TW200403526A - Polycarboxylic acid resin and photosensitive resin composition containing the same - Google Patents

Abstract

A sensitive resin composition and a cured product containing the same are provided. The sensitive resin composition includes a polycarboxylic acid resin, [A] at least one of the above resin composition and [B] an addition polymerization compound having one and more ethylene unsaturated bonds, [C] a photopolymerization initiator, and [D] a solvent, wherein the polycarboxylic acid resin is obtained by reacting (a) a reactant obtained by reacting a compound (a1) with a compound (a2) under the condition of formula (P), with (b) a monocarboxylic acid containing unsaturated groups to obtain (c) the reactant, and further reacting (c) the reactant with (d) an acid anhydride. (a1) an epoxy compound having at least two or more epoxy groups in the molecule. (a2) a multi-valence carboxylic acid. Formula (P): (the epoxy equivalent of the epoxy compound) > (the carboxylic acid equivalent of the multi-valence carboxylic acid).

Description

200403526 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a photosensitive resin composition containing a polyacrylic acid resin, a polycarboxylic acid resin as an adhesive polymer, and a cured product thereof. ^ Danxuan is a photosensitive resin composition suitable for use in a color filter material photosensitive resin composition, a color filter film, a color filter distance adjuster, and a color filter interlayer insulating film. [Prior art]

Color-sensitive resin compositions containing alkaline soluble resins, pigments, and photopolymerization initiators are widely used in the manufacture of color filter plates that make up components such as color liquid crystal display devices and color solid-state imaging devices. As a method for manufacturing a color filter using these colored photosensitive resin compositions, it is known to form, for example, a layer (1) (FIG. 丨) (^) above the t ( 1) A method of irradiating light (4) with a photomask (3) and developing it after exposure (Fig. 1 (b)). The coloring photosensitive resin composition layer (1) is exposed during light exposure, and the light (4) is not exposed. The unirradiated area of the irradiated light is removed by imaging, and the irradiated area (12) that is known to be irradiated with light remains because it is not removed, forming a black substrate or daylight (Figure ⑷). In order to improve the mechanical strength of the formed black substrate: daylight, heat treatment is usually performed after development. By changing the color of the pigment contained in the colored photosensitive resin composition and repeating the above operations, the black base material (5BM) and the three primary colors of Z (5R, 5G, 5B) can be sequentially formed. Obtain the target swatch (picture). In these manufacturing methods, in order to form finer black substrates or to form finer high-transmittance color pigments, it is preferable to use a pigment having a smaller particle size to pigment pigments contained in the photosensitive resin composition. In addition, in order to form a thinner black substrate or colored pigment, it is necessary to increase the concentration of the pigment contained in the colored photosensitive resin composition. [Summary of the Invention] An object of the present invention is to provide a photosensitive resin composition capable of obtaining high resolution, and in particular, a colored photosensitive resin composition capable of obtaining high resolution φ when a pigment having a small particle size is used at a high concentration. . In order to meet these requirements, the present inventors have conducted intensive research and found that by using a specific polycarboxylic acid resin, the above-mentioned problems can be solved, and the present invention has been completed. 'That is, the present invention provides a reactant obtained by reacting (a) a compound (al) with a compound (a2) under the formula (P) and (b) an unsaturated monocarboxylic acid Reaction to obtain (c) reactant, polycarboxylic resin obtained by reacting (c) reactant with (d) acid anhydride, [A] the above resin composition, and [B] having at least one ethylenic property A polymerizable addition compound of an unsaturated bond, [C] a photopolymerization initiator, and [D] a photosensitive resin composition composed of a solvent and a cured product of the above-mentioned photosensitive resin composition. (al) Compound: Epoxy compound (a2) compound having at least two epoxy groups in the molecule. Polyvalent carboxylic acid-Formula (P): '(epoxy equivalent number of epoxy compound) > (polyvalent Number of carboxylic acid equivalents of carboxylic acids] [Embodiment] The polyacrylic acid resin of the present invention (hereinafter also referred to as the polyacid resin) is 334839 200403526. The compound (al) and the compound (a2) under the conditions of formula (I) The obtained reactant (hereinafter referred to as component (a)) is reacted with (b) an unsaturated acid containing an unsaturated group (hereinafter referred to as component ⑻) to obtain a fluorene reactant (hereinafter referred to as component ⑷). ⑷ and acetic acid are also called components (physical reaction ⑷) compounds: epoxy compounds (a2) compounds with at least 2 epoxy groups in the molecule, polyvalent weilic acid

Formula (p) ··· Number of carboxylic acid equivalents of valent carboxylic acid) is an epoxidation (epoxy equivalent number of epoxy compound) shown in the following formula ⑴ > (ideal compound compound among poly (a I) compounds (Hereinafter referred to as the epoxy compound (I)). Η κ H2C—

佧 30 ％ »2C ^ CH2 0) [wherein R] and R2 are each independently a hydrogen atom, X is a single bond or the following formula G-1) to any of the formula (1-8), alkynyl or ii Prime atom ~ — 2 valence residue shown in the formula

R3 is an alkylene group, and R4 is a hydrogen atom, an alkyl group, or a glycidyl group. m is an integer of 0 to 5 ', and η is an integer of 0 to 10. However, if η is 2 to 10, the number of repeating units R to R4 may be the same or different] 314839 7 200403526

The epoxy compound (1) can be obtained by a known method. For example, the epoxy compound (1) can be obtained by reacting a corresponding diol component with an appropriate amount of epoxy propane. ~ Ί〇 口 w V 1 j Τ VJT 1 / κ ％% sign ~ For example, methyl ethyl, n-propyl, isopropyl, n-butyl, third butyl and other carbon atoms to 5 alkyl groups . Examples of the halogen atom include an alkylene group of R3 such as a plate atom, a chlorine atom, and a molybdenum atom. Examples of the halogen atom include a carbon number such as a fluorenyl group, an ethylene group, and a tetramethylene group. Violent. The alkylene can also have: a substituent. Examples of the substituent include ^ Niu Qiao such as a hydroxyl group, a halogen atom; 栌 Α which may have a carbon number of 1 to 10; κκκ < adobe, an anti-atomic number of 1 to 10, and a carbon atom number of 6 Fangmei to 15 / Yandian. 0 earth, aralkyl with 7 to 15 atoms; alkenyl with 2 to 10 stone atoms; ethoxy with 2 to 10 human atoms Here, the halogen atom can be listed and exemplified by a chlorine atom, a bromine atom, and the like. Alkyl groups of 1 to 10 may be listed as J, for example, methyl, ethyl, propyl and the like. Examples of the alkyl group when the group is substituted include the number of carbon atoms! To ^ yl # ° 10 ethoxy groups may be listed as propyl, propoxy, butoxy and the like. Η 甲 乳 基 碳 数 6 至] 5 夕 # # Examples of terrestrial soil include phenyl, naphthyl, etc. 314S29 8 200403526 Atoms with 7 to 15 carbon chains 2 to 10 can be listed as two : Yldiyloxy: fluorenyloxy having 2 to 10 atoms can be exemplified by acetic acidoxy, τ 醯 :::: diol compounds derived from epoxy compounds are represented by the general formula m & (III) η »R2 R2 [^^ 1 ^ each has the same meaning as the above] 5 Λζ ^ A bisphenol compound with a single bond of a horse, as specifically as the second two is the double test, 3,3,1 ##. Tongues can be listed as examples: ^ (19? Double-valent compounds of bivalent residues, specifically, benzyl) nu, 9 9, storage double (4 province-based benzyl) seedlings, 9 ,, Bis (4, mesitylmethylbenzyl) nu, 9,9bis (4 'mesityl-3-chlorophenyl) nus, 9,9-bispyridinyl · 3-molyloxybenzyl to M4 ~ Cycloyl is said to be phenyl), 9,9_bis (4-Cydoxy-3-fluorenyl, 3,2%, 9%, (cardiohydroxy-3,5 'difluorenylbenzyl), 9% Bis (4 · lactone) seedlings, 9,9-bis (4-hydroxy, n ,; styrenyl) are represented by the formula (10). One example is a two-year-old compound showing a divalent residue. Specifically, sodium, bis (4-di-4′-methylphenyl), bis (4-hydroxy · 3,5 · dimethylphenylγ1 ^, 3,5, dichlorophenyl) ketone, and the like. It is a bisphenol compound represented by the formula (I — 3U & _). Specifically, t can be listed. 3] 4839 9 200403526 Such as bis (4-hydroxyphenyl) flavone, bis (4-hydroxy-3,5- Difluorenylphenyl) fluorene, bis (4-hydroxy-3,5-dichlorophenyl) sulfene, etc. X is a bisphenol compound having a divalent residue represented by formula (1-4), specifically, , 'Examples include bis (4-hydroxyphenyl) hexafluoropropane , Bis (4-hydroxy3,5-dimethyl • ylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, etc. X is represented by formula (1-5) Specific examples of the bisphenol compound having a divalent residue include bis (4-hydroxyphenyl) difluorenylsilane, and bis (4-hydroxy-3,5-diφfluorenylphenyl) difluorenyl. Silane, bis (4-hydroxy-3,5-dichlorobenzyl) difluorenylsilane, etc. X is a bisphenol compound having a divalent residue represented by the formula (1-6), and specific examples include bis (4-hydroxyphenyl) pinane, bis (4-hydroxy3,5-dichlorophenyl) pinane, bis (4-hydroxy-3,5-dibromophenyl) pinane, phenol novolac,曱 phenol novolac and so on.

