JP4872233B2 - Colored photosensitive resin composition and color filter formed using the same - Google Patents

Description

  The present invention relates to a colored photosensitive resin composition and a color filter formed using the same.

  A pixel of a color filter used in a liquid crystal display device is formed using a colored photosensitive resin composition.

  In the formation of each pixel, in detail, a colored photosensitive resin composition containing any one of the three colors R, G, and B is applied on a substrate using a coating apparatus, and a volatile component is formed. Is removed by heating or the like, and then exposed through a mask. Then, in the case of a negative type, the unexposed part is developed, and in the case of a positive type, the exposed part is developed and removed with a developer such as an alkaline aqueous solution. A pattern is formed, and the obtained pattern is subjected to heat treatment (hereinafter sometimes referred to as post-baking) to form a pixel. Then, a pixel is formed by the same operation using the remaining two colored photosensitive resin compositions of the three colors R, G, and B, respectively.

The colored photosensitive resin composition used in this way needs to be able to form a film with high hardness after post-baking, and in addition to the colorant, binder resin, photopolymerizable compound, photopolymerization initiator and solvent, an epoxy compound (A total amount of the photopolymerizable compound and the epoxy compound is about 20% by mass fraction with respect to the solid content of the colored photosensitive resin composition). (For example, refer to Patent Document 1).
However, the solubility is not sufficient, that is, in the case of the negative type, when removing the non-exposed part with a developer such as an alkaline aqueous solution, there is a problem that the dissolution rate is slow and a residue may remain. There has been a demand for a colored photosensitive resin composition which gives a film having high hardness after post-baking and has excellent solubility.

JP 2004-151705 A

  An object of the present invention is to provide a colored photosensitive resin composition having a high hardness after post-baking and having excellent solubility.

  Therefore, the present inventors have intensively studied the composition of the colored photosensitive resin composition, and in the colored photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, When the amount of the polymerizable compound or the amount of the epoxy compound is included, the total amount of the amount of the epoxy compound and the amount of the photopolymerizable compound is in a certain range with respect to the solid content of the colored photosensitive resin composition. The present inventors have found that the photosensitive resin composition becomes a colored photosensitive resin composition having a high hardness after post-baking and having excellent solubility, and has completed the present invention.

  That is, the present invention provides a colored photosensitive resin composition comprising a colorant (a), a binder resin (b), a photopolymerizable compound (c), a photopolymerization initiator (d), and a solvent (f). When the photosensitive resin composition does not contain the epoxy compound (e), the amount of the photopolymerizable compound (c) is (c) and (e) when the colored photosensitive resin composition contains the epoxy compound (e). A colored photosensitive resin composition having a total amount of more than 31% and not more than 45% in terms of mass fraction relative to the solid content of the colored photosensitive resin composition is provided. Moreover, this invention provides the color filter formed using the said colored photosensitive resin composition. Furthermore, the present invention provides a liquid crystal display device comprising the color filter.

  Since the colored photosensitive resin composition of the present invention is a colored photosensitive resin composition that gives a high hardness film after post-baking and has excellent solubility, it is suitable for the production of color filters for liquid crystal display devices. Furthermore, according to the colored photosensitive resin composition of the present invention, when an ITO film is deposited on the pixel of a color filter formed using the same, the pixel is wrinkled or the ITO film is disconnected. In particular, it can be suitably used in the case of manufacturing a color filter by depositing ITO without forming an overcoat. Further, there is little undissolved material on the substrate, and the pencil hardness of the pixel portion is also low. Since the present invention is good and can produce a high-quality color filter, and further, since there is no mass reduction at the post-baking temperature, contamination in the baking furnace can be improved. It is extremely useful to.

The colored photosensitive resin composition