JP2007057651A - Colored photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition which has a high pigment concentration and ensures high resolution and less residue in formation of a color filter using a photopolymerization system. <P>SOLUTION: The colored photosensitive resin composition comprises (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a solvent and (F) a surface tension depressant selected from polyether modified silicones, polyester modified silicones, alkyl modified silicone or acryl modified silicones, etc. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a colored photosensitive resin composition used for forming a color filter.

  In recent years, color filters used in image sensors such as CCDs and CMOSs have increased in pixels, and it is necessary to increase the resolution and reduce the film thickness. However, when a pigment is used as a colorant, in order to obtain the same color density when the film thickness is reduced, the pigment density must be increased, and a colored photosensitive resin composition having a high pigment density is used for coloring. When the filter was formed, there was a tendency that more residue remained (see, for example, Patent Document 1).

JP-A-8-271723, page 2, right column, line 4-page 2, right column, line 10

  An object of the present invention is to provide a new colored photosensitive resin composition with little residue in the formation of a color filter.

  As a result of intensive investigations to find a colored photosensitive resin composition that can solve the above-described problems, the present inventors have found that a colored photosensitive resin composition containing a specific compound solves the above problems. As a result, the present invention has been completed.

  That is, the present invention is a color containing (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a solvent, and (F) a surface tension reducing agent. A photosensitive resin composition is provided.

  The present invention also provides a pattern formed by using the colored photosensitive resin composition, a color filter including the pattern, and an image sensor including the color filter.

  According to the colored photosensitive resin composition of the present invention, it is possible to form a color filter pattern with little residue in forming a color filter.

  The colored photosensitive resin composition of the present invention contains (A) a colorant. Examples of the colorant (A) include at least one selected from the group consisting of pigments and dyes.

Specific examples of the pigment include compounds classified as pigments by Color Index (published by The Society of Dyers and Colorists). Specifically, for example, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7 and 36;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7. Among them, C.I. I. Pigment yellow 138, 139, 150, C.I. I. Pigment red 177, 209, 254, C.I. I. Pigment red violet 23, C.I. I. Pigment blue 15: 3, 15: 6 and C.I. I. It is preferable to contain at least one pigment selected from CI Pigment Green 7 and 36.

  Examples of the dye include acid dyes and their sulfonamide derivatives and oil-soluble dyes. Preferred examples of the dye include C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Acid Green 9, C.I. I. Acid Green 16, C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow 162, C.I. I. Solvent Orange 56, C.I. I. Solvent Blue 67 etc. are mentioned.

  Moreover, the compound represented by general formula (IV) can also be used.

D [(— SO ₂ N (R ⁸ ) R ⁹ ) _n ] (IV)

[In the formula (IV), D represents a dye matrix such as pyridone, xanthene, triphenylmethane, azo, anthraquinone, pyrazolone and phthalocyanine.
n represents an integer of 1 to 4.
R ⁸ and R ⁹ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by an oxygen atom, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an alkyl moiety. Having an alkyl cyclohexyl group having 1 to 4 carbon atoms, an aliphatic alkoxyalkyl group having 3 to 15 carbon atoms, an aliphatic ester group having 4 to 10 carbon atoms, and an aryl group portion having 6 to 10 carbon atoms and an alkyl moiety A substituent such as an aralkyl group having 1 to 5 carbon atoms is represented. However, R ⁸ and R ⁹ are not simultaneously hydrogen atoms. When n is 2 to 4, the plurality of R ⁸ and R ⁹ may be the same or different from each other. ]

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by the oxygen atom include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert. -Butyl group, n-pentyl group, n-hexyl group, octyl group, dexyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl group, 1,6- Substitution in which one or two or more oxygen atoms are introduced at any position of the dimethylheptyl group, 2-ethylhexyl group, 1,1,5,5-tetramethylhexyl group, or each aliphatic hydrocarbon group. Group (however, when two or more oxygen atoms are present, the oxygen atoms are not adjacent to each other).
Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, isobornyl group, cyclopentadiyl. An enyl group etc. are mentioned.
Examples of the alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl moiety include 2-methylcyclohexyl group and 2-ethylcyclohexyl group.
Examples of the aliphatic alkoxyalkyl group having 3 to 15 carbon atoms include ethoxy-n-propyl group, isopropoxy-n-propyl group, octoxy-n-propyl group, 3-ethoxy-n-propyl group, and 3- (2-ethylhexyloxy) -n-propyl group and the like can be mentioned.
Examples of the aliphatic ester group having 4 to 10 carbon atoms include n-propoxycarbonyl-n-propyl group, ethoxycarbonylbutyl group, propionyloxyethyl group, and butyryloxybutyl group.
Examples of the aralkyl group having 6 to 10 carbon atoms in the aryl group moiety and 1 to 5 carbon atoms in the alkyl moiety include benzyl group, phenethyl group, 1-methyl-3-phenyl-n-propyl group, and the like. .

  Among the dyes represented by the formula (IV), preferable examples include those listed below.

  These dyes may be used alone or in admixture of two or more.

  The above pigments and dyes are optionally treated with rosin, surface treatment using a derivative having an acidic group or basic group introduced, grafting onto the surface of the dye with a polymer compound, sulfuric acid atomization method, etc. A pulverization process using an organic solvent, a cleaning process using an organic solvent or water for removing impurities, a removal process using an ionic impurity ion exchange method, or the like may be performed.

  (A) The colorant is a dispersion in which pigments and dyes are uniformly dispersed in the solution by containing a dispersant or a part or all of the binder resin (B) as necessary. Obtainable.

Examples of the dispersant include cationic, anionic, nonionic, and amphoteric surfactants, and they may be used alone or in combination of two or more.
Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, etc. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), Megafax (manufactured by Dainippon Ink & Chemicals, Inc.) , Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS), PB821 (Ajinomoto Fine Techno Co., Ltd.) Manufactured).
When using a dispersing agent, the usage-amount is a mass fraction with respect to a coloring agent, Preferably it is 0.1-100 mass%, More preferably, it is 5-50 mass%. It is preferable that the amount of the dispersant used be in the above range because a uniform dispersion tends to be obtained.

The content of the colorant (A) used in the colored photosensitive resin composition of the present invention is a mass fraction with respect to the solid content in the colored photosensitive resin composition, preferably 20 to 65% by mass, and more preferably. Is 25 to 60% by mass, particularly preferably 27 to 55% by mass, and further preferably 30 to 50% by mass. Here, the solid content in the present specification refers to (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, The ratio of the total amount of components that are not liquid at room temperature among the components that are added as necessary.
(A) When the content of the colorant is in the above range, the color density when a color filter is obtained is sufficient, and the binder resin can be contained in the composition in an amount more than necessary. Is preferable because a sufficient pattern can be formed.

  The colored photosensitive resin composition of the present invention contains (B) a binder resin. The (B) binder resin preferably contains a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the structural unit derived from the (meth) acrylic acid is preferably 16 mol% or more and 40 mol% or less, more preferably 18 in terms of mole fraction in all the structural units constituting the (B) binder resin. It is from mol% to 38 mol%. If the content of the structural unit derived from meth (acrylic) acid is in the above range, the solubility of the non-pixel portion is good during development, and the residue tends not to remain in the non-pixel portion after development. Yes, it is preferable.

