3-2) Drying method
基板上に感光性榭脂組成物を供給した後の乾燥は、ホットプレート、 IRオーブン、 コンペクシヨンオーブンを使用した乾燥法によるのが好ましい。また、温度を高めず、 減圧チャンバ一内で乾燥を行う減圧乾燥法を組み合わせても良い。乾燥の条件は、 溶剤成分の種類、使用する乾燥機の性能などに応じて適宜選択することができる。 乾燥時間は、溶剤成分の種類、使用する乾燥機の性能などに応じて、通常は、 40〜 100°Cの温度で 15秒〜 5分間の範囲で選ばれ、好ましくは 50〜90°Cの温度で 30 秒〜 3分間の範囲で選ばれる。 The drying after supplying the photosensitive resin composition on the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a competition 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 15 seconds to 5 minutes at a temperature of 40 to 100 ° C, preferably 50 to 90 ° C, depending on the type of solvent component and the performance of the dryer used. At temperature 30 It is selected in the range of seconds to 3 minutes.
[0226] (3— 3)露光方法  [0226] (3-3) Exposure method
露光は、感光性榭脂組成物の塗布膜上に、ネガのマスクパターンを重ね、このマス クパターンを介し、紫外線又は可視光線の光源を照射して行う。またレーザー光によ る走査露光方式によっても良い。この際、必要に応じ、酸素による光重合性層の感度 の低下を防ぐため、光重合性層上にポリビニルアルコール層などの酸素遮断層を形 成した後に露光を行ってもよい。上記の露光に使用される光源は、特に限定されるも のではない。光源としては、例えば、キセノンランプ、ハロゲンランプ、タングステンラ ンプ、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、中圧水銀灯、低圧水銀灯 、カーボンアーク、蛍光ランプなどのランプ光源や、アルゴンイオンレーザー、 YAG レーザー、エキシマレーザー、窒素レーザー、ヘリウム力ドミニゥムレーザー、青紫色 半導体レーザー、近赤外半導体レーザーなどのレーザー光源などが挙げられる。特 定の波長の光を照射して使用する場合には、光学フィルタを利用することもできる。  The exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive resin composition and irradiating an ultraviolet or visible light source through this mask pattern. Further, a scanning exposure method using a laser beam may be used. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for the exposure is not particularly limited. Examples of light sources include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, and fluorescent lamps, as well as argon ion lasers and YAG lasers. Laser light sources such as excimer laser, nitrogen laser, helium-powered Dominium laser, blue-violet semiconductor laser, and near-infrared semiconductor laser. An optical filter can also be used when irradiating with a specific wavelength of light.
[0227] (3— 4)現像方法  [0227] (3-4) Development method
上記の露光を行った後、アルカリ性ィ匕合物と界面活性剤とを含む水溶液、又は有 機溶剤を用いる現像によって、基板上に画像パターンを形成することができる。この 水溶液には、更に有機溶剤、緩衝剤、錯化剤、染料又は顔料を含ませることができる  After performing the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution containing an alkaline compound and a surfactant or an organic solvent. This aqueous solution can further contain organic solvents, buffering agents, complexing agents, dyes or pigments.
[0228] アルカリ性ィ匕合物としては、水酸化ナトリウム、水酸ィ匕カリウム、水酸化リチウム、炭 酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、ケィ酸ナトリウム、 ケィ酸カリウム、メタケイ酸ナトリウム、リン酸ナトリウム、リン酸カリウム、リン酸水素ナト リウム、リン酸水素カリウム、リン酸二水素ナトリウム、リン酸二水素カリウム、水酸化ァ ンモ -ゥムなどの無機アルカリ性化合物や、モノー'ジ—又はトリエタノールァミン、モ ノ 'ジ一又はトリメチルァミン、モノ一'ジ一又はトリェチルァミン、モノ一又はジイソ プロピルァミン、 n—ブチルァミン、モノ一'ジ一又はトリイソプロパノールァミン、ェチ レンィミン、エチレンジィミン、テトラメチルアンモ-ゥムヒドロキシド（TMAH)、コリン などの有機アルカリ性ィ匕合物が挙げられる。これらのアルカリ性ィ匕合物は、 2種以上 の混合物であってもよい。 [0229] 界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシ エチレンアルキルァリールエーテル類、ポリオキシエチレンアルキルエステル類、ソル ビタンアルキルエステル類、モノグリセリドアルキルエステル類などのノ-オン系界面 活性剤、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、ァ ルキル硫酸塩類、アルキルスルホン酸塩類、スルホコハク酸エステル塩類などのァ- オン性界面活性剤、アルキルべタイン類、アミノ酸類などの両性界面活性剤が挙げら れる。 [0228] 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. Include alkaline I 匕合 thereof. These alkaline compounds may be a mixture of two or more. [0229] Examples of the surfactant 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.
[0230] 有機溶剤としては、例えば、イソプロピルアルコール、ベンジルアルコール、ェチル セロソルブ、ブチルセ口ソルブ、フエ二ルセ口ソルブ、プロピレングリコール、ジァセト ンアルコールなどが挙げられる。有機溶剤は単独で用いても良ぐ水溶液と併用して 使用してもできる。  [0230] Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butylcetosolve, phencelesolve, propylene glycol, diaceton alcohol and the like. The organic solvent can be used alone or in combination with a good aqueous solution.
[0231] (3— 5)熱硬化処理方法  [0231] (3-5) Thermosetting method
現像の後の基板には、熱硬化処理を施すのが好ましい。この際の熱硬化処理条件 は、温度は 100〜280°Cの範囲、好ましくは 150〜250°Cの範囲で選ばれ、時間は 5〜60分間の範囲で選ばれる。  The substrate after development is preferably subjected to a 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.
[0232] [4]リブ (液晶分割配向突起）  [0232] [4] Ribs (Liquid crystal alignment protrusions)
リブ (液晶分割配向突起）とは、液晶表示装置の視野角を改善するために、透明電 極上に形成する突起をいい、前記突起のスロープを利用して液晶を局所的に傾け、 一画素内で液晶を多方向に分割させるものである。以下、リブの形成方法を詳述す る。  A rib (liquid crystal split alignment protrusion) is a protrusion formed on a transparent electrode in order to improve the viewing angle of a liquid crystal display device. By using the slope of the protrusion, the liquid crystal is locally tilted. The liquid crystal is divided in multiple directions. Hereinafter, a method for forming the rib will be described in detail.