X is a bisphenol compound having a divalent residue represented by formula (1-7), and specific examples thereof include 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy3) , 5-Difluorenylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-fluorenylphenyl) propane , 2,2-bis (4-hydroxy-3-chlorophenyl) propane, etc. X is a bisphenol compound having a divalent residue represented by formula (1-8), and specific examples include bis (4-hydroxyphenyl) ether and bis (4-hydroxy3,5-difluorenylphenyl) ) Ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, etc. These bisphenol compounds may be used singly or in combination of two or more kinds. In the epoxy compound (1), the one having X as the divalent residue represented by the formula (I-1) is better than 10 314839 ZUU4UJDZ0. ：：： The oxygen compound ⑴ also uses ^ ... and ... as hydrogen atoms, and the formula (1 The oxygen atom on the benzene ring substituted with R1 and R2 is the fourth hydrogen atom-a compound with no divalent residue ; Ri is methyl, ... and the R4 atom is: 0: X for oxygen on a benzene ring substituted with R1, R2

R4 is a hydrogen atom, a compound of divalent residue represented by t); R1H ring is an ethylene group, and X is for benzenes N and I12 substituted with R], R2; Γ atom is represented by formula (1_1) at the fourth position * A compound with a divalent residue; χ is in the gas atom, R is an alkylene group represented by -C (CH3) H-CH2-, and the oxygen atom on the substituted stupid ring is the formula in the fourth position. 2: Compound of the residue-] is a methyl group, ... is a chlorine atom, a 4th group, and X is a divalent residue represented by the formula (M) for an oxygen atom on a benzene ring substituted with a square foot 2 Compounds are preferred. The polyvalent carboxylic acid of the compound (2) which reacts with the (al) compound will be described below. / 1 mol and I ′ carboxyl I is a compound having at least two carboxylic acid groups in one molecule, and one having an unsaturated bond is preferred. Examples of the polyvalent carboxylic acid include grass house propylene glycol & succinic acid, glutaric acid, adipic acid, malic acid, maleic acid, tartaric acid, itaconic acid, benzylic acid, tetrahydrobenzenediene Formic acid, hexahydroxylylene, s-methylmethylbridgedtetrahydrobenzene ^ + — methyl-3, tetrabridged acid, methyltetrahydrobenzenedicarboxylic acid, oxalic acid, pyromellitic acid, _ # ^ . A monomethyl ketone dicarboxylic acid, benzophenone tetracarboxylic acid, bibenzyl tetracarboxylic acid, lian cage. ^ &Quot; This monocarboxylic acid, diphenyl ether tetracarboxylic acid, etc., ideally, maleic acid can be listed. ， She Minque „Tianma 驮, Itaconic acid, Tetrahydrophthalic acid, Chlorhexidine. These can be used alone or in combination of two or more types.】] 314839 200403526 in (al) and (a2) ) Reaction, as the diluent to use, for example, methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate,% ethyl butyl acetate, ethyl lactate Esters, diethylene glycol difluorene, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, ethyl methyl hydrazone, cyclohexanone, ethyl carbitol acetate, Butyl carbitol acetate, propylene glycol ether ether acetate Temple solvents are preferred. _ In particular, in the reaction between the (al) compound and the (a2) compound, it is advisable to use a catalyst in order to promote reaction. Examples of the catalyst include triethylamine, τ-diamine, and methyl. Triethylammonium gasification, benzyltrimethylammonium bromide, benzyltrimethylammonium group, dibenzyl hydrogen, dibenzyl hydrogen antimony, chromium octoate, octanoic acid dream, etc. The amount used is preferably from 0 to 1 to 10 masses for the reaction raw material mixture. (2) When the compound has an unsaturated double bond, in order to prevent f-combination in the reaction, an anti-polymerization agent is preferably used. Examples of the anti-polymerization agent include benzene— Phenol methyl p-catechol, terephthalic acid, monocatechol, catechol, pyrosol, etc. The amount used is preferably from 0.001 to 1 liter in and out of the reaction raw material mixture. The reaction temperature is better The reaction temperature is 60 to 150 ° C. The reaction time is preferably 5 to 60 hours. The reaction of the (al) chemical compound in the winter invention is [(epoxy equivalent)> ((carboxylic acid equivalent) Number)], usually the equivalent number ratio is (珲 oxygen) · (acidification) = 100: 1 to 1001 99. Preferably 100: 20 to 〇 & am p;%, more preferably from 100: 50 to 100: 90. If the above equivalent ratio is ι〇 :: 100 to 99:99, it is easy to obtain the photosensitive resin composition containing the polyacid resin in the end. It is preferable to obtain a balance of sensitivity, developability, and resolvability. 31839312 200403526, and preferably. Next, (b) an unsaturated monocarboxylic acid (component) will be described. Examples of the component (b) of the present invention include (b) Acrylic acid, acrylic acid dimer, methacrylic acid, dot-styrenic acrylic acid, m-furfuryl acrylic acid, butenoic acid, α-cyanocinnamic acid, cinnamic acid; saturated or unsaturated dibasic anhydride with 1 The semi-vinegars of the reactant of the (fluorenyl) acrylate derivative having one hydroxyl group in the molecule; the half-esters of the reactant of the saturated or unsaturated dibasic acid and the monoglycidyl compound containing an unsaturated group. Examples of the half esters include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic acid needle, methylhexahydrobenzene dicarboxylic acid needle, and methyltetrahydrophthalic anhydride. Saturated and unsaturated dibasic acid anhydrides such as itaconic anhydride, fluorenyl methyl bridge tetrachlorophthalate, etc. Ding Bing, (fluorenyl) acrylic acid polyethylene glycol mono-ion, (meth) acrylic acid glycerol diglycerol, (meth) acrylic acid tris (methyl) acrylic acid trimethyl propylene propylene dimer (fluorenyl) pentaerythritol triacetate, Group) Diquatyltetraol pentaester of propionate, (fluorenyl) acrylate of phenyl glycidyl ether, etc.! In the molecule-(fluorenyl) acrylate derivatives with 1 hydroxyl group are added at equal levels ... or saturated or unsaturated diacids: for example, patella: maleic acid, adipic acid, phthalic acid , Tetrachlorobenzene ..., hexaphenylene compound, horse ® ... and monoglycidyl containing unsaturated groups (such as (fluorenyl) glycidyl acrylate, 3J4839 13 200403526 ο

