TW200301401A - Coloured photosensitive resin composition - Google Patents

Abstract

The present invention provides a coloured photosensitive resin composition containing (A) pigment, (B) binder polymer, c photopolymerized compound, (D) photopolymerization initiator, (E) pigment dispersing agent, and (F) solvent. The said coloured photosensitive resin composition can be coated on the surface of a glass sheet by spin coating , and heated at 100 DEG C for 3minutes to evaporate the volatile substance to form a film (thickness 1.6 μ m). When the film thus obtained was dipped into the alkaline solution(containin 0.05% potassium hydroxide, 0.2% butylnaphethalene sodium sulfonate by mass ratio ) of a mass 2500 times the film, and stirred the solution for 80 seconds at 300rpm with stirrer, or dipped into the solvent of a mass 2500 times the film, and stirred the solution for 80 seconds at 300rpm with stirrer, 90% particle size is smaller than 0.5 μ m and the maximal size is smaller than 1.0 μ m, as determined by light scattering method. The present invention also provides a colour pattern forming method by using the said coloured photosensitive resin composition, and a colour filter producing method by using the colour pattern.

Description

20030K01 V. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to a colored photosensitive resin composition. [Prior art] A colored photosensitive resin composition (c ο 1 〇uredresist) is a colored photosensitive resin composition (resist) containing a colorant, and it is known to contain (A) a colorant and (B) an adhesive Polymers, (C) photopolymerizable compounds, and (D) photoinitiated polymerization initiators are, for example, materials useful for forming a coloring pattern constituting a color filter (c ο 1 urfi 11 er). Here, the color filter 1 is, for example, an optical element for colorizing a display image assembled in a color liquid crystal display device, or an optical element for obtaining a color image incorporated in a color solid-state imaging element. The coloring pattern 2 is a color pixel such as a red pixel, a green pixel, or a blue pixel. Such a coloring pattern 2 is usually formed on a substrate 3 to form a color filter 1 (as shown in FIG. 1). ). A color pixel is a colored transparent layer, and the light passing through this layer will present the color of each color pixel. As a method for forming a coloring pattern 2 using such a coloring photosensitive resin composition, a layer made of the coloring photosensitive resin composition (hereinafter, also referred to as a coloring photosensitive resin composition layer) formed on the substrate 3 is known. 4 (as shown in Fig. 2 (a)), after exposure to light 6 (as shown in Fig. 2 (b)), the method of developing (as shown in Fig. 2 (c)). After the exposure, in the colored photosensitive resin composition layer 4, an unirradiated area 41 which is not irradiated with light 6 and an irradiated area 4 2 which is irradiated with light are generated (see FIG. 2 (b)). The unirradiated area 4 will be removed during subsequent imaging (see Figure 2 (c)). On the other hand, the irradiated area 42 remains in the subsequent development and forms the colored pattern 2. So, coloring pattern 2

314256.ptd Page 7 V. Description of the invention (2) It is preferable that the cross-sectional shape is that the width of the substrate side (W) is wider than the width of the upper side (W!). Figure), or the width W on the substrate 3 side is a rectangular shape that is equal to the width on the upper side (W) (Figure 5 (b)). In the method for forming such a coloring pattern, in order to form a coloring pattern in a short irradiation time, it is preferable to irradiate a light irradiated with a small amount of light in the irradiation field. Therefore, as the colored photosensitive resin composition, a highly sensitive one which can sufficiently form a colored pattern even with a small amount of light irradiation is generally used. Such a highly sensitive coloring photosensitive resin composition is preferably one capable of forming a desired coloring pattern even when the amount of light is excessively irradiated. However, the conventional high-sensitivity colored photosensitive resin composition is that if the amount of light is increased, the cross-sectional shape of the colored pattern 2 is likely to be wider on the substrate 3 side (W) than on the upper side. (W 0 is a narrow reverse tapered shape (as shown in Figure 5 (c)). Furthermore, when developing, the coating film surface is very hard, and the coating film does not dissolve in the developing solution and peels off. Cracks (fragments) of the cross section are generated due to poor adhesion, and there is a problem of uneven spots caused by the cracks of the cross section after the color filter is formed. [Abstract] The object of the present invention is to provide a high sensitivity At the same time, when developing &, a coloring photosensitive resin composition capable of forming a stomach-shaped pattern with a cross-sectional shape that is tapered or rectangular in shape without cracks, a method for forming a coloring pattern using the composition, and A method for manufacturing a color filter. Therefore, as a result of diligent research, the present inventors found that if a coating film is immersed in an aqueous solution or solution K under specific conditions, the particle size distribution of the particles in the aqueous solution or solvent is measured, and the accumulation thereof 9 0% In a specific maximum particle size diameter and

314256.ptd Page 8 20030K01 V. Description of Invention (3) The colored photosensitive resin composition in the range of (3) can solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention relates to the following inventions. [1] A colored photosensitive resin composition containing (A) pigment, (B) adhesive polymer, (C) photopolymerizable compound, (D) photoinitiated polymerization initiator, and (E) pigment dispersion The agent and the (F) solvent are characterized in that the colored photosensitive resin composition is on the surface of a glass substrate, and the colored photosensitive resin composition is applied by a spin coating method at 100 ° C. Dry for 3 minutes to volatilize the volatiles to form a film (film thickness is 1.6 / m), and immerse the obtained film in an aqueous alkaline solution of 2,500 times the mass of the film (each containing hydroxide by mass fraction) Potassium 0.05%, sodium butylnaphthalenesulfonate 0.2% in water), the solution was stirred at 30 Or pm for 80 seconds using a stirrer, and the particle content in the aqueous solution was measured using a light scattering method The particle size distribution has a cumulative 90% particle size of 0.5 // m or less and a maximum particle size of 1.0 / in or less. [2] —A colored photosensitive resin composition containing (A) pigment, (B) adhesive polymer, (C) photopolymerizable compound, (D) photoinitiated polymerization initiator, and (E) pigment The dispersant and the (F) solvent are characterized in that the colored photosensitive resin composition is on the surface of a glass substrate, and the colored photosensitive resin composition is coated by a spin coating method at 100 ° C. Dry for 3 minutes to volatilize the volatiles to form a film [thickness of 1.6 mm], immerse the obtained film in the solvent of 2 500 mass times of the film, and use a stirrer to dissolve the solvent at 3 0 r PM was stirred for 80 seconds, and the cumulative particle size distribution of the coating film components contained in the solution was measured using a light scattering method when the cumulative 90% particle size was 0 · 5 // m or less, and the maximum particle size was 1. 0 // m or less.