[0233] (4- 1)塗布及び現像方法  [0233] (4-1) Application and development methods
ブラックマトリクスとレッド、ブルー、グリーンのカラーフィルタを設け、更にその上に、 150nm厚の ITOを蒸着した通常 0. l〜2mm厚の透明基板上に、本発明の感光性 榭脂組成物をスピナ一、ワイヤーバー、フローコーター、ダイコーター、ロールコータ 一、スプレー等の塗布装置を用いて塗布する。組成物の塗布膜厚は通常 0. 5〜5 mである。該組成物からなる塗布膜を乾燥した後、乾燥塗膜上にフォトマスクを置き、 該フォトマスクを介して画像露光する。露光後、未露光の未硬化部分を現像にて除 去することにより、画素を形成する。通常、現像後得られる画像は、 5〜20 /ζ πιの巾 の細線再現性が求められ、高画質のディスプレーの要求からより高精細な細線再現 性が要求さる傾向にある。高精細な細線を安定し再現する上で、現像後の細線画像 の断面形状は、非画像と画像部のコントラストが明瞭な矩形型が、現像時間、現像液 経時、現像シャワーの物理刺激などの現像マージンが広く好まし 、。 The photosensitive resin composition of the present invention is spinnered on a transparent substrate having a thickness of 0.1 to 2 mm, on which a black matrix and color filters of red, blue and green are further deposited, and further, ITO having a thickness of 150 nm is deposited thereon. 1. Apply using a coating device such as wire bar, flow coater, die coater, roll coater or spray. The coating thickness of the composition is usually 0.5 to 5 m. After drying the coating film made of the composition, a photomask is placed on the dried coating film, and image exposure is performed through the photomask. After exposure, pixels are formed by removing unexposed uncured portions by development. Usually, the image obtained after development has a width of 5-20 / ζ πι Thin line reproducibility is required, and there is a tendency for higher fine line reproducibility to be demanded due to the demand for high-quality displays. In order to stably reproduce high-definition fine lines, the cross-sectional shape of the fine line image after development is a rectangular shape with clear contrast between the non-image and the image area, such as development time, developer aging, physical stimulation of the development shower, etc. A wide development margin is preferred.
[0234] (4 2)加熱方法  [0234] (4 2) Heating method
本発明では、現像後の画像は、矩形型に近い断面形状を有している。リブの形状 に必要なアーチ状の形状を得るために、通常 150°C以上、好ましくは 180°C以上、 更に好ましくは 200°C以上、通常 400°C以下、好ましくは 300°C以下、更に好ましく は 280°C以下で、且つ、通常 10分以上、好ましくは 15分以上、更に好ましくは 20分 以上、通常 120分以下、好ましくは 60分以下、更に好ましくは 40分以下の加熱処理 を施し、矩形状の断面形状をアーチ状の形状に変形させ、幅 0. 5〜20 /ζ πι、高さ 0 . 2〜5 /ζ πιのリブを形成させる。この加熱時の変形の範囲としては感光性榭脂組成 物と加熱条件を適宜調整し、加熱前の細線画像 (矩形画像断面形状)の側面と基板 平面から形成される接触角（W1)が上記加熱処理後の細線画像の側面と基板平面 から形成される接触角（W2)を比較した場合、 W1ZW2が 1. 2以上、好ましくは 1. 3 以上、更に好ましくは 1. 5以上、通常 10以下、好ましくは 8以下になるようにする。加 熱温度が高い程、又は加熱時間が長い程変形率が大きぐ反対に加熱温度が低い 程、又は加熱時間が短!、程その変形率は低 、。  In the present invention, the developed image has a cross-sectional shape close to a rectangular shape. In order to obtain the arched shape necessary for the rib shape, it is usually 150 ° C or higher, preferably 180 ° C or higher, more preferably 200 ° C or higher, usually 400 ° C or lower, preferably 300 ° C or lower, further Preferably, the heat treatment is performed at 280 ° C. or lower and usually 10 minutes or longer, preferably 15 minutes or longer, more preferably 20 minutes or longer, usually 120 minutes or shorter, preferably 60 minutes or shorter, more preferably 40 minutes or shorter. Then, the rectangular cross-sectional shape is transformed into an arch shape to form ribs having a width of 0.5 to 20 / ζ πι and a height of 0.2 to 5 / ζ πι. As the range of deformation during heating, the photosensitive resin composition and heating conditions are adjusted as appropriate, and the contact angle (W1) formed from the side surface of the thin line image (rectangular image cross-sectional shape) before heating and the substrate plane is When comparing the contact angle (W2) formed from the side of the thin line image after heat treatment and the substrate plane, W1ZW2 is 1.2 or more, preferably 1.3 or more, more preferably 1.5 or more, usually 10 or less. , Preferably 8 or less. The higher the heating temperature or the longer the heating time, the larger the deformation rate. Conversely, the lower the heating temperature or the shorter the heating time, the lower the deformation rate.
[0235] [液晶表示装置]  [0235] [Liquid crystal display device]
液晶表示装置は、通常、カラーフィルタ上に配向膜を形成し、この配向膜上にスぺ 一サーを散布した後、対向基板と貼り合わせて液晶セルを形成し、形成した液晶セ ルに液晶を注入し、対向電極に結線して完成する。配向膜としては、ポリイミド等の榭 脂膜が好適である。配向膜の形成には、通常、グラビア印刷法及び Ζ又はフレキソ 印刷法が採用され、配向膜の厚さは数 lOnmとされる。熱焼成によって配向膜の硬 化処理を行った後、紫外線の照射ゃラビング布による処理によって表面処理し、液 晶の傾きを調整しうる表面状態に加工される。  In a liquid crystal display device, an alignment film is usually formed on a color filter, a spacer is spread on the alignment film, and a liquid crystal cell is formed by bonding to a counter substrate, and a liquid crystal cell is formed on the formed liquid crystal cell. And is connected to the counter electrode to complete. As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, a gravure printing method and a wrinkle or flexographic printing method are usually employed, and the thickness of the alignment film is set to several lOnm. After the alignment film is hardened by thermal firing, the surface treatment is performed by treatment with a rubbing cloth, which is irradiated with ultraviolet rays, so that the surface state is adjusted so that the inclination of the liquid crystal can be adjusted.
[0236] スぺーサ一としては、対向基板とのギャップ（隙間）に応じた大きさのものが用いられ 、通常 2〜8 mのものが好適である。カラーフィルタ基板上に、前述の如ぐフォトリ ソグラフィ法によって透明榭脂膜のフォトスぺーサー (PS)を形成し、これをスぺーサ 一の代わりに活用することもできる。対向基板としては、通常、アレイ基板が用いられ[0236] As the spacer, a spacer having a size corresponding to the gap (gap) with the counter substrate is used, and a spacer of 2 to 8 m is usually preferable. On the color filter substrate, the photo A photospacer (PS) with a transparent resin film can be formed by sography, and this can be used in place of the spacer. An array substrate is usually used as the counter substrate.
、特に TFT (薄膜トランジスタ)基板が好適である。 In particular, a TFT (thin film transistor) substrate is suitable.
[0237] 対向基板との貼り合わせのギャップは、液晶表示装置の用途によって異なるが、通 常 2〜8 mの範囲で選ばれる。対向基板と貼り合わせた後、液晶注入口以外の部 分は、エポキシ榭脂等のシール材によって封止する。シール材は、 UV照射及び Z 又は加熱することによって硬化させ、液晶セル周辺がシールされる。  [0237] The gap for bonding to the counter substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 to 8 m. After bonding to the counter substrate, the portions other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and Z or heating, and the periphery of the liquid crystal cell is sealed.
