TWI243837B - Photo-sensitive resin composition - Google Patents

Abstract

The invention provides a photo-sensitive resin composition which has excellent properties of development, adhesion, heat resistance, non residual, and improved pretilt angle of the pattern. The composition comprises (A) an organic binder having a carboxylic group, (B) an ethylenically unsaturated compound, (C) a photoinitiator, (D) an organic solvent and (E) a pigment; wherein the organic binder (A) comprises an organic binder (A1) having a weight average molecular weight of 8000-18000 and an organic binder (A2) having a weight average molecular weight of 20000-40000, and the weight ratio of (A1)/(A2)=10% to 90%/90% to 10%.

Description

1243837 Case No. 91 1 Amended in March 14898. 5. Description of the invention (1) The present invention is developed with excellent developing properties and improved feelings. In terms of quality and quality, there are four types of dispersion methods, blue and green. The light dispersion of the pigment dispersion method and the effect of the pigment emission of 10 to 60% in the present invention, so if the positive sensitivity of the conductor is insufficient, it will agglomerate and form. Generally, it is used as a negative photoresist. The cost and other advantages include the development and adhesion of multifunctional mono-solvents and additives in the past. Related to the adhesion of a photoresist group, matt resin group, nowadays, more commonly used 'colored light color The color heat produced by organic pigments, the current photosensitivity, is a low problem for exposure photosensitive resin photoresist. On the other hand, large particles, or acidic radicals, have a south sensing point, and are present, pigments, and the like. The photosensitivity and heat resistance are used to borrow light into products. Residues. The color filter is made of dyed material, and the color filter has become the composition of the sexual resin. Therefore, the surface is polymerized by developing the polymerization type and the material is exposed to the widest photosensitivity, and then the test solution is described in detail. That is, a method with a tilt angle of the image and a thermal light sheet, and the printing is made on each sheet with a color filter composition of UV and UV light pigments. The pan method uses an initiator method, a brush method, and a glass-based solid light source painted with a high-precision light sheet. Resin Resin, good material, organic, based on electrographing method and palette, will be included in red pigment. The mainstream is made from density and better. In the content, it accounts for the absorption and dispersion rate, which is much higher than the pigments in semi-resistive agents. Color photoresist composition, and its design diversity. Its components include adhesives and resin compositions, which often cannot take into account the coating film and the properties of the solvent, such as Japanese Public License Hei 8-1 2 2 5 1 7 and Hei 9-1 0 6 0 7 1 and so on. Japanese Open Charter

ill 1243837 Case No. 91 1 March 14898 Amendment V. Description of the Invention (2) 9-1 3 4 0 0 4 Although there are two types of organic binders with different molecular weights, the molecules mentioned above are missing. The present invention is to modify the resin composition due to the residue on the glass substrate and the inclination angle binder (A), the organic bond containing the carboxylic acid group containing ethyl (C), the organic solvent-based adhesive (A), and the like. 10% ~ 90〇 / 〇 / 90 ° / 〇〜1 The following is a sense of the present invention containing a carboxylic acid group (A). It has excellent long-term storage stability and solvent resistance, etc. In order to make the photosensitive component carboxylic acid-containing The ethylenic insufficiency caused by the present invention, especially the one containing carboxylic acid groups, is too high, the developing property of the coating film is not good, and the above-mentioned disadvantages cannot be improved. Intensive research, the photosensitivity of the invention contains High and low molecular weight organic adhesive resins, good adhesion, developability, heat resistance, and other properties. Its composition includes carboxylic acid group-containing organic munylic unsaturated compounds (B), light Starter (D), pigment (E); among them, the carboxylic acid group-containing organic is composed of a Wei acid-containing agent (A 1) having a weight average molecular weight of 8000 to 18000 and a weight average molecular weight of 2 0 0 0 0 to 4 0 0 0 0 Organic adhesive (A2), and (A1) / (A2) 2 0% ° Each component of the invention is made Fine DESCRIPTION: organic binder: photosensitive resin composition containing binder properties. The resin composition having the properties of setting, adhesion, coatability, developability, and heat resistance can be dissolved in an alkaline developing solution, and a base acrylic or methacrylic resin is used. The organic binders used are copolymers containing carboxylic acid groups, copolymers of one or more ethylenic monomers and other copolymerizable and monomers. Examples of ethylenic monomers are as follows: acrylic, methyl