314256.ptd Page 9 \ Fifth, description of the invention (4) [3] [1] or [2] The colored photosensitive resin composition described in which the solid content of the colored photosensitive resin composition is determined by mass fraction In total, (A) the pigment content i is 15% to 50%, (B) the content of the adhesive polymer is 20% to 55%, and the content of (C) the photopolymerizable compound is 1 01 至 1 质量 份。 0% or more and 45% or less, (D) content of the photoinitiated polymerization initiator is 3% or more and 20% or less, and (A) pigment 1 part by mass, (E) pigment dispersant is 0.01 to 1 parts by mass . [4] The colored photosensitive resin composition according to any one of [1] to [3], wherein (D) the photoinitiated polymerization initiator is an acetophenone-based photoinitiated polymerization initiator. The coloring photosensitive resin composition according to any one of [5 感光 1] to [4], wherein (E) the pigment dispersant is a polydacrylic dispersant, an ester-based dispersant, or an ethyl aminoacetate Department of dispersant. [6] A method for forming a coloring pattern, which is characterized in that: the color photosensitive resin composition described in any one of [1] to [5] is coated on a substrate, and a coating film is formed after drying, The layer is developed after exposure. [7] A method for manufacturing a color filter, which is characterized in that the method for forming a coloring pattern described in [6] is repeatedly performed on a desired color. [8] The method for producing a color filter according to [7], wherein the desired colors are red, green & and blue. [f% method] The colored photosensitive resin composition of the present invention (hereinafter, simply referred to as the colored photosensitive resin composition) contains (A) a pigment, (B) an adhesive polymer, (C) a photopolymerizable compound, (D) a photoinitiated polymerization initiator, (E) a pigment dispersant, and (F) a solvent.

3] 4256.ptd Page 10 20030K01 V. Description of the invention (5) (A) The pigment may be an organic organic pigment or an inorganic inorganic pigment. Inorganic pigments include: metal oxides, metal complex salts, inorganic salts of barium sulfate (primary pigments), and the like. Among these pigments, organic pigments are very useful. As for the organic pigment, specifically, the pigment classified as a pigment (P i g m e n t) in the Coloun Index (published by The Society of Dyers and Co ll oi s t s). Specifically, CI Pigment Yellow 1, CI Pigment Yellow 3, C.I. Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17 , CI Pigment Yellow 20, CI Pigment Yellow 2 4, C. I. Pigment Yellow 3, C. I. Pigment Yellow 5 3, CI Pigment Yellow 8 3, C · I · Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 1 0 9, C. I. Pigment Yellow 1 1 0, CI Pigment Yellow 1 1 7, C. I. Pigment Yellow 1 2 5, CI Pigment Yellow 128, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 1 3 9, C. I. Pigment Yellow 1 4 7, C. I. Pigment Yellow 1 4 8, C. I. Pigment Yellow 1 50, C. I. Pigment Yellow 1 5 3, C I. Pigment Yellow 1 5 4, CI Pigment Yellow 166, CI Pigment Yellow 173 and other yellow pigments, C. I. Pigment Orange 1 3, CI Pigment Orange 3 1, C. I. Pigment Orange 3 6, CI Pigment Orange 3 8. C. I. Pigment Orange 4 0, CI Pigment Orange 4 2. C. K Pigment Orange 4 3. C. I. Pigment Orange 5 1. CI Pigment Orange 5 5. CI Pigment Orange 5 9. CI Pigment Orange 6. 1. C. I. Pigment Orange 6 4. C. I. Pigment Orange 6 5. C. I. Pigment Orange 71. CI Color Orange 73 and other orange pigments, C. I. Pigment Red 9, CI Pigment Red 9 7, CI Pigment Red 105, C. I. Pigment Red 1 2 2, C. I. Pigment Red 1 2 3, C. I. Pigment Red 1 4 4, C. I. Pigment Red 1 4 9, CI Pigment Red 1 6 6, C. I. Pigment Red 1 6 8, CI Pigment Red 1 »

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314256.ptd Page 11 20030K01 'V. Description of the Invention (6) 1 7 6, C. I. Pigment Red 1 7 7, C · I · Pigment Red 1 8 0, C. I. Pigment Red 1 9 2, 1.1 .Pigment Red 215, (: .1.Pigment Red 216, (: .1.Pigment Red 2 2 4 ,, (: .1 · Pigment Red 2 4 2, CI Pigment Red 2 5 4, C. I.Pigment Red 2 6 4. CI Pigment Red 2 6 5 and other red pigments, CI Pigment Blue 1 5. CI Pigment Blue 15: 3, CI Pigment Blue 15: M, C. I. Pigment Blue 1 5: 6, CI Pigment Blue 6 Blue pigments such as 0, CI pigment violet 1, CI pigment violet 1 9, CI pigment violet 2 3, CI pigment violet 29, CI pigment violet 32, CI pigment violet 36, CI pigment violet 38 and other purple pigments, _ CI pigment Green pigments such as green 7, CI pigment green 36, brown pigments such as CI pigment brown 2, 3, CI pigment brown 25, etc. These pigments can be used individually or in combination of two or more. These organic pigments, According to need, rosin treatment, surface treatment using pigment derivatives introduced with acidic or experimental groups, surface treatment of pigments using polymer compounds, etc. may be used, and sulfur may be used. The micronization treatment such as the acid microparticle method, or the washing treatment using an organic solvent or water to remove impurities. The particle size of these organic pigments is about 10 nm to 150 nm. The volatile component I contained in the colored photosensitive resin composition is a solid content (hereinafter referred to as the solid content) after volatilization, which is usually 5% or more in terms of mass fraction, which can form a sufficiently colored coloring pattern is: 15%, more preferably 20% or more, particularly preferably 30% or more, usually 60% or less, and preferably 45% or less. In addition, when an organic pigment is used, the amount of the organic pigment used The total amount of pigment is usually 50% by mass fraction.

314256.ptd Page 12 20030K01 5. In the description of the invention (7), it is preferably more than 55%, and the total amount of pigment (100%) is organic pigment. (B) As the adhesive polymer, for example, a copolymer of (fluorenyl) acrylic acid and (fluorenyl) fluorenyl acrylate can be used, and the content of the (fluorenyl) acrylic acid structural unit is 25% or more in mole fractions4 0% or less, an acid value of 90 or more and 160 or less, and a weight average molecular weight (Mw) of 2 or more and 4 or less and 0 or less are more suitable. The acid value of the adhesive polymer can be obtained by dissolving 1 g of the adhesive polymer in a mixed solvent of 10 cm and 40 cm in acetone, and then measuring it with Pt. Determine it. The weight average molecular weight (Mw) is based on polystyrene as a reference value using Gel Permeation Chromatography (GPC). The content of the adhesive polymer in the colored photosensitive resin composition is usually 5% or more, preferably 20% or more, and usually 90% or less, and preferably 5 5 of the solid content. % Or less. (C) A photopolymerizable compound is a compound capable of polymerizing by living radicals, acids, and the like generated from a photo-initiated polymerization initiator by light irradiation, and examples thereof include polymerizable carbon-carbon unsaturated bonds. Compounds etc. These photopolymerizable compounds are preferably polyfunctional polymer compounds having four or more functions. Examples of polyfunctional photopolymerizable compounds having four or more functions include pentaerythritol tetrapropionate, pentaerythritol tetra-fluorenyl acrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta-fluorenyl acrylate, dipentaerythritol Hexa-acrylate, dipentaerythritol hexa-fluorenyl acrylic acid, etc. The content of the photopolymerizable compound in the colored photosensitive resin composition,