  Examples of the other monomer that leads to the constituent unit of the binder resin other than the constituent unit derived from (meth) acrylic acid include, for example, aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, and unsaturated compounds. Carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl group or mono at the end of the polymer molecular chain Examples thereof include macromonomers having a methacryloyl group, monomers derived from units represented by formula (II), and monomers derived from units represented by formula (III).

[In Formula (II) and Formula (III), R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

R ³ and R ⁴ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 2-ethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, etc., preferably hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert. -A butyl group is mentioned, More preferably, a hydrogen atom, a methyl group, and an ethyl group are mentioned.

Specific examples of the binder resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, and methacrylic acid / styrene. / Benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / monomer leading to a structural unit represented by formula (II) (wherein, in formula (II), R ¹ represents a methyl group, R ² Represents a hydrogen atom.) / Benzyl methacrylate copolymer, methacrylic acid / monomer leading to the structural unit represented by formula (III) (wherein, in formula (II), R ¹ represents a methyl group, R ² represents a hydrogen atom.) / benzyl methacrylate copolymer, methacrylic acid / formula (III) Monomer (however, here, in the formula (II), R ¹ represents a methyl group, R ² represents a hydrogen atom.) For guiding the structural unit / dicyclopentanyl methacrylate / benzyl methacrylate copolymer, methacrylic Acid / monomer leading to the structural unit represented by formula (III) (in this case, in formula (III), R ¹ represents a methyl group and R ² represents a hydrogen atom) / styrene copolymer / A tricyclodecanyl methacrylate copolymer is preferred.

  The acid value of the (B) binder resin used in the present invention is preferably 50 to 150, more preferably 55 to 135, and particularly preferably 60 to 135. When the acid value is in the above range, the solubility in the developer is improved and the unexposed area is easily dissolved, and the sensitivity is increased so that the pattern of the exposed area remains during development and the remaining film ratio tends to be improved. Is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and is usually obtained by titration using an aqueous potassium hydroxide solution. Can do.

  (B) Content of binder resin is a mass fraction with respect to solid content of a coloring photosensitive resin composition, Preferably it is 15-35 mass%, More preferably, it is 18-33 mass%, Most preferably Is 21-31 mass%. (B) It is preferable that the content of the binder resin be in the above range because a pattern can be formed and the resolution and the remaining film ratio tend to be improved.

Binder resin having a component represented by the formula (II), for example, methacrylic acid / a component represented by the formula (II) (in this case, in the formula (II), R ³ and R ⁴ are methyl groups) The benzyl methacrylate copolymer is obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer, and the obtained two-component polymer and a compound represented by the formula (V-1) (however, Here, in formula (V-1), R ⁵ represents a methyl group).

Methacrylic acid / constituent component represented by formula (III) (in this case, in formula (III), R ³ and R ⁴ represent a methyl group) / styrene copolymer / tricyclodecanyl methacrylate copolymer The coalescence can be obtained by reacting a monomethacrylate copolymer having a benzyl methacrylate, methacrylic acid, or tricyclodecane skeleton with a carboxyl group of the methacrylic acid.

  (B) The polystyrene-reduced weight average molecular weight of the binder resin is preferably 5,000 to 35,000, more preferably 6,000 to 30,000, and particularly preferably 7,000 to 28,000. . When the molecular weight is within the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution tends to be improved, which is preferable.

  The colored photosensitive resin composition of the present invention contains (C) a photopolymerizable compound. (C) The photopolymerizable compound is a compound that can be polymerized by active radicals, acids, etc. generated from (D) a photopolymerization initiator when irradiated with light, for example, polymerizable carbon-carbon unsaturated Examples thereof include compounds having a bond.

  The photopolymerizable compound (C) is preferably a trifunctional or higher polyfunctional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Is mentioned. The (C) photopolymerizable compound may be used alone or in combination of two or more, and the content thereof is a mass fraction with respect to the colored photosensitive resin composition, preferably 5 to 90% by mass. Yes, more preferably 10 to 80% by mass, particularly preferably 20 to 70% by mass. (C) When the content of the photopolymerizable compound is in the above range, curing is sufficiently performed, the film thickness ratio before and after development is improved, and undercut is difficult to enter into the pattern, and the adhesion is good. It is preferable because it tends to become.

The colored photosensitive resin composition of the present invention contains (D) a photopolymerization initiator. Examples of the photopolymerization initiator (D) include triazine compounds, acetophenone compounds and biimidazole compounds, active radical generators, and acid generators.
Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) ) Such -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.
Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -[4- (1-methylvinyl) phenyl] propan-1-one oligomers and the like are preferable, and 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one is preferable. .
Examples of the biimidazole compound include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl)- 4,4 ′, 5,5′-tetra (p-carboethoxyphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-bromophenyl) Biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis ( o-chlorophenyl) -4,4 ', 5 5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (2,6-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o -Nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole and the like. Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5 5'-tetraphenylbiimidazole is mentioned.

  An active radical generator generates an active radical when irradiated with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.

  Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the oxime compounds include O-acyloxime compounds, and specific examples thereof include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O—. Benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1-one oxime-O-acetate 1- (4-phenylsulfanyl-phenyl) -butan-1-one oxime-O-acetate and the like.

  Examples of active radical generators other than those exemplified above include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2′-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. can also be used. .

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium-p-toluenesulfonate, 4-acetoxyphenyl.・ Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl Tosylate, benzoin tosylate and the like can be mentioned.

  Among the compounds described above as the active radical generator, there are compounds that generate an acid simultaneously with the active radical. For example, a triazine photopolymerization initiator is also used as an acid generator.

  (D) Content of photoinitiator is a mass fraction with respect to the total amount of (B) binder resin and (C) photopolymerizable compound, Preferably it is 0.1-20 mass%, More preferably Is 1 to 15% by mass. If the content of the photopolymerization initiator is in the above range, the sensitivity is increased, the exposure time is shortened, and the productivity is improved. Is preferable because the line width tends not to be too large.

The colored photosensitive resin composition of the present invention may further contain (G) a photopolymerization initiation assistant. (G) The photopolymerization initiation assistant is preferably a compound that is used in combination with (D) a photopolymerization initiator and is used to promote polymerization of a photopolymerizable compound that has been polymerized by the photopolymerization initiator. is there.
Examples of the (G) photopolymerization initiation assistant include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and the like.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4, Examples thereof include 4′-bis (ethylmethylamino) benzophenone, and among these, 4,4′-bis (diethylamino) benzophenone is preferable.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. Can be mentioned.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  (G) The photopolymerization initiation assistant may be used alone or in combination of two or more. Moreover, as (G) photopolymerization start adjuvant, a commercially available thing can also be used, and as commercially available (G) photopolymerization start adjuvant, EAB-F (made by Hodogaya Chemical Co., Ltd.) is mentioned, for example. Etc.

  Examples of the combination of (D) photopolymerization initiator and (G) photopolymerization initiation assistant in the colored photosensitive resin composition of the present invention include, for example, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2- Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenyl-n-propan-1-one / 4,4′-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propane- 1-one / 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexyl Phenyl ketone / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] -n-propan-1-one oligomer / 4,4 ′ -Bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, and the like are preferable, and 2-methyl 2-morpholino-1- (4-methylthiophenyl) -n-propan-1-one / 4,4′-bis (diethylamino) benzophenone.

  When these (G) photopolymerization initiation assistants are used, the amount used is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, per mol of (D) photopolymerization initiator. .