Page 6 1243837 Case No. 9Π14898 Amendment V. Description of the Invention (3) Unsaturated monocarboxylic acids such as acrylic acid, butenoic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; maleic acid, maleic anhydride Unsaturated dicarboxylic acids (anhydrides) such as fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; unsaturated polyvalent carboxylic acids (anhydrides) having a valence of 3 or more Classes and more. These carboxylic acid group-containing ethylenic monomers can be used alone or in combination of two or more. In addition, the aforementioned other copolymerizable ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, gaseous ethylene, and methoxyethylene; acrylic acid fluorene Esters, methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyric acrylate, butyl methacrylate, acrylic acid 2-ethyl ester, fluorenyl 2-hydroxyethyl acrylate, benzyl acrylate and benzyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, fluorenyl acrylic acid Unsaturated succinic acid esters such as stearyl ester, octadecyl methacrylate, stilbyl methacrylate, bisacrylic acid stilbene succinic acid, etc .; aminoethyl acrylate, Unsaturated carboxylic acid urethanes such as aminoethyl methacrylate, aminopropyl methacrylate, aminopropyl methacrylate, etc .; unsaturated ethylenyl acrylate, epoxy propyl acrylate, etc. Glycidyl carboxylic acid; vinyl acetate, vinyl propionate, Vinyl carboxylates such as vinyl acid esters, vinyl benzoate, etc .; unsaturated ethers such as vinyl methyl ether, vinyl ether, allyl epoxy propyl ether, fluorinated allyl epoxy propyl ether ; Acrylonitrile, methacrylonitrile, α-acrylonitrile, vinyl cyanide and other cyanide vinyl compounds; acrylamide, fluorenyl acrylamide, α-acrylamide, N-hydroxyethyl propylene Unsaturated fluorenamines such as amidine, N-hydroxyethylammonium acrylamide, maleimide

1243837 Case No. 91114898 Amendment V. Description of the Invention C4) or unsaturated sulfonium imines; 1,3-butadiene, isopropylene, chloropropylene, etc. aliphatic conjugated diene; polystyrene, polyacrylic acid Methyl esters, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polysiloxane, etc. have monoacryloyl or monomethylpropyl groups at the ends of the molecular chain of the polymer (Methacry 1 〇y 1). These other unsaturated monomers may be used alone or in combination of two or more. The aforementioned carboxylic acid group-containing copolymer is ① acrylic acid and / or methacrylic acid and 0 are selected from the group consisting of methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl vinegar acrylate, and benzoic acid acrylate Copolymers of at least one other unsaturated monomer in the group consisting of esters, phenyl methacrylate, styrene, polystyrene macromonomers, and polymethyl methacrylate macromonomers are preferred. Specific examples of preferred carboxylic acid group-containing copolymers include: acrylic acid / benzyl acrylate copolymer, acrylic acid / benzyl acrylate / styrene copolymer, acrylic acid / methyl acrylate / styrene copolymer, acrylic acid / Acrylic monomer / polyethylene megamonomer copolymer, Acrylic acid / methyl methacrylate / polymethyl methacrylate megamonomer copolymer, Acrylic acid / acrylic acid acrylate / polyethylene megamonomer copolymer, acrylic acid / Methyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / phenyl methacrylate copolymer, acrylic acid / phenyl methacrylate / styrene copolymer, acrylic acid / methyl methacrylate / stupid Ethylene copolymer, acrylic acid / benzyl acrylate / polyethylene macromonomer copolymer, acrylic acid / benzyl methacrylate / polymethylmethacrylate macromonomer copolymer, acrylic acid / methyl methacrylate / Polyethylene macromonomer copolymer, acrylic acid / fluorenyl acrylate / polymethylmethacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / fluorenyl acrylic acid

Page 8 1243837 Case No. 91 Rev. 114114898 V. Description of the invention (5) Methyl ester / polyethylene macromonomer copolymer, acrylic acid / methacrylic acid 2-hydroxyethyl ester / benzyl methacrylate / polyfluorene Methyl acrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / benzyl ethylene copolymer, methacrylic acid / methyl acrylate / benzyl ethylene copolymer, methacrylic acid / benzyl methacrylate / polyethylene Bulk copolymer, methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / methyl acrylate / polyethylene megamonomer copolymer, methacrylic acid / methyl acrylate / poly Ammonium methyl acrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / methyl methacrylate / Styrene copolymer, methacrylic acid / benzyl methacrylate / polyethylene megamonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate megamonomer copolymer, methacrylic acid / A Methyl acrylate / polyethylene macromonomer copolymer, methacrylic acid / fluorenyl acrylate acrylate / polymethyl fluorenyl acrylate macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / fluorenyl Monomethyl acrylate / polyethylene macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / monomethyl methacrylate / polymethyl methacrylate macromonomer copolymer and the like. Among these carboxyl-containing copolymers, particularly preferred are fluorenyl acrylic acid / fluorenyl benzyl methacrylate copolymer, fluorenyl acrylic acid / fluorenyl methacrylic acid benzyl ester / copolymer of ethylene, methacrylic acid / fluorenyl methacrylate / Stupid ethylene copolymer, methacrylic acid / phenylmethyl methacrylate / polyethylene macromonomer copolymer, methacrylic acid / phenylmethyl methacrylate / polymethylmethacrylate macromonomer copolymer, methyl Acrylic acid / methyl methacrylate / polyethylene macromonomer copolymer, fluorenyl acrylic acid / fluorenyl acrylic acid