[0238] 周辺をシールされた液晶セルは、パネル単位に切断した後、真空チャンバ一内で 減圧とし、上記液晶注入口を液晶に浸漬した後、チャンバ一内をリークすることによつ て、液晶を液晶セル内に注入する。液晶セル内の減圧度は、通常、 1 X 10— 2〜1 X 1 0— 7Paであるが、好ましくは 1 X 10— 3〜1 X 10— 6Paである。また、減圧時に液晶セルを 加温するのが好ましぐ加温温度は通常 30〜100°Cであり、より好ましくは 50〜90°C である。減圧時の加温保持は、通常 10〜60分間の範囲とされ、その後液晶中に浸 漬される。液晶を注入した液晶セルは、液晶注入口を UV硬化榭脂を硬化させて封 止すること〖こよって、液晶表示装置 (パネル）が完成する。 [0238] The liquid crystal cell whose periphery is sealed is cut into panels, and then the pressure is reduced in the vacuum chamber. After the liquid crystal inlet is immersed in the liquid crystal, the inside of the chamber leaks. Liquid crystal is injected into the liquid crystal cell. Decompression degree in the liquid crystal cell is usually a 1 X 10- 2 ~1 X 1 0- 7 Pa, preferably 1 X 10- 3 ~1 X 10- 6 Pa. In addition, it is preferable that the liquid crystal cell is heated at the time of depressurization. The heating temperature is usually 30 to 100 ° C, more preferably 50 to 90 ° C. Heating during decompression is usually in the range of 10 to 60 minutes and then immersed in the liquid crystal. A liquid crystal cell filled with liquid crystal is completed by sealing the liquid crystal injection port with a UV curable resin, thereby completing the liquid crystal display (panel).
[0239] 液晶の種類には特に制限がなぐ芳香族系、脂肪族系、多環状化合物等、従来か ら知られている液晶であって、リオトロピック液晶、サーモト口ピック液晶等のいずれで も良い。サーモト口ピック液晶には、ネマティック液晶、スメスティック液晶及びコレステ リック液晶等が知られて 、るが、 、ずれであっても良 、。  [0239] Liquid crystal types that are conventionally known, such as aromatic, aliphatic, and polycyclic compounds that are not particularly limited, may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. . Nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known as thermo-mouth pick liquid crystals, but they may be misaligned.
実施例  Example
[0240] 次に、合成例えば、実施例及び比較例を挙げて本発明をより具体的に説明するが 、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。なお、 以下にお 1、て「部」は「重量部」を表す。  [0240] Next, the present invention will be described more specifically with reference to synthesis, for example, Examples and Comparative Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist. In the following, “part” means “part by weight”.
[0241] [アルカリ可溶性不飽和榭脂の合成]  [0241] [Synthesis of alkali-soluble unsaturated rosin]
<合成例 1 >  <Synthesis example 1>
温度計、冷却管、撹拌機を取り付けたフラスコに窒素ガスパージを施してから、 5, 5 ，一（1ーメチルェチリデン）ビス [2—シクロへキシルフェノール] (下記式（1) ) 100部 と、ェピクロルヒドリン 700部とを仕込み、溶解させた。更に、 65°Cに加熱し、水酸ィ匕 ナトリウム 11部を 90分かけて分割添加し、その後、更に 65°Cにて 2時間、 70°Cにて 1 時間反応させた。反応終了後、 130°Cでェピクロルヒドリンを留去し、水洗を 3回繰り 返し、下記式（2)で表されるエポキシィ匕合物を得た。得られたエポキシ化合物は、白 色粉体であり、エポキシ当量は 257gZeqであった。 A flask equipped with a thermometer, condenser, and stirrer was purged with nitrogen gas, and then 5, 5, 1- (1-methylethylidene) bis [2-cyclohexylphenol] (the following formula (1)) 100 And 700 parts of epichlorohydrin were charged and dissolved. Further, heat to 65 ° C and 11 parts of sodium were added in portions over 90 minutes, and then further reacted at 65 ° C for 2 hours and at 70 ° C for 1 hour. After completion of the reaction, epichlorohydrin was distilled off at 130 ° C, and washing with water was repeated three times to obtain an epoxy compound represented by the following formula (2). The obtained epoxy compound was a white powder, and the epoxy equivalent was 257 gZeq.
[0242] [化 28] [0242] [Chemical 28]
Figure imgf000072_0001
式 ( 2 )
Figure imgf000072_0001
Formula (2)
Figure imgf000072_0002
Figure imgf000072_0002
[0243] 得られたエポキシ化合物 100部、アクリル酸 29部、 p—メトキシフエノール 0. 06部、 トリフエ-ルホスフィン 2. 6部、プロピレングリコールモノメチルエーテルアセテート 12 6部を反応容器に仕込み、 120°Cで 2時間、更に 95°Cで酸価が 5mg— KOHZg以 下になるまで撹拌した。酸価が目標に達するまで 10時間を要した (酸価 4. 0)。 [0243] 100 parts of the resulting epoxy compound, 29 parts of acrylic acid, 0.06 part of p-methoxyphenol, 2.6 parts of triphenylphosphine, and 6 parts of propylene glycol monomethyl ether acetate 12 were charged into a reaction vessel, 120 ° The mixture was stirred at C for 2 hours and further at 95 ° C until the acid value was 5 mg-KOHZg or less. It took 10 hours for the acid value to reach the target (acid value 4.0).
[0244] <合成例 2>  [0244] <Synthesis Example 2>
合成例 1で得られた反応液 257部にプロピレングリコールモノメチルエーテルァセ テート 60部をカ卩え、へキサメチレンジイソシァネート 10. 7部を添カ卩し、 90°Cで 3時間 反応させ、更にトリメリット酸無水物 28. 5部を添加し、 90°Cで更に 3時間反応させ、 酸価 96、 GPCで測定したポリスチレン換算の重量平均分子量 2580のアルカリ可溶 性不飽和榭脂 (A— I)溶液を得た。  Add 257 parts of the reaction solution obtained in Synthesis Example 1 to 60 parts of propylene glycol monomethyl etherate, add 10.7 parts of hexamethylene diisocyanate, and react at 90 ° C for 3 hours. Further, 28.5 parts of trimellitic anhydride was added, and the mixture was further reacted at 90 ° C for 3 hours. Acid value 96, alkali-soluble unsaturated resin having a weight average molecular weight of 2580 in terms of polystyrene measured by GPC A solution (A-I) was obtained.
[0245] <合成例 3> 合成例 1で得られた反応液 80部にプロピレングリコールモノメチルエーテルァセテ ート 15部を加え、ビフエ-ルテトラカルボン酸二無水物 9. 6部を添加し、 120°Cで 2 時間反応させ、更にテトラヒドロ無水フタル酸 5部を添加し、 95°Cで 3時間反応させ、 酸価 106、 GPCで測定したポリスチレン換算の重量平均分子量 3700のアルカリ可 溶性不飽和榭脂 ( A— Π)溶液を得た。 [0245] <Synthesis Example 3> Add 80 parts of propylene glycol monomethyl ether acetate to 80 parts of the reaction solution obtained in Synthesis Example 1, add 9.6 parts of biphenyltetracarboxylic dianhydride, and react at 120 ° C for 2 hours. Furthermore, 5 parts of tetrahydrophthalic anhydride was added, reacted at 95 ° C for 3 hours, and an alkali-soluble unsaturated resin (A-Π) solution having an acid value of 106 and a polystyrene-equivalent weight average molecular weight of 3700 measured by GPC Got.