Examples of the solvent (E) contained in the colored photosensitive resin composition of the present invention include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like.
Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Over DOO, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxy pentyl acetate, anisole, phenetole, and the like methyl anisole.
Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.
Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.
Examples of other solvents include N-methylpyrrolidone and dimethyl sulfoxide.
These solvents may be used alone or in combination of two or more.

  Among the above solvents, a solvent containing propylene glycol monomethyl ether acetate is preferably used. (E) When a solvent contains propylene glycol monomethyl ether acetate, the content is a mass fraction with respect to a solvent, Preferably it is 50-97 mass%, More preferably, it is 60-95 mass%.

  (E) Content of a solvent is a mass fraction with respect to a coloring photosensitive resin composition, Preferably it is 70-90 mass%, More preferably, it is 75-88 mass%. (E) It is preferable for the content of the solvent to be in the above-mentioned range since the in-plane uniformity at the time of coating is good, and the color density when the color filter is formed is sufficient and the display characteristics are good.

The colored photosensitive resin composition of the present invention contains (F) a surface tension reducing agent.
(F) The surface tension reducing agent is selected from compounds having a function of reducing the surface tension of the colored photosensitive resin composition containing the surface tension reducing agent. Such a surface tension reducing agent can be selected from commercially available surfactants, leveling materials, antifoaming agents, defoaming agents, foam stabilizers and paint additives.
The surface tension reducing agent is basically a compound containing both a polar group and a hydrophobic group. Structurally, products of silicone compounds and fluorine compounds are commercially available. The surface tension reducing agent can be selected from the above-mentioned compounds, but a silicone-based or fluorine-based surface tension reducing agent is preferable.
The silicone-based surface tension reducing agent is preferably selected from polyether-modified silicones, polyester-modified silicones, alkyl-modified silicones, acrylic-modified silicones, silicone-modifieds, and the like, more preferably the surface of polyether-modified silicones A tension reducing agent is selected.
The fluorine compound is selected from fluoroalkyl silicones, fluoroalkyl carboxylic acids, fluoroalkyl alcohols, fluoroalkyl ethers, fluoroalkyl quaternary ammonium salts and the like.
Among these, it can mix | blend individually or in mixture of 2 or more types.

The addition amount of the surface tension reducing agent is a mass fraction with respect to the solid content of the colored photosensitive resin composition, preferably 0.001% by mass to 1.1% by mass, more preferably 0.01% by mass or more. It is 1.0 mass% or less, Most preferably, it is 0.02 mass% or more and 0.8 mass% or less. When the content of the surface tension reducing agent is in the above range, it is preferable that a residue is hardly left in an unexposed portion when a pattern is formed using a colored photosensitive resin composition containing the surface tension reducing agent.
For example, commercially available products include polyether-modified silicones BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-320, BYK- 325, BYK-330, BYK-331, BYK-332, BYK-333, BYK-341, BYK-344, BYK-375, BYK-UV3500, BYK-UV3510, BYK-UV3530, BYK-UV3570;
BYK-310, BYK-315, BYK-370, which are polyester-modified silicones
BYK-322 and BYK-323 which are aralkyl-modified silicones;
Acrylic modified silicones BYK-352, BYK-354, BYK-355, BYK-356, BYK-357, BYK-358, BYK-359, BYK-361;
Examples include silicone modified BYK-Silclean 3700 (manufactured by Big Chemie Japan Co., Ltd.).
Examples of the fluorine compound include Floren AC-300, Floren AC-900, Floren AO-3, Floren AKS, Flownon SB-110N, Flownon SB-210, Flownon SB-510, Flownon SB-551 ( Kyoeisha Chemical Co., Ltd.), EF-305, EF-306A (manufactured by Shin-Akita Kasei Co., Ltd.), Emar 0, Emar AD-25R, Emar TD, Emar E-27C, Emar NC-35, Rheodor MS-50 , Leodole SP-L10, Leodole AO-10, Leodole TW-L120, Leodole TW-O120, Leodole Super TW-S120, Leodole 430, Neoperex F-25, Neoperex No25, Emanon 1112, Emanon 4110, EMANO-NN 299, Emazole L-10H, Emazole P-120, Emazole O120 (manufactured by Kao Corporation), Emulgen 105, Emulgen 108, Emulgen 147, Emulgen 210, Emulgen 320P, Emulgen 404, Emulgen 430, Emulgen 903, Emulgen 906, Emulgen 920, Emulgen 950, Emulgen 705, Emulgen PP-150, Emulgen PP-230, Emulgen PP-250, Emulgen PP-290, Amit 105, Amit 308, Amit 320, Cotamine 24P, Cotamine D-86P, Amphithol 24B, Amphithal 86B (Manufactured by Kao Atlas Co., Ltd.).

Further, a surfactant may be included. Examples of the surfactant include a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom. Examples of the silicone surfactant include surfactants having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (manufactured by Torresilicone), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.) and the like.
Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFuck F142D, F171, F172, F173, F177, F183, and R30 (Dainippon Ink Chemical Co., Ltd.) ), EFTOP EF301, EF303, EF351, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Surflon S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.), E5844 (Daikin Fine Chemical Co., Ltd.) Laboratory), BM-1000, BM-1100 (manufactured by BM Chemie).
Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Mega Fuck R08, BL20, F475, F477, F443 (manufactured by Dainippon Ink & Chemicals, Inc.), Surfinol 61, Orphine B, Olphin P, Surfinol 82, Surfinol 104, Olfin Y, Dinol 604, Surfinol 440, Surfinol 465, Surfinol 485, Surfinol 2502 (all manufactured by Nissin Chemical Industry Co., Ltd.) can be mentioned.
These surfactants may be used alone or in combination of two or more.

  The colored photosensitive resin composition of the present invention may contain an organic acid having a molecular weight of 1,000 or less. Examples of the organic acid having a molecular weight of 1,000 or less include the organic acids disclosed in JP-A-5-343631. Specifically, malonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, itaconic acid, mesaconic acid, fumaric acid, phthalic acid, acrylic acid, Methacrylic acid is mentioned, Preferably malonic acid, oxalic acid, fumaric acid, and phthalic acid are mentioned. By containing an organic acid having a molecular weight of 1,000 or less, the residue tends to be even better, which is preferable.

  The colored photosensitive resin composition of the present invention further includes a filler, a polymer compound other than the binder resin, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, an organic acid, an organic amino compound, and a curing agent. Etc. may be contained.

  Examples of the filler include fine particles such as glass and alumina.

  Examples of the polymer compound other than the binder resin include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

  Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-amino-n-propylmethyldimethoxysilane, N -(2-aminoethyl) -3-amino-n-propyltrimethoxysilane, 3-amino-n-propyltriethoxysilane, 3-glycidoxy-n-propyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloro-n-propylmethyldimethoxysilane, 3-chloro-n-propyltrimethoxysilane, 3-methacryloxy-n-propyltrimethoxysilane, 3- Mercapto-n-propyltrimethoxysilane, etc. And the like.

  Examples of the antioxidant include 4,4'-thiobis (6-tert-butyl-3-methylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.

Examples of the ultraviolet absorber include benzotriazoles such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole;
Benzophenone series such as 2-hydroxy-4-octyloxybenzophenone;
Benzoate systems such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate;
And triazines such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol.

  Examples of the aggregation preventing agent include sodium polyacrylate.