1243837 __Case No. 91Π4898_ 年月 日 __ V. Description of the invention (6) S5 / Polyfluorenyl methyl acrylate macromonomer copolymer, fluorenyl propionate / 2-hydroxyethyl methacrylate / Benzyl methacrylate / polyethylene macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / phenylmethyl methacrylate / polymethyl methacrylate macromonomer copolymer. In addition, if the organic binder used in the present invention contains a dagger. ~ C22 alkyl carboxylic acid alkyl ester can make the coating film have better adhesion and good appearance. When the aforementioned organic binder contains 40 to 80% by weight of benzyl acrylate, better heat resistance can be obtained. The carboxylic acid group-containing organic binder (A) of the present invention measures molecular weight by gel permeation chromatography_layer analysis method (GPC), which is: _ weight average molecular weight of 8 0 0 0 to 1 8 0 0 0 A carboxylic acid group-containing organic adhesive (A 1) and a carboxylic acid group-containing organic adhesive (A2) having a weight average molecular weight of 2 0 0 0 to 4 0 0 0, and (A1) / (A2) = 10% to 90 ° / 〇 / 90% to 10%. And ('/ 11) / (eight 2) = 30% ~ 70% / 70% ~ 30% is better. At least one molecular weight range (p e a k) between 80,000 to 1,800,000, and between 20,000 to 40,000 in the above-mentioned quantitative chart measured by GPC. (A 1), (A 2) is preferably a copolymer of at least one acrylic monomer and one or more selected from acrylate monomers and styrene monomers, and (Al), (A2) Can be the same or different. When the molecular weight range and content ratio of the aforementioned (A1) and f (A 2) are within the range, the resin composition has good developability and adhesion, no residue, and good inclination angle and heat resistance. (B) Ethylene unsaturated group-containing compound The ethylenically unsaturated group-containing compound (B) used in the present invention is an ethylenically unsaturated compound having one ethylenically unsaturated group, for example, '

Page 10 1243837 Case No. 91Π4898 Amended in May, V. Description of the Invention (7) 有 Yes · Propylamine, (Methyl) Propionate Morin, 7-Amino-3,7 ~ dimethyloctyl ( Fluorenyl) acrylate, isobutoxymethyl (meth) acrylamide, isobornyl hydroxyethyl (meth) acrylate, isobornyl (fluorenyl) acrylate, 2-ethylhexyl (fluorene Group) acrylate, ethyl diethylene glycol (meth) acrylate, third octyl (meth) acrylamide, diacetone (meth) acrylamide, difluorenylaminoethyl (methyl) Acrylate, dodecyl (meth) acrylate, dicyclopentene hydroxyethyl (meth) acrylate, dicyclopentene (meth) acrylate, N, N-dimethyl (meth) Acrylamine, tetrakiphenyl (f-based) propionic acid S, 2-tetrakis-benzyloxyethyl (fluorenyl) propionic acid S, tetrarhamyl (fluorenyl) acrylate, tetrabromo Benzoyl (fluorenyl) acrylate, 2-tetrabromobenzyloxyethyl (meth) acrylate, 2-trichlorobenzyloxyethyl (meth) acrylate, tribromophenyl (meth) acrylate Acid ester, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinylcaprolactam, N -vinylpyrrolidone, benzyloxyethyl (meth) acrylate, pentachlorobenzyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (fluorenyl) acrylic acid Esters, polypropylene glycol mono (fluorenyl) acrylate, norbornyl (meth) acrylate, methyltriethylene glycol (fluorenyl) acrylate. Examples of ethylenically unsaturated compounds having two or more ethylenically unsaturated groups are as follows: ethylene glycol di (fluorenyl) acrylate, dicyclopentene di (fluorenyl) acrylate, triethylene glycol diacrylate , Tetraethylene glycol di (fluorenyl) acrylate, tricyclodecane diyl di (meth) acrylate, tris (2-hydroxyethyl) isocyanate di (fluorenyl) acrylate, tris (2-hydroxyethyl) Base) isocyanate tri (meth) acrylate, caprolactone modified three (2-hydroxyethyl) isocyanate

