TW200403524A - Coloring photosensitive resin composition - Google Patents

Abstract

The present invention provides a coloring photosensitive resin composition comprises binder resin(A), photo-polymerization monomer(B), photo-polymerization initiator(C), coloring material (D) and solvent (E), wherein the photo- polymerization initiator (C) of the coloring photosensitive resin composition comprises (1) polyfunctional thiol compound and (2) acetophenone compound. The present invention provides a method of pattern formation by platting such coloring photosensitive resin composition over the plate, removing the volatile component from the platting coloring photosensitive resin component from the platting coloring photosensitive resin composition layer, and exposing the volatile component removed layer to light through the photo mask to develop the pattern, and a color filter comprises the pattern forming by the above method and a liquid crystal display apparatus equipped such color filter.

Description

200403524 发明, Description of the invention: [Technical field to which the invention belongs]

The present invention relates to a photosensitive resin composition widely used in ultraviolet curable inks and photoresistance, and more particularly to a colored resin composition, which is suitable for use as an antifoam in forming a color liquid: : Coloring pixels used in devices or video units, etc.). [Prior art] The color filter film in a color liquid crystal display device or an image unit is generally made of red, green, and blue pixels on a substrate such as a glass substrate or a wafer. -A black matrix with shading is usually set in these days. At the same time, in order to form pixels of various colors, generally, a substrate formed with a light-shielding layer is coated with a spinnerite with an anti-name solution containing a considerable amount of pigment, and then dried (pre-heated) and coated on the coating film. The method of illuminating and developing, therefore, it is necessary to repeatedly operate each color required on the color phosphor film to obtain an image containing each color. For this resist, a composition containing a pigment and a binder, such as a tree, a photopolymerizable monomer, and a photopolymerization initiator is used. The black matrix is also formed using a black pigment-containing resist. The photopolymerization initiator used in 泫 resistance will affect the necessary characteristics and quality of the finished color film. Therefore, it is necessary to review the surface smoothness and pattern shape of the color filter film with high sensitivity and use. , High resistance to fakes and credibility. What is the usable coloring photosensitive resin composition layer? Uncensored compounds, compounds of compounds and imidazole compounds, compounds of compounds and imidazole compounds, and acetamidine 314811 6 200403524 compound «st benzene, etc. No. 6-2 Qi9i3, JP-A No. 24484 and JP-A No. W61G14, etc.). Those with higher sensitivity can use polyfunctional thiol compounds, bisimidazole compounds, titaniumcene compounds, triphlene compounds and oxadiazole compounds. Select a mixture of more than one kind, 2-piperidinium 6 bis (trichloromethyl) Three coaxes, and a two-item consisting of the above three coax compounds, a dihydrazone compound, and a hydrogen donor (Japanese Unexamined Patent Publication No. 1 () · 253δ15 and Japanese Unexamined Patent No. 2) ). However, the color filter film made of the photosensitive resin composition with these three coax compounds as the photopolymerization initiator component has the aforementioned advantages, but its disadvantage is the color transmittance of the pigment Problems such as low storage stability, etc. [Summary of the Invention] Therefore, the object of the present invention is to provide a color-sensitive photosensitive tree moon composition having high sensitivity and high storage stability even when containing a high-concentration coloring material. And-a kind of high-quality color made of the above-mentioned colored photosensitive resin composition, which has good surface smoothness, pattern shape, and light transmittance, and is a calender film. ^ The result of a scrutiny review by Ben Ming et al. Found a specific photopolymerization The coloring photosensitive resin composition of the hair coloring agent can solve the above-mentioned problems, and the cost of the invention is%. That is, the present invention provides a coloring photosensitive resin composition containing (A) a binder resin and (B) a photopolymerization monomer. (C) a photopolymerization initiator, (D) a coloring material, and (E) a solvent, and (c) the photopolymerization initiator contained in the colored photosensitive resin composition is (1) a polyfunctional thiol compound and ( 2) Ethylbenzene compound 7 3] 4811 200403524 'Substance & pattern formation method, in which the colored photosensitive resin composition is coated on a substrate, and the volatility of the coated colored photosensitive resin composition layer i is removed. Ingredients and a light-shielding mask that removes the volatile components of the colored photosensitive resin composition layer v 1 to illuminate the pattern to make the pattern '·, and a circular pattern of colored shirts containing / made by the method' Film and device The liquid crystal display device of the color filter film. [Embodiment] φ 纟 The coloring photosensitive resin composition of the invention is mainly used for dispersing pigment resists, and (E) solvents generally disperse pigments (d) ) Coloring material, while re-dissolving Or disperse (A) binder resin, (B) photopolymerizable monomer and (C) photopolymerization initiator, and any (F) other additives. (A) The binder resin is alkali-soluble and can be used as a coloring material. Dispersant. The binder resin usable in the present invention is preferably a polymer containing a constituent unit derived from an unsaturated carboxylic acid, and the polymer may be a monopolymer derived from a constituent unit containing an unsaturated carboxylic acid. However, it is preferable to copolymerize with other constituent units derived from monomers that can be copolymerized with constituent units derived