By adding an amine compound, it is possible to further reduce the residue on the substrate in the unexposed area during development, and to provide a pixel having excellent adhesion to the substrate.
Examples of the organic amine compound include n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n- Monoalkylamines such as octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, Dialkylamines such as di-n-pentylamine and di-n-hexylamine;
Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicycloalkylamines such as dicyclohexylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n -Trialkylamines such as butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine;
Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine;
Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol Kind;
Monocycloalkanolamines such as 4-amino-1-cyclohexanol;
Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, din-pentanolamine, di-n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, tri-isopropanolamine, tri-n-butanolamine, tri-isobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine;
Tricycloalkanolamines such as tri (4-cyclohexanol) amine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 Aminoalkanediols such as 1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanols such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol;
Amino group-containing cycloalkanemethanols such as 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1- Aromatic amines such as naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
Examples include aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid.

  Examples of the curing agent include a compound that can react with a carboxyl group in the binder resin by being heated to crosslink the binder resin, and a compound that can be polymerized alone to cure the colored pattern. . As said compound, an epoxy compound, an oxetane compound, etc. are mentioned, for example, An oxetane compound is used preferably.

  Here, as the epoxy compound, for example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, other aromatic epoxy resins , Alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oil, brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof Aliphatic, cycloaliphatic or aromatic epoxy compounds, epoxidized butadiene (co) polymers, epoxidized isoprene (co) polymers, glycidyl (meth) acrylate (co) polymers, triglycidyl Examples include isocyanurate.

  Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  When the colored photosensitive resin composition of the present invention contains an epoxy compound, an oxetane compound, or the like as a curing agent, it may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Good. Examples of the compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators.

Examples of the polyvalent carboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3 Aromatic polycarboxylic acids such as 3,3 ', 4,4'-benzophenonetetracarboxylic acid;
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid And alicyclic polyvalent carboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid.

Examples of the polyvalent carboxylic acid anhydrides include aromatic phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. Carboxylic anhydrides;
Aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Kind;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polycarboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride, and nadic anhydride;
Examples include ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic acid and glycerin tristrimellitic anhydride.

  As said carboxylic acid anhydride, you may use what is marketed as an epoxy resin hardening | curing agent. Examples of the epoxy resin curing agent include ADEKA HARDNER EH-700 (manufactured by Asahi Denka Kogyo Co., Ltd.), RIKACID HH, and MH-700 (all manufactured by Shin Nippon Rika Co., Ltd.).

  The above curing agents may be used alone or in combination of two or more.

  As a method for preparing the colored photosensitive resin composition of the present invention, for example, a dispersion of a colorant is prepared by dispersing a colorant such as a pigment in the solvent (E) together with a dispersant. Furthermore, (B) binder resin, (C) photopolymerizable compound, (D) photopolymerization initiator and other additives as necessary dissolved in a solvent are dissolved, and the above-mentioned (A) colorant is dispersed. The method of mixing with a liquid and adding a solvent further as needed is mentioned.

  In addition, the colored photosensitive resin composition of the present invention is usually enclosed in a container and distributed and stored.

A general method for producing a color filter for an image sensor using the colored photosensitive resin composition of the present invention is as follows. A step of applying and drying the colored photosensitive resin composition of the present invention on a substrate, a step of pattern exposure of the obtained dry coating film with an i-line stepper, a step of alkali development after exposure, and a step of heat treatment A color filter is obtained by sequentially performing the above steps for each color (usually three colors, in some cases four or more colors) to form pixels.
More specifically, the colored photosensitive resin composition of the present invention is dried on a suitable substrate by a spin coater or the like so that the film thickness when dried is generally 0.1 to 5 μm, preferably 0.2 to 2 μm. Then, it is left in an oven at 100 ° C. for 3 minutes to obtain a smooth coating film.
The substrate is not particularly limited, but is a glass plate, a plastic plate, an aluminum plate, a substrate for an electronic component such as a silicon wafer for an image sensor, a transparent resin plate, a resin film, a cathode ray tube display surface, a light receiving surface for imaging feeling, Wafers on which solid-state image sensors such as CCD, BBD, CID, and BASIS are formed, contact image sensors using thin film semiconductors, liquid crystal display surfaces, color electrophotographic photoreceptors, substrates for electrochromy (EC) display devices, etc. Is mentioned. Further, it is preferable to perform a high adhesion treatment to improve the adhesion to the color filter layer on the substrate. Specifically, after a thin coating with a silane coupling agent or the like is applied on the substrate in advance, a pattern of the colored photosensitive resin composition is formed, or the colored photosensitive resin composition is previously incorporated with a silane coupling agent. Also good.
If there is a step on the substrate, apply the colored photosensitive resin composition of the present invention after coating the substrate with a planarizing film for eliminating the step and smoothing the coating surface. Can do. For example, an image sensor such as a CCD is composed of a photoelectric conversion unit (photodiode) that generates electrons on a silicon substrate in accordance with the amount of received light and a read gate unit for outputting the generated electrons. If light hits the gate part, it causes noise and accurate data is not output.Therefore, a light shielding film layer is formed on the top of the readout gate part, and there is a step between the photodiode part without the light shielding film layer. It may have occurred. When a colored photosensitive resin composition is applied on such a step and a color filter is directly formed, the optical path length becomes long, so that the image becomes dark and the light condensing property becomes inferior. In order to improve this, it is preferable to form a transparent flattening film between the CCD and the color filter in order to fill the step. As a material for the planarizing film, a photosensitive resin composition obtained by removing a coloring component from the colored photosensitive resin composition in the present invention, an acrylic or epoxy thermosetting resin, a photocurable resin, or the like. Is mentioned.
After applying the colored photosensitive resin composition, in order to obtain a dry coating film by removing the solvent, drying under reduced pressure or pre-baking is usually performed. As a method for drying under reduced pressure, for example, there is a method in which a substrate coated with the coated colored photosensitive resin composition is placed at a temperature of 50 to 120 ° C. at a pressure of 0.1 to 100 Torr. Examples of the pre-baking method include heat drying using high-temperature air and the like, and heat drying using a hot plate or the like (80 to 140 ° C., 50 to 200 seconds).
Next, the colored photosensitive resin composition layer is exposed using a light source such as i-line through a mask for transferring a pattern to be formed.
Furthermore, the colored photosensitive resin composition layer after exposure is brought into contact with a developer, and the unexposed portion is removed to obtain a pattern.
There is no restriction | limiting in particular in the developing solution used for development of a coloring photosensitive resin composition, A conventionally well-known developing solution can be used. Of these, quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH) and organic alkaline aqueous solutions such as diethanolamine are preferable.
Further, post-baking is preferably performed in order to sufficiently cure the pattern obtained after the development to increase the mechanical strength and form a permanent film.
For example, in the production of a three-color filter, the first formed pattern is then subjected twice to the application of a colored photosensitive resin composition of another color, exposure, and development. At this time, post-baking is performed so as not to cause pattern omission due to color mixing, exposure, and development with the applied colored photosensitive resin composition. This post-baking uses the same method as pre-baking, but is performed at a higher temperature and for a longer time than the pre-baking conditions. For example, it is performed at 100 to 250 ° C. for 1 to 60 minutes.
As described above, it is possible to form a pattern of each color and finally obtain a color filter.
In addition, when forming a colored photosensitive resin composition film using the colored photosensitive resin composition of the present invention, the colored photosensitive resin composition film used later is a colored photosensitive resin composition film formed in advance. Since it is difficult to remain on the color filter, the color mixture in the color filter is reduced, which is preferable.

  Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and includes the meaning equivalent to the description of the claims and all modifications within the scope.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

<Synthesis of binder resin (B1)>
333 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, after the temperature of the solution in the flask was raised to 100 ° C., 22.0 g (0.10 mol) of dicyclopentanyl methacrylate (FA-513M; manufactured by Hitachi Chemical Co., Ltd.), 70.5 g of benzyl methacrylate (0 .40 mol), 43.0 g (0.5 mol) of methacrylic acid, 3.6 g of azobisisobutyronitrile and 164 g of propylene glycol monomethyl ether acetate were added dropwise to the flask using a dropping funnel over 2 hours. After completion of the dropwise addition, stirring was further continued at 100 ° C. for 5 hours.
After the stirring was completed, air was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was changed to air. Then, 35.5 g of glycidyl methacrylate [0.25 mol (based on methacrylic acid used in this reaction)] In a molar fraction, 50 mol%)], 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a solution containing resin B1. (Solid content 38.5% by mass, acid value 80 mg KOH / g).
Here, the acid value is a value measured as an amount (mg) of potassium hydroxide necessary to neutralize 1 g of a polymer having an acid group such as carboxylic acid, and is usually a potassium hydroxide aqueous solution having a known concentration. It is calculated | required by titrating using.
The obtained resin B1 had a polystyrene equivalent weight average molecular weight of 9,000.

About the measurement of the polystyrene conversion weight average molecular weight of said binder resin, it carried out on condition of the following using GPC method.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent; THF
Flow rate: 1.0 ml / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μl
Detector; RI
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The components used in this example are as follows, and may be omitted below.
(A-1) Colorant: C.I. I. Pigment Red 254
(A-2) Colorant: C.I. I. Pigment Yellow 139
(A-3) Colorant: C.I. I. Pigment Green 7
(A-4) Colorant: C.I. I. Pigment Green 36
(A-5) Colorant: C.I. I. Pigment Blue 15: 6
(A-6) Colorant: C.I. I. Pigment Violet 23
(B-1) Resin B1
(C-1) Photopolymerizable compound: Dipentaerythritol hexaacrylate (D-1) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (G- 1) Photopolymerization initiation assistant: 4,4'-bis (diethylamino) benzophenone (E-1) Solvent: Propylene glycol monomethyl ether acetate (E-2) Solvent: Ethyl 3-ethoxypropionate (F-1) Surface tension Reducing agent: BYK-UV3510 (manufactured by Big Chemie Japan Co., Ltd.)
(F-2) Surface tension reducing agent: BYK-Silclean 3700 (manufactured by Big Chemie Japan Co., Ltd.)
(H-1) Surfactant: Megafac F475 (Dainippon Ink Chemical Co., Ltd.)

Example 1
[Preparation of colored photosensitive resin composition 1]
(A-1) 0.6376 parts by mass (A-2) 0.1904 parts by mass Acrylic dispersant 0.2060 parts by mass (B-1) 1.3544 parts by mass (C-1) 0.1738 parts by mass ( D-1) 0.0556 parts by mass (G-1) 0.0139 parts by mass (E-1) 6.5470 parts by mass (E-2) 0.8200 parts by mass (F-1) 0.0007 parts by mass ( H-1) Colored photosensitive resin composition 1 was obtained by mixing 0.0005 parts by mass. The content of the surface tension adjusting agent was 0.38% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition 1.

[Pattern formation 1]
Next, on the glass (# 1737; manufactured by Corning), Sumiresist PR-1300Y-PG (manufactured by Sumitomo Chemical Co., Ltd.) is spin-coated, and heated at 100 ° C. for 1 minute to remove volatile components. A 0.5 μm resin layer was formed. Next, this glass was heated at 230 ° C. for 15 minutes to cure the resin layer, thereby forming a support with a flattened film. The colored photosensitive resin composition 1 is applied onto this support by spin coating, and then heated on a hot plate at 100 ° C. for 3 minutes to volatilize volatile components to form the colored photosensitive resin composition layer 1. did. After cooling, the colored photosensitive resin composition layer 1 was exposed by irradiating with i-line [wavelength 365 nm] through a photomask. An ultra-high pressure mercury lamp was used as the i-line light source, and the light was irradiated after being converted into parallel light. The amount of irradiation light was 150 mJ / cm ² . As the photomask, a photomask for forming linear color pixels having a line width of 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, and 100 μm was used. Next, a glass substrate after exposure [a colored photosensitive resin composition film is formed on the surface. ] Is developed by immersing in a developer (SOPD; manufactured by Sumitomo Chemical Co., Ltd.) at 23 ° C. for 80 seconds in pure water to obtain a 0.05% TMAH concentration), washed with pure water, A glass substrate (red) patterned with a 0.7 μm thick line and space pattern was obtained.

[Evaluation 1]
Of the coating layer of the substrate obtained above, the transmittance (average of 400 nm to 780 nm) of the portion where the coating layer was removed by development was measured using a microspectrophotometer (OSP-SP-200; Olympus Corporation). ), It was 99.9%.

[Pattern formation 2]
(A-3) 0.4212 parts by mass (A-4) 0.1620 parts by mass (A-2) 0.2268 parts by mass Ester-based dispersant 0.1954 parts by mass (B-1) 1.3801 parts by mass ( C-1) 0.1771 parts by mass (D-1) 0.0708 parts by mass (G-1) 0.0142 parts by mass (E-1) 6.512 parts by mass (E-2) 0.8200 parts by mass ( F-1) 0.0007 parts by mass (H-1) Colored photosensitive resin composition A was obtained by mixing 0.0005 parts by mass. The content of the surface tension modifier was 0.39% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition A.

Separately, on the glass (# 1737; manufactured by Corning), the colored photosensitive resin composition A obtained above was applied by spin coating, and then the volatile components were volatilized at 100 ° C. for 3 minutes to give a colored photosensitive resin composition. A film was formed. After cooling, the colored photosensitive resin composition film was exposed by irradiating i-line (wavelength 365 nm) through a photomask. An ultra-high pressure mercury lamp was used as the i-line light source, and the light was irradiated after being converted into parallel light. The amount of irradiation light was 150 mJ / cm ² .
As the photomask, a photomask for forming linear color pixels having a line width of 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, and 100 μm was used.
Next, the exposed glass substrate was developed by immersing it in a developing solution (SOPD; manufactured by Sumitomo Chemical Co., Ltd.) at 23 ° C. with pure water to obtain a 0.05% TMAH concentration for 80 seconds. And a colored glass substrate (green) patterned with a line and space pattern was obtained. When the brightness of this pattern portion was measured using a microspectrophotometer (OSP-SP-200; manufactured by Olympus Corporation), the brightness was 53.4.
Next, the colored photosensitive resin composition 1 (red) is applied onto the obtained colored glass substrate (green) by a spin coating method, and then the volatile components are volatilized at 100 ° C. for 3 minutes to give a colored photosensitive resin composition. One film was formed.
Next, the obtained glass substrate [the film of the colored photosensitive resin composition A and the film of the colored photosensitive resin composition 1 are formed on the surface. ] Is developed by immersing in a developing solution (SOPD; manufactured by Sumitomo Chemical Co., Ltd., diluted with pure water to a concentration of 0.05% TMAH) for 80 seconds, washed with pure water, and colored. The film | membrane of the photosensitive resin composition 1 was removed and the colored glass substrate (green) which patterned the line and space pattern was obtained.