314256.ptd Page 13. V. Description of the invention (8) The mass fraction of the solid component is usually 1% to 60%, preferably '3% to 50%, particularly preferably 10%. Above 4 5%. (D) Examples of the photo-initiated polymerization initiator include an active radical generator capable of generating active radicals upon irradiation with light, an acid generator which generates an acid, and the like. Examples of the living radical generator include: acetamidine-based photoinitiated polymerization initiator, benzoin-based photoinitiated polymerization initiator, Sancang-based photoinitiated polymerization initiator, and benzofluorene-based photoinitiated polymerization initiation Agent. Among these, an acetophenone-based photoinitiated polymerization initiator is preferable, and 2-fluorenyl-2-morpholinyl-1- (4-fluorenylthiophenyl) propane-1-one is more preferable. As a pretty ingredient. Acetylbenzene-based photo-initiated polymerization initiators may be exemplified by 2-fluorenyl-2-morpholinyl-1- (4-fluorenylthiophenyl) propane-1-one, diethoxyacetamidine, 2-hydroxy-2-methyl-1 -phenylpropane-1 -one, fluorenyldifluorenyl ketal, 2-meryl-2-methyl-1- [4- (2-hydroxyethoxy (Phenyl) phenyl] propane-1-one, hydroxycyclohexylphenylfluorenone, 2-benzyl-2 -difluorenylamine-1-(4-morpholinyl) butane-1-one, 2- An oligomer of hydroxy-2-fluorenyl-1- [4- (bumethylvinyl) phenyl] propan-1-one and the like. Benzoin photoinitiated polymerization initiators can be exemplified: benzoin, benzoin ethyl ether S, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl triphenylene Initiating polymerization initiators can be exemplified: 2,4-bis (trifluoromethyl-6- (4-fluorenoxyphenyl) -1,3,5-trigon, 2, 4-bis (trifluorophenyl) ) -6- (4-Methoxynaphthyl) -1,3,5-trioxo, 2,4-bis (trichlorofluorenyl) -6-piperyl-1,3,5-trioxo, 2,4-bis (trichloromethyl) -6- (4- 曱

314256.ptd Page 14 20030K01 V. Description of the invention (9) Oxystyryl) -1,3, 5-Sangen, 2, 4-bis (trifluorofluorenyl) -6-[2-(5- Fluorenylfuran-2-yl) ethynyl-1,3,5-trioxo, 2,4-bis (trifluorofluorenyl) -6- [2- (furan-2-yl) ethynyl]- 1,3,5-Sangen, 2,4-bis (trichlorofluorenyl) -6- [2- (4-diethylamino-2 -fluorenylphenyl) ethynyl] -1,3 , 5-Sangen, 2, 4-bis (trifluorofluorenyl) -6- [2- (3, 4-dioxophenyl) ethynyl] -1,3,5-trioxine, etc. Phenylbenzene benzene-based photo-initiated polymerization initiators can be exemplified by: benzophenone, methyl o-phenylhydrazone benzoate, 4-phenylphenylfluorenyl, 4-phenylfluorenyl-4'-fluorenyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) benzene, benzene, 2,4,6-trimethylbenzoic acid, etc. Examples of the active radical generator include: 2,4,6-trimethylphenylphosphonium diphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'- Tetraphenyl-1,2 dibiimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzodiazone, 9,10-phenanthrene, aromatic ring dilute titanium compounds and the like. Examples of the acid generator include 4-hydroxyphenyldimethylfluorene p-fluorenylphenylsulfonate, 4-hydroxyphenyldifluorenylfluorene hexafluoroantimonate, and 4-ethoxyloxyphenyldifluorene. Phenylpyrene p-toluenesulfonate, 4-Ethyloxyphenyl · methyl · ▼ ylpyrene hexafluoroantimonate, triphenylpyrene p-toluenesulfonate, triphenylpyrene hexafluoroantimonate S purpose, sulfonium salts such as diphenyl iodopyrene p-toluene sulfonate, diphenyl iodohydrazine hexafluoroantimonate, or nitrofluorenyl tosylate, benzoin Class, etc. ^ In addition, among the above compounds as active radical generators, there are also compounds that generate acids at the same time as the active radical generators, for example, active radical generators such as trioxin photo-initiated polymerization initiators, and can also be used as acid generators. use.

314256.ptd page 15. 5. Description of the invention (10) These photo-initiated polymerization initiators can be used alone or in combination of two or more. The content of the photoinitiated polymerization initiator in the colored photosensitive resin composition is usually 1% or more and 25% or less, preferably 3% or more and 20% or less, based on the mass fraction of the solid content. The colored photosensitive resin composition may contain a photo-initiated polymerization initiator. Photoinitiated polymerization initiators are compounds that are used in combination with photoinitiated polymerization initiators to promote the polymerization of photopolymerizable compounds. The photo-initiated polymerization initiation aid may be exemplified by a thiononone-based photo-initiated polymerization initiation aid. Examples of thia allanone-based photoinitiated polymerization initiators include 2-isopropylthioallanone, 4-isopropylthiol; |, ketones, 2,4-diethylthioallanone, 2,4-dichlorothiazialone, 1-chloro-4-propoxythiozanone, etc. Examples of amine-based photoinitiated polymerization starting aids include triethanolamine, fluorenediethanolamine, triisopropanolamine, 4-difluorenylaminobenzoic acid ethyl ester, and 4-difluorenylaminobenzoic acid ethyl ester. Ester, 4-Difluorenylaminobenzoic acid isoamyl ester, 2-Difluorenylaminoethyl benzoate, 4-Difluorenylaminobenzoic acid 2-ethylhexyl ester, N, N-Di Fluorenyl p-anisidine, 4, 4'-bis (dimethylamino) phenylhydrazine (commonly known as Michler's ketone), 4,4-bis (diethylamino) benzoic acid benzene [with _ " EAB-F "], (available commercially from Bosco Chemical Industries, Ltd.), 4, 4'-bis (ethylmethylamino) benzene, etc. Examples of alkoxy onion-based photoinitiated polymerization initiators are: 9,10-dioxo onion, 2-ethyl-9,1 0-dioxo onion, and 9,1 0-diethyl Oxygen onion, diethyl-9,1 0 -diethoxy onion and so on.