Chunxiong, etc.) Unsaturated monocarboxylic acids, such as half-esters, etc., obtained by the reaction at equal molar ratios. Component (b) may be used alone or in combination of two or more. Regarding the compounding ratio of the component (a) and the component (b), the equivalent ratio of the remaining% oxygen in the component (a) to the carboxylic acid of the component (b) is usually 1: 0.5 to 1: 2, which is 10.8. Up to I25, more preferably 1: 1. If the equivalent ratio of the residual bad milk group in the component (a) to the carboxylic acid in the component (b) is 1: 0.5 to 1 ·· 2, the obtained polyweilic acid resin is used as a binder resin to make it photosensitive. In the case of an object, the sensitivity tends to be higher, which is preferable. In the reaction between component (a) and component (13), 'as di-3-ethoxypropionate ethyl ester, 3-ethoxypropionate ethyl ester,' preferably, for example, ester, 3-methoxybutyl ethyl Acid esters, ethyl lactate, diethyl cellosolve, e.g. > ethoxypropionate, 2-heptane, iso, M, khexanone, ethyl carbitol acetate, butyl Card i soil 同 S with, 曱 _acetate and other solvents. -Ethyl acetate, cationic glycol 3] 4839] 4 200403526 In the reaction between the component (a) and the component (b), a catalyst should be used in order to promote the reaction. Examples of the catalyst include triethylamine, benzyldimethylamine, methyldiethylammonium chloride, T-based trimethylammonium bromide, benzyltrimethylammonium iodide, phenylphosphine, and Phenyl antimony hydrogen, chromium octoate, and octanoate are preferably exemplified by fluorenyldimethylammonium bromide and the like. The mass fraction of the amount of the catalyst to be used for the total amount of the reaction raw material mixture is usually from 01 to 10% by mass, preferably from 0.2 to 5% by mass. 'Qiao J |; polymerization in the reaction, anti-polymerization agents should be used. Examples of the anti-polymerization agent include p-dihydroxybenzene, methyl < -p-phenylene disulfide, p-diphenyldiamine, carbamide, and coke. It is preferably such that the amount by mass of the reactants and chemical compounds is ㈣ to 1% by mass. The reaction temperature is preferably 60 to 150 ° C. ", The reaction time is 5 to 60 hours. By reacting the component (c) and the component (d), the lipid can be made into a polyacid tree component. For example, a slow acid needle with two or more rebel groups can be cited. Examples of the carboxylic acids 6f with more than one retarding group include oxalic acid, malonic acid, No. sac = buhrv malic acid, maleic acid, fumaric acid, clothing: acid: citrate: tartaric acid, tartaric acid, Tetrahydrobenzenedipic acid, hexahydrobenzidine diazadisulfide_selenic acid, methyltetrahydrobenzenedipic acid, formazan /, dibenzylic acid, trimellitic acid, mesitylene tetra-acid,- -Examination of pure carboxylic acid anhydrides, such as tetramethylene acid, biphenyltetraweilic acid, biphenyltetracarboxylic acid, etc.曱 Anhydride, dione ', ketotetracarboxylic acid monoanhydride, dibenzyltetracarboxylic dianhydride. 曱 314839 15 200403526 The ratio of the knife (C) to the component ⑷ is the component ((d) of the anhydride unit. Volume L The ratio of Ai Jiji to ingredients 08 to 〇0, usually 1: 1 to · 1, preferably 1: 1 ^] '2 ° The ratio of the amount of ingredient ⑷ to ingredient 于 is above the above standard: Better to ° · 1, then in the developer solution Solubility may change to a moderate level ... It is better to use the solvent (or solvent) or the ingredient (c) and the ingredients, but it is better to do it in a solvent. • For example, 3-ethoxypropionic acid can be used as the solvent. " Purpose, and dagger, 7 1U sheep L & ethyl propionate " Yiluo Luo, .Dai agent acetate, 3-methoxy butyl acetate, ethyl lactate,. Ethyl ether, butyl acetate, methyl 3-methoxypropionate '2-heptanone, hexanone' ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl 8 ^ acetic acid, and the like. These solvents can be used alone or in combination of two or more kinds, and the amount of the solvent used is preferably 0.5 parts by mass to 1 part by mass of the component (c): 20 parts by mass or less. ) When performing the reaction, it may be mixed in a solvent if necessary, and the reaction temperature is usually 20 ° C or higher and 2001 or lower. The obtained polycarboxylic acid resin is isolated from the reaction mixture and can be used for the coloring photosensitive resin composition of the present invention. It can also be used after purification, or it can be used as it is without isolating the reaction mixture. The polystyrene-equivalent weight average molecular weight is generally 1,000 to 5M00, preferably 1550 to 20, _. If the weight average molecular weight mentioned above is not less than 50, _, then it is regarded as adhesion. The use of resins tends to improve the properties of resolution, imaging edges, and site pollution when making photosensitive resin compositions. It is better. The acid is 314839 16 200403526 and the price is preferably 50 to 200. More It is preferably at least 7 () and m. If the acid value is in the above range, it is used as an adhesive resin. When the photosensitive resin composition is made, the properties of resolution, development edge and site pollution tend to be better. should. The photosensitive resin composition (hereinafter also referred to as the photosensitive resin composition) described herein is a polymerizable addition compound containing [A] the polyacrylic acid resin, [B] having at least] ethylenic unsaturated bonds , [C] Photopolymerization initiator and [D] solvent composition. The content of the main polyacid resin in the photosensitive resin button product is usually 10 to 80% by weight, preferably 20 to 60% by weight. In addition, the photosensitive resin composition, as a binder resin, and the polyacrylic acid resin, may also contain other binder resins commonly used in the photosensitive resin composition. 0 female stem CJH —r-. 3 Temple For example, an alkali-soluble polymer having a carboxyl group can be used. Examples of such soluble copolymers having a retardation group include (meth) acrylic acid / (meth) acrylic acid methyl ester copolymers: (meth) acrylic acid / (meth) acrylic acid Acrylic acid copolymer, (meth) acrylic acid "methyl" Acrylic acid 2-Ethyl alcohol / (meth) acrylic acid alcohol-resistant copolymer, (methyl) acrylic acid methyl (meth) acrylic acid Roasted acid methyl alcohol / polystyrene macromonomer copolymer, (meth) acrylic acid / (meth) acrylic acid methyl formaldehyde poly f-based acrylic methyl δ | macromonomer copolymer, (methyl ) Acrylic acid / (fluorenyl) acrylic acid Tg | / Polystyrene macromonomer copolymer based) Acrylic acid / (fluorenyl) acrylic acid fluorene / polyfluorene acrylic acid Noodles, methacrylic acid / (meth) acrylic acid ... / (meth) acrylic acid: stilbene-styrene copolymer, (meth) acrylic acid / ( Methyl) acrylic acid 2-sodium Ss / (fluorenyl) acrylic acid / polymethacrylic acid macromonomers total 314839] 7 200403526 Polymer, methacrylic acid / styrene / (meth) Benzyl acrylate ...- phenylmaleic anhydride imine copolymer, (meth) acrylic acid / succinic acid mono (2-propenyloxy) (Ester) / styrene / benzyl (meth) acrylate / N-benzylmaleic anhydride imine copolymer, (meth) acrylic acid / succinic acid mono (2-propenyloxyethyl) / styrene / Allyl (meth) acrylate / N_phenylmaleic anhydride imine copolymer, (fluorenyl) acrylic acid / benzyl (meth) acrylate / N_phenylmaleic anhydride imide, amine / phenylethyl烨 / (meth) acrylate glycerol monoester copolymer and the like. Next, a polymerizable addition compound (hereinafter referred to as an ethylenically unsaturated compound) having [E] at least one ethylenic unsaturated bond will be described. Examples of ethylenically unsaturated compounds include compounds having a polymerizable carbon atom-carbon atom unsaturated bond of more than two, preferably two or more, and can be listed as Hing = unsaturated weilic acid and aliphatic polyvalent alcohol vinegar; not Yu and diacid and lipid divalent polyamines, such as amidine. Each of these compounds can be a monomer, a vector, that is, an oligomer of 3, 4 or more oligomers. ; Prepolymerization can be a mixture. Here, the unsaturated carboxylic acid includes, for example, acrylic acid, amidinoitaconic acid, butenoic acid, methacrylic acid, and maleic acid. a, Bad #Slow & Polyesters with aliphatic polyhydric alcohols Monomers of monomers I can be exemplified by ethylene glycol dipropylene glycol, diacrylic acid: ethyl alcohol, dibutyl alcohol Diol §, Tetramethylene glycol dipropionate, Acrylene S, propylene, propylene, pentyl succinate, neopentyl glycol diacrylate, trimethyl triacrylate, trimethylolpropanetris (trimethylpropane Base) ethers, tripropylenes; Ling 2 alcohol ethane_, dipropionic acid hexamethylene glycol, cyclohexanyl alcohol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, one by one C3] 4839 18 200403526 pentaerythritol dilute acid, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, six Sorbitol acrylate, tris (propyleneoxyethyl) polyisocyanate, polyester acrylic oligomer, etc. Examples of the fluorenyl acrylate include tetramethylene glycol difluorenyl acrylate, diethylene glycol dimethyl acrylate, neopentyl glycol difluorenyl acrylate, trimethylol propane trimethyl acrylate, Trimethanolethane trimethacrylate, ethylene glycol difluorenyl acrylate, -butanediol difluorenyl acrylate, hexanediol difluorenyl acrylate, quaternary tetramethylene difluorenyl propylene Dilute esters, pentaerythritol trimethyl acrylate, pentaerythritol tetramethyl propionate, dipentaerythritol dimethyl acrylate, dipentaerythritol hexamethyl acrylate, sorbitol trimethyl acrylate, sorbose Alcohol tetrafluorenyl acrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) benzyl] difluorenylmethane, bis [p-(fluorenylpropenyloxyethoxy) Phenyl] difluorenoxane and the like. Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, i, 4-butanediol diitaconate, and Glycoldiol diitaconate, pentaerythritol diitaconate, sorbitan tetraitaconate and the like. Examples of the methacrylic acid ester include 0 methacrylic acid esters such as ethylene glycol dibutyrate, tetramethyl glycol monobutyrate, pentaerythritol dibutyrate, and sorbitol tetra-dibutyrate. For example, ethylene glycol diisobutyrate, pentaerythritol diisobutyrate, sorbitol tetramethacrylate and the like. 19 314839 200403526 Maleic acid esters can be exemplified by ethylene glycol dimaleate, triethylene glycol dimaleic acid, quaternary tetrol dimaleic acid, sorbitol tetramaleic acid, etc .: Examples include mixtures of such ester monomers. Specific examples of the aliphatic polyvalent amine compound and the ammonium monomer of an unsaturated carboxylic acid may include, for example, stilbene stilbene, melamine bis-methylpropionamine ^ 1, 6: hexamethylene bis · Acrylamide, 1 > 6 · hexamethylene bis-methacrylamide, diethylenetriamine tripropylammonium amine, benzene: methyl bisacryl acrylamide, etc. The present-methylbis ... ethylenically unsaturated compound can also be a polyisocyanate compound having an isocyanate ester group of ^ or more in the molecule. &Quot; ^ ^ ^ The ethylene monomer shown by the general formula (2) The obtained ethyleneuria compound (Japanese Patent Publication No. 48_4ms) h2c = c—C—0-CH2 * ^ CH— R10 〇 \-/ π · i ”(2) (where R] 0 and R]] Each independently is a hydrogen atom or a fluorenyl group) and 'can also be a urinary acryl type' (Japanese Patent Laid-Open No. 51_37193