Page 11 1243837 Case No. 91 Amended in January 114898 V. Description of the Invention (8) Tris (fluorenyl) acrylate, trishydroxymethylpropanetri (fluorenyl) acrylate, ethylene oxide (hereinafter referred to as "E0" ) Modified trimethylolpropane tri (meth) acrylate, propylene oxide (hereinafter referred to as "P0") modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (methyl) ) Acrylate, neopentyl glycol di (fluorenyl) acrylate, bisphenol A diglycidyl ether both terminal (fluorenyl) acrylic additions, 1,4-butanediol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (methyl) ) Acrylate, dipentaerythritol hexa (meth) acrylic acid, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate , Dipentaerythritol five modified by caprolactone Fluorenyl) acrylate, ditrihydroxymethylpropane tetra (fluorenyl) acrylate, E0 modified bisphenol A di (meth) acrylic acid S purpose, P 0 modified bis S sub-A di (methyl) Acrylate, E 0 modified hydrogenated bisphenol A di (meth) acrylate, P 0 modified hydrogenated bisphenol A di (meth) acrylic acid S purpose, E 0 modified bis S fraction F two ( Fluorenyl) acrylic acid S, phenylfluorene polyglycidyl ether (fluorenyl) acrylate and the like. Among the aforementioned ethylenically unsaturated compounds, particularly preferred are trimethylolpropane tri (fluorenyl) acrylate, E0 modified trihydroxymethylpropane tri (fluorenyl) acrylate, and P0 modified third Trimethyl propylene tris (fluorenyl) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetramethyl (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (methyl) Based) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol penta (methyl)

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Page 12 1243837 __Case No. 91 1 14898_ Month, Day, Amendment _ V. Description of the invention (9) Propionate j: Hexanoic acid ester, ditrihydroxymethylpropylpropionate tetra (meth) acrylate. Based on 100 parts by weight of a carboxylic acid group-containing organic binder (A), the amount of the ethylenically unsaturated group-containing compound (B) used in the present invention is 20 to 300 parts by weight . (C) Photoinitiator The photoinitiator (C) used in the present invention is at least one selected from the group consisting of acetophenone-based compounds (acet ophe η ο ne) and at least one selected from the group consisting of biimida compounds (biimida) ζ ο 1 e), in which acetophenone compounds (such as p-dimethylaminoacetophenone), a, a'-dioxoyloxy 4 azo acetophenone (a, a '-dimeth〇xyazOxyacet〇phenone), 2,2, -Difluorenyl-2-phenylacetophenone (2,2'-(1111161:) 171-2-pheny1 acetophenone) · p-methoxybenzyl Acetamidine (p-methoxy — acetophenone), 2-fluorenyl- [4- (methylthio) benzyl phenol] (2-methyl- [4- (methylthio) phenol]), 2-morphone l -propyl isopropyl (2 — morph 〇lin 〇 一 l—pro pan one), 2-benzyl-2N, N-dimethylmethanyl-1- (4-morpholinobenzyl) -1- Butanone [2-benzyl-2-N, N-dimethy lami nod- (4-morpholinophenyl) -l-butanone]. And birazole compounds (B iimida ζ ο 1 e), such as 2, 2 '- (O-benzylphenol) —4,4,5,5, -dibenzyl φ • g min ϋ y2,2 '-(〇-c hlorophenyl) -4,4 ', 5,5, -diphenylimidazole], 2,2'-(o-fluorobenzol) -4,4,5,5'-diphenylimide ^ [2,2 ' Mono (〇 一 flu〇r〇phenyl) -4,4 ', 5,5'-diphenylimidazole], 2,2'-(o-methoxyphenol) -4,4 '5,5'-diphenyl quotient米 ° 坐 (2,2 '-(〇-11161: 11〇 \ 乂 01161 ^ 1) -4,4'5,5'-'