314256.ptd Page 16 V. Description of the invention (11) When using these photo-initiated polymerization initiators, the amount used is usually less than 10 moles per 1 mole of the photo-initiated polymerization initiator, preferably It is from 0.01 to 5 mol. In the present invention, as the photo-initiated polymerization initiator, an acetophenone-based photo-initiated polymerization initiator is preferably used, and as the photo-initiated polymerization initiator, a thia onion-based photo-initiated polymerization initiator is preferably used. The coloring photosensitive resin composition contains (E) a pigment dispersant. Since the pigment dispersant is contained, the pigment can be contained in a uniformly dispersed state, so that a uniformly colored coloring pattern can be obtained. As these pigment dispersants, it is preferable to use a poly-D-acryl-based dispersant, an ester-based dispersant or a urethane-based dispersant. These dispersants can be used individually or in combination of 2 or more types. The content of the pigment dispersant is usually 0.01 mass part or more, preferably 0.5 mass part or more, usually 1 mass part or less, and preferably 0.5 mass part or less per mass part of the pigment. . The colored photosensitive resin composition is produced in a state diluted with a (F) solvent and stored. (F) The solvent is the same solvent as that used for ordinary colored photosensitive resin compositions, and examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol. Ethylene glycol monoalkyl ethers such as alcohol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and trans diethylene glycol dibutyl Diethylene glycol dialkyl ethers such as ethers, glycol alkyl ether acetates such as fluorenyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monofluorenyl ether acetate, propylene glycol Monoethyl ether acetate, propylene

314256.ptd Page 17 \ Fifth, the description of the invention (12) glycol monopropyl ether acetate, ethoxybutyl acetate and ethoxypentyl acetate, etc. Aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as methyl ethyl fluorenone, acetone, methyl amyl fluorenone, fluorenyl isobutyl fluorenone, and cyclohexanone, 'ethanol, Alcohols such as propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, esters such as ethyl 3-ethoxypropionate, ethyl 3-propoxypropionate, 7-butyrolactone And other cyclic esters. These solvents can be used singly or in combination of two or more. The content of the solvent in the colored photosensitive resin composition in the state of solvent dilution is usually 50% to 90% in terms of mass fraction. Hereinafter, it is preferably about 60% to 85%. In the present colored photosensitive resin composition diluted with a solvent, (A) pigment is usually dispersed in the composition. (B) An adhesive polymer, (C) a photopolymerizable compound, (D) a photoinitiated polymerization initiator, and (E) a pigment dispersant, which are dissolved in a (F) solvent. * I This coloring photosensitive resin composition is formed on the surface of a glass substrate. After coating the composition by a coating method, it is dried at 100 ° C for 3 minutes and the volatile components are evaporated to form a film (film thickness is 1. 6 // m), the obtained film was immersed in an alkali aqueous solution of 2,500 times the mass of the film (containing 0.05% by weight of potassium hydroxide and butylnaphthylsulfonic acid, respectively) Sodium 0.2% aqueous solution), using a stirrer at 300 rpm: stir the aqueous solution for 80 seconds, and determine the position of the aqueous solution by light scattering method.

314256.ptd Page 18, 20030K01 V. Description of the invention (13) The particle size distribution with particles, which accumulates 90% of the particle size is below 0.5 " m, and the maximum particle size is 1. 0 // m below the color sensitivity Sexual resin composition. In addition, the colored photosensitive resin composition of the present invention is formed on the surface of a glass plate, and after the composition is applied by a spin coating method, it is dried at 100 ° C for 3 minutes and the volatile matter is evaporated to form a film (film thickness 1.6 m / m), the obtained film was immersed in the solvent of 2500 mass times of the film, and the aqueous solution was stirred at 300 r pm using a stirrer for 80 seconds, and scattered by light The method determines the particle size distribution of the coating film components contained in the solution. The cumulative 90% particle diameter is 0.5 // m or less, and the maximum color diameter is 1. 0 // m or less of the colored photosensitive composition. As the glass substrate, for example, a glass substrate of "# 7 0 5 9" manufactured by Corning Corporation can be used. If a film with a thickness of 1.6 / m is to be formed, the amount of solvent used is appropriately selected, for example, the rotation speed and temperature when the colored photosensitive resin composition is applied by a spin coating method. For example, to increase the film thickness In this case, you can reduce the amount of solvent used, reduce the number of rotations, and lower the temperature. If you want to reduce the film thickness, you can increase the amount of solvent used, increase the number of rotations, or increase the temperature. When the% particle size is 0.5 // m or less, and the maximum particle size is 1 · 0 // m or less (the same applies when the alkali solution is impregnated or the (F) solvent is impregnated), the pigment dispersant is preferably A polyaziridine-based dispersant, an ester-based dispersant, or an amino phosphonate-based dispersant is used. The colored photosensitive resin composition may contain a filler, a polymer compound other than the (B) adhesive polymer, an adhesion promoter, an oxidation inhibitor, an ultraviolet absorber, an aggregation inhibitor, an organic acid, and an organic amine-based compound. , Hardeners and other additives.

314256.ptd Page 19 • V. Description of the invention (14) Examples of fillers include glass, alumina and other fine particles. • (B) Polymer compounds other than the adhesive polymer can be exemplified by polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. Adhesion promoters can be exemplified: vinyltrimethoxysilane, vinyltriethoxy stone yaki, ethylene cumene (2- methoxy) stone yaki, N-(2-aminoethyl)- 3 -aminopropylfluorenyldimethoxy stone yaki, N_ (2-aminoethyl) _ 3 -aminopropyltrimethoxy ash, 3-aminopropyltriethoxy oxalate , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxyfluorenyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane , 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-fluorenylpropoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Wait. Antioxidants can be exemplified by 2,2-thiobis (4-fluorenyl-6-tert-butylphenol), 2,6-ditert-butylphenol, and the like. Examples of the ultraviolet absorber include 2- (3-tertiarybutyl-5-fluorenyl-2-hydroxyphenyl) -5-gasbenzotriazole, alkoxybenzofluorene, and the like. Examples of the agglomeration preventing agent include sodium polyacrylate and the like. Examples of organic acids include: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethyl & acetic acid, hexanoic acid, diethylacetic acid, heptanoic acid, octanoic acid and other aliphatic monocarboxylic acid mists, oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glutaric acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid , Fluorenyl succinic acid, tetramethyl succinic acid, cyclohexanedicarboxylic acid, itenic acid, citral enanthic acid, maleic acid, fumaric acid, mesaconic acid