), Polyester acrylates (; JP Sho UA 49 4λ10ΐ \ 3 on the Gazette, JP Sho 49-4d9l, GS Sho u rs * nail Λ Bulletin), photohardenable single month [Japan Adhesive Association of Journalists, page 20 (4 years)]] and so on. The mass percentage of the solid content of the ethylenically unsaturated compound composition of No. 7 No. 7 pp. 300 to 308 = for the photosensitive resin, preferably 10% or more and 40% or less. Hanging from 5 / above 50% to use the summer formula κ, the use of market unsaturated compounds In the above standards, if it is above 5% < then the sensitivity, imaging, and resolution balance is below 0 'then It is better to have the tendency to easily balance. In addition, the solid content of this photosensitive 314839 20 200403526 resin composition is a total of eight components from which the solvent component is removed. Next, the [c] photopolymerization initiator will be described. , Μ photopolymerization initiation] Ethylbenzene photopolymerization initiator, benzoin 1 also can be used ^ — first polymerization initiator, benzophenone photopolymerization initiator, D xanthone ketone photon β initiators, stilbene-based photopolymerization initiators, phosphine-based photopolymerization initiation 1 and the like, and acetamidine-based photopolymerization initiators include, for example, 7-ethoxyacetamidobenzene, 2-meryl- 2-fluorenyl-1-benzylpropan-1-ene, hydrazone _ earth-fluorenyl_acetal, 2-meryl-2-fluorenyl-bu [4- (2-hydroxyethoxy) benzyl Propyl] propanyl "@ 同 ， 1 · Sythelocyclohexylphenyl ketone, 2-fluorenyl-2-morpholinyl diphenyl phenyl) propan-1-one, 2-benzyldione Fluorenylamino-1- (cardiomorpholine melamine, soil) butan-1-1, 2-meryl-2-fluorenylfluorenylvinyl) benzyl] _ meaning of a few "-a same oligomer Seeking 0 Benzoin-based photopolymerization initiators can be exemplified by Shishi Niu 1st night ”such as Benzoin, Benzoin A, Benzoin Ether, Benzoin Isopropyl Ether, Benzo ^ q Bingding, and so on. Examples of the benzophenone-based photopolymerization initiator include dibenzone, o-benzyl benzoic acid methyl ester, chlorophenyl dibenzyl ketone, 4-benzyl u-yl dibenzyl sulfide, 3, 3, 4,4, -tetrakis (tertiary-butylperoxoyl) benzophenone, 2,4,6 difluorenylbenzophenone, etc. For example, 2-isopropylthioxanthol is the same as 2 5 4.

Examples of the photopolymerization initiators for sulfonium isocyanate include isopropylthioxanthone, 2, rendiethylthioxanthone, and 4-membered oxythioxan. " Find πyouzhonghe initiator (basic milk base) -1,3 · 5 -2 ,. 4-雔 f -Pitts (dimethymethyl) -6- (4-methyl π) -1, j, 5-diazine,? 4-Bis (digas, 1 diloxymethyl) + piperyl mountain 3 314839 21 200403526 ^, ^, trichloroarsine is called methoxyphenethenyl ... ^ tris, bis (trichloroτyl) _6_ [2_ (5_methylfuran_2_yl) ethenyltrifluorene, 2,4-bis (trichlorofluorenyl) -6- [2_ (fluorene.South I-yl) ethenyl] _135_triple , 2,4-bis (trichloromethyl) -6 cases of 4-diethylamino-2-methylphenyl) 'ethenyl K3,5-triazine, 2,4_bis (trichloromethyl) It's called Indio · dioxophenoxyvinyl; | -1,3,5-triazine and so on.

Examples of the oxadiazole-based photopolymerization initiator include 5-gas-p-methoxyphenyl) 2-chlorofluorenyloxadiazole and 5-gas-p-butoxyphenylethenyl 2-trichloromethylσ-oxazine Two tr sit and wait. … Other photopolymerization initiators can also use 2,4,6_trifluorenylphenylfluorenyl diphenylphosphine oxide, 2,2, -bis (o-chlorophenyl) _4,4,5,5, Tetrabenzyl ^, bi-imidazole, 10-butyl_2-chloroacridone, 2-ethylanthraquinone, biphenylfluorene, 9, phenanthrenequinone, camphorquinone, methyl benzoate Pentadienyl titanium bis (pentafluorobenzyl) and other titanium compounds.

/, Diazine-based photopolymerization initiator and dioxin. Permanent photopolymerization initiators are preferred. These photopolymerization initiators may be used individually 'or in combination of two or more kinds. The amount of the photopolymerization initiator is a total of the present polycarboxylic acid resin and other adhesive polymers added when necessary. 〇OO mass parts are usually 3 mass parts or more and 60 mass parts or less, preferably 5 mass parts or more and 40 mass parts. It is more preferably 10 parts by mass or less and 30 parts by mass or less. The use of the photopolymerization initiator is more than 1 part to 60 parts by mass of J shell, the sensitivity will not be reduced, and this ‘Λ light! ± The photosensitive resin composition formed by the resin composition 314839 22 200403526 The strength of the layer also tends to be difficult to decrease, which is preferable. The photosensitive resin composition may also contain a bishuangba + σ Μ hair promoter. The photopolymerization initiation aid is used to promote the photopolymerization reaction. Examples of the photopolymerization initiation aid include triethanol ^ -Zizhi, fluorenyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl vinegar, * ethyl gallate, 4-dimethylaminobenzyl Isoamyl gallate

2-ethylhexyl ester, benzoic acid 2 'diamidoethyl phenyl hydrazine I amine, 4 4,-雔 甲 甲 甲 其, # Ν, Ν- di 曱 phenyl peptone? And (a month (Feminine) benzophenone (commonly known as A + &amp; diacetone whose h <,% is non-Hilson's ketone), 4, 4, and (one ethyl ether female) a 曱 g with the same, 9, ι〇 _Di- 帀 ¢ 1 i. T-lactone, 2-ethyl-9,10-one-lactone, 9,10-diethoxy,) Sheng. Xi Sheng 丄 1 person ~, / ethyl-9,10_diethoxy onion temple. This photopolymerization initiation aid can be used in combination for a long time. Use these to 1: Use ’alone or more than two kinds of ^ ^ ^ When the initiator is used, the amount used is for light bearing. The initiator i Moore is usually above 0 moles and below 10 moles.