from unsaturated carboxylic acid Λ. Specific examples of the aforementioned constituent units derived from unsaturated carboxylic acids can be exemplified. The constituent units derived from acrylic acid and the constituent units derived from acryl-based acrylic acid. The constituent units derived from acrylic acid and the constituent units derived from acryl-based acrylic acid may each independently contain constituent units derived from an unsaturated unsaturated acid, or both. In addition, there are other unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides such as crotonic acid, itaconic acid, maleic acid, fumaric acid, and the like. The group is composed of 314811 8 200403524 or more. Unit, or if the constituent unit from α-hydroxymethyl acrylic acid contains hydroxyl and carboxyl constituent units in the same constituent unit, and if the binder resin contains these constituent units, it generally also contains constituent units derived from acrylic acid Or from the constituent units of fluorenyl acrylic acid. Each of them may contain one kind or two or more kinds of these constituent units. The binder resin used in the present invention is preferably one containing a composition unit copolymerizable with a composition unit derived from an unsaturated carboxylic acid. The copolymerizable composition unit is composed of a composition derived from a fluorenyl acrylate compound. Copolymers of units are preferred. ^ Specific examples of the constituent units constituting the fluorenyl acrylate may include: fluorenyl (fluorenyl) acrylate, ethyl (fluorenyl) acrylate, butyl (fluorenyl) butyl, fluorenyl (fluorenyl) acrylate, ( Composition units such as hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate, etc. derived from substituted or unsubstituted unsaturated carboxylic acid alkyl esters, derived from cyclopentyl (meth) acrylate, (meth) ) Cyclohexyl acrylate, fluorenyl cyclohexyl (meth) acrylate, cycloheptyl (fluorenyl) acrylate, cyclooctyl (meth) acrylate, cyclopentene (meth) acrylic acid Ester, cyclohexene acrylate (fluorenyl), cycloheptenyl acrylate (fluorenyl), cyclooctenyl acrylate (fluorenyl) capadienyl acrylate, isobornyl acrylate (fluorenyl) acrylate , Pinane (meth) acrylate, tricyclodecyl (meth) acrylate, tricyclodecyloxyethyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate Ene vinegar, (fluorenyl) acrylic acid ene vinegar, (meth) propylene Component units of unsaturated carboxylic acid alicyclic esters such as dicyclopentenyl acid dicyclopentenyl ethoxylate, etc., derived from unsaturated carboxylic acids such as glycidyl (meth) acrylate The constituent unit of the epoxy propyl ester is derived from (fluorenyl) propane 3.148Π 200403524 The unsaturated carboxylic acid oxetane and other constituent units are derived from (fluorenyl) acrylic oligoethylene diene g | · Composition units of unsaturated carboxylic acid esters of mono-esters of diols such as mono-esters, which are composed of (substituted or unsubstituted alkyl esters derived from (fluorenyl) acrylic acid), and (Methenyl) propylene is preferably composed of cyclic group Sa. Specifically, it is derived from (methyl) acrylic acid, methyl (meth) acrylic acid, ethyl (butyl) acrylic acid, (methyl) Base) Two dilute acids TS purpose, (fluorenyl) acrylic acid-2_ via ethylene glycol, (meth) acrylic acid amino ethylene glycol composition unit is better, especially from benzyl (meth) acrylate The constituent units are even better. ^ In addition, the aforementioned copolymer may contain other constituent units copolymerizable with constituent units derived from unsaturated carboxylic acid 2 and constituent units derived from (meth) acrylate compound. The other copolymerizable units can be exemplified as follows: Composition of aromatic vinyl compounds such as stupene, 0-methylstyrene, vinyl toluene, etc. The constituent units of esters are derived from t-units of ethyl cyanide compounds such as (fluorenyl) propionitrile nitrile and α · propylene chloride, and are derived from maleic acid needles such as N-phenylmaleic acid needle imine. The constituent units of amine compounds, etc. . . The other copolymerizable unit may be used alone or in combination of two or more kinds in the production of the (A) adhesive resin. In (A) '4 agent resins, the composition unit constituting the unsaturated polyacid is generally preferably 10 to 50% by mass based on the total weight of the binder resin, or preferably in the range of 5 to 40% by mass. . Constituent units derived from unsaturated carboxylic acids, in the former :: quasi 10 to 50% by mass, the imaging solution can be completely dissolved, so there is no residue on the substrate of the light portion, and the light is illuminated during development Part of the painting 3148]] 10 200403524 The film of the prime part is not degraded, and the whole of the day prime does not tend to peel off, so it is better. (A) The weight-average molecular weight of the binder resin is preferably in the range of 10 to 100, and more preferably in the range of 15, to 50, in terms of polyethylene. (A) The weight-average molecular weight of the binder resin is in the range of ι, ∼ to 10,000, ㈣ ㈣ ㈣ Fan ㈣ is not easy to cause film loss during development, and the non-bookin part has a good tendency to release during development, so it is more good. -The (A) binder resin is generally in the composition in an amount of 2% by mass based on the total solids, preferably in the range of 10 to 70% by mass. (A) Adhesive sodium resin is the aforementioned standard 5 to 90 0 mass iγ # θ 蚪 below Jeong-ri, which can be used for imaging solution =, so there is no residue on the substrate of the unlit part, and For example, the film of the pixel part of the first part will not be degraded, and the non-day part has the suffix ::, sexual tendency 'is better. Composition in this book; is the difference between the weight of the composition minus the weight of the solvent. μ The photopolymerization contained in the colored photosensitive resin composition of the present invention is capable of photopolymerization and can be used for the following reasons: Mouth list: polymerized by the action of the first polymerization initiator described later and later