314256.ptd Page 20 V. Description of the Invention (15) Aliphatic dicarboxylic acids such as glyceric acid, aconitic acid, decomposed camphoric acid, phenylarsinic acid, phenylarsinic acid, cumic acid Aromatic dicarboxylic acids, such as diphenyl phenyl acid, calylic acid, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, trimellitic acid, etc. Aromatic polycarboxylic acids such as gallic acid and pyromellitic acid. Examples of organic amine compounds include: n-propylamine, isopropylamine, n-butylamine, isobutylamine, second butylamine, third butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine (N-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-fluorenylcyclohexylamine, 3-fluorenylcyclohexylamine, 4-methylcyclohexylamine, etc.) Amines, methylethylamine, diethylamine, fluorenyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutyl Di (cyclo) alkylamines such as amines, di-second butylamines, di-third butylamines, di-n-butylamines, di-n-hexylamine, fluorenylcyclohexylamine, ethylcyclohexylamine, difluorenyl Ethylamine, fluorenyldiethylamine, triethylamine, difluorenyl-n-propylamine, diethyl-n-propylamine, fluorenyl-di-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine Triamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-second butylamine, tri-third butylamine, tri-n-pentylamine, tri-n-hexylamine, difluorenyl ring Hexylamine, diethylcyclohexylamine, fluorenyldicyclohexylamine, ethylbicyclo Tri (cyclo) alkylamines such as amines, tricyclohexylamine, 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1 -butanol , 5-amino-1 -pentanol, 6 -amino-1 -hexanol, 4-amino-1-

314256.ptd Page 21

V. Description of the invention (16) Mono (cyclo) alkanolamines such as cyclohexanol, 'diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di Di (cyclo) alkanolamines such as n-pentanolamine, di-n-hexanolamine, bis (4-cyclohexanol) amine, triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, Tris (cyclo) alkanolamines such as triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tris (4-cyclohexanol) amine, 3-amino-1,2-propanediol, 2-amine 1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1,2-cyclohexanediol 4-amine -1,3-cyclohexanediol, 3-dimethylamino 1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-difluorenylamino 1,3 -Amine (cyclo) diols such as propylene glycol, 2-diethylamino-1,3-propanediol, etc. Cyclohexanone alcohol, 4-aminocyclohexanone alcohol, 4-dimethylaminocyclopentane alcohol, 4-diethylaminocyclopentane alcohol, 4-dimethylamino ring Hexane Alcohol-containing naphthenic alcohols such as alcohols, 4-diethylaminocyclohexane alcohol, / 9-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutane Acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminopentanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 1-aminocyclopropanecarboxylic acid, 1-amino ring Aminocarboxylic acids such as hexanecarboxylic acid 4-aminocyclohexanecarboxylic acid, aniline, o-anisylaniline, m-anisylaniline, p-anisylaniline, p-ethylaniline, p-n-propylaniline, p-isopropyl Propylaniline, p-n-butylaniline, p-tert-butylamine, p-naphthylamine, 2-naphthylamine, N, N-dimethylbenzylamine, Ν, Ν-diethylaniline, p-methyl-N , N-Difluorenylaniline and other aromatic amines

314256.ptd Page 22 20030K01 V. Description of the invention (17), o-amino T alcohol, m-amino ▼ alcohol, p-amino T alcohol, p-diamidinoamino benzyl alcohol, p-diethylamino group Amino benzyl alcohols such as alcohols, o-amino group S, m-amino group S, p-amino group S, p-dimethylamino group, i-amino phenol groups such as p-diethylaminophenol, m-amine Aminobenzoic acids such as p-phenylbenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, and the like. The hardener may be, for example, a compound which can crosslink the adhesive polymer by reacting with a tether group in the adhesive polymer (B) by heating. In addition, a compound which can polymerize itself and harden a colored pattern can also be mentioned. Examples of such compounds include epoxy compounds, oxetane compounds, and the like. The epoxy compound may be exemplified by a double S-type A epoxy resin, a hydrogenated double S-type A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a novolac epoxy resin, Other aromatic epoxy resins, cycloaliphatic epoxy resins, miscellaneous soil oxygen resins, glycidyl S resins, glycidylamine resins, epoxy resins such as epoxy resins, or epoxy resins Brominated derivatives, epoxy resins, and aliphatic, alicyclic or aromatic epoxy compounds other than their desertified derivatives, butadiene (co) polymer epoxides, isoprene ( Co-polymer epoxides, (co) polymers of glycidyl (fluorenyl) acrylate, triglycidyl isotricyanate, etc. Examples of oxetane: carbonate dioxetane, diphenylene dioxetane, adipate dioxetane, terephthalate dioxetane , Cyclohexanedicarboxylic acid dioxetane, and the like.

314256.ptd Page 23. V. Description of the invention (18) The epoxy compound of the present invention, the polyhydric carboxylic acid anhydride type polycarboxylic acid, terephthalic acid, 3, 3, 4, 4, -Phenylsuccinic acid, lysine, fumaric acid, hexahydropic acid, terephthalic acid, 1,2, pentanetetracarboxylic acid, etc. 0 Colored photosensitive oxetanyl and oxetan compounds. Here, the acid generators can be exemplified: pyromellitic acid, pyromellitic acid glutaric acid, hexamethylene, itaconic acid, etc., 3,4-difluorene 4-cyclopentanetriol 1, 2, 4, 5 -Cyclic polycarboxylic anhydrides can be exemplified: acid anhydrides, 3,3 ', 4,4'-benzene benzenes, itanthic anhydride, succinic anhydride, glyceric anhydride, maleic acid esters, family polycarboxylic anhydrides , Hexahydrophthalic anhydride, 3,4-ditricarboxylic anhydride, 1,2,4-cyclohexane1,2,4,5-cyclohexanetetracarboxylic acid two-group polycarboxylic anhydride, in the composition, such as When a compound or the like as a curing agent is contained, a compound capable of advancing the oxetane skeleton of the butylene oxide compound may also be included: polycarboxylic acids, and the like. Phthalic acid, 3,4-Difluorenylphthalic acid, isophthalic trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and other aromatic polycarboxylic acids, diacids, 1, 2, 3, 4 -Butanetetracarboxylic acid, equine aliphatic polycarboxylic acids, tetrahydrophosphonic acid, hexahydroisophosphoric acid, hexahydrocarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid Isoaliphatic polycarboxylic acids, phthalic anhydride, pyromellitic anhydride, trimellitic tetracarboxylic dianhydride and other aromatic polycarboxylic anhydrides, citraconic anhydride, dodecyl succinic anhydride, 1, 2, 3, 4- Butyl tetrahydrophthalic anhydride such as butanetetracarboxylic dianhydride, 1,2,4-cyclopentanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, anhydride, heminic anhydride, nacinic anhydride, etc., alicyclic