[0246] <合成例 4>  [0246] <Synthesis Example 4>
ビスフエノール A型エポキシ化合物（下記式（3)、エポキシ当量 186gZeq) 100部 、アクリル酸 40部、 p—メ卜キシフエノール 0. 06部、卜リフエ-ルホスフィン 2. 4部、プ ロピレングリコールモノメチルエーテルアセテート 126部を反応容器に仕込み、 95°C で酸価が 5mg— KOHZg以下になるまで撹拌した。酸価が目標に達するまで 10時 間を要した (酸価 1. 0)。次いで、得られた反応液にプロピレングリコールモノメチル エーテルアセテート 40部をカ卩え、イソホロンジイソシァネート 19. 5部を添加し、 90°C で 3時間反応させ、更にトリメリット酸無水物 39. 3部を添加し、 90°Cで 3時間反応さ せ、酸価 113、 GPCで測定したポリスチレン換算の重量平均分子量 2400のアルカリ 可溶性不飽和榭脂 ( A— III)溶液を得た。  Bisphenol A-type epoxy compound (following formula (3), epoxy equivalent 186 gZeq) 100 parts, acrylic acid 40 parts, p-methoxyphenol 0.06 parts, polypropylene phosphine 2.4 parts, propylene glycol monomethyl The reaction vessel was charged with 126 parts of ether acetate and stirred at 95 ° C until the acid value was 5 mg-KOHZg or less. It took 10 hours for the acid value to reach the target (acid value 1.0). Next, 40 parts of propylene glycol monomethyl ether acetate was added to the resulting reaction solution, 19.5 parts of isophorone diisocyanate was added, and the mixture was reacted at 90 ° C for 3 hours, and trimellitic anhydride 39. 3 parts were added and reacted at 90 ° C for 3 hours to obtain an alkali-soluble unsaturated resin (A-III) solution having an acid value of 113 and a polystyrene-equivalent weight average molecular weight of 2400 measured by GPC.
[0247] [化 29] 式 ( 3 )
Figure imgf000073_0001
[0247] [Chemical 29] Formula (3)
Figure imgf000073_0001
<合成例 5> <Synthesis Example 5>
ビスフエノール A型エポキシ化合物（上記式（3)、エポキシ当量 186g/eq) 100部 、アクリル酸 40部、 p—メ卜キシフエノール 0. 06部、卜リフエ-ルホスフィン 2. 4部、プ ロピレングリコールモノメチルエーテルアセテート 126部を反応容器に仕込み、 95°C で酸価が 5mg— KOHZg以下になるまで撹拌した。酸価が目標に達するまで 10時 間を要した (酸価 1. 0)。次いで、得られた反応液にプロピレングリコールモノメチル エーテルアセテート 40部をカ卩え、イソホロンジイソシァネート 17. 5部を添加し、 90°C で 3時間反応させ、更にトリメリット酸無水物 46. 8部を添加し、 90°Cで 3時間反応さ せ、酸価 136、 GPCで測定したポリスチレン換算の重量平均分子量 2840のアルカリ 可溶性不飽和榭脂 ( A— IV)溶液を得た。 Bisphenol A type epoxy compound (formula (3) above, epoxy equivalent 186 g / eq) 100 parts, acrylic acid 40 parts, p-methoxyphenol 0.06 parts, phenylphenolphosphine 2.4 parts, propylene The reaction vessel was charged with 126 parts of glycol monomethyl ether acetate and stirred at 95 ° C until the acid value was 5 mg-KOHZg or less. It took 10 hours for the acid value to reach the target (acid value 1.0). Next, 40 parts of propylene glycol monomethyl ether acetate was added to the resulting reaction solution, 17.5 parts of isophorone diisocyanate was added, and 90 ° C was added. For 4 hours, and then add 46.8 parts of trimellitic anhydride, react at 90 ° C for 3 hours, acid value 136, alkali-soluble unsaturated with polystyrene equivalent weight average molecular weight of 2840 measured by GPC A rosin (A-IV) solution was obtained.
[0249] <合成例 6 >  [Synthesis Example 6]
フルオレンビスフエノール型エポキシ化合物（下記式 (4)、エポキシ当量 231gZeq ) 100部、無水コハク酸とトリス（アタリロイ口キシメチル)エタノールの反応混合物（酸 価 90. 5) 273. 2部、 p—メトキシフエノール 0. 19部、トリフエ-ルホスフィン 7. 4部、 プロピレングリコールモノメチルエーテルアセテート 368部を反応容器に仕込み、 90 °Cで酸価が 5mg— KOH/g以下になるまで撹拌した。酸価が目標に達するまで 10 時間を要した (酸価 1. 0)。次いで、上記反応により得られた反応液 80部にプロピレ ングリコールモノメチルエーテルアセテート 6部を加え、イソホロンジイソシァネート 2. 6部を添加し、 90°Cで 3時間反応させ、更にトリメリット酸無水物 4. 1部を添加し、 90 °Cで 3時間反応させ、酸価 57、 GPCで測定したポリスチレン換算の重量平均分子量 2949のアルカリ可溶性不飽和榭脂 (A-V)溶液を得た。  Fluorene bisphenol type epoxy compound (following formula (4), epoxy equivalent 231gZeq) 100 parts, reaction mixture of succinic anhydride and tris (atariloy oxymethyl) ethanol (acid value 90.5) 273.2 parts, p-methoxyphenol 0.19 parts, 7.4 parts of triphenylphosphine, and 368 parts of propylene glycol monomethyl ether acetate were charged in a reaction vessel and stirred at 90 ° C. until the acid value was 5 mg-KOH / g or less. It took 10 hours for the acid value to reach the target (acid value 1.0). Next, 6 parts of propylene glycol monomethyl ether acetate are added to 80 parts of the reaction solution obtained by the above reaction, 2.6 parts of isophorone diisocyanate are added, and the mixture is reacted at 90 ° C. for 3 hours, and further trimellitic acid. 4.1 parts of anhydride was added and reacted at 90 ° C. for 3 hours to obtain an alkali-soluble unsaturated resin (AV) solution having an acid value of 57 and a polystyrene equivalent weight average molecular weight of 2949 measured by GPC.
[0250] [化 30] 式 （4 )  [0250] [Chemical 30] Formula (4)
Figure imgf000074_0001
Figure imgf000074_0001
[0251] <合成例 7 > [0251] <Synthesis example 7>
フルオレンビスフエノール型エポキシ化合物（上記式 (4)、エポキシ当量 231g/eq ) 100部、無水コハク酸とトリス（アタリロイ口キシメチル)エタノールの反応混合物（酸 価 90. 5) 273. 2部、 p—メトキシフエノール 0. 19部、トリフエ-ルホスフィン 7. 4部、 プロピレングリコールモノメチルエーテルアセテート 368部を反応容器に仕込み、 90 °Cで酸価が 5mg— KOHZg以下になるまで撹拌した。酸価が目標に達するまで 10 時間を要した (酸価 1. 0)。次いで、上記反応により得られた反応液 80部にプロピレ ングリコールモノメチルエーテルアセテート 6部をカ卩え、へキサメチレンジイソシァネー ト 1. 9部を添加し、 90°Cで 3時間反応させ、更にトリメリット酸無水物 3. 8部を添加し 、 90°Cで 3時間反応させ、酸価 52、 GPCで測定したポリスチレン換算の重量平均分 子量 3113のアルカリ可溶性不飽和榭脂 (A— VI)溶液を得た。 Fluorene bisphenol type epoxy compound (formula (4), epoxy equivalent 231g / eq) 100 parts, reaction mixture of succinic anhydride and tris (atariloy oxymethyl) ethanol (acid value 90.5) 273.2 parts, p— Methoxyphenol 0.19 parts, Triphenylphosphine 7.4 parts, 368 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel and stirred at 90 ° C. until the acid value was 5 mg-KOHZg or less. It took 10 hours for the acid value to reach the target (acid value 1.0). Next, add 80 parts of propylene glycol monomethyl ether acetate to 80 parts of the reaction solution obtained by the above reaction, add 1.9 parts of hexamethylene diisocyanate, and react at 90 ° C. for 3 hours. Further, 3.8 parts of trimellitic anhydride was added, reacted at 90 ° C. for 3 hours, and acid-soluble 52, an alkali-soluble unsaturated resin having a weight-average molecular weight of 3113 in terms of polystyrene measured by GPC (A — VI) A solution was obtained.