In addition to the early functional monomer, it may also be a 2 ^^ J functional monomer. In order to be 2…, 3 or more functional, monofunctional and monofunctional: Specific examples include nonylphenyl carbitol, acrylic acid, 2-propyl-3-hydroxyphenoxy acrylate, 2 ethyl US p its a γ alcohol, acrylic acid -2- acetyl, acetyl ethyl hexamethyl hexyl propionate carbidine N-vinylpyrrolidone and so on. Specific examples of the alcohol / di-A + form include ethylene glycol di (meth) propanedion / Methyl) acrylate, neopentyl-alcohol bis (meth) acrylate, and bis (methyl) Triethyl _stst G acrylate — crisp, bis (A propylene 3148 Π 200403524 ethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. Specific examples of the trifunctional or higher-functional polyfunctional monomer include tris (fluorenyl) acrylic acid, tris (methyl) propionate, tris (fluorenyl) pentaerythritol acrylate, pentaerythritol tetra (meth) acrylate, penta (fluorene) Based) dipentaerythritol acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Among them, it is preferable to use a bifunctional monomer or a polyfunctional monomer having 3 or more functions.

(B) The content of the photox kappa monomer is generally 1 to 60 parts by mass based on the total amount of (A) the binder resin and (B) the photopolymerizable monomer in the colored photosensitive resin composition. , 5 to 50 parts by mass range is better. (B) The content of the photopolymerizable monomer is preferably in the range of from 1 to 60 parts by mass based on the foregoing, since the strength and smoothness of the pixel part tend to be good. Next, the (C) photopolymerization initiator contained in the colored photosensitive resin composition of the present invention contains (1) a polyfunctional thiol compound and (2) an acetophenone compound. Containing (1) a polyfunctional thiol compound and (2) an acetophenone compound, the obtained colored photosensitive resin composition has high sensitivity, and using the film formed therefrom, the strength and smoothness of the daylight portion All are good. In addition to adding a polyfunctional thiol compound and (2) an acetophenone compound, (3) a photopolymerization initiation adjuvant can 'make the obtained color sensory button tree into a higher sensitivity', so it can be added. It is preferable to improve the productivity of manufacturing a color phosphor film.

0) The polyfunctional compound contained in the colored photosensitive resin composition of the present invention is a compound containing two or more thiol groups in the molecule, and particularly, a polyfunctional aliphatic polyfunctional group having a thiol group of 3 or more months. A thiol compound is preferred. Examples of the aliphatic polyfunctional thiol compound used in the present invention include aliphatic dithiols such as dioxazyl alcohol, nonanethiol, and aralkylmeril, such as 4-phenylenedithiol, and the like. 3148Π 12 200403524 dithiol, butanediol dithioglycolate, diol dithiopropionate ethyl · Sf-monothioglycolic acid, butanediol dithiopropionate, trimethyl Propane trithioglycolic acid, Cedetate, Tetrathioglycolic acid vinegar, Three compounds of thioglycolic acid | Purpose, Trihydroxymethylpropane trithioglycolate, Hydroxypropyl propane trithiopropionic acid Esters, trihydroxy, pentaerythritol tetrathiopropionate, pentaerythryl ethyl trithiopropionate, and other polybasic thiopropionates, etc. Hydroxypropylpropane trithioglycolic acid and pentaerythritol tetrathiopropionate are preferred, especially pentaerythritol tetrathiopropionate and the like. Examples of the (2) acetophenone compound contained in the colored photosensitive resin composition of the present invention include the following compounds. (a) Diethyloxyacetamidine, monomethyl-2 ** methylphenylpropane-1-one, benzyldimethylketal, 1 [4 '(2-syl Ethoxy) phenyl] -2-methylpropanyl-ketone, -Cyclohexylphenylketone, 2-methylmethylthiophenyl) _2_morpholinopropane-one, 11 the same, Burning -1-hydrazone is similar to the present methyldimethylamino-1- (4-morpholinophenyl) butanyldiyl-2-methyl · 丨-[heart (bumethyl vinyl) benzyl Polymer and so on. A photopolymerization initiator that can be used in this field as well as the effect of the present invention can be used in combination, such as benzoin, 31481] 13 200403524 Benzene benzene, thioxanthone , S-Three Cultivation, Anthracene and other initiators. More specific examples include the following compounds, which may be used alone or in combination of two or more kinds. (b) Benzoin, Benzoin, Benzoin ether, Benzoin ether, Benzoin isopropyl ether, Benzoin isobutyl ether, etc. (c) Benzoinbenzene Benzobenzene, 〇-benzene Fluorenyl phenyl benzoate, 4-phenylbenzoate, sulfurized 4-benzyl-4'-fluorenyldiphenyl, 3,3 ', 4,4'-tetrakis (tertiary-butyl -Peroxy carboxyl) benzophenanthrene, 2,4,6-trimethylbenzylbenzene, etc. (d) thioxanthone 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4 -Diethylthioxanthone, 2,4-digasthioxanthone, 1-gas-4-propoxythioxanthone and the like. (e) s-Tricot 2,4 · bis (trichlorofluorenyl) -6- (4 · methoxyphenyl) -1,3,5-trioxane, 14 314811 200403524 2,4_bis ( Trichloromethyl) -6- (4-methoxynaphthylnaphthyl), 2,4-bis (trifluoromethyl) -6-piperidyl-I, 3,5-trisyl, 2.4-bis (tri Carbino) -6- (4-methoxyoxystyryl) -1,3,5-trioxo, 2.4-bis (trichloromethyl) -6- [2- (5-fluorenylfuran-2 -Yl) vinyl] -1,3,5-trioxine, 2.4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-sanko , 2,4-bis (dimethyl) -6- [2- (4-diethylamino-2-fluorenylphenyl) vinyl] -1,3,5-trioxane, 2.4-bis (Trichloromethyl) -6- [2- (3,4-Dioxophenyl) vinyl] -1,3,5-Sanken, etc. (f) Anthracene 9.10-Dioxanthracene , 2-ethyl-9,10-diethoxyanthracene, 9.10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. (g) Other oxidation-2,4, 6-trimethylphenylphenylphosphonium diphenylphosphine, 2,2'-bis (〇-chlorobenzyl) -4,4'-5,5'-tetraphenyl-1,2'-bisimidazole 10-butyl-2-acridone chloride, 2-ethylanthraquinone, phenylfluorenyl, 9, 1 0 -Phenanthrenequinone, 15 314811 200403524 camphorquinone, methyl phenylglyoxylate, titaniumcene compound, etc. It can also be used together with ^ U 4 in the initiator, and (3) photopolymerization bow | 瓠 adjuvant. Light The polymerization initiation adjuvant is preferably ^ 4 hydrazone female compound, and the aromatic amine compound is good. The photopolymerization initiation adjuvant is carved, and more specific examples include triethanolamine, fluorenyl-7 alcoholamine, and triisopropyl alcohol. Alcohol amines and other aliphatic faces # 人 ^ ~ B, Moon female compounds, 4-Dimethylaminophenyl benzoate