314256.ptd Page 24 20030K01 V. Description of the invention (19) Ester-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic anhydride, glycerol and trimellitic anhydride. Carboxylic anhydrides are commercially available as epoxy resin hardeners. Such epoxy resin hardeners can be exemplified by: the trade name "Ediga Hadana EH-7 0 0" (Asahi Chemical Industry Co., Ltd.), the trade name "Rigacito HH" (New Yueben Physical and Chemical Co., Ltd. )), Trade name Γ Μ Η-7 0 0 "(new Yueben Physicochemical (stock)) and so on. These hardeners can be used individually or in combination of 2 or more types. When it is desired to form the layer 4 made of this solid component on the substrate 3, for example, the substrate 3 may be coated with a photosensitive resin composition of its own color and the (F) solvent may be removed. When the colored photosensitive resin composition is to be applied, a method capable of coating the substrate with a uniform thickness, for example, a spin coating method (s p i η co a t i n g) may be used. If the (F) solvent is to be removed after coating, for example, heating may be used. The heating temperature is, for example, a range of 60 ° C to 120 ° C. The layer 4 composed of the present solid component thus formed is a layer composed of the solid component obtained by removing (F) a volatile component such as a solvent from the colored photosensitive resin composition. These layers 4 made of these solid components are generally formed to have a thickness of 0.8 // m or more and 2.5 // m or less. When it is desired to form a layer made of the solid component in these thicknesses, For example, the amount of the solvent contained in the colored photosensitive resin composition and the rotation speed and temperature when the colored photosensitive resin composition is applied by the spin coating method may be selected. For example, if the thickness is to be increased, the solvent is reduced. The amount of use, reduce the number of rotations, or reduce the temperature, if you want to thin, increase the amount of solvent, increase the number of rotations, or increase the temperature

m 1

IS 11 lb Μ 314256.ptd page 25 20030K01. 5. Description of the invention (20) degrees. ‘The irradiation light is preferably an i-line, and the i-line is light having a wavelength of 3 6 5 nm. The i-line parallel light can be irradiated by an exposure machine used in manufacturing the color filter. For example, when irradiating linear i-line parallel light with a line width (w) of 100 // m, for example, irradiating ^ -line parallel light through a gap (s1it) with a line width of 1 0 // // m. Imaging of a hydrocarbon irradiated with i-ray parallel light can be performed by an immersion method in an alkaline aqueous solution. Examples of the alkaline aqueous solution include an aqueous solution containing potassium hydroxide and sodium butyl naphthalene lutein. Specific examples include: 100 parts by mass of the aqueous solution, the content of hydroxide _ is 0.05 parts by mass, and the content of sodium butylnaphthoate is 0.1 part by mass. The temperature of the alkaline aqueous solution is usually about 23 ° C and the impregnation time is usually about 40 seconds to 120 seconds. After immersion, it is usually washed with water to remove the current developing solution. After development, for example, heating at a temperature of 180 ° to 240 ° C for 20 minutes can form a colored pattern, but these colored patterns are linear. For the colored photosensitive composition, for example, for the present solid content, it is preferable that (A) the content of the colorant is 15% to 50% in terms of mass fraction, and (B) the content of the adhesive is in terms of mass fraction as Above 20% and below 55%, (C) Photopolymerizable compound is from 10% to 45% by mass, and (D) Photoinitiated polymerization initiator content is 3% by volume fraction Above 20%, and for (A) pigment 1 part by mass, (E% material dispersant is 0.01 to 1 part by mass. The method for forming a coloring pattern of the present invention is characterized by using the coloring photosensitivity The resin composition forms a coating film on the substrate 2 and develops the layer after exposure. In addition, the manufacturing method of the color filter of the present invention is characterized by adopting the method for forming a coloring pattern described above, and Manufacturing method

314256.ptd Page 26 V. Description of the invention (21) It is sufficient to have the method of forming the colored pattern. Specifically, a layer 4 made of the present solid content is formed on the substrate 2 (as shown in FIG. 2 (a)), and the layer 4 made of the present solid content is exposed (as shown in FIG. 2 (b)) , Just carry out the development (such as Fig. 2 (c)). Examples of the substrate 3 include flat substrates such as glass substrates, broken wafers, and plastic plates. The substrate may also be transparent. When a silicon wafer is used as the substrate, a charge coupled device (CCD), a thin film transistor (TFT), or the like can be formed on the surface of the silicon wafer or the like. In order to form the layer 4 made of the solid component, the substrate 3 may be coated with the colored photosensitive resin composition diluted with the (F) solvent. The coating method may be any method that can coat the colored photosensitive resin composition on the substrate in a uniform thickness, and examples thereof include a spin coating method (s p i η coat i ng method) and the like. After coating, the solvent was removed. To remove the solvent, for example, heating is sufficient. The layer 4 formed from the solid component thus formed is a layer formed from the solid component after removing (F) solvents and other volatile components from the colored photosensitive resin composition, and its thickness is usually 0.8 / im or more 3 // m or less. Next, the layer 4 made of this solid component is exposed (Figure 2 (b)). During the exposure, for example, the light 6 may be radiated through the photomask 5. The light 6 usually uses ultraviolet rays called an i-line (wavelength 3 6 5 nm). The light is irradiated through a photomask, but the photomask 5 here is a light-shielding layer 52 provided on the surface of the glass plate 51 for shielding the light. The part of the glass plate that is not provided with a light-shielding layer is a light-transmitting part 5 3 through which light will pass, and the layer 4 made of the solid component is exposed in accordance with the pattern formed by the pattern of the light-transmitting part to generate no light. All

314256.ptd Page 27 V. Description of the invention (22) Unirradiated area 4 1 irradiated, and irradiated area 4 2 irradiated by light. The amount of light irradiated on the irradiation field 4 2 is based on the type or content of the colorant used (A), the weight average molecular weight of the adhesive polymer, the content, the composition of the monomer unit, and (C) the photopolymerizable compound. The type, content, and (D) the type and content of the photoinitiated polymerization initiator are appropriately selected. After exposure, development is performed (see Fig. 2 (c)). When developing, for example, the layer 4 made of the solid component after exposure may be brought into contact with the developing solution. Specifically, the substrate 3 having the layer 4 made of the solid component on its surface is immersed in Just in the developer. As the developing solution, an alkaline aqueous solution is usually used. Examples of the alkaline aqueous solution include aqueous solutions of basic compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide. As a result of imaging, the unirradiated areas 41 in the layer made of this solid component, which are not illuminated by light, will be removed. On the other hand, the light irradiated area 4 2 is left as it is to constitute the coloring pattern 2. After development, it is usually washed with water and dried to obtain the desired colored pattern 2. It can be heated after drying. The heating of the colored pattern tends to increase the hardness to increase its mechanical strength. If the colored photosensitive resin composition contains a hardener, the mechanical strength can be further enhanced. The heating degree is usually 180 ° C or higher, preferably 200 ° C or higher, and usually 250 ° C or lower. The cross-sectional shape of the colored pattern 2 formed in this way is a tapered shape or a rectangular shape. On the substrate 3 on which the coloring pattern 2 is formed in this manner, the solid component containing different coloring agents and colored in different colors is formed.