Page 13 1243837 _ Case No. 91 1 14898_ Year Month Date __ V. Description of the invention (10) 011] 1161 ^ 111〗 11 (1 & 2〇16), 2,2 '-(p-methoxybenzylphenol ) -4,4'5,5'- Diben S * _, ^ [2,2 '-(p-methoxyphenyl) -4,4,5,5,-(11011611 乂 1111] 1 (132〇16] , 2,2 '-(2,2', 4,4'-methoxybenzol) -4,4 '5,5'-dibenzol imidazole [2,2'-(2,2 ', 4 , 4'-methoxyphenyl) -4,4'5,5'-diphenylimidazole], 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5-tetraphenyl-1,2' -Two flavors [2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bi imidazole], etc. Among them, 2-fluorenyl-2-N , N-Diamidine-1- (4-morpholinophenyl) -1-butan 3 with [2-benzyl-2-N, N-dimethylamin〇-l- (4-morpholinophenyl) M-butanone] and 2, 2'-bis (2-aminophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-: ^^ [2,2'-bis (2-chlorophenyl) -4 , 4 ', 5,5'-tetrapheny 1-1, 2'-biimida ζ ο 1 e] combined with a photoinitiator is more effective. The photosensitive resin composition of the present invention may Further add a benzophenone (benz〇phe η〇ne) -based compound as a photoinitiator, such as Thioxanthone, 2,4-: 6 * _ ^ _ (2,4-diethyl thioxanthanone), D Sekouton g same 4 — ^ IKthioxanthone — 4 — sulfone), benzophenone, 4,4'-bis (dimethylamine) dibenzone [4,4 '-bis ( dimethylamin〇) benzophone], 4,4'-bis (diethylamino) benzophenone [4,4'-bis (diethylamino) benzobenzoone], etc .; Others still have Sf (benzil), acetyl ) And other α-diketones, benzoin and other acyl alcohols, benzoin inethylether, benzoin in ethyl ether (diethyl ether) benzoin ethylether), benzoin isopropyl I 11 ill IS I 11 1 1 1 11 111 II 1 IS 1 iillli 1 Page 14 1243837 ___ Case No. 91114898 _ month month day __ V. Invention Note (11) ether) and other acyl alcohol ethers (acyl〇in ethers), 2, 4, 6- Ξ methylphenyl hydrazone diphenyl phosphine oxide (2, 4, 6-tr 1 in ethy 1-be η ζ oy 1 diphenylph osphineoxide), bis- (2,6-dimethoxybenzyl) -2,4,4-trimethylphenylphosphine oxide [1 ^ 8- (2,6- (11 社 1: 11〇 乂) ^ -56: 12〇; ^ 1) -2, 4, 4-trimethylbenzyl phosphineoxide], etc., < acylphosphineoxide, anthraquinone, 1,4-naphthalenequinone (1, 4-naphthoquinone) and other quinones, phenacyl chloride, tribromomethyl pheny1su1fone, tris (trifluoromethyl) — s- 三 〇 秦 麄 [ Tris (trichlormethyl) -s-triazine] and other halogen compounds, di-tert-butylperoxide and other peroxides. Among them, benzophenone-based compounds are preferred, especially 4, 4, -bis (diethylamine) dibenzone [4, 4 '-bis (di ethyl amino) be η ζ ophe η ο ne ] Best results. The amount of the photoinitiator used is 1 to 50% by weight based on the total amount of the ethylenically unsaturated group-containing compound (B) and the photoinitiator (C). (D) Organic solvent The photosensitive resin composition of the present invention contains an organic solvent, and its main purpose is to adjust its fluidity and viscosity. Therefore, the solvent used can be completely dissolved with other φ organic components, and its volatility must be so high that it can be evaporated from the dispersion with only a small amount of heat under normal pressure. Therefore, solvents with a boiling point below 180 ° C under normal pressure are most commonly used. These solvents include aromatic (Aromatic) systems such as benzyl, benzene, and dioxane; alcohols (A 1 cohoi), such as methanol and ethanol ; Ethers, dialkyl ethers such as ethylene glycol mono-n-propyl ether; esters, such as diethyleneglycol dimethyl ether, tetrahydrofuran

Page 15 1243837 _Case No. 9Π 14898_ Year __iLi:-V. Description of the invention (12), ethyleneglycol monomethyl ether, ethyleneglycol monoethyl ether , Ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, diethyleneglycol in methyl 〇methyl ether, diethylene glycol Diethyleneglycol mono ethyl ether, diethyleneglycol monobutyl ether, diethyleneglycol monobutyl ether, propylene glycol monomethyl ether S_ (propyleneglycol mono methyl ether

acetate), propyleneglycol monoethyl ether acetate, propyleneglycol monopropyl ether acetate; S is the same as (K e t ο n e) series, such as acetoacetone, acetone. Among them, esters are preferred. It also uses propylene glycol ether acetate, propylene glycol ethyl acetate, propylene glycol ethyl acetate, or both, and it is used for storage stability and coating of the photosensitive resin composition. Best cloth. The organic solvent (D) of the present invention is used in an amount of 60 to 90% by weight based on the entire photosensitive resin composition. (E) Pigment The pigment (E) of the present invention can use various inorganic pigments or organic pigments φ. Inorganic pigments include metal oxides, metal salts, and other eight materials. Specifically, metal oxides such as iron oxides and copper oxides, such as metal oxides and copper oxides, and composite oxides of the foregoing metals can be taken as examples. Organic pigments For example:

Page 16 1243837 Case No. 91114898 Amendment V. Description of the Invention (13) C. I. Pigment Yellow 1 1, 2 4, 3 1, 5 3, 138, 139, 150, 151, 154, CI Pigment Orange 36 , 38, 43, 51 C. I. Pigment Red 1 0 5, 122, 1 4 9, 1 5 0, 177, 2 0 9, 254 110 83, 99, 1 67 108, 109, 155, 171, 175, 176