酉 Purpose, 4-dimethylamine benzoate ethyl • 曱 S, 4-dimethylamine benzoate isoamyl 4-dimethylamine benzoate 2-ethylpt — violent S, benzoate- 2-Difluorenylamine protects N, N-Difluorenyl-p-toluidine, 4,4, _bis (dimethylamine) phenylhydrazine (commonly known as helerone), 4,4, -bis (di Ethylamine) Aromatic amine compounds of stupid benzene, (C) p-adhesive resins and (B) photopolymers in photopolymerization initiators total a mass of 10CM. The content is generally up to 40 parts by mass of MdDO parts by mass; the content of benzene ethyl benzene compound is generally 0 "to 40 parts by mass, and the best is by mass. In addition (3) photopolymerization initiation auxiliary In this case, the content thereof is preferably 100 parts by mass with respect to (a) the binder resin and (B) the photopolymerizable monomer, and the mass is preferably from 0.001 to 40 parts by mass, and]] to 30 parts by mass. (]) More The total amount of functional thiol compounds and (2) acetophenone compounds, and (3) photopolymerization initiation adjuvants, if necessary, is generally from 0.2 to 50 parts by mass based on the aforementioned standard, and from 4 to 40 parts Better quality. (1) Multifunctional thiol compounds When the amount and (2) the amount of the acetic acid benzene compound are within the above-mentioned range, the coloring photosensitive resin composition has high sensitivity, and the intensity of the daylight portion made of the aforementioned colored photosensitive resin composition, first 3148] ]] 6 200403524 The smoothness of the surface of the above-mentioned f-prime tends to be good, so it is preferred. (1) the amount of the polyfunctional thiol compound and (2) the amount of the acetophenone compound plus (3) the light: synthetic The amount of triggering adjuvant is within the aforementioned range, or the total amount of (1H3) is within the former range ^ 'The sensitivity of the colored photosensitive resin composition obtained will be further improved by using the uranium coloring photosensitive resin composition (D) The coloring material is a general pigment, as long as it is an organic pigment or an inorganic pigment used in a general pigment-dispersed resist. The inorganic pigment may be exemplified. Examples are metal compounds such as metal oxides or metal complex salts, and specific examples thereof include oxides of metal such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, or composite metal oxidation. Specific examples of organic pigments include color (Colou 1 Index) (published by The Society of Colourists) compounds classified as pigments. Specific examples include compounds with the following colorant classification (C · I ·) numbers, but are not limited to This: CI · Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166 and 173; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 5], 59, 61, 64, 65 A 71; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166 , 168, 176, 177, 180, 192, 215, 216, 224, 242, and 254; CI · Pigment Purple 14, 19, 23, 29, 32, 33, 36, 37, and 38; C · I · Pigment Blue ί 5 (1 5: 3, 1 5 ·· 4, 1 5: 6 etc.), 2 1, 2 2, 28, 60, and 64; 3) 481] 17 200403524 CI · Pigment Green 7, i〇, 15, 25,% and 47; C.I. Pigment Grazing Color 2 8; CI Pigment Black 1 and 7 etc. These (D) coloring materials can be used singly or in combination of two or more kinds of μ4, and four or more kinds. (D) The content of krypton is generally about 5 to 60% by mass, and preferably 55% by mass to solids in the colored photosensitive resin composition.含量 The content of colored materials