314256.ptd Page 28 V. Description of the invention (23) Layer 4 '(as shown in Figure 3 (a)), expose the layer 4' (as shown in Figure 3 (b)), and develop the image (page 3 ( c) figure), then another colored pattern 2 'can be formed. Furthermore, by using the colored photosensitive resin composition colored in different colors and repeating the above operations, the colored pattern 2 "(eg, figure 4) of three primary colors, such as red, green, and blue, can be sequentially formed, and manufactured with Color filter 1 of coloring pattern 2 (as shown in Fig. 1). [Example] Hereinafter, the present invention will be described in more detail with reference to the examples, but the present invention is not limited to these examples. Method for measuring the particle size: According to the light scattering method, the device used was a Microtrac PARTICLE-SIZE ANALYZER UPA150, model 9230 UPA, manufactured by LEED & NORTH RUP COMPANY. Example 1 [Production of blue colored photosensitive resin composition] A copolymer of (B) fluorenyl acrylic acid and benzyl acrylic acid [ratio of fluorenyl acrylic unit to fluorinated methacrylic acid unit, and its mass ratio (Mo Ear ratio) is 30:70, the acid value is 113, the weight average molecular weight is 2500 0 0] 0.8 2 8 parts by mass, (C) dipentaerythritol hexaacrylate 0.8 8 2 parts by mass (D) Photoinitiated polymerization initiator [2-fluorenyl-2-morpholinyl -1- (4-methylthiophenyl) propane-1 -one] 0 · 1 9 9 parts by mass of (D) photoinitiated polymerization initiation aid [2,4-difluorenylthio onionone] 0 · 0 9 9 parts by mass and

314256.ptd Page 29 'V. Description of the invention (24) (F) Propylene glycol monofluorenyl ether acetate 6. 5 2 2 parts by mass, after mixing, a mixture (1) is prepared. This mixture (1) was mixed with (A) pigment [C · I. Pigment Blue 15: 6] 1 · 0 3 6 parts by weight, (A) pigment [C. I · Pigment Violet 2 3] 0 · 0 1 6 parts by weight, (E) a polyaziridine-based dispersant 0.298 parts by mass and (F) a propylene glycol monofluorenyl acetate 5.17 parts by mass, and the resulting mixture (2) is mixed, A colored photosensitive resin composition (blue) was obtained. [Solubility] On the surface of a glass substrate [made by Corning, "# 7 0 5 9"] 3, the colored photosensitive resin composition obtained above was applied by spin coating, and then dried at 1 0 (TC The volatiles were volatilized for 3 minutes to form a colored photosensitive resin composition layer [thickness of 1.6 / m] 4. The coating film was immersed in an alkali image liquid [containing potassium hydroxide in a mass fraction of 0. 0. 05%, sodium butylnaphthalenesulfonate 0.2% aqueous solution], using a stirrer to stir the imaging solution at 300 rpm for 80 seconds, when the glass substrate was observed, the coating film was dissolved, and the glass substrate The transmittance is 100%. Furthermore, the particle size fraction of the particles present in the dissolving imaging solution is checked. As a result, the cumulative 90% particle size is: 0.08 5 // m, and the average particle size is: 0. 0 5 // m, maximum particle size: 0.15 // m. In the same manner, the obtained coating film was immersed in propylene glycol monomethyl ether acetate, and acryl was stirred at 300 r pm using a stirrer. After 80 seconds of diammonium monoethyl ether acetate, when the glass substrate was observed, it was found that the coating film was dissolved, and the transmittance of the glass substrate was 100%. Furthermore, check the two after dissolution. Yue glycol monoethyl ether

314256.ptd Page 30 V. Description of the invention (25) The result of the particle size distribution of the particles present in the acetate solution is a cumulative 90% particle size: 0. 0 8 5 " m, average particle size ·· 0. 0 5 // m, maximum particle diameter: 0. 1 5 // m 〇 [Formation of blue pixels] On the surface of a glass substrate [manufactured by Corning Corporation, "# 7 0 5 9"] 3 by spin coating The colored photosensitive resin composition obtained as described above was applied, and then dried at 100 ° C. for 3 minutes to volatilize the volatile matter to form a colored photosensitive resin composition layer [thickness: 1.6 / m]. 4. After cooling, the colored photosensitive resin composition layer 4 was irradiated with i-rays [wavelength 3 6 5 nm] 6 through a photomask 5 and exposed. The light source of the i-ray is an ultra-high pressure mercury lamp, which is made into parallel light and then irradiated. The amount of irradiation light is 150 mJ / cm2. Photomasks are formed using line widths of 3 // m, 4 // m, 5 // m, 6 // m, 7 // m, 8 // m, 9μm, 10 // m, 20 // m, Masks for linear color pixels of 30 // m, 40 // m, 50 // m, and 10 0 // m. Next, the exposed glass substrate [when a colored photosensitive resin composition layer is formed on the surface] 3 is immersed in a developing solution [containing 0.5% by weight of potassium hydroxide and butylnaphthalenesulfon, respectively, in terms of mass fraction. Sodium 0.2% aqueous solution] for 80 seconds for development, after washing with pure water, and heating at 220 ° C for 20 minutes to form a red pixel 2 (Figure 2 (c)) . The cross-sectional shape of the formed blue pixel was a tapered shape, which was good without surface cracks. Example 2 [Production of blue-colored photosensitive resin composition] A polyacridine-based dispersant of Example 1 was changed to an aminophosphonate, and the rest were mixed in the same manner as in Example 1 to obtain Color sensitivity