[0252] <合成例 8 >  [0252] <Synthesis Example 8>
日本化薬社製「XD— 1000」（ジシクロペンタジェン 'フエノール重合物のポリグリシ ジルエーテル、重量平均分子量 700、エポキシ当量 252gZeq) 75. 1部、合成例 1 で合成したビスフエノール型エポキシィ匕合物（前記式（2) ) 76部、アクリル酸 43. 8部 ゝ p—メトキシフエノール 0. 06部、トリフエ-ルホスフィン 2. 4部、及びプロピレングリコ ールモノメチルエーテルアセテート 136. 8部を反応容器に仕込み、 100°Cで酸価が 3. 0mg—KOH/g以下になるまで攪拌した。酸価が目標に達するまで 12時間を要 した (酸価 2)。次いで、上記反応により得られた反応液にプロピレングリコールモノメ チルエーテルアセテート 197部を加え、イソホロンジイソシァネート 22. 6部、ジブチ ルスズジラウレート 0. 02部を添加し、 90°Cで 3時間反応させた。更にテトラヒドロ無水 フタル酸 29. 4部、トリメリット酸無水物 33. 7部を添加し、 90°Cで 4時間反応させ、酸 価 100、 GPCで測定したポリスチレン換算の重量平均分子量 4000のアルカリ可溶 性不飽和榭脂 (A-VII)溶液を得た。  “XD-1000” manufactured by Nippon Kayaku Co., Ltd. (polyglycidyl ether of dicyclopentadiene phenol polymer, weight average molecular weight 700, epoxy equivalent 252 gZeq) 75. 1 part, bisphenol type epoxy compound synthesized in Synthesis Example 1 Product (formula (2)) 76 parts, acrylic acid 43.8 parts ゝ p-methoxyphenol 0.06 parts, triphenylphosphine 2.4 parts, and propylene glycol monomethyl ether acetate 136.8 parts The vessel was charged and stirred at 100 ° C until the acid value was 3.0 mg-KOH / g or less. It took 12 hours for the acid value to reach the target (acid value 2). Next, 197 parts of propylene glycol monomethyl ether acetate is added to the reaction solution obtained by the above reaction, 22.6 parts of isophorone diisocyanate and 0.02 part of dibutyltin dilaurate are added, and 3 parts at 90 ° C. Reacted for hours. Further, 29.4 parts of tetrahydrophthalic anhydride and 33.7 parts of trimellitic anhydride were added, reacted at 90 ° C for 4 hours, an acid value of 100, and an alkali capable of a weight average molecular weight of 4000 in terms of polystyrene measured by GPC. A soluble unsaturated rosin (A-VII) solution was obtained.
[0253] <合成例 9 >  [Synthesis Example 9]
合成例 1で用いたビスフエノール (前記式（1) ) 77. 7部、グリシジルメタタリレート 56 . 6部、 p—メ卜キシフエノール 0. 06部、卜!;フエ-ルホスフィン 2. 6部、及びプロピレン グリコールモノメチルエーテルアセテート 126部を反応容器に仕込み、 100°Cで 15 時間反応させ、反応液を得た。  Bisphenol used in Synthesis Example 1 (previous formula (1)) 77.7 parts, glycidyl metatalylate 56.6 parts, p-methoxyphenol 0.06 parts, 卜!; And 126 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel and reacted at 100 ° C. for 15 hours to obtain a reaction solution.
上記反応液 263部にプロピレングリコールモノメチルエーテルアセテート 60部をカロ え、へキサメチレンジイソシァネート 10. 7部を添カ卩し、 90°Cで 3時間反応させ、更に トリメリット酸無水物 28. 5部を添カ卩し、 90°Cで更に 3時間反応させ、酸価 95、 GPCで 測定したポリスチレン換算の重量平均分子量 2300のアルカリ可溶性不飽和榭脂 (AAdd 263 parts of the above reaction mixture to 60 parts of propylene glycol monomethyl ether acetate, add 10.7 parts of hexamethylene diisocyanate, react at 90 ° C for 3 hours, and trimellitic anhydride 28 Add 5 parts, react at 90 ° C for another 3 hours, acid value 95, GPC Measured polystyrene-reduced weight average molecular weight 2300 alkali-soluble unsaturated rosin (A
— vm)溶液を得た。 — Vm) solution was obtained.
[0254] [ブラックマトリクス形成評価]  [0254] [Black matrix formation evaluation]
<実施例 1 >  <Example 1>
合成例 1で得られたアルカリ可溶性不飽和榭脂 (A—I)溶液を 60重量部（固形分 換算 30重量部）、ジペンタエリスリトールへキサアタリレートを 10重量部、「CGI— 24 2」（チバ 'スぺシャリティーケミカル社製。構造式は下記の通り。）を 4重量部、ウレタン 系窒素原子含有高分子分散剤としてビックケミー ·ジャパン (株)製商品名「Disperb ykl82jを用いて分散を行ったカーボンブラック分散体溶液 224部（固形分換算 56 重量部。うちカーボンブラック 43重量部、高分子分散剤 13重量部）を、プロピレング リコールモノメチルエーテルアセテート 218重量部に混合して感光性黒色榭脂組成 物を得た。  60 parts by weight (30 parts by weight in terms of solid content) of the alkali-soluble unsaturated resin (A—I) solution obtained in Synthesis Example 1, 10 parts by weight of dipentaerythritol hexaatalylate, “CGI-24 2” 4 parts by weight (manufactured by Ciba Specialty Chemicals Co., Ltd., structural formula is as follows), dispersed as a urethane-based nitrogen atom-containing polymer dispersant using the product name “Disperb ykl82j” manufactured by Big Chemie Japan Co., Ltd. 224 parts (56 parts by weight in terms of solid content, of which 43 parts by weight of carbon black and 13 parts by weight of polymer dispersant) were mixed with 218 parts by weight of propylene glycol monomethyl ether acetate. A black rosin composition was obtained.