[Evaluation 2]
The transmittance (average of 400 nm to 780 nm) after dissolving the coating layer formed of the colored photosensitive resin composition A of the substrate obtained above was 99.8%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition A was measured, it was 53.1. The decrease in brightness before and after the treatment with the colored photosensitive resin composition 1 was 0.3. there were.
The transmittance and brightness were measured using a microscopic spectrophotometer: OSP-SP-200 (manufactured by Olympus), and the transmittance was an average value of values measured in increments of 5 nm between 400 nm and 780 nm. As for the decrease in brightness, the difference in brightness before and after lamination was determined for the following chromaticity.

Red pixel: x = 0.607
Green pixel: y = 0.544
Blue pixel: y = 0.117

Example 2
[Preparation of colored photosensitive resin composition 2]
(A-3) 0.4212 parts by mass (A-4) 0.1620 parts by mass (A-2) 0.2268 parts by mass Ester-based dispersant 0.1954 parts by mass (B-1) 1.3801 parts by mass ( C-1) 0.1771 parts by mass (D-1) 0.0708 parts by mass (G-1) 0.0142 parts by mass (E-1) 6.512 parts by mass (E-2) 0.8200 parts by mass ( F-1) 0.0007 parts by mass (H-1) A colored photosensitive resin composition 2 was obtained by mixing 0.0005 parts by mass. The content of the surface tension adjusting agent was 0.39% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition 2.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 2, in the same manner as in Example 1, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) ) To be 99.9%.

[Evaluation 2]
As a result of evaluating in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 2, the transmittance (400 nm) after dissolving the coating layer of the substrate was evaluated. The average of ˜780 nm was 99.8%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition A was measured, it was 52.9, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 2 was 0.5. there were.

Example 3
[Preparation of colored photosensitive resin composition 3]
(A-5) 0.4968 parts by mass (A-6) 0.1242 parts by mass Acrylic dispersant 0.2174 parts by mass (B-1) 1.4018 parts by mass (C-1) 0.2540 parts by mass ( D-1) 0.1429 parts by mass (G-1) 0.0238 parts by mass (E-1) 6.5179 parts by mass (E-2) 0.8200 parts by mass (F-1) 0.0008 parts by mass ( H-1) Colored photosensitive resin composition 3 was obtained by mixing 0.0005 parts by mass. The content of the surface tension adjusting agent was 0.44% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition 3.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 3, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) was the same as in Example 1. ) Was 99% or more.

[Evaluation 2]
As a result of evaluating in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 3, the transmittance (400 nm) after dissolving the coating layer of the substrate was evaluated. The average of ˜780 nm was 99.9%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition A was measured, it was 53.2, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 3 was 0.2. there were.

Comparative Example 1
[Preparation of colored photosensitive resin composition 4]
(A-1) 0.6376 parts by mass (A-2) 0.1904 parts by mass Acrylic dispersant 0.2060 parts by mass (B-1) 1.3557 parts by mass (C-1) 0.1740 parts by mass ( D-1) 0.0557 parts by mass (G-1) 0.0139 parts by mass (E-1) 6.5463 parts by mass (E-2) 0.8200 parts by mass (H-1) 0.0005 parts by mass By mixing, a colored photosensitive resin composition 4 was obtained.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 4, in the same manner as in Example 1, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) ) To be 97%.

[Evaluation 2]
(A-3) 0.4212 parts by mass (A-4) 0.1620 parts by mass (A-2) 0.2268 parts by mass Ester-based dispersant 0.1954 parts by mass (B-1) 1.3814 parts by mass ( C-1) 0.1773 parts by mass (D-1) 0.0709 parts by mass (G-1) 0.0142 parts by mass (E-1) 6.5305 parts by mass (E-2) 0.8200 parts by mass ( H-1) Colored photosensitive resin composition B was obtained by mixing 0.0005 parts by mass.

  When the brightness of the pattern portion of the colored photosensitive resin composition B was measured using a microspectrophotometer (OSP-SP-200; manufactured by Olympus Corporation) in the same manner as in Example 1, the brightness was 53.3. Met.

  Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 4 and the colored photosensitive resin composition A was changed to the colored photosensitive resin composition B. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 94%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition B was measured, it was 50.2, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 4 was 3.1. there were.

Comparative Example 2
[Preparation of colored photosensitive resin composition 5]
(A-3) 0.4212 parts by mass (A-4) 0.1620 parts by mass (A-2) 0.2268 parts by mass Ester-based dispersant 0.1954 parts by mass (B-1) 1.3814 parts by mass ( C-1) 0.1773 parts by mass (D-1) 0.0709 parts by mass (G-1) 0.0142 parts by mass (E-1) 6.5305 parts by mass (E-2) 0.8200 parts by mass ( H-1) Colored photosensitive resin composition 5 was obtained by mixing 0.0005 parts by mass.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 5, in the same manner as in Example 1, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) ) To be 96%.

[Evaluation 2]
Evaluation was made in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 5 and the colored photosensitive resin composition A was changed to the colored photosensitive resin composition B. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 91%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition B was measured, it was 48.7, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 5 was 4.6. there were.

Comparative Example 3
[Preparation of colored photosensitive resin composition 6]
(A-5) 0.4968 parts by mass (A-6) 0.1242 parts by mass Acrylic dispersant 0.2174 parts by mass (B-1) 1.4029 parts by mass (C-1) 0.2542 parts by mass ( D-1) 0.1430 parts by mass (G-1) 0.0238 parts by mass (E-1) 6.5172 parts by mass (E-2) 0.8200 parts by mass (H-1) 0.0005 parts by mass By mixing, a colored photosensitive resin composition 6 was obtained.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 6, in the same manner as in Example 1, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) ) To be 97%.

[Evaluation 2]
Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 6 and the colored photosensitive resin composition A was changed to the colored photosensitive resin composition B. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 95.0%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition B was measured, it was 50.5, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 6 was 2.8. there were.

Example 4
[Preparation of colored photosensitive resin composition 7]
(A-1) 0.6376 parts by mass (A-2) 0.1904 parts by mass Acrylic dispersant 0.2060 parts by mass (B-1) 1.3520 parts by mass (C-1) 0.1735 parts by mass ( D-1) 0.0555 parts by mass (G-1) 0.0139 parts by mass (E-1) 6.5485 parts by mass (E-2) 0.8200 parts by mass (F-1) 0.0021 parts by mass ( H-1) Colored photosensitive resin composition 7 was obtained by mixing 0.0005 parts by mass. The content of the surface tension modifier was 1.17% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 7, in the same manner as in Example 1, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) ) To be 99.9%.

[Evaluation 2]
(A-3) 0.4212 parts by mass (A-4) 0.1620 parts by mass (A-2) 0.2268 parts by mass Ester-based dispersant 0.1954 parts by mass (B-1) 1.3777 parts by mass ( C-1) 0.1768 parts by mass (D-1) 0.0707 parts by mass (G-1) 0.0141 parts by mass (E-1) 6.5327 parts by mass (E-2) 0.8200 parts by mass ( F-1) 0.0021 part by mass (H-1) 0.0005 part by mass was mixed to obtain a colored photosensitive resin composition C. The content of the surface tension adjusting agent was 1.15% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.
When the brightness of the pattern portion of the colored photosensitive resin composition C was measured using a microspectrophotometer (OSP-SP-200; manufactured by Olympus Corporation) in the same manner as in Example 1, the brightness was 53.1. Met.

  Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 7 and the colored photosensitive resin composition A was changed to the colored photosensitive resin composition C. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 99.8%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition C was measured, it was 52.9, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 7 was 0.2. there were.

Example 5
[Preparation of colored photosensitive resin composition 8]
(A-3) 0.4212 parts by mass (A-4) 0.1620 parts by mass (A-2) 0.2268 parts by mass Ester-based dispersant 0.1954 parts by mass (B-1) 1.3777 parts by mass ( C-1) 0.1768 parts by mass (D-1) 0.0707 parts by mass (G-1) 0.0141 parts by mass (E-1) 6.5327 parts by mass (E-2) 0.8200 parts by mass ( F-1) 0.0021 part by mass (H-1) 0.0005 part by mass was mixed to obtain a colored photosensitive resin composition 8. The content of the surface tension adjusting agent was 1.15% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 8, in the same manner as in Example 1, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) ) To be 99.9%.

[Evaluation 2]
Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 8 and the colored photosensitive resin composition A was changed to the colored photosensitive resin composition C. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 99.8%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition C was measured, it was 52.7, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 8 was 0.4. there were.

Example 6
[Preparation of colored photosensitive resin composition 9]
(A-5) 0.4968 parts by mass (A-6) 0.1242 parts by mass Acrylic dispersant 0.2174 parts by mass (B-1) 1.3395 parts by mass (C-1) 0.2536 parts by mass ( D-1) 0.1426 parts by mass (G-1) 0.0238 parts by mass (E-1) 6.5193 parts by mass (E-2) 0.8200 parts by mass (F-1) 0.0024 parts by mass ( H-1) Colored photosensitive resin composition 9 was obtained by mixing 0.0005 parts by mass. The content of the surface tension modifier was 1.33% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 9, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) was the same as in Example 1. ) To be 99.9%.

[Evaluation 2]
The colored photosensitive resin composition 1 of Example 1 was evaluated in the same manner as in Example 1 except that the colored photosensitive resin composition 9 and the colored photosensitive resin composition A were changed to the colored photosensitive resin composition C. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 99.9%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition C was measured, it was 53.0, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 9 was 0.1. there were.

Example 7
[Preparation of colored photosensitive resin composition 10]
(A-1) 0.6376 parts by mass (A-2) 0.1904 parts by mass Acrylic dispersant 0.2060 parts by mass (B-1) 1.3374 parts by mass (C-1) 0.1716 parts by mass ( D-1) 0.0549 parts by mass (G-1) 0.0137 parts by mass (E-1) 6.5575 parts by mass (E-2) 0.8200 parts by mass (F-2) 0.0103 parts by mass ( H-1) 0.0005 mass parts was mixed and the colored photosensitive resin composition 10 was obtained. The content of the surface tension adjusting agent was 0.57% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.
[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 10, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) was the same as in Example 1. ) To be 99.9%.

[Evaluation 2]
(A-3) 0.4212 parts by mass (A-4) 0.1620 parts by mass (A-2) 0.2268 parts by mass Ester-based dispersant 0.1954 parts by mass (B-1) 1.3631 parts by mass ( C-1) 0.1749 parts by mass (D-1) 0.0700 parts by mass (G-1) 0.0140 parts by mass (E-1) 6.5417 parts by mass (E-2) 0.8200 parts by mass ( F-2) 0.0140 mass part (H-1) 0.0005 mass part was mixed and the colored photosensitive resin composition D was obtained. The content of the surface tension modifier was 0.78% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.
When the brightness of the pattern portion of the colored photosensitive resin composition D was measured using a microspectrophotometer (OSP-SP-200; manufactured by Olympus Corporation) in the same manner as in Example 1, the brightness was 53.2. Met.

  Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 10 and the colored photosensitive resin composition A was changed to the colored photosensitive resin composition D. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 99.9%. Furthermore, when the brightness of the coating layer formed by the colored photosensitive resin composition D was measured, it was 52.9, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 10 was 0.3. there were.

Example 8
[Preparation of colored photosensitive resin composition 11]
(A-3) 0.4212 parts by mass (A-4) 0.1620 parts by mass (A-2) 0.2268 parts by mass Ester-based dispersant 0.1954 parts by mass (B-1) 1.3631 parts by mass ( C-1) 0.1749 parts by mass (D-1) 0.0700 parts by mass (G-1) 0.0140 parts by mass (E-1) 6.5417 parts by mass (E-2) 0.8200 parts by mass ( F-2) 0.0140 mass part (H-1) 0.0005 mass part was mixed and the colored photosensitive resin composition 11 was obtained. The content of the surface tension modifier was 0.78% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 11, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) was the same as in Example 1. ) To be 99.9%.

[Evaluation 2]
Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 11 and the colored photosensitive resin composition A was changed to the colored photosensitive resin composition D. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 99.8%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition D was measured, it was 52.8, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 11 was 0.4. there were.

Example 9
[Preparation of colored photosensitive resin composition 12]
(A-5) 0.4968 parts by mass (A-6) 0.1242 parts by mass Acrylic dispersant 0.2174 parts by mass (B-1) 1.3880 parts by mass (C-1) 0.2515 parts by mass ( D-1) 0.1415 parts by mass (G-1) 0.0236 parts by mass (E-1) 6.5264 parts by mass (E-2) 0.8200 parts by mass (F-1) 0.0102 parts by mass ( H-1) Colored photosensitive resin composition 12 was obtained by mixing 0.0005 parts by mass. The content of the surface tension adjusting agent was 0.57% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 12, in the same manner as in Example 1, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) ) To be 99.9%.

[Evaluation 2]
Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 12 and the colored photosensitive resin composition A was changed to the colored photosensitive resin composition D. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 99.9%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition D was measured, it was 53.1, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 12 was 0.1. there were.

Example 10
[Preparation of colored photosensitive resin composition 13]
(A-1) 0.6376 parts by mass (A-2) 0.1904 parts by mass Acrylic dispersant 0.2060 parts by mass (B-1) 1.3209 parts by mass (C-1) 0.1695 parts by mass ( D-1) 0.0542 parts by mass (G-1) 0.0136 parts by mass (E-1) 6.577 parts by mass (E-2) 0.8200 parts by mass (F-2) 0.0197 parts by mass ( H-1) 0.0005 mass parts was mixed and the colored photosensitive resin composition 13 was obtained. The content of the surface tension modifier was 1.09% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.
[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 13, in the same manner as in Example 1, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) ) To be 99.9%.

[Evaluation 2]
(A-3) 0.4212 parts by mass (A-4) 0.1620 parts by mass (A-2) 0.2268 parts by mass Ester-based dispersant 0.1954 parts by mass (B-1) 1.3477 parts by mass ( C-1) 0.1730 parts by mass (D-1) 0.0692 parts by mass (G-1) 0.0138 parts by mass (E-1) 6.5512 parts by mass (E-2) 0.8200 parts by mass ( F-2) 0.0194 parts by mass (H-1) 0.0005 parts by mass were mixed to obtain a colored photosensitive resin composition E. The content of the surface tension adjuster was 1.08% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.
When the brightness of the pattern portion of the colored photosensitive resin composition E was measured using a microspectrophotometer (OSP-SP-200; manufactured by Olympus Corporation) in the same manner as in Example 1, the brightness was 53.3. Met.

  Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 13 and the colored photosensitive resin composition A was changed to the colored photosensitive resin composition E. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 99.9%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition E was measured, it was 53.1, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 13 was 0.2. there were.

Example 11
[Preparation of colored photosensitive resin composition 14]
(A-3) 0.4212 parts by mass (A-4) 0.1620 parts by mass (A-2) 0.2268 parts by mass Ester-based dispersant 0.1954 parts by mass (B-1) 1.3477 parts by mass ( C-1) 0.1730 parts by mass (D-1) 0.0692 parts by mass (G-1) 0.0138 parts by mass (E-1) 6.5512 parts by mass (E-2) 0.8200 parts by mass ( F-2) 0.0194 mass part (H-1) 0.0005 mass part was mixed and the colored photosensitive resin composition 14 was obtained. The content of the surface tension adjuster was 1.08% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 14, in the same manner as in Example 1, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) ) Was 99.9% or more.

[Evaluation 2]
Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 14 and the colored photosensitive resin composition A was changed to the colored photosensitive resin composition E. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 99.9%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition E was measured, it was 53.0, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 14 was 0.3. there were.

Example 12
[Preparation of colored photosensitive resin composition 15]
(A-5) 0.4968 parts by mass (A-6) 0.1242 parts by mass Acrylic dispersant 0.2174 parts by mass (B-1) 1.3745 parts by mass (C-1) 0.2490 parts by mass ( D-1) 0.1401 parts by mass (G-1) 0.0233 parts by mass (E-1) 6.5347 parts by mass (E-2) 0.8200 parts by mass (F-1) 0.0195 parts by mass ( H-1) 0.0005 mass parts was mixed and the colored photosensitive resin composition 15 was obtained. The content of the surface tension adjuster was 1.08% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 15, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) was the same as in Example 1. ) To be 99.9%.

[Evaluation 2]
The colored photosensitive resin composition 1 of Example 1 was evaluated in the same manner as in Example 1 except that the colored photosensitive resin composition 15 and the colored photosensitive resin composition A were changed to the colored photosensitive resin composition E. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 99% or more (99.9%). Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition E was measured, it was 53.2, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 15 was 0.1. there were.

Comparative Example 4
[Preparation of colored photosensitive resin composition 16]
(A-1) 0.6376 parts by mass (A-2) 0.1904 parts by mass Acrylic dispersant 0.2060 parts by mass (B-1) 1.3197 parts by mass (C-1) 0.1694 parts by mass ( D-1) 0.0542 parts by mass (G-1) 0.0135 parts by mass (E-1) 6.5684 parts by mass (E-2) 0.8200 parts by mass (F-2) 0.0203 parts by mass ( H-1) 0.0005 mass parts was mixed and the colored photosensitive resin composition 16 was obtained. The content of the surface tension adjuster was 1.13% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 16, the transmittance after dissolving the coating film layer of the substrate (average of 400 nm to 780 nm) was the same as in Example 1. ) Was measured to be 98%.

[Evaluation 2]
(A-3) 0.4212 parts by mass (A-4) 0.1620 parts by mass (A-2) 0.2268 parts by mass Ester-based dispersant 0.1954 parts by mass (B-1) 1.3453 parts by mass ( C-1) 0.1726 parts by mass (D-1) 0.0691 parts by mass (G-1) 0.0138 parts by mass (E-1) 6.5526 parts by mass (E-2) 0.8200 parts by mass ( F-2) 0.0207 parts by mass (H-1) 0.0005 parts by mass were mixed to obtain a colored photosensitive resin composition F. The content of the surface tension adjusting agent was 1.15% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.
When the brightness of the pattern portion of the colored photosensitive resin composition F was measured using a microspectrophotometer (OSP-SP-200; manufactured by Olympus Corporation) in the same manner as in Example 1, the brightness was 53.3. Met.

  Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 16 and the colored photosensitive resin composition A was changed to the colored photosensitive resin composition F. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 96%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition F was measured, it was 50.9, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 16 was 2.4. there were.

Comparative Example 5
[Preparation of colored photosensitive resin composition 17]
(A-3) 0.4212 parts by mass (A-4) 0.1620 parts by mass (A-2) 0.2268 parts by mass Ester-based dispersant 0.1954 parts by mass (B-1) 1.3453 parts by mass ( C-1) 0.1726 parts by mass (D-1) 0.0691 parts by mass (G-1) 0.0138 parts by mass (E-1) 6.5526 parts by mass (E-2) 0.8200 parts by mass ( F-2) 0.0207 parts by mass (H-1) 0.0005 parts by mass were mixed to obtain a colored photosensitive resin composition 17. The content of the surface tension adjusting agent was 1.15% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 17, in the same manner as in Example 1, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) ) Was measured to be 98%.

[Evaluation 2]
Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 17 and the colored photosensitive resin composition A was changed to the colored photosensitive resin composition F. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 96%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition F was measured, it was 50.4, and the decrease in brightness before and after the treatment with the colored photosensitive resin composition 17 was 2.9. there were.

Comparative Example 6
[Preparation of colored photosensitive resin composition 18]
(A-5) 0.4968 parts by mass (A-6) 0.1242 parts by mass Acrylic dispersant 0.2174 parts by mass (B-1) 1.3690 parts by mass (C-1) 0.2480 parts by mass ( D-1) 0.1395 parts by mass (G-1) 0.0233 parts by mass (E-1) 6.5538 parts by mass (E-2) 0.8200 parts by mass (F-2) 0.0233 parts by mass ( H-1) 0.0005 mass parts was mixed and the colored photosensitive resin composition 18 was obtained. The content of the surface tension modifier was 1.29% by mass in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition.

[Evaluation 1]
Except for changing the colored photosensitive resin composition 1 of Example 1 to the colored photosensitive resin composition 18, in the same manner as in Example 1, the transmittance after dissolving the coating layer of the substrate (average of 400 nm to 780 nm) ) Was measured to be 98%.

[Evaluation 2]
Evaluation was conducted in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was changed to the colored photosensitive resin composition 18 and the colored photosensitive resin composition A was changed to the colored photosensitive resin composition F. As a result, the transmittance (average of 400 nm to 780 nm) after dissolving the coating layer of the substrate was 96%. Furthermore, when the brightness of the coating layer formed with the colored photosensitive resin composition F was measured, it was 51.1. The decrease in brightness before and after the treatment with the colored photosensitive resin composition 18 was 2.2. there were.

  The colored photosensitive resin composition of the present invention can form a color filter having a good residue, and the obtained color filter can be used for an image sensor or a liquid crystal display device.

Claims (6)

  A colored photosensitive resin composition comprising (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a solvent, and (F) a surface tension reducing agent.   (F) The colored photosensitive resin composition according to claim 1, wherein the surface tension reducing agent is a polyether-modified silicone, a polyester-modified silicone, an alkyl-modified silicone, or an acrylic-modified silicone.   The content of (F) the surface tension reducing agent is 0.001% by mass or more and 1.1% by mass or less in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition. Colored photosensitive resin composition.   The pattern formed using the coloring photosensitive resin composition in any one of Claims 1-3.   A color filter comprising the pattern according to claim 4. An image sensor comprising the color filter according to claim 5.