When the color of the film is written in the range of… 2…, it is particularly suitable for the degree of heart injury, and the peeling of the non-daytime part during development is reduced, and it is not easy to generate residues, so it is preferable. (E) Solvents can be used in this field. Specific examples thereof include monoalcohol, ethylene glycol monoethyl ^ ^ ^ ^ Ridding ^ ^ 0 Zao ether, ethylene glycol soap propyl ether, ethylene glycol monobutane ether; … Alcohol, diethylene terephthalate, diethylene glycol, diethylene glycol, etc., diethylene glycol, etc. · 'methyl cellosolve, B ethyl — _ 7 ^ ethyl acetic acid, etc.) Alcohol, ethyl cellosolve, acetate bond, acetic acid vinegar; propylene glycol monomethyl acetate, acetic acid, propylene, S-early ether acetate, 氐 -σ 円, methoxy-early acetic acid, methoxyl Butyl acetate, methyl ethyl, fluorenyl acetate, ethylidene glycol, ethyl ether, and acetic acid; aromatic, fumes such as stupid, stupid, mesitylene, etc .; methyl ethyl steel, propane, fluorene, butane steel, cyclohexanone, etc. _ Class; ethanol, propanol, butanol, hexanol, cyclohexanol,? -Age ^%, Hexa 3-I, I-proton, Glycerol, and other alcohols; Ethyl 3-ethoxypropionate, Sheep: Methyl propionate and other sls; 7 'Butyrolactone and other cyclamates Purpose class and so on. This nettle (E) solvent is conceivable — alone or in combination of two or more. (E) The amount of the solvent containing * is beautiful. The coloring photosensitive resin composition ": 3 " is preferably 60 to 90 mass%, 70 to 85 mass 31481] 18 200403524%. The content of (E) / cereal is in the range of 60 to 90 parts by mass based on the aforementioned standard, and its coatability is good, so it is preferable. The coloring photosensitive resin composition of the present invention can also be mixed with a filler if necessary. And other polymer compounds, pigment dispersants, adhesion aids, antioxidants, ultraviolet absorbers, anticoagulant materials, etc. ()?) Specific examples of fillers include glass, silica, alumina, etc., etc. Specific examples of the fluorene molecular compound include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether ester, polyfluoroalkyl propionate, and the like. As a pigment cutter, a commercially available pigment dispersant can be used, and Examples include polysiloxane-based, fluorine-based, ester-based, cationic-based, anionic-based, non-ionic, amphoteric and other surfactants, each of which may be used alone or in combination of two or more kinds thereof. Examples of the aforementioned surfactants Examples include polyethylene oxide alkyl ethers, poly Ethyloxybenzylbenzyl, polyethylene glycol di-g, sorbitol fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethane, polyethyleneimine, etc., and products KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), pr.ducts Co., Ltd. X, Megafacs (manufactured by Daikimoto Ink Chemical Industry Co., Ltd.), Frond (Sumitomo 3M Co., Ltd.) (Manufactured by the company), AsahiGuard, Surfon (the above is manufactured by Asahi Glass Co., Ltd.), 8011114 mouth 3 (861 ^ 03 company), EFKA (manufactured by EFKA CHEMICALS), PB821 (Ajino (Manufactured by E. Co., Ltd.), etc. Specific examples of adhesion aids include ethylenetrimethoxysilane, ethylenetriethoxysilane, ethylenetri (2-methoxyethoxy) silane, N- ( 2-Aminoethyl) -3-aminopropylfluorenyltrimethoxysilane, N- (2-aminoethyl) _3_amine314811 19 200403524 propyldimethoxysilane, 3_ ^ ^ ^ Trisylpropyltriethoxysilane, 3-glycidylpropylpropyltrimethoxysilane, imp 1 propylpropylpropylpropyldimethoxysilane :) Element, 2- (3,4-epoxycyclohexylfluorenyl) ethyltrimethoxysilane, 3-chloropropyl Acrylic methoxypropyltrimethoxy,% Hydroxythiopropyltrimethoxy # Temple 0 Antioxidants Specific | With Λ like 2,2 _thiobis (4 · fluorenyl · 6-section three

Butyl group), 1,6-di-tertiary group + methyl group, etc. Specific examples of the ultraviolet absorber include 2? Third m-thruyl group (5-fluorenylphenyl) · 5 · chlorobenzotrisalyl, methoxybenzylbenzene and the like. Specific examples of the anticoagulant include sodium polyacrylate. The colored photosensitive resin composition of the present invention can be adjusted in the following manner, for example. That is, the rhenium coloring material is first mixed with the rhenium solvent, and then the average particle diameter of the material is ground with beads. .2 ... to the extent. At this time, if necessary; the pigment dispersant is used, and the rhenium-bonded grease can be fully or partially blended. 〇Kind of the dispersion (pulverizing main agent), and then add the rest of the ⑷ binder Shuyuezhi purpose, (B) photopolymerization monomer and (c) photopolymerization initiator, you can also add ^ For other ingredients used, if necessary, additional solvent is added to a predetermined concentration to obtain the intended colored photosensitive resin composition. The prepared colored photosensitive resin composition of the present invention can be applied to a substrate, for example, as follows, and cured by light and developed to form a black matrix or a colored image. That is, the composition is spin-coated on a substrate (generally a glass plate), and then the solvent is removed by heating and drying to obtain a smooth film. At this time, the thickness of the main film is about 1 to 3 " m. The obtained coating film can be used for further protection, such as 20 1 丨 48] 1 200403524, the black matrix or circle to form the target n. The early image is irradiated with ultraviolet light through a negative mask. On this day, I ’d better use a double-sided photomask to avoid single-handedly to Hanzhi Temple device, so that the illuminated part can evenly illuminate the parallel light, and come to 11 ^ # 刀 正月 and the uniform photomask can be aligned with the substrate The correct position w is then followed by a dilute alkali solution pile to form ° at night, contact the hardened coating film, so that the day,