C I. Pigment Violet 1 9, 2 3, 3 2, 3 9 I. Pigment Blue 1, 2, 1 5, 1 5: 3 I. Pigment Green 7, 3 6, 3 7 I. Pigment Brown 2 3, 2 5, 2 8 I. Pigment black 1, 7. The pigment can be used alone or as a mixture of two or more. (A) is used as the basis, and the amount of (E) is 20 to 500 parts by weight. The pigment can be used in combination with dispersants such as cationic, anionic, and nonionic. Surfactants such as ammonium, amphoteric fluorine and the like are taken as examples. The aforementioned surfactants are, for example, polyethylene oxide dodecyl ether, polyethylene oxide stearin, polyethylene oxide oleyl ether, and other polyethylene oxide alkyl ethers; Polyethylene oxide alkyl phenyl ethers such as polyethylene oxide octyl styryl ether, polyethylene oxide nonyl styryl ether; polyethylene glycol dilaurate, polyethylene glycol distearate Polyethylene glycol diesters such as sorbitan fatty acid esters; polyesters modified with fatty acids; grade 3 polyamines modified with polyamines; the following are trade names: KP (Shin-Etsu Chemical Industry System), Privlon (produced by Kyoeisha Oil Chemical Industry), Evdorp (produced by Teckmploo Dakouz), Mekafuk (produced by Dainippon Ink Chemical Industry), Frodo (Made by Sumitomo 3M), Avicardo, Saffron (made by Asahi Glass) 15: 6, 16, 22, 60, 66

C

C is 100 parts by weight in the present invention. These dispersants can be polysiloxane-based,

m

Page 17 1243837 _ Case No. 91Π4898 _ Month and Day __ 5. Description of the invention (14) and so on. These surfactants can be used alone or in combination of two or more. Relative to 100 parts by weight of the pigment (E), the aforementioned surfactants are generally used in an amount of less than 30 parts by weight, and preferably 5 to 20 parts by weight. In the composition of the present invention, various additives such as a filler, a polymer compound other than the adhesive resin of the present invention, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, and the like can be blended as necessary. Specific examples of these additives include fillers such as glass and aluminum; and other organic binders (A) such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroacrylates. Polymer compounds; vinyltrimethoxy | kisoba yaki, ethoxydiethoxy shibain, ethoxytri (2-methoxyethoxy) shiba yaki, N- (2-aminoethyl) -3 -aminopropylmethyldimethoxyshiyoshiin, N- (2-aminoethyl) -3 -aminopropyltrimethoxyshiyoshino, 3-aminopropyltriethoxysilane, 3 -cyclo Oxypropoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-Gaspropylmethyldimethoxylithium, 3-Gaspropyltrimethoxysilane, 3-Methacryloxypropyltrimethoxysilane, 3-Hydroxythiopropyltrimethoxy Silane and other adhesion promoters; 2, 2-thiobis (4-fluorenyl-6-t-butylphenol), 2, 6-di-t-butylphenol and other antioxidants; 2- (3 -t-butyl-5-methyl-2 -hydroxyphenyl) -5 -chlorobenzotriazole, alkoxy φ group UV absorbing agents such as benzyl ketone; and anti-aggregating agents such as sodium polyacrylate. The composition of the present invention is the above-mentioned components (A) to (E), and if necessary, various mixers and dispersers can be used for mixing and dispersing to prepare other additives and solvents. As the mixer and the disperser, a conventionally known one can be used. Example ^

Page 18 1243837 _ Case No. 91 1 14898_ YYYY__ V. Description of invention (15) In terms of: homogenizer, kneader, ball mill, 2 or 3 axis grinder, paint shaker, sand Sand grinder, such as stone grinder, plastic film grinder. For a better preparation method, firstly add the pigment and the organic binder into the solvent and mix uniformly. If necessary, use a 1 or 2 mixer to knead while heating to completely mix the pigment and the organic binder to obtain a uniform colored body. Methods. Secondly, a solvent is added to the obtained colored body, and if necessary, a dispersant or various additives can be added, and various sand mixers (such as a plastic film mill) using a ball mill or glass beads as a dispersion medium are used for dispersion. At this time, if the particle diameter of the glass beads is smaller, a dispersion having a smaller pigment dispersed particle size is obtained. At this time, the dispersion was controlled to a constant temperature, and a dispersion result with good reproducibility was obtained. The dispersion obtained here can be removed by centrifugation or decantation if necessary. The pigment particle size of the dispersion liquid thus obtained is preferably 1 // or less. Furthermore, it is preferably 0. 0 2 // from 0. 3 //. The colored dispersion obtained in this way is mixed with an ethylenically unsaturated group-containing compound and a photoinitiator to obtain a photosensitive resin composition of the present invention. The composition of the present invention can be applied on a substrate by a coating method such as spin coating, cast coating, or newspaper coating to form a radiation-sensitive composition layer, which is exposed between specified mask patterns, and can be exposed by using Immerse at 2 3 ± 2 ° C for 4 seconds in developing solution for 30 seconds to 5 minutes, and then develop a pattern by coloring. The radiation used at this time is preferably ultraviolet rays such as g rays, h rays, and i rays. Examples of the substrate include soda-lime glass, hard glass (Plexus glass), quartz glass used in liquid crystal display devices, and the like