Then, add% 〇D # to the [D] solvent, and then use it. Examples of the various agents that can be used in the sensitive resin composition include 曱 Λ Λ 1, n-butyl acetate, isobutyl acetate, methyl ethyl pentoxide, isoamyl acetate, glutamidine & ^ ^ iso Butyl ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid, methyl acetate, n-lactic acid, lactic acid &quot; purpose, ethyl lactate λ 6 ^ ψ ethyl acetate, Butyl Glycolate, Ethoxy Acetyl Ethyl Acetate, Ethyl Ethyl Ethyl Ethyl Acetate_ Omega®, Ethyl Acetyl Acetate, Ethoxy Ethyl Acetate, Ethoxy Acetate ^ 7 Λ S Methyl Hydroxypropionate, 3-Hydroxypropanoic Acid Ethyl Acetate, 3-Methoxypropanoic Acid and Its Stone Shape ® Name> Ethyl Ethoxypropionate, Ethyl 3-Ethoxypropionate, 3-Ethoxypropoxylates 7 ^ acetone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, hydroxypropionate Ethyl Acetate, Ethyl 2-Methoxypropionate, 2-Methoxy Propionate, Ethyl 2-Ethoxypropionate, 314839 23 200403526 Ethyl 2-Ethoxypropionate, 2- Methyl hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 2-methyloxy-2-methylpropionic acid Ester, 2-ethoxy -2-yl Yue

Ethyl propionate, ethyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-carbonylbutyrate, ethyl 2-carbonylbutyrate, 2- Ethoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3 -fluorene 3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate , 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-fluorenyl- 3-Methoxypentylacetate, 3-Methoxy-3-Methoxypentylacetate, 3-Methoxy-4-Methoxypentylacetate, 4-Methyl-4- Esters such as methoxypentyl acetate; diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl lysin acetate, ethyl lysin Acid ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol ether ether acetate, propylene glycol ether acetate, propylene glycol propyl ether acetate, etc. Class; Yue-yl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; Yue benzene, diethyl benzene Yue, Yue three aromatic hydrocarbons such as benzene and the like. Preferable examples include ethyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lysone acetate, 3-methoxybutyl acetate, ethyl lactate, and diethyl Glycol Dimethyl Ether, Butyl Acetate, 3-Methoxypropionate, 2-Heptanone, Cyclohexanone, Ethyl Carbitol Acetate, Butyl Carbitol Ethyl Acetate, Propylene Glycol Ether acetate and the like. These solvents may be used alone or in combination of two or more. The amount of solvent used is 24 314839 W, in μ denier: The solid content of the photosensitive resin composition as a whole is more than 2% and the percentage is usually 2% or more and 50% or less. The amount is 10% to 45%. The thickness of the solvent coating film is within the range of 2% or more and 50% or less', which is more likely to improve the sentence. When used, the composition is used as a color-sensitive photosensitive resin composition so that the photosensitive resin composition may further contain an [E] pigment. Pigment Yan Yan, can also be organic pigments. Inorganic pigments can be both # ν; ζ ϊ L a β 戸 戸 + For example, mongolian compounds such as monoxides and metal complexes. The metal can be Λ, ”N is iron, cobalt, aluminum, cadmium, lead, copper, titanium,‘ beauty, network, front, and green. The metal oxide and metal coordination compound may be a single oxide or coordination compound, or a composite oxide or coordination compound composed of two or more metals. Organic shakiness can be listed according to the Color Index [Dye and Color Association f T1, θ c μ ·

Clety Of Dyers and Colourists) compounds classified as pigments. Examples of organic pigments such as CI and 4 include CI · Pigment · Yellow-1, CI Color · H vapor color "3, C.1 · Pigment · Yellow] 2, CI · Pigment · Yellow-13, CI Header, Steam Color-14 , C.1 · Pigment · Yellow-15, CI Pigment · Yellow-16, = .1 · Pigment · Yellow_17, CI · Pigment · Yellow_2, Cl Pigment Yellow ^ CJ · Pigment · Yellow-31, CI · Pigment · Yellow-55, CI Pigment · Two-colored 60, CJ · Pigment · Yellow, CI · Pigment · Yellow-65, CI Yan ^ K color Q1, CJ.Pigment. Yellow-73, CI · Pigment. Yellow-74, CI 『Material Steam Color_8], .C, 1 · Pigment · Yellow-83, CI Pigment · Yellow-93, 25% 314S39 200403526

〇.1. Pigment, Yellow-95, 0: .1. Pigment. Yellow-97, (: .1. Pigment. Yellow-98, CI Pigment · Yellow-100, CI Pigment · Yellow-101, CI · Pigment · Yellow-104, CI Pigment · Yellow-106, CI Pigment · Yellow-108, CI Pigment · Yellow-1 0 9, CI Pigment · Yellow-1 1 0, C.I · Pigment · Yellow-1 1 3, C. I · Pigment · Yellow-1 1 4, C · I · Pigment · Yellow-1 1 6, C · I · Pigment · Yellow-1 17, CI Pigment · Yellow-1 19, CI · Pigment · Yellow-120, CI Pigment · Yellow-126, CI · Pigment · Yellow-127, CI · Pigment · Yellow-128, CI Pigment · Yellow-129, CI · Pigment · Yellow-138, CI · Pigment · Yellow-139, CI · Pigment · Yellow -150, CI Pigment · Yellow 151, CI Pigment · Yellow-152, CI · Pigment · Yellow-153, CI Pigment. Yellow-154, CL Pigment · Yellow-155, CI · Pigment · Yellow-156, CI Pigment · Yellow-166, CI Pigment · Yellow-168, CI Pigment · Yellow-175 and other yellow organic pigments, CI Pigment · Orange 1, CI Pigment · Orange 5, CI Pigment · Orange 13, CI Pigment · Orange 14, CI · Pigment · Orange 16, CI pigment Orange 17, CI pigments Orange 24, CI pigments Orange 34, CI pigments Orange 36, CI pigments Orange 38, CI pigments Orange 40, CI pigments Orange 43, CI pigments Orange 46, CI pigments Orange 49. CI pigment · orange 51, CI pigment · orange 61, CI pigment · orange 63, CI pigment · orange 64, CI pigment · orange 71, CI pigment · orange 73 and other orange organic pigments, CI · pigment · purple 1, CI Pigment · Purple 19, CI Pigment. Purple 23, CI Pigment · Purple 29, CI · Pigment · Purple 32, CI · Pigment · Purple 36, CI Pigment · Purple 38 and other purple organic pigments, CI Pigment · Red 1, CI Pigment · Red 2, CI Pigment · Red 3, 26 314839 200403526 CI Pigment. Red 4, CI Pigment · Red 5, CI Pigment CI Pigment · Red 7, CI Pigment · Red 8, CI Pigment CI Pigment · Red 10, CI Pigment · Red 1 CI Pigment CI Pigment Red 14, CI Pigment Red 15, CI Pigment CI Pigment Red 17, CI Pigment Red 18, CI Pigment CI Pigment Red 21, CI Pigment Red 22, CI Pigment CI Pigment · Red 30, CI Materials: Red 3 CI Pigment CI Pigment Red 37, CI Pigment Red 38, CI Pigment CI Pigment Red 4 CI Pigment Red 42, CI Pigment 1, CI Pigment Red 48: 2, CI Pigment Red 48 Red 48: 4, CI Pigment Red 49: 1, CI 49: 2, CI Pigment Red 50: 1, CI Pigment Red Pigment Red 53 ... CI Pigment Red 57 C Pigment 1. CI Pigment · Red 58: 2, CI · Pigment · Red 58 Material · Red 60: 1, CI Pigment. Red 63: 1, (: .1 · 6 3: 2, C.I · Pigment · Red 6 4 : 1, C · I · Pigment · Red Pigment · Red 83, CI Pigment · Red 88, CI Pigment · h CI Pigment · Red 97, CI Pigment · Red 101, CI 102, CI Pigment · Red 104, CI Pigment · Red 105, Red 106, CI Pigment · Red 108, CI Pigment · Red G Pigment · Red 113, CI Pigment · Red 114, CI Pigment · CI Pigment · Red 123, CI Pigment · Red 144, CI 1 4 6, C · I .Pigment. Red 1 4 9, CI Pigment · Red 1 50, Red 1 5 1, C · I. Pigment · Red 1 6 6, C. I · Pigment · Red g · Red 6 -· Red 9, • Red 1 2, • Red 1 6, • Red 1 9, • Red 23, • Red 32, • Red 40, • Red 48 · ·: 3, CI pigments · Red 52: 1, CI • Red 5 7:: 4, CI pigments, red 81: 1, CI colored 90: 1, pigments, red CI pigments, ^ 1 12, CI, red 122, pigments, red CI pigments, L] 68, CI 27 314839 200403526 Pigment · Red 170, CI Pigment · Red 17: l, CI Pigment · Red 172, CI Pigment · Red 174, CI Pigment · Red 175, CI Pigment · Red 176, CI Pigment · Red 177, CI Pigment · Red 178, CI Pigment · Red 179, CI Pigment · Red 180, CI Pigment · Red 185, CI Pigment · Red 187, CI Pigment · Red 188, CI Pigment · Red 190, CI Pigment · Red 193, CI · Pigment · Red 194 , CI Pigment · Red 202, CI Pigment · Red 206, CI · Pigment · Red 207, CI Pigment · φ Red 208, CI Pigment · Red 209, CI Pigment · Red 215, CI Pigment · Red 216, CI Pigment · Red 220 , CI Pigment · Red 224, CI Pigment · Red 226, CI Pigment · Red 242, CI Pigment · Red &quot; 243, CI, Pigment · Red 245, C 丄 Pigment · Red 254, CI Pigment ·-Red 255, CI Pigment · Red 264, CI Pigment · Red 265 and other red organic pigments, C 丄 Pigment · Blue 15, CI Pigment · Blue 15: 3, CI Pigment · Blue 15: 4, CI Pigment · Blue 15: 6, CI Pigment · Blue 60 and other blue φ organic pigments, CI pigment Green organic pigments such as green 7, CI pigments, green 36, CI pigments, brown organic pigments such as brown 23, CI pigments, and brown 25, CI organic pigments, black organic pigments such as black 1, CI, pigments, and black 7. These organic pigments can be used individually or in combination of two or more kinds of daytime pigments corresponding to the purpose. -Ideal organic pigment among these organic pigments, and examples of the yellow organic pigment include CI pigment. Yellow-117, CI Pigment · Yellow-128, CI Pigment · Yellow-129, CI Pigment · Yellow-] 38, CI Pigment · Yellow -150, 28 3) 4839 C · 1 · Pigment · Yellow-1 5 5, Red organic pigments include 178, C.I · Pigment · Red-Red 254, etc., CJ · Pigment · Yellow-185, etc., C · 1 · Pigment · Red 166, CI · Pigment · Red 209, Ci · Pigment · Red 242, CI · Pigment · Black organic pigments can be listed c 箄 ， 争 # # 丄 颜 枓 · Black 1, CI Pigment · Black 7 Temple, More ideal organic look