The light part dissolves and visualizes, and you can be surprised at the black matrix or image that AA serves the purpose. After shame, you can add 150 ℃ according to its requirements. "" Member Kawagawa 230 C, after 10 to 60 minutes 々 hardening (post-heating). 1 The development of the image after light irradiation to form a pattern The liquid is generally an aqueous solution containing a test compound and a surfactant. The basic compound can be used as an inorganic or organic basic compound. Examples of inorganic basic compounds can be used in & " Examples of such a version include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, dichloro sodium phosphate, extra-scale lice monoammonium, ammonium dihydrogen diammonium, dihydrogen carbamic acid, sodium oxalate, stone The name of the mountain acid is potassium, sodium osmium, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia, etc. Specific examples of organic test compounds include tetramethyl hydroxide, nitrogen oxidation- 2-Ethylethyltriazine, mesopine _ τo early T bismuth, monomethylammonium, trimethylammonium, monoethylammonium, diethylammonium, triethylsulfonium, monoisopropylammonium, diisopropylammonium, ethanol Bond, etc. These inorganic or organic basic compounds can be used individually or in combination of two or more kinds. The preferable concentration of the basic compound in the developing solution is in the range of 0.001 to 0% by mass, and 0.03 to 5 masses. / More preferably. The surfactant in the alkaline developing solution can be any non-ionic interfacial activity. Agents, anionic surfactants or cationic surfactants. Specific examples of nonionic surfactants include polyethylene oxide scales, polyethylene oxide based aromatic test, polyethylene oxide based aromatic test. Basal scale, and other 314811 2] 200403524% ethoxylated ethylene derivative, treatment animal 7, knee / strict # 丁 玍 物 & 虱 ethylene / 虱 崁 propylene copolymer, mountain xylose Sf · 3f fatty acid, Flat Calcium ^ Japanese sorbitan fatty acid ester of sorbitan, poly% milk ethylene sorbitan fatty acid vinegar, glycerol fatty acid vinegar, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. Anionic Specific examples of the surfactant include higher alcohols such as sodium lauryl sulfate and sodium oleyl sulfate, sodium sulfates such as sodium lauryl sulfate and sodium sulfate, and twelve-base benzene. Continued acid, twelve

Alkyl aryl sulfonates such as sodium alkyl naphthalene sulfonate. Specific examples of the cationic surfactant include amine salts such as stearic acid, dodecyltrimethyl chloride and the like, or fourth-order recording. -These surfactants can be used individually or in combination. However, the concentration of the surfactant in the experimental imaging solution on A,... Is generally in the range of 0.1% by mass, and more preferably 0.05 to 8% by mass. Better quality of 0.001 to 5 ❹ / 〇 and 4 乂 The dry coating film obtained by coating and drying throwing the Benlemin colored photosensitive resin composition is formed into a pattern and developed by light irradiation; after that, you can The two colors of the coloring material in the coloring photosensitive resin composition are obtained: phase pixels or black matrices, and the color filter film can be obtained through repeated operations of the number of colors required for the color light-transmitting film. That is, a. ^, ^ ^ ^ ^ I color transition light film is arranged on the ^ ... color matrix and three primary color pixels of red, green and blue, so the photosensitive resin is colored with the present invention containing a coloring material of equivalent color If the composition is operated as described above, the black matrix or day pigment of the color can be obtained, and the other colors are also similar to the coloring material of the coloring material of the present invention. The photosensitivity is 314811 22 200403524. The resin composition is as above, that is, black. The matrix and the three primary colors are arranged on a substrate. @Times, when the daylight and black matrix are arranged on the substrate, and then the colored photosensitive resin composition of other colors needs to be processed, the substrate with the pixel and black matrix disposed thereon, and then coated and dried. : The coloring photosensitive resin composition # of the heart, and the color field is generally not yet configured. ":, The color matrix is illuminated by the light to form a map, and the lighted part can be configured with pixels of other colors and Black matrix. When #, any one or three of the day element, the matrix of the work of the present invention and-疋 ..., the colored photosensitive resin composition can be adapted. In addition, the black matrix of the light-shielding layer ::: such as chromium In this case, it is of course unnecessary to form a black matrix with the colored photosensitive resin composition of this invention. 丄 In addition, the color made of the colored photosensitive resin composition of the present invention: the light film surface The difference in the thickness of the inner film is small. For example, in the case of a film, the difference in the thickness of the in-plane film can be square,, or less than 5 # m, or even 0.05 # m. Therefore, 'the color filter obtained by the The film has excellent smoothness and translucency 丨 born in combination The color liquid crystal display device can be made into a liquid crystal panel of excellent quality. ~, Leather The embodiment of the present invention has been described above, but the embodiment of the present invention disclosed above is merely an example, and the scope of the present invention is not limited. Limitation: The scope of the present invention is as shown in the scope of the patent application, and includes the meanings of 4 items in the 4 scope records of AND, and all changes within the scope. ~ P will be explained in more detail with male examples. The present invention, but the present invention is not limited by these examples. In the examples, the content and the amount used are% and parts. When there is no special? Tomorrow refers to the quality standard. 314811 23 ZUU4UJ ^ 24 (Example l ) Among the ingredients listed in Table 1, Hong Ba Ye Qi. Before taking each pigment and ester pigment: the total amount of two agents and a part of the amount of solvent propylene glycol monomethyl called B followed by 5, and then charged by a ball mill. Disperse the pigment in parts, and then add j: a little bit containing the rest of the propylene glycol monomethyl ether acetate to obtain a photosensitive resin composition solution. (Table 1) (D) 5.30 parts 2.04 parts 4.08 parts