Page 19 1243837 Case No. 91 Rev. 114114898 V. Description of the invention (16) Those who show conductive films or substrates of photoelectric conversion devices (such as silicon substrates) used in solid-state imaging devices, etc. These substrates generally form isolation The black peeling of each pixel. In addition, as the developing solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium phosphosilicate, ammonia water, ethylamine, diethylamine, diethyl Methylethanolamine, Tetramethylammonium hydroxide, Tetraethylammonium hydroxide, Choline, Rot, Piperidine, 1, 8-Diaza- [5,4,0]-7-Undecene And other basic compounds, 0. 0 0 1 to 10% by weight, preferably 0. Use this to wash the sample with water (H ~ 1 retesting water purification. If the invention is organic, there will be a one-degree meter. The initial dosage of the oil bath is a temperature of 1000ml of the component produced by the polymerization of a to f 〇 (AMBN small time product from the dissolved alkaline aqueous solution formed by the amount of resin shown in the example for the amount of resin). In addition, when the developing solution composed of a solution is developed, it is generally explained by the following examples after the development. The manufacturing example of the binder (A)] Nitrogen inlet, agitator, heater, condensation tube and a temperature The four-necked round-bottomed flask was introduced into a mixture as shown in Table 1 under a nitrogen atmosphere. When stirred, it was raised to 10 (TC, and then the amount listed in Table 1 or ADVN) was dissolved in the organic solvent PG EA, and added to a four-necked round-bottomed flask at equal intervals. The polymerization was completed. After that, it was taken out of the four-neck round bottom flask. Therefore, the resin solution was obtained with a monomer mixture, and the degree of conversion was more than 99.5%. The average weight of the solution measured by gel permeation chromatography was shown in Table 1. 1 to 7 and Comparative Examples 1 to 5]

Page 20! 243837 — ^ __ Case No. 91114898_year month f fujinzhen __ 5. Description of the invention (17) The organic binder (A) obtained in the aforementioned manufacturing example was used according to the formula shown in Table 2 Various photosensitive resin compositions. The various compositions obtained were mixed with a shaker. Then, a coating film of about 2 // m was obtained by spin coating on the broken glass substrate, and pre-baked at 85 ° C for 5 minutes. Then irradiate with ultraviolet light (exposure machine Canori plA-501 F) 20 0mJ / cm2, immerse in developing solution at 23 ° C for 2 minutes, then wash with pure water 'and bake at 2 0 C for 60 minutes To obtain the desired pattern coating on the glass substrate. [Evaluation method] Molecular weight measurement: According to the gel permeation chromatography (GPC) method of Waters Co. MPany, and the measurement under the following conditions: column: KD-8 0 6 Μ detector: Water RI-2 4 1 0 Mobile phase: THF (flow rate 1 · 0 cc / mi η) Using standard molecular weight polystyrene as the measurement standard development speed: The time from the coating film immersed in the developer to the peeling of the coating film in the non-exposed area is Development speed. Evaluation based on the following criteria: 〇: 1 2 ~ 2 5 seconds △: 8 ~ 1 1 second or 2 6 ~ 30 0 seconds X: less than 8 粆 or more than 30 seconds 3. Development range: coating film immersed in developing solution The time from when the coating film in the exposed area is peeled off is the development range. Evaluation based on the following criteria: 〇: greater than 120 seconds

Page 21 1243837 Case No. 911 Amended in January 14898 5. Description of the invention (18) X: less than 60 seconds 4. Development color difference (△ Eab * Measure the five chromaticities of the coating film before and after development. The difference is Development color difference Δ E ab *. Evaluation based on the following criteria: 〇 less than 1 · 5 Δ 1. 5 to 3 X greater than 3 Adhesiveness: According to JIS. 5 4 0 0 (1 9 0 0) 8.5 Adhesion test In the determination of the base plate method of 3. 5 • 2, the post-bake (p ◦ stbake) ore film was cut into 100 base plates with a knife, and then taped and then peeled off to calculate the torn off base plate. The number of items is evaluated according to the following criteria: 0 or less △ 6 to 49 9 X 50 or more 6. Residue: After the coating film is developed, use a cotton swab and acetone to wipe the surface of the non-exposed area of the glass substrate. Observe the state of the cotton swabs and evaluate them according to the following criteria: 〇: Cotton swabs have no pigment attached X: Cotton swabs have pigment attached VII. Inclination angle: As shown in the first figure, the edge of the cross section of the day (10) and the glass substrate The angle (Θ) of (2 0) is the inclination angle. According to the following Prospective evaluation: ○: less than 40 ° X: greater than 40 degrees