^ C.I.Pigment · Yellow · 150, C.L Yan 枓 · Red 254, c I knot # .τ,,, $, Shake · Black 1, C.I · Pigment · Black 7 and so on. The color pigments used in the coloring photosensitive resin composition used for the black substrate used include, for example, carbon black 'stone lite 09, Japanese Patent Application Laid-Open No. 6-116η%, and fe ^ 〇〇〇〇5 Etc.), azo-based black pigments (Japanese Laid-Open Patent Publication No. 2-216102, etc.), temples) can also use the above-mentioned CI · Pigment · Black, CI Pigment · 堃 Ben 7 stems ^ ..., Black 7 Temple Black Organic Pigments, etc. The black pigment can also be used. "Use such as the 4-inch Kaiping 9-95625, the inch-opening Kaiping 9-124969 ^ reported in the 4-inch Kaiping 20〇1-1 06938 3, Carbon black. It is also possible to use black pigments coated with inorganic materials as shown in 4 inch 2000b 1 15043i. The average particle diameter of the pigment used is usually not less than 0 claws and not more than 0.01 '// m and not more than 0.1 / Zm / 4 e m. The average particle size of the pigment is above 〇〇〇1 # m 〇 ″ β 丨 the target range of k + Bu on the scholar w 1, then the formation of the color filter 4 has a tendency to obtain high transmittance, It is preferable that the pigment particles in the color photosensitive resin composition tend to be easily dispersed. 々 Pigments of these particle sizes can be obtained by micronization by a common method such as a kneading method, a sulfuric acid method, and an alkali reduction dissolution method. The surface of the material of Yan Xi t ^ m can also be modified by Shu Yueyue and others (Japanese Unexamined Patent Publication No. 8-259876, etc.). 314839 29 200403526 When the photosensitive resin composition is a coloring photosensitive resin composition, the mass percentage of the solid content of the coloring photosensitive resin composition (the component juice excluding the ^ ^) in the pigment is usually 20% by mass or more. 60 Berry meaning or less, preferably 25 mass% or more and M mass% or less, and more preferably 30 mass% or more and 50 mass% or less. If the amount of pigment used is above the above-mentioned reference, it is preferable that the intended black substrate or pixel can be formed if the amount is 20% by mass or more and 60% by mass or less. In the present invention, the mass ratio of the above-mentioned adhesive resin / ethylenically unsaturated compound is preferably 1.5 or more and 5 or less. Better quality ratio is 2 or more and 4 or less.