C · I · Pigment Green 3 6 Yellow 150 (A) Adhesive resin methyl phenyl acrylate / fluorenyl acrylic copolymer (bei composition ratio 80/20, 35,000 styrene equivalent) (B) Photopolymerizability Monomer 2.04 parts pentaerythritol hexa (fluorenyl) acrylate (C) photopolymerization initiator benzyl-2-monomethylaminomorpholinophenyl) _butanone 1.11 parts (IRGACURE 369 manufactured by Clba Geigy) Λ \ ✓ '«τ, > KAYARAD DPHA manufactured by Donghua Pharmaceutical Co., Ltd.) 4,4, bis (ν, N-diethylamino) _benzidine (EAB manufactured by Hodogaya Chemical Co., Ltd.- F) Quaternary tetra-S-tetrathiopropionate vinegar 0.28 parts 0.85 parts 1-hole anti-organic chemical worker (童, 、, (E) solvent propylene glycol monoethyl ether acetate 82.00 parts (F) additive pigment dispersant (Polyester) 2.08 parts Sumi-spoxy ESCN-195XL 〇41 parts 1_ (made by Sumitomo Chemical Industry Co., Ltd.) 24 3148Π 200403524 The total amount of pigment and pigment in each of the above components is propylene glycol monomethyl ether acetate The knife " 丨 is then mixed with the solvent / Ichinoseki and the total pigment dispersant 20 Berry / 0 machine a, and then the ball mill is fully dispersed pigment glycol monomethyl ether B The remaining ingredients of the ester are mixed: the composition containing the rest of the propylene is added. ~ The color-sensitive photosensitive tree is then washed on a 2 忖 square # 7059 panel made by Corning Corporation, and sequentially washed with neutral detergent, water and alcohol. And dried. The glass plate was then spin-coated with the photosensitive resin composition (Table 丨) prepared as above, and then pre-heated in a dust-free heating box for 3 minutes with a lott. After cooling, the coating was coated with a resist Reagent substrate and quartz glass photomask (with light transmittance! Step change mode in the range of 100% and line / space mode in the range of 1 micrometer to 50 micrometers) The interval i〇〇 # 'under atmospheric pressure with Ushio motor The high-pressure mining lamp manufactured by the company was irradiated with light at 40 mJ / cm. After that, the above coating film was immersed at room temperature with 0 ·] 2 ° /. Non-ionic surfactant and 0.4% The image was developed in a potassium hydroxide aqueous imaging solution to a predetermined time, and washed with water and then heated at 220 ° C for 30 minutes. At the same time, the surface of the substrate was observed after each pre-heating, after development and after heating 'The results of the following items are shown in Tables 2 and 3. (Example 2) Example 2- Fluorenyl-2-diamidino-morpholinophenyl) · Butanone changed to 2-methyl-2-morpholino (4-thiofluorenylphenyl) propane- ^ one (Ciba-Geigy System, 'IRGACURE 907 ,,), the other operation is the same as in Example 1. (Example 3) 0.41 parts of Sumi-epoxy ESCN · 195XL in Example 2 was changed to 25 314811 200403524 to the adhesive polymer in Table 1, and the other operations were the same as in Example 2. (Example 4) 7.34 parts of pigments in Example 2 were changed to 6.10 parts of C.I. pigment red 254, 1.24 parts of C.I. pigment red 177, and the other operations were the same as in Example 2. (Example 5)

7.34 parts of the pigment in Example 2 was changed to 6.24 parts of the C.I. pigment blue 15: 6, 1.10 parts of the C.I. pigment purple 23, and the other operations were the same as in Example 2. (Comparative Example 1) 0.65 parts of pentaerythritol tetrathiopropionate in Example 1 was changed to 0.65 parts of 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-trioxine (Made by Nihon Siber Hegner KK ,, Sangen-PP ,, etc.), and the other operation is the same as that of Example 1. (Comparative Example 2) In Comparative Example 1, 1.11 parts of 2-benzyl-2-diamidino-1- (4-morpholinophenyl) butanone was changed to 1.1 1.1 parts of 2-fluorenyl- 2-morpholino (4-thiofluorenylphenyl) propanone, and 0.65 parts of 2,4-bis (trichlorofluorenyl) -6-piperyl-1,3,5-trioxane changed to 0.65 Parts of 2-hydrothiobenzothiazole were the same as in Example 1. 26 3148Π 200403524 (Table 2) Example 1 Example 2 Example 3 Example 4 Example 5 Surface Roughness * 1 No. 0 〇〇〇〇〇〇〇〇 7 〇 〇〇〇〇〇〇sensitivity * 2 (mJ / cm2 ) 20 100 100 20 160 Brightness * 3 55.8 55.7 55.8 18.8 5.0 Film thickness * 4 (βm) 1.7 1.8 1.7 1.7 1.8 Pattern shape * 5 〇— 〇〇〇〇 Comprehensive evaluation 〇〇〇〇〇〇 (Table 3)