[0255] [化 31] [0255] [Chemical 31]
Figure imgf000076_0001
Figure imgf000076_0001
[0256] このようにして得た感光性黒色榭脂組成物を 10cm角ガラス基板上にスピンコートし 、ホットプレート上で 90°Cで 150秒乾燥した。乾燥後の膜厚は、 l /z mであった。次に 、このサンプルをマスクを通して高圧水銀灯で像露光した後、温度 23°C、濃度 0. 1 重量％の KOH水溶液を用 V、てスプレー現像をすることにより黒色画素（ブラックマト リックス)を形成した。 [0257] <実施例 2> [0256] The photosensitive black resin composition thus obtained was spin-coated on a 10 cm square glass substrate and dried on a hot plate at 90 ° C for 150 seconds. The film thickness after drying was l / zm. Next, this sample was image-exposed with a high-pressure mercury lamp through a mask, and a black pixel was formed by spray development using a KOH aqueous solution at a temperature of 23 ° C and a concentration of 0.1% by weight. did. <Example 2>
アルカリ可溶性不飽和榭脂 (A-I)をアルカリ可溶性不飽和榭脂 (A-III)に変更し た以外は実施例 1と同様にして感光性黒色榭脂組成物を得、更に黒色画素を形成し た。  A photosensitive black resin composition was obtained in the same manner as in Example 1 except that the alkali-soluble unsaturated resin (AI) was changed to the alkali-soluble unsaturated resin (A-III), and a black pixel was formed. It was.
[0258] <実施例 3 >  <Example 3>
アルカリ可溶性不飽和榭脂 (A-I)をアルカリ可溶性不飽和榭脂 (A-VII)に変更 した以外は実施例 1と同様にして感光性黒色榭脂組成物を得、更に黒色画素を形成 した。  A photosensitive black resin composition was obtained in the same manner as in Example 1 except that the alkali-soluble unsaturated resin (A-I) was changed to the alkali-soluble unsaturated resin (A-VII), and further black pixels were formed.
[0259] <実施例 4>  [0259] <Example 4>
アルカリ可溶性不飽和榭脂 (A-I)をアルカリ可溶性不飽和榭脂 (A-VIII)に変更 した以外は実施例 1と同様にして感光性黒色榭脂組成物を得、更に黒色画素を形成 した。  A photosensitive black resin composition was obtained in the same manner as in Example 1 except that the alkali-soluble unsaturated resin (A-I) was changed to the alkali-soluble unsaturated resin (A-VIII), and further black pixels were formed.
[0260] <比較例 1 >  [0260] <Comparative Example 1>
アルカリ可溶性不飽和榭脂 (A-I)をアルカリ可溶性不飽和榭脂 (A-II)に変更し た以外は実施例 1と同様にして感光性黒色榭脂組成物を得、更に黒色画素を形成し た。  A photosensitive black resin composition was obtained in the same manner as in Example 1 except that the alkali-soluble unsaturated resin (AI) was changed to the alkali-soluble unsaturated resin (A-II), and a black pixel was formed. It was.
[0261] 実施例 1〜4及び比較例 1で調製した感光性黒色榭脂組成物と形成された画素に つ!、て、以下の項目で評価し、表 1に結果を記した。  [0261] The photosensitive black resin composition prepared in Examples 1 to 4 and Comparative Example 1 and the formed pixels were evaluated on the following items, and the results are shown in Table 1.
[0262] <密着性> [0262] <Adhesion>
20 μ mのマスクパターンを忠実に再現する露光量における解像可能なレジストの 最小パターン寸法を 200倍の倍率で顕微鏡観察した。最小パターン寸法が 10 m 以下を密着性 good、 10 mを超えるものを密着性 inferiorとした。  The minimum resist pattern size that can be resolved at an exposure that faithfully reproduces a 20 μm mask pattern was observed with a microscope at a magnification of 200 times. The minimum pattern dimension of 10 m or less was defined as good adhesion, and the pattern exceeding 10 m was defined as adhesion inferior.
[0263] <画素シャープ性 > [0263] <Pixel sharpness>
20 μ mのマスクパターンを忠実に再現する露光量における細線黒色画素の形状を 1000倍の倍率で顕微鏡観察した。直線性の良好なものを画素シャープ性 good、突 起や凸凹のあるレジストパターンを画素シャープ性 inferiorとした。  The shape of the fine black pixels at an exposure that faithfully reproduces the 20 μm mask pattern was observed with a microscope at a magnification of 1000 times. A pixel pattern with good linearity is defined as pixel sharpness, and a resist pattern with protrusions or irregularities is defined as pixel sharpness inferior.
[0264] <保存安定性 > [0264] <Storage stability>
感光性黒色榭脂組成物を 35°C、 10°Cの 2条件で 2週間保管し、未露光部の膜が 現像されるのに要する時間について比較した。現像時間が 10%以上変化したものを 保存安定性 inferior,変化率が 5%未満のものを保存安定性 good、 1 %未満のものを 保存安定性 very goodとした。 The photosensitive black coffin composition is stored for 2 weeks under two conditions of 35 ° C and 10 ° C. The time required for development was compared. Those with a development time of 10% or more were designated as storage stability inferior, those with a change rate of less than 5% as good storage stability, and those with less than 1% as storage stability very good.
[0265] [表 1] [0265] [Table 1]
Figure imgf000078_0001
Figure imgf000078_0001
[0266] 表 1より、特定のアルカリ可溶性不飽和榭脂を用いる本発明によれば、保存安定性 、基板への密着性に優れた感光性着色榭脂組成物により、エッジ形状が良好な画素 を形成することができることが分力ゝる。 [0266] From Table 1, according to the present invention using a specific alkali-soluble unsaturated resin, a pixel having a good edge shape by a photosensitive colored resin composition excellent in storage stability and adhesion to a substrate. Can be formed.
[0267] [フォトスぺーサ一形成評価]  [0267] [Evaluation of photospacer formation]
<実施例 5〜9及び比較例 2 >  <Examples 5 to 9 and Comparative Example 2>
( 1)感光性榭脂組成物の調製  (1) Preparation of photosensitive resin composition
表 2に示すアルカリ可溶性不飽和榭脂 100部（固形分）と、重合性モノマーとしてジ ペンタエリスリトールへキサアタリレート（日本化薬 (株）製「KAYARAD DPHAJ ) 8 0部と、光重合開始剤として 2—メチルー [4— (メチルチオ）フエ-ル]— 2—モルフォ リノ一 1—プロパノン (チバガイギ社製「Irgacure907」）3部と、界面活性剤としてフッ 素系界面活性剤（大日本インキ化学工業社製「メガファック F475」）0. 01部と、シラ ンカップリング材として 3—グリシドキシプロピルトリメトキシシラン（東レダウコ一-ング 社製「SH6040」） 5部とを混合し、固形分濃度が 35重量％になるようにプロピレング リコールモノメチルエーテルアセテートに溶解させた後、ミリポアフィルタ（0. 2 μ χη) で濾過して、感光性榭脂組成物を得た。  100 parts of an alkali-soluble unsaturated resin shown in Table 2 (solid content), dipentaerythritol hexaatalylate (“KAYARAD DPHAJ” 80 parts by Nippon Kayaku Co., Ltd.) as a polymerizable monomer, and a photopolymerization initiator 2-methyl- [4- (methylthio) phenol] — 2-morpholino 1-propanone (“Irgacure907” manufactured by Ciba-Gaigi) and fluorine-based surfactant (Dainippon Ink Chemical Co., Ltd.) “Mega-Fuck F475” manufactured by Kogyo Co., Ltd.) and 0.01 part of 3-glycidoxypropyltrimethoxysilane (“SH6040” manufactured by Toray Dow Co., Ltd.) as a silane coupling material were mixed and solid After dissolving in propylene glycol monomethyl ether acetate so that the partial concentration became 35% by weight, it was filtered through a Millipore filter (0.2 μχη) to obtain a photosensitive resin composition.