In addition, when manufacturing or preserving the photosensitive resin composition, in order to prevent the unnecessary thermal polymerization of ::: unsaturated compounds, a small amount of heat resistance = 〇 刈 can be added. Examples of suitable heat-resistant polymerization agents include haloquinone, p-methoxyphenol, di-third-butyl-p-phenol, pyrogenol 'third-butyl-phthalate ^, 4,4'-thiobis (3 · methyl winter tertiary-butylbenzene age), 2,2 into methylen (methyl 6-second-butylphenol), N-nitrosamine hydroxylamine Salt, etc. The addition amount of the thermal polymerization preventive agent is preferably 1% by weight based on the mass of the entire composition.芏 &gt; This photosensitive resin composition can be compounded with various fillers if necessary: ..., polymer compounds, surfactants, promoters, etc .: J, anti-emulsifier, ultraviolet absorber, anti-coagulant, etc. Specific examples of such adhesive additives such as polyethylene glycolate include fillers such as glass and alumina; polypropylene baking acid, $ ethylene glycol monofluorene, and polyvinyl chloride-based propionate compounds ( A) South molecular compounds other than; 314839 30 200403526 non-ionic, cationic, anionic surfactants; vinyldimethoxysilane, vinyltriethoxysilane, vinyltri (2 • methoxy Ethoxy) silane, N- (2-aminoethyl) _3-aminopropylmethyldihydrazine, Naminoamino) Dongaminopropyltrimethoxy, ^ aminopropyl Triethoxysilane, 3-glycidoxypropyltrimethoxysilane H-oxypropoxypropylfluorenyldimethoxylithium, 2- (3,4-epoxycyclohexylethyl Trimethoxy Shixuyuan, 3-chloropropylmethyldimethyl: trimethoxychan, 3-methylpropoxypropyltrimethoxychan = -yl-based dimethoxy Adhesion promoters such as alkane; 2,2_thiobis (&quot; yl i tertiary-butyl phenol), 2,6_di-tert-butylphenol and other oxidation inhibitors. Di: Butyl-5-methyl Benzyl-2-Cyclophenylchlorobenzotriazine. Sulfuric Acid Dibenzo-Tongsi Ultraviolet Absorber: Anti-agglomerating agent such as sodium polyacrylate. The intermediate of this photosensitive resin composition may also contain carboxylic acid It is preferably a low-molecular-weight hair having a molecular weight of less than 1,000. Θ ^ An acid or an organic amine compound having a molecular weight of at least one amine group in the molecule of less than 1,000. Specific examples of the slow acid include formic acid and valeric acid acetate. , Trimethylacetic acid, hexamellitic monomonocarboxylic acid 4 acid, propylene: bis: diacetic acid, heptanoic acid, caprylic acid and other pimelic acid, suberyl I azelaic acid, adipic acid, adipic acid , Malonic acid, ethylmalonic acid, i-decanedioic acid, undecanedicarboxylic acid 'methyl-based materials, citraconic acid malonic acid, f-based gallic acid, tetramethylcamphoric acid, etc. Cardiac dipicnic acid; 6 trimellitic acid, aconitic acid, fluorenyl phenyl acid, difluorene: r; s: benzoic acid, benzoic acid, cumic acid, dibenzyl dicarboxylic acid, p-phenylhydrazone aromatic mono ㈣; phthalic acid, iso & quo t; Metabolic acid, trimesic acid, trimesic acid 314839 31 200403526 Tetracarboxylic acid, pyromellitic acid and other related formula | carboxylic acids; phenylacetic acid, hydrogenated atropine, hydrogenated cinnamic acid, bitter Apricot ^ 1- ^, benzyl succinic acid, atropic acid, cinnamic acid, cinnamic acid cinnamate, cinnamic acid ^-His Majesty®, cinnamic acid, coumaric acid, diregular cinnamic acid and other carboxylic acids Organic amine compounds can be listed as I μ — for example, n-propylamine, isopropylamine, n-butylamine, 月 monthly female, di-butylamine, melamine, butylamine, n-pentylamine, n-hexylamine, and n-heptyl , N-nonyl, Γ% and other monoalkanes Ar ^ g ammonium amine, n-undecylamine, n-dodecylamine 'early base fe class; cyclop 4 group cyclohexylamine, di: dimethylcyclohexyl Monoethylamines such as cyclic amines, diethylamine, 3-ethylcyclohexylamine, 4-ethylcyclohexyl-n-propylamine, di-n-propylamine, diethylamine, methyl-n-propylamine, ethylenedibutylamine, Second: _ —: Heart, di-n-butylamine, diisobutylamine, amines; fluorenylcyclohexylamine: B ::; diamines such as di-n-fluorenamine, di-n-hexylamine, and other "amines" Temple early alkyl monocycloalkylamines; Amine, diamyl ^ T-ethylamine 'methyldiethylamine, triyldi-n-propylamine, tri-n-propylamine, 1 fluorenyl-n-propylamine, ethylene tri-n-butylamine, three from: di; propylamine' Tri-n-butylamine, tri-isobutylamine, base amines; diamidine / trinylamine, tri-n-pentylamine, tri-n-hexylamine and other triane faces ： Ά 月 女 类 ·, methyl dicyclohexyl 7 ^ alkyl early ^ alkyl; tricyclohexylamine: "― monohexyl dicyclohexylamine alcohol, ramino group per ... , "Diol, 3-amino] -propanyl, 1 P oxo, ^ butanol, amine · 1-pentanol, _ · pentanol amines; cardioamine ... Yan Bu 1, diethanolamine, -τ 工 ^ drunk temple early alkanolamine-Tianding-n-propanolamine, diisopropanolamine, _ Π: butyl ^ ~ Xingbutanolamine, di-i, butane Diamines such as chiral amines, fluorenol amines, and di-n-hexanol amines; di314839 32 200403526 (4-cyclohexanol) amines, and other dicyclofluorenol amines; tris-triisopropanolamine, tri-n-butanol Amines, / n-di-n-propanolamine, ~ x-butanolamine,:, &gt; trialkanolamines such as n-hexanolamine; tri ^ ~ pentanol Amines, three types; 3-aminodeca-2-propanediol, its hexanol) amines such as tricycloalkanolamine butanediol, 4-amido _ !. 3_ butyl earth ten 3-propanediol, 4- Amine-U2-diethylamino monool, di-M-propylene glycol, 3-yl-U · propylene glycol, and other amine chain burners-alcohols: 3 · propylene glycol, 2-diethylamine alcohols, cardioamines, etc. Amino ring diyl groups such as alcohols; ... cyclopentane methanol, 4-amino cyclopentane methanol, etc. containing amines such as amines, amines, cyclohexane, and methanol.普 田 W 甲 甲子 子, 4-dimethylamino group = 'methyl ·, 4-diethylamino cyclopentane methanol, cardiodimethylamine ... methyl H ethylamino cyclohexane methanol, etc. Cyclic chain burning methanol'f alanine, 2-aminobutyric acid, 3-aminobutyric acid, cardiac aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid , 5, valeric acid, 6-aminocaproic acid ,! -Aminocyclopropanecarboxylic acid, raminocyclohexanecarboxylic acid, 'aminocyclohexanecarboxylic acid' and other amine carboxylic acids; aniline, o-methylaniline, m-methylbenzylamine, p-1-aniline , P-ethylaniline, p-n-propylaniline, p-isopropylaniline, p-n-butylbenzylamine, p-tertiary-butylaniline, neilamine, 2-naphthylamine, N, N -Dimethylaniline 'N, N-diethylaniline, p-methyl-N, N-dimethylaniline and other aromatic amines; o-aminobenzyl alcohol, m-aminobenzyl alcohol, p- Amino T-alcohol, p-dimethylaminomethanol, p-diethylaminomethanol, uranyl alcohol, o-aminobenzene g, m-aminobenzene g, p-aminobenzene g points, amino-benzyl phenols such as p-dimethylaminobenzylphenol, p-diethylaminophenol; m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p -Diethyl 314839 200403526 Aminobenzoic acid and the like. In the present invention, the carboxylic acid and the organic amine compound may be used alone, or more than one kind may be used in combination. In the present photosensitive resin composition, the respective amounts of the carboxylic acid and the organic amine 2 compound are generally from 0.001 to 100% by mass, and preferably from 0.001 to 10% by mass of the entire composition. . ,

The photosensitive resin composition is applied to the substrate through application methods such as spin coating, flow coating, and roller coating, and then dried to form a layer derived from the photosensitive: lipid composition. # Is exposed by a predetermined mask model, The image liquid forms a pull type. This photosensitive resin composition contains a photosensitive resin composition, and forms a color model (color plate?). Exposure = The radiation used is better to use, such as line, h-line, i-line, etc .: The thickness of the film after drying is usually ...... m, preferably 02 to m, more preferably 0.2 to 3.0 # m. When the photosensitive resin composition is a colored photosensitive resin composition, on the board: the substrate to be used may be, for example, glass-breaking, oxidizing, and oxidizing its # # #, lymine, polyimide, polyimide Wait. Demonstrate substrates are also processed as appropriate, such as chemical treatment, plasma treatment, and organic vapor silane coupling agents. Lice phase reaction method The imaging solution can be used as long as it can dissolve the liquid in the light part. And body d: .. and product 1 will dissolve the exposed or experimental water solution. A composition of various organic solvents that can be used organically is B quarkine, which can be exemplified by the above-mentioned solvents used in the preparation of the photosensitive resin group B. For example, sodium qi, sodium lice, potassium oxide, sodium carbonate, sodium silicate, 314839 200403526 sodium T-silicate, ammonia, ethylamine, di-ammonium ethanolamine, hydroxylated tetrahydrofuran, hydroxyl Tetraethylamine, choline, pyridorum pyridine, 1,8-diazabicycloside -... carbon diluent and other test compounds are dissolved to a concentration; 0.001 to 10% by mass, preferably 0 ... 01 to 1 L, Bailey% alkaline aqueous solution. The qualitative aqueous solution may be added with an appropriate amount of an aqueous solvent such as formazan or ethanol or a surfactant. There are various imaging conditions. For example, the image processing method can be used for shower imaging method, spray imaging method, immersion imaging method, refining imaging method, etc. The imaging m can be set in the range of _ to 4 (rc. Imaging. The time is generally set to 10 seconds to 300 seconds. Using the developing solution 4 composed of these alkaline and mixed / night, generally washed with water after development. Although the above is a description of the embodiment of the present invention The embodiments of the present invention as shown above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention includes the meanings and scopes equivalent to those disclosed in the scope of patent applications, as well as those disclosed in the scope of patent applications. All changes in the following. The present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Example 1 A bisphenol diglycidyl ether was placed in a four-neck beaker with a capacity of 300 ml. 46.3g, itaconic acid 8.7g, benzyltriethylammonium chloride 009g, tetraethyl desertification 0.18g, methoxyquinone 0.02g and propylene glycol monomethyl ether acetate 55g, under heating and stirring Reaction at 120 ° C for 4 hours, transparent Tone-viscous liquid. To the obtained viscous-adjusted liquid was added 4.8 g of propylene glycol monomethyl ether acetate and 4.8 g of acrylic acid, and the reaction was performed at 120 ° for 8 seconds. 314839 35 200403526 as compound A _Γ !: 'Put compound A55g, tetrazine dicarboxylic acid anhydride called propionolite ^ _1G.2g' under 12th-generation heating and stirring to carry out a small day guard to obtain a pale yellow transparent resin solution A1. The obtained resin The weight average molecular weight (Mw) was 8200 and the acid value was 100. 实施 例 2