Page 22 1243837 Case No. 91114898 Amendment V. Description of the invention (19) 8. Heat resistance: The coating on the glass substrate is prepared, and its light transmittance is measured by light with a wavelength of 4 00 ~ 7 0 0 3 Change, and then leave it at 250 ° C for 60 minutes, and then measure the change in transmittance with light with a wavelength of 400 ~ 700 nm, and change the transmittance by 5% or less according to the proportion of change Δ The change in transmittance is 5% to 10 〇 / 〇X. The change in transmittance by more than 10% is shown in Table 2 according to the above evaluation method. Description of the attached table: Table 1: The proportion of ingredients in the manufacturing example of the organic binder (A) of the present invention and the weight average molecular weight of the resulting resin solution. Table 2: Composition ratios and evaluation results of Examples and Comparative Examples of the present invention < t

Page 23 1243837_Case No. 91114898 V. Description of the invention (20) Years and months (1) PGMEA if ^^ l · ^ 丨 llc ^^ g ^ plOpyleneglycol monomethyl ether acetate) 65100 65.00 26.56 26 "75 Ren.59 5013 1.04 1.52 0.51 1101 2.30 PGMEA 65.00 65.00 65.00 65.00 诮; & 1¾¾ 漭 舛 碯 26.90 26.20 26 · 43: M.32 1-61 ^ 1 ^ 1¾¾ 4.16 5.83 I 2.88

f 漭 2- 菡 0 鲥 鄹 1.53 1.49 丨 3.QQ 1 ^ Screen 羯 1-^^ iroli 0.98 · 1.89 AMBI2: 1.40 0.50 0.80 0.60 1 £ Oblique 锊 璺 (-tf-0 / ο) Suwei ind Oxygen 00 tto / o) > 丨:

Hr 0.70

ADVN Reliance (S%) 5801 54862 Cold + # 10811 37479 1554 Ren 2360017 Page 24 1243837_ Case No. 91 1 14898 V. Description of the invention (21) Month a (1) PGMEA ι (propyleneglycol monomethyl ether acetate)-^ ¾¾ (2) sp jealous ^ furnace (Bu-^ tick &) ^ 5;

C .. Lff? MIID L ^ BI (F (Frequently Quite Many) Vs. irs- 逵 (D) (畸 4f2 总 客 逵 (C) (畸 45 >) 笳 笳 笳 念 Hi # 茹 璺 (> (畤 45 >) > '^ Shang, 11 1¾ Wei 潞 stupid 绫 Cafe (Agb *)

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A 130 so πο 22 22 120 50 50 〇〇〇〇〇〇〇 [> 130 so 170 22 79 22 120 70 30 ο 〇ο c 〇〇〇〇130 130 so 170 22 22 120 30 70 lr4l ^ iHIM ^ 〇〇〇〇〇 〇〇

A 130 so 170 22 22 120 90 10 D > 〇 〇 〇 〇 〇 〇 130 830 170 22 22 22 120 10 90 〇 〇 〇 〇 〇 〇 〇 130 830 170 22 22 120 90 10 〇 〇 〇 〇 〇 〇

X 130 0030 170 22 22 120 100 〇 130 830 170 22 120 100 〇 〇 〇 〇 130 830 i 22 120 100 IC ^ IKI-I ^ I ^ [> 〇

A 130 so 170 22 22 22 120 80 20 〇 〇 〇 〇

X 130 so 170 ΊΊ 22 120 000 20 Page 25 1243837

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Claims (1)

1243837 Case No. 91114898 Moon Correction VI. Application Patent Scope 1. A photosensitive resin composition, which includes a carboxylic acid group-containing organic binder (A), an ethylenically unsaturated compound (B), Photoinitiator (C), organic solvent (D), pigment (E); based on 100 parts by weight of carboxylic acid group-containing organic binder (A), the ethylenically unsaturated group-containing compound ( B) is used in an amount of 20 to 300 parts by weight, pigment (E) is used in an amount of 20 to 500 parts by weight, and light initiator (C) is used in an ethylenic unsaturated state Based compound (B) and photoinitiator (C) in a total amount of 1 to 50% by weight, and the organic solvent (D) is used in an amount of 60 to 90% by weight of the entire photosensitive resin composition; The carboxylic acid-based organic binder (A) consists of a weight average molecular weight of 8 0 0 to 1 8 0 0 0 and a weight average molecular weight of 2 0 0 0. 0 ~ 4 0 0 0 0 is composed of a carboxylic acid group-containing organic binder (A2), and (Α1) / (Α2) = 10% ~ 90% / 90% ~ 10% 〇2, according to the application A photosensitive resin composition described in item 1 of the patent scope, wherein the organic binder (A) containing a carboxylic acid group is an ethylenic monomer containing one or more carboxylic acid groups and other copolymerizable ethylenic properties Copolymer of unsaturated monomers. Page 27