[0268] (2)スぺーサーパターンの形成 表面に ITO膜を形成したガラス基板の該 ITO膜上にスピナ一を用いて、上記榭脂 組成物を塗布した後、 80°Cで 3分間ホットプレート上で加熱乾燥して塗膜を形成した 。得られた塗膜に所定パターンマスクを用いて、 365nmでの強度が 32mWZcm2で ある紫外線を用いて、露光量が lOOmiZcm2となるよう露光した。この際の紫外線照 射は空気下で行った。次いで 23°Cの 0. 1%ΚΟΗ水溶液で最小現像時間の 2倍の 時間スプレー現像した後、純水で 1分間リンスした。ここで、最小現像時間とは、同現 像条件にて、未露光部が完全に溶解される時間を意味する。これらの操作により、不 要な部分を除去し、 lO ^ mX lO ^ mのスぺーサーパターンを得ることができた。スぺ ーサーパターンの形成された基板をオーブン中 235°Cで 30分間加熱し硬化させ、 高さ 4 μ mのスぺーサーパターンを得た。 [0268] (2) Spacer pattern formation After applying the above resin composition on the ITO film of the glass substrate having the ITO film formed on the surface using a spinner, the film was heated and dried on a hot plate at 80 ° C. for 3 minutes to form a coating film. . The obtained coating film was exposed to ultraviolet rays having an intensity at 365 nm of 32 mWZcm 2 using a predetermined pattern mask so that the exposure amount was lOOmiZcm 2 . The ultraviolet irradiation at this time was performed under air. Next, spray development was performed with a 0.1% aqueous solution at 23 ° C. for twice the minimum development time, and then rinsed with pure water for 1 minute. Here, the minimum development time means a time during which the unexposed area is completely dissolved under the same image condition. By these operations, unnecessary portions were removed, and a spacer pattern of lO ^ mXlO ^ m was obtained. The substrate on which the spacer pattern was formed was cured by heating in an oven at 235 ° C for 30 minutes to obtain a spacer pattern having a height of 4 μm.
[0269] (3)回復率及び弾性の評価 [0269] (3) Evaluation of recovery rate and elasticity
上記（2)で得られたスぺーサーバターンの荷重負荷'除荷による回復率を島津ダイ ナミック超微小硬度計「DUH - W201 S」を用いた負荷—除荷試験により評価した。 測定温度 23°Cにて、直径 50 mの平面圧子により、一定速度でスぺーサ一に荷重 を加え (0. 22gfZsec)、荷重が 5gfに達したところで 5秒間保持し、続いて同速度に て除荷を行った。この試験より、図 1に示す最大変位 H [max]及び最終変位 H [Last ]を求め、回復率（％) = (H [max]— H [last] ) /H [max] X 100を算出して結果を The recovery rate of the space server turn obtained in (2) above by load-unloading was evaluated by a load-unloading test using Shimadzu Dynamic Ultra Hardness Tester “DUH-W201 S”. A load was applied to the spacer at a constant speed with a flat indenter with a diameter of 50 m at a measurement temperature of 23 ° C (0.22 gfZsec), and when the load reached 5 gf, the load was held for 5 seconds, and then kept at the same speed. Unloading. From this test, the maximum displacement H [max] and the final displacement H [Last] shown in Fig. 1 were obtained, and the recovery rate (%) = (H [max] – H [last]) / H [max] X 100 was calculated. And the result
^： ^した o ^: ^ O
[0270] また、弾性の指標として、負荷時の変位が 0. 25 μ mの時の荷重 N (gf)を求め、結 果を表 2に示した。  [0270] As an index of elasticity, the load N (gf) when the displacement at the time of loading was 0.25 μm was obtained, and the results are shown in Table 2.
[0271] (4)負荷時の変位が 0. 25 μ mの時の荷重 N (gf)の評価 [0271] (4) Evaluation of load N (gf) when displacement under load is 0.25 μm
得られた感光性榭脂組成物を 70°Cで 72時間密封下で保存し、室温放置した場合 との粘度の変化の度合いを下記式より求めた。  The obtained photosensitive resin composition was stored sealed at 70 ° C. for 72 hours, and the degree of change in viscosity when left at room temperature was determined from the following formula.
変化度合い (％) = [ (70°C72時間保存品の粘度)一 (室温保存品の粘度) ]  Degree of change (%) = [(viscosity of products stored at 70 ° C for 72 hours) one (viscosity of products stored at room temperature)]
Z [室温保存品の粘度] X 100  Z [Viscosity of room temperature storage product] X 100
[0272] 変化度合いの絶対値が 3%未満のものを保存安定性 very good, 5%未満のものを 保存安定性 good、 5%以上のものを保存安定性 inferiorとした。変化の度合いが大き ければ大き 、ほど、保存品安定性が低 、ものである。 [0273] [表 2] [0272] Storage stability was very good when the absolute value of the degree of change was less than 3%, storage stability was good when it was less than 5%, and storage stability inferior was 5% or more. The greater the degree of change, the lower the preservation stability. [0273] [Table 2]
Figure imgf000080_0001
Figure imgf000080_0001
[0274] 表 2より、特定のアルカリ可溶性不飽和榭脂を用いる本発明によれば、保存安定性 に優れた感光性榭脂組成物により、長期保存後の取り扱い性に優れたスぺーサーを 形成することができる。  [0274] From Table 2, according to the present invention using a specific alkali-soluble unsaturated resin, a photosensitive resin composition excellent in storage stability provides a spacer excellent in handleability after long-term storage. Can be formed.
[0275] 本発明を特定の態様を用いて詳細に説明したが、本発明の意図と範囲を離れるこ となく様々な変更が可能であることは当業者に明らかである。  [0275] Although the invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.
なお、本出願は、 2004年 8月 9日付で出願された日本特許出願 (特願 2004— 27 2372)及び 2005年 7月 19日付で出願された日本特許出願（特願 2005— 208750 )に基づ 、ており、その全体が引用により援用される。  This application is based on a Japanese patent application filed on August 9, 2004 (Japanese Patent Application No. 2004-27 2372) and a Japanese patent application filed on July 19, 2005 (Japanese Patent Application No. 2005-208750). And are incorporated by reference in their entirety.

Claims

請求の範囲 The scope of the claims
[1] 有機結合材を含有する感光性榭脂組成物であって、該有機結合材が、分子内に 少なくとも 2個以上のエポキシ基を有するエポキシィ匕合物（a)と、不飽和基含有カル ボン酸 (b)との反応物を、更にイソシァネート基を有する化合物（c)と反応させること により得られるアルカリ可溶性不飽和榭脂を含有することを特徴とする感光性榭脂組 成物。  [1] A photosensitive resin composition containing an organic binder, wherein the organic binder contains an epoxy compound (a) having at least two epoxy groups in the molecule and an unsaturated group A photosensitive resin composition comprising an alkali-soluble unsaturated resin obtained by further reacting a reaction product with a carboxylic acid (b) with a compound (c) having an isocyanate group.