[Production of colored photosensitive resin composition] [E] The average particle diameter is 0.003 // m parts by mass and 12 parts by mass of the dispersant [A] conversion of the resin solution component obtained in the synthesis example), black Pigment (ci · Pigment Black 7): 40 parts by mass [pigment] 52 parts by mass, liquid A1 [adhesive polymer] 33 parts by mass (solid [B] dipentaerythritol hexaacrylate [compound with addition]] 10 parts by mass , [C] 2, Heart bis (trichloromethyl) · budipate base agent] 5.0 parts by mass and polymerizable with ethylenic excess and bond • 1, '5-diazine [Photopolymerization initiation [D] Propylene glycol monomethyl ether acetate [solvent] 3 74 Photosensitive resin composition (black). The mass parts are mixed to obtain coloring [formation of colored photosensitive resin composition layer], and the colored photosensitive resin composition obtained above is obtained. Apply to the surface of a glass substrate ["# 7059" by König Company] using a spin coating method, and heat at 100 c. Allow to dry for a minute to form a layer derived from the colored photosensitive resin composition on the substrate. This originates from drying The layer thickness of the subsequent colored photosensitive resin composition was 1.2 β η. [Formation of coloring model ( Evaluation of the image)] 314839 36 200403526 On the substrate on which the layer derived from the above-mentioned colored photosensitive resin composition was formed, a light mask having an L / S (line and interval Hne an (j Space) model) of 5 μm was used, Ultra-high pressure mercury lamp was irradiated with ultraviolet rays (irradiation amount of 200 mJ / cm2) for exposure. The coloring photosensitive resin composition layer after the exposure was immersed in a developing solution [containing 0.01% by mass of hydroxide Potassium, non-ionic surfactant-containing aqueous solution] was developed for 50 seconds until the unexposed portion was dissolved. After development, it was washed with water and heated at 230 ° C for 20 minutes to form a black coloring model on the substrate (2) ( Black substrate). Observe that the black substrate has a good reproducibility with an L / S model at 5 // m, and the linearity of the model is also good. [Evaluation of margin] The immersion time (development time) of the image liquid is other than seconds. The same operation as above is performed to form a black substrate. When observed with the same optical microscope as above, a good reproduction of the L / S model at 5 // m is formed. [Evaluation of sensitivity] In addition to the use of light-shielding layer, the light transmittance is in stages The changed mask model is used as a mask model. Except for exposure, the same operation as above is performed to find the minimum light exposure (sensitivity) necessary to form the model. The obtained sensitivity is 100 mJ / cm2, which is very high. Comparative Example 1 Except for the copolymer of methacrylic acid methyl ester and fluorenyl acrylic acid [mole fraction of t-acrylic acid t-ester unit content is 65%, mole fraction of fluorenyl acrylic acid unit content The ratio is 35%, and the weight-average molecular weight in terms of polystyrene is 13,000,000. 30 parts by mass replaces the adhesive polymer used in Example 2 and 314839 37 200403526. The amount of pentaerythritol hexaacrylate is 13 parts by mass. Other than that, it carried out similarly to Example 2, and obtained the colored photosensitive resin composition (black), and formed the layer (thickness #melon) derived from the colored photosensitive resin composition. [Evaluation] The same operation as in Example 2 was performed except that the substrate forming the layer derived from the colored photosensitive resin composition obtained above was used instead of forming the substrate derived from the layer obtained from Example 2.疋%, the unexposed part which should be dissolved out in the development of 50 seconds is completely undissolved. In addition, when the time like is 70 seconds, the unexposed portion that is required to dissolve dissolves, but the 5 β m coloring model completely disappears and cannot be formed at all. The sensitivity sought in the same manner as in Example 2 was 300 mJ / cm2. The polychitoic acid resin of the present invention can be suitably used as a polymer of a photosensitive resin composition. In particular, if a colored photosensitive tree product containing a pigment is used, high resolution and high sensitivity can be obtained. The boundary of the image is also f and good. It is also the same when a pigment with a small diameter is used at a high concentration, and it is ideal to obtain high sensitivity, high resolution, and a wide range of imaging limits. The photosensitive resin composition in July is particularly suitable for coloring photosensitive resin compositions for color filter plates, protective films for color filter plates, distance plates for color filter plates, and interlayer insulating films for color filter plates. [Brief description of the drawings] Figures 1) U) to (C) are schematic diagrams of the process of forming a colored photosensitive resin composition on a substrate into a pixel and a black substrate. Figure 2 314839 38 200403526 is a part of the pattern diagram of the color plate example. Layers derived from colored photosensitive resin composition 2 Substrate 3 Cover type 4 Light 5 Daylight, black substrate 5R, 5G, 5B: Color daylight 5BM Black substrate 6 Color filter 11 No light irradiation area 12 Light irradiation area 3 1 glass plate 32 light shielding layer 33 light transmitting portion 39 314839

Claims (1)

200403526 Patent application scope 1. A polycarboxylic acid resin, characterized in that the reactant obtained by reacting (a) the compound (al) with the compound ii) under the condition of formula (ρ) contains Saturated order reaction to obtain the amidine reactant, &amp; early completion of the acid Φ obtained by reacting the component (C) with (d) anhydride, (al) compound: a molecule with at least two compounds in the molecule Oxidation (a2) compound ... Polyvalent carboxylic acid formula (P): = number of epoxy equivalents of oxygen compound) &gt; (acid equivalent of polyvalent polyacids 2) = polyline acid resin of the scope of patent application! Where the compound 3 is a compound represented by the following formula (I), / H ^ CCH2-fOR3) -C). 0R ^ j 〇 ^ 3〇-faCH2CH-CH2 〇) [wherein R] and R2 are each independently gas month X, 00 Liaoyuan? , Alkyl, or * prime atom,. Λ is an early bond or the following formula (1)) to formula (κ8), which is a divalent residue represented by any formula, R. Is an alkylene group, R4 is a hydrogen atom, Λ Α alkyl group or glycidyl group, m is an integer of 0 to 5, n is 0 to 10, 敕 1 π positive number L 疋, and η is an integer of 2 to 0, R to R4 of 矸 τ υ in different iterative units can be the same, and "different". 314839 40 200403526 ch2 (Ι · 6) 3〇 / (Ι · 7), 〇, (1-8) 3. The polycarboxylic acid resin according to item 1 or item 2 of the patent application scope, wherein the (a2) compound is It is a polyvalent carboxylic acid having an unsaturated double bond. • Polysuccinic acid resins of any of items 丨 to 3 of the Shishengu patent scope, where 'the' (a2) is at least one selected from the group consisting of maleic acid and fumaric itacone tetrahydrone Compounds composed of adipic acid and chlorobridged acid. 5 :: The polycarboxylic acid tree of any one of items 1 to 4 in the scope of claim ii, said, (b) the monocarboxylic acid containing an unsaturated group is at least selected from acrylic acid and metformite One type of κΏ is a group of under-methacrylic acid and butenoic acid. 6 · Rushen No. 5 Qing patent scope, among them, any one of the two polycarboxylic acid anhydrides, diamines such as those transported from tetrahydrobenzyl dimethylbenzyl tetracarboxylic dianhydride and biphenyl . A group consisting of carboxyl-monoanhydride 7 ^ heavy photosensitive tree moon purpose composition, which is characterized by the patent scope! Any of the items from item 6 to item 6. If applied, it consists of polymerizable A polyacid with [A] ethylenic excess and bonds, [B] at least a photopolymerization initiator, and [D] a solvent. σ σ compounds, δ · As in the scope of the patent application, the proactive tree wall composition, where the 314S39 4] 200403526 composition contains [E] pigment. 7. Among them, this item to item 9 9. If the patent is applied, the photosensitive resin group of item ... [E] Pigment is a black pigment made of carbon black. 10 · —A hardened product characterized by being formed by the photosensitive resin composition as described in any one of the scope of application for patent Ί. 3] 4839 42