314256.ptd page 31 20030K01 'V. Description of the invention (26) Resin composition (blue). / [Solubility of coating film] Except not using the colored photosensitive resin composition 5 obtained in Example 1 but using the colored photosensitive resin composition obtained above, the rest was operated in the same manner as in Example 1 and the obtained coating was inspected. As a result of the particle size distribution of the particles present in the imaging solution after the film was dissolved, the cumulative particle size was 90%. Particle size: 0.08 5 //. M, average particle size ·· 0.45 μm, maximum Particle size ·· 0. 1 5 // m. In addition, the results of examining the particle size distribution of the particles present in the propylene glycol monofluorenyl ether acetate solution were cumulative 90% particle diameter: 0.08 5 // m, average particle diameter 0.05 // m, maximum Particle size: 0.15 // m. [Formation of Blue Pixels] Except that the colored photosensitive resin composition obtained in Example 1 was used instead of the colored photosensitive resin composition obtained in Example 1, the remaining blue pixels were obtained in the same manner as in Example 1. The shape of the cross section is a tapered shape, which is good without cracks. Comparative point] 1 [Production of blue colored photosensitive resin composition] (B) The copolymer of methacrylic acid and benzylfluorenyl acrylic acid [the ratio of fluorenyl acrylic monomer ▲ to T-based fluorenyl acrylic acid unit Ratio (mole ratio) is 3 0 ·· 7 acid value is 1 1 3, weight average molecular weight is 2 5 0 0 0] 0.8 2 8 parts by mass, (C) dipentaerythritol hexaacrylate 0 · 8 2 8 (D) Photoinitiated polymerization initiator [2-fluorenyl-2-morpholinyl-1- (4-methylthiophenyl) propane-1 -one] 0, 1 9 9 parts by mass, ( D) Photo-initiated polymerization initiator [2,4-diethylthiasialone] 0 · 0 9 9 mass

314256.ptd page 32 20030K01 V. Description of the invention (27) parts, and (F) propylene glycol monomethyl ether acetate 6. 5 2 2 parts by mass After mixing, a mixture (1) was prepared. This mixture (1) was combined with (A) pigment [CI · Pigment Blue 15: 6] 1.03 0 parts by weight, (eight) pigment [(: .1. Pigment Violet 23] 0.016 parts by weight, (Ε ) 0.298 parts by mass of a denatured acrylic dispersant and 5.18 parts by mass of (F) propylene glycol monofluorenyl ether acetate, and the resulting mixture (2) was mixed to obtain a colored photosensitive resin composition [Solubility of the coating film] The same procedure as in Example 1 was performed except that the coloring photosensitive resin composition obtained in Example 1 was used instead of the coloring photosensitive resin composition obtained in Example 1. The obtained coating film was stirred in a developing solution and propylene glycol monomethyl ether acetate, and a piece of the coating film was peeled off. To the extent that it can be visually confirmed, the developing solution and the propylene glycol monomethyl ether acetate were separated. No coloring [Blue pixel formation] The blue photosensitive resin composition obtained in Example 1 was used in the same manner as in Example 1 except that the colored photosensitive resin composition obtained in Example 1 was not used. The cross-sectional shape of the color pixel is inverse taper, and the cracks on the side wall are very severe. Effect Ming] of the present invention the colored photosensitive resin composition, based upon the high sensitivity and simultaneously developing, cross-sectional shape can be formed as a forward tapered shape or a rectangular shape without cracks

314256.ptd Page 33 200301101 \ V. Description of the invention (28) Those who color the pattern.

314256.ptd Page 34 20030K01 Simple illustration of the drawing [Simplified illustration of the drawing]

Figures 1 (a) and (b) are model diagrams showing an example of a color patch. Figures 2 (a) to (c) are model diagrams showing the process of forming a colored pattern. Figures 3 (a) to (c) are model diagrams showing the process of forming the colored patterns. Figures 4 (a) to (c) are model diagrams showing the process of forming colored patterns. Figures 5 (a) to (c) are model diagrams showing cross-sectional shapes of colored patterns. 1 Color filter 1: 2, ', 2M coloring pattern 2B blue pixel 2G green pixel 2R red pixel 3 substrate 4, 4, 4, 4Π coloring photosensitive layer 5 photomask 6 light 51 glass plate 52 Light-shielding layer 53 Light transmitting portion 314256.ptd Page 35

Claims (1)

20030K01, 6. Application scope 1. A colored photosensitive resin composition containing (A) pigment, (B) adhesive polymer, (C) photopolymerizable compound, (D) photo-initiated polymerization The initiator, (E) pigment dispersant, and (F) solvent are characterized in that the colored photosensitive resin composition is on the surface of a glass substrate, and the colored photosensitive resin composition is applied by a spin coating method. , Dried at 100 ° C for 3 minutes to volatilize the volatiles to form a film (film thickness of 1.6 / m), and the obtained film was immersed in an alkaline aqueous solution of 2500 mass times of the film ( It contains an aqueous solution of 0.05% rhenium hydroxide and 0.2% sodium butylnaphthoate in terms of mass fractions respectively, and the aqueous solution was stirred at 300 r pm for 80 seconds using a stirrer, ft The particle size distribution of the particles contained in the aqueous solution was measured using a light scattering method, with a cumulative 90% particle size of 0.5 < m or less and a maximum particle size of 1 · 0 // m or less. 2. A colored photosensitive resin composition containing (A) pigment, (B) adhesive polymer, (C) photopolymerizable compound, (D) photoinitiated polymerization initiator, and (E) pigment dispersion The agent and the (F) solvent are characterized in that the colored photosensitive resin composition is on the surface of a glass substrate, and the colored photosensitive resin composition is applied by a spin coating method at a temperature of 10 ° C. Dry for 3 minutes to volatilize the volatiles to form a film [thickness of 1.6 / m], immerse the obtained film in 2 500 mass times of the solvent in the film, and use a stirrer to dissolve the solvent to Stir at 80 rpm for 80 seconds, and use a light scattering method to measure the particle size distribution of the coating film components contained in the solvent. The cumulative particle size of 90% is 0 · 5 // m or less, and the maximum particle size is 1.0 / / m below. 3. If the colored photosensitive resin composition of the first or second item of the patent application scope, wherein the solid content of the colored photosensitive resin composition is as follows, 314256.pid Page 36 6. The mass fraction of patent application range, the content of (A) pigment is 15% to 50%, and the content of (B) adhesive polymer is 20% to 55% Below, (C) the content of the photopolymerizable compound is 10% to 45%, and (D) the content of the photoinitiated polymerization initiator is 3% to 20%, and 1 part by mass of the (A) pigment (E) The pigment dispersant is from 0.01 to 1 part by mass. 4. The coloring photosensitive resin composition according to any one of claims 1 to 3, wherein (D) the photoinitiated polymerization initiator is an acetophenone-based photoinitiated polymerization initiator. 5. The coloring photosensitive resin composition according to any one of claims 1 to 4, in which (E) the pigment dispersant is a polyπ-acrylic dispersant, an ester-based dispersant, or an amine group. Formic acid S is a dispersant. 6. —A method for forming a coloring pattern, which is characterized in that: the coloring photosensitive resin composition in any one of claims 1 to 5 of the scope of patent application is coated on a substrate, and a coating film is formed after drying, and The developer is exposed after exposing this layer. 7. A method for manufacturing a color filter, which is characterized by: repeatedly implementing a method for forming a coloring pattern of item 6 of the scope of patent application for a desired color. 8. The manufacturing method of the color filter according to item 7 of the patent application, wherein the required colors are red, green and blue. u 314256.ptd p. 37