WO2006016467A1 - Photosensitive resin composition, color filter and liquid crystal display device - Google Patents
Photosensitive resin composition, color filter and liquid crystal display device Download PDFInfo
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- 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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- 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
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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
- 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
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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
- 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
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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
- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- 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
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- 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
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- 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
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- 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
Description
Claims
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JP2004232372 | 2004-08-09 | ||
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JP2005-208750 | 2005-07-19 | ||
JP2005208750A JP4839710B2 (en) | 2004-08-09 | 2005-07-19 | Photosensitive resin composition, color filter, and liquid crystal display device |
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JP (1) | JP4839710B2 (en) |
KR (1) | KR100848518B1 (en) |
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WO (1) | WO2006016467A1 (en) |
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JP4837315B2 (en) * | 2005-06-29 | 2011-12-14 | 凸版印刷株式会社 | Photosensitive resin composition for photospacer and color filter for liquid crystal display device using the same |
JP2008170972A (en) * | 2006-12-14 | 2008-07-24 | Fujifilm Corp | Method for patterning photosensitive resin composition, color filter, manufacturing method thereof, and display device |
KR101477026B1 (en) * | 2006-12-20 | 2014-12-29 | 미쓰비시 가가꾸 가부시키가이샤 | Oxime ester compound, photopolymerization initiator, photopolymerizable composition, color filter, and liquid crystal display device |
JP2009031709A (en) * | 2007-06-28 | 2009-02-12 | Jsr Corp | Radiation-sensitive composition for forming color filter for solid-state imaging device, color filter, and solid-state imaging device |
TW200919086A (en) * | 2007-08-10 | 2009-05-01 | Wako Pure Chem Ind Ltd | Negative photosensitive resin composition, spacer and liquid crystal display device |
KR100915408B1 (en) * | 2007-09-19 | 2009-09-03 | 주식회사 케이씨씨 | UV-curable and alkali-developable modified (co)polymer and process for preparing the same |
JP5147499B2 (en) * | 2008-02-13 | 2013-02-20 | 富士フイルム株式会社 | Photosensitive coloring composition, color filter and method for producing the same |
JP2010002569A (en) * | 2008-06-19 | 2010-01-07 | Toppan Printing Co Ltd | Photosensitive coloring composition and color filter substrate using the same |
KR20120033893A (en) * | 2010-09-30 | 2012-04-09 | 코오롱인더스트리 주식회사 | Photopolymerizable resin composition |
JP6037706B2 (en) * | 2011-12-22 | 2016-12-07 | 東京応化工業株式会社 | Photosensitive resin composition, color filter, and liquid crystal display device |
KR101760147B1 (en) * | 2011-12-22 | 2017-07-20 | 도쿄 오카 고교 가부시키가이샤 | Photosensitive resin composition, color filter, and liquid crystal display device |
JP6095104B2 (en) * | 2012-12-26 | 2017-03-15 | 日本化薬株式会社 | Active energy ray-curable resin composition, colored spacer for display element, and black matrix |
JP6075763B2 (en) * | 2013-03-22 | 2017-02-08 | 日本化薬株式会社 | Active energy ray-curable resin composition, and colored spacer and / or black matrix for display element using the same |
JP6233775B2 (en) * | 2013-09-30 | 2017-11-22 | 富士フイルム株式会社 | Photosensitive resin composition, cured resin and color filter |
JP6309755B2 (en) | 2013-12-25 | 2018-04-11 | 東京応化工業株式会社 | Photosensitive resin composition |
JP6768302B2 (en) * | 2016-02-16 | 2020-10-14 | 株式会社Dnpファインケミカル | Colored resin compositions for color filters, color filters, and display devices |
TWI756253B (en) * | 2017-08-14 | 2022-03-01 | 奇美實業股份有限公司 | Photosensitive resin composition and method for manufacturing the same, black matrix, pixel layer, protection film, color filter, and liquid crystal display apparatus |
KR20190077220A (en) * | 2017-12-25 | 2019-07-03 | 닛뽄 가야쿠 가부시키가이샤 | Sealant for display, and liquid crystal display using the same |
KR20190077219A (en) * | 2017-12-25 | 2019-07-03 | 닛뽄 가야쿠 가부시키가이샤 | Sealant for display, and liquid crystal display using the same |
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TW200613914A (en) | 2006-05-01 |
KR20060121954A (en) | 2006-11-29 |
JP4839710B2 (en) | 2011-12-21 |
KR100848518B1 (en) | 2008-07-25 |
JP2006079064A (en) | 2006-03-23 |
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