[2] 請求項 1において、前記エポキシィ匕合物（a)が下記一般式 (I— a)で表される化合 物を含む感光性榭脂組成物。  [2] The photosensitive resin composition according to claim 1, wherein the epoxy compound (a) includes a compound represented by the following general formula (Ia).
[化 32]  [Chemical 32]
CH2— CH— CHo— O— X— 0_CH2 _CH— CHゥ ■( I 一 a) \ / \ / CH 2 — CH— CHo— O— X— 0_CH 2 _CH— CH ■ (I 1 a) \ / \ /
o o  o o
ヽ  ヽ
Figure imgf000081_0001
ン 請求項 1において、前記化合物（c)力イソシァネート基を分子内に 2個以上有する 感光性榭脂組成物。
Figure imgf000081_0001
2. The photosensitive resin composition according to claim 1, wherein the compound (c) has at least two isocyanate groups in the molecule.
請求項 2において、前記一般式 (I a)における Xが下記一般式 (IIA)、 （IIB)、 (IIC )の 、ずれかで表される感光性榭脂組成物。  3. The photosensitive resin composition according to claim 2, wherein X in the general formula (Ia) is represented by any deviation of the following general formulas (IIA), (IIB), and (IIC).
[化 33]
Figure imgf000082_0001
[Chemical 33]
Figure imgf000082_0001
( IB)
Figure imgf000082_0004
Figure imgf000082_0002
(IB)
Figure imgf000082_0004
Figure imgf000082_0002
Figure imgf000082_0003
Figure imgf000082_0003
上記一般式 (IIA)、（IIB)、（IIC)中、 I^ R16及び nは前記一般式 (II)におけると同 我 V'd Oo In the general formulas (IIA), (IIB), and (IIC), I ^ R 16 and n are the same as those in the general formula (II).
請求項 4にお!/、て、前記一般式 (ΠΑ)が下記一般式 (IIAa)又は（IIAb)で表される 感光性榭脂組成物。  5. A photosensitive resin composition according to claim 4, wherein the general formula (ΠΑ) is represented by the following general formula (IIAa) or (IIAb).
[化 34] [Chemical 34]
Figure imgf000083_0001
上記一般式 (IIAa)、 （IIAb)中、 R1, R2は前記一般式 (II)におけると同義である。
Figure imgf000083_0001
In the general formulas (IIAa) and (IIAb), R 1 and R 2 have the same meaning as in the general formula (II).
[6] 請求項 1にお 、て、更に光重合開始剤を含有する感光性榭脂組成物。 6. The photosensitive resin composition according to claim 1, further comprising a photopolymerization initiator.
[7] 請求項 1において、更に色材を含有する感光性榭脂組成物。 7. The photosensitive resin composition according to claim 1, further comprising a coloring material.
[8] 請求項 1に記載の感光性榭脂組成物を用いて形成されたカラーフィルタ。 [8] A color filter formed using the photosensitive resin composition according to claim 1.
[9] 請求項 1に記載の感光性榭脂組成物を用いて形成された部材を有する液晶表示 装置。 [9] A liquid crystal display device having a member formed using the photosensitive resin composition according to claim 1.
[10] 有機結合材を含有する感光性榭脂組成物であって、該有機結合材が、分子内に 少なくとも 2個以上のフ ノール性水酸基を有するフ ノール性水酸基含有ィ匕合物 (f )と、不飽和基含有エポキシ化合物 (g)との反応物を、更にイソシァネート基を有する 化合物 (c)と反応させることにより得られるアルカリ可溶性不飽和榭脂を含有すること を特徴とする感光性榭脂組成物。  [10] A photosensitive resin composition containing an organic binder, wherein the organic binder has a phenolic hydroxyl group-containing compound having at least two phenolic hydroxyl groups in the molecule (f ) And an unsaturated group-containing epoxy compound (g), and further containing an alkali-soluble unsaturated resin obtained by further reacting with a compound (c) having an isocyanate group. A rosin composition.
[11] 請求項 10において、前記フ ノール性水酸基含有化合物 (f)が下記一般式 (I— f) で表される化合物を含む感光性榭脂組成物。  [11] The photosensitive resin composition according to claim 10, wherein the phenolic hydroxyl group-containing compound (f) comprises a compound represented by the following general formula (If).
[化 35] HO-X-OH ' ( I— f) [Chemical 35] HO-X-OH '(I— f)
Figure imgf000084_0001
ノ 請求項 10において、前記化合物（c)力イソシァネート基を分子内に 2個以上有する 感光性榭脂組成物。
Figure imgf000084_0001
The photosensitive resin composition according to claim 10, wherein the compound (c) has two or more isocyanate groups in the molecule.
請求項 11において、前記一般式 (I f)における Xが下記一般式 (ΠΑ)、 （ΠΒ)、 (II C)の 、ずれかで表される感光性榭脂組成物。  12. The photosensitive resin composition according to claim 11, wherein X in the general formula (If) is represented by a deviation of the following general formulas (ΠΑ), (ΠΒ), and (II C).
[化 36] [Chemical 36]
Figure imgf000085_0001
Figure imgf000085_0001
Figure imgf000085_0002
上記一般式 (ΠΑ)、 (ΙΙΒ)、 (IIC)中、尺1〜!^6及び nは前記一般式 (II)におけると同 義である。
Figure imgf000085_0002
In the general formulas (ΠΑ), (ΙΙΒ), and (IIC), the scales 1 to! ^ 6 and n are as defined in the general formula (II).
請求項 13にお 、て、前記一般式 (ΠΑ)が下記一般式 (IIAa)又は（IIAb)で表され る感光性榭脂組成物。  The photosensitive resin composition according to claim 13, wherein the general formula (ΠΑ) is represented by the following general formula (IIAa) or (IIAb).
[化 37] [Chemical 37]
Figure imgf000086_0001
上記一般式 (IIAa)、 （IIAb)中、 R1, R2は前記一般式 (II)におけると同義である。
Figure imgf000086_0001
In the general formulas (IIAa) and (IIAb), R 1 and R 2 have the same meaning as in the general formula (II).
[15] 請求項 10において、更に光重合開始剤を含有する感光性榭脂組成物。 15. The photosensitive resin composition according to claim 10, further comprising a photopolymerization initiator.
[16] 請求項 10において、更に色材を含有する感光性榭脂組成物。 16. The photosensitive resin composition according to claim 10, further comprising a coloring material.
[17] 請求項 10に記載の感光性榭脂組成物を用いて形成されたカラーフィルタ。 [17] A color filter formed using the photosensitive resin composition according to [10].
[18] 請求項 10に記載の感光性榭脂組成物を用いて形成された部材を有する液晶表示 装置。 [18] A liquid crystal display device having a member formed using the photosensitive resin composition according to claim 10.
PCT/JP2005/013284 2004-08-09 2005-07-20 Photosensitive resin composition, color filter and liquid crystal display device WO2006016467A1 (en)

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