Comparative example 1 Comparative example 2 Surface roughness * 1 0th 〇〇7th 〇〇sensitivity * 2 (mJ / cm2) 80 > 400 brightness * 3 54.6 55.6 film thickness * (β m) 1.7 1.7 pattern shape * 5 〇Comprehensive evaluation of no day element ΔX Note in the table * 1: Visually observe the surface of the coating film after preheating at 23 t / day 0 and day 7. (0: No difference. △: Slightly worse. X: Poor.) + 2: The minimum amount of light necessary after development to form a pattern with no rough surface. + 3: Measure the C light source in the pixel part with a micro-spectrophotometric device, and expose the CIE chromaticity (X, y, Y) of the field at 2 degrees. The larger the Y value in the same chromaticity (x, y), the higher the brightness. Chroma adjustments are Green (0.285, 0.5 89), Red (0.650, 0.325), and Blue (0.141, 0.060). 27 31481] 200403524 4: Probe-type film thickness meter (Dektak3 type manufactured by ULVAC). After the heating, the film thickness of the day element was measured. Sensitivity, brightness and film thickness were measured at 23 ° C / 0th day after blending. 5. Observe the cross section of the pixel with a scanning electron microscope after imaging and post-heating (22o t χ minutes) with a light amount of 200mj / cm3. (Non-inverted cone: 0, inverted cone: X) Υ: The substrate was immersed in various solvents at 23 ° C for 30 minutes at a light intensity of 200 mJ / cm3 and the development process was omitted. The color change (AEab *) and (ΔΕΑ * <3; 0, 3; X) before and after the dipping were measured, and the adhesion of the coating film after the dipping was measured. Adhesiveness was determined by dividing the blade into 100 lmmx lmm cells, and then peeling off with an adhesive tape to calculate the number of cells remaining on the substrate. :: Illuminated at 200 mJ / cm3 with light irradiation, omit the development process, and heat the substrate at 23 (TC for 120 minutes. Determine the color before and after the test (AEab) (AEab * <3; 0, △ εα * -3; X). From Tables 2 and 3, it can be seen that the examples containing the photopolymerization initiator of the present invention] to 5 can maintain high sensitivity, high brightness, and preservation of An Yisheng on average. Comparison of the photopolymerization initiator containing (c) of the present invention ^ [2] Although the color sensitive photosensitive silk scarf has a high poem colored photosensitive resin composition, among them, there are those with poor brightness and storage stability. The resin composition has excellent sensitivity and storage stability even if it contains a high-concentration coloring material. Therefore, the surface smoothness of the coloring pixels obtained by coloring the photosensitive resin composition of the present invention is 3148Π 28 200403524, and the shape of the pattern And brightness are excellent. Therefore, when a color filter film is prepared by using the coloring photosensitive resin composition of the present invention as a pigment dispersion resist, a color filter film with high productivity and high quality can be obtained. 29 314811

Claims (1)

200403524 The scope of patent application: L 弁, two-color t-light resin composition, which contains ⑷ binder grease, (B) ♦ D-type early body, (c) photopolymerization initiator, and coloring solvent. Zhu Han stated that the color-sensitive photosensitive resin composition of the first dry patent of the patent, in which (A) the binder resin is a compound containing a monomer derived from an unsaturated carboxylic acid. Commitment 3. If you apply for item 1 or 2 of the scope of the patent application, Piangu &# Feiyu 2 shall be composed of a color-sensing anterior resin, /, and (A) the binder resin is derived from unsaturated Groups of carboxylic acids and polymers derived from (meth) acrylic compounds. ° 4 · If the scope of patent application is 篦 1. The coloring resin composition according to any one of items s1 to s3, wherein (1) polyguan Λ ~ () xi yueb is a compound of aliphatic polyfunctional thiol Compound person. 5. The coloring photosensitive resin composition according to any one of items i to 4 of the scope of application for a patent, wherein (C) the photopolymerization initiator is another one containing (3) a photopolymerization initiation adjuvant. &-Method for forming a pattern 'is applying the colored photosensitive resin composition of items in the patent application [item] to $ 1 on the substrate i, and then removing the volatility on the coated colored photosensitive resin composition layer The layer is irradiated with a layer on which the volatile component is removed from the colored photosensitive resin composition layer by two masks to make a pattern develop. 1. The color shirt filter is a pattern formed by the method including the item 6 of the patent application scope. / 7 3148Π 30 200403524 8. —A liquid crystal display device, in which a color filter film as set forth in the scope of patent application No. 7 is installed. 31 314811 200403524 指定 Designated Representative Picture: There is no picture in this case. (I) The designated representative map in this case is: (). (2) Brief description of the representative symbols of the components in this representative diagram: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: There is no chemical formula in this case. 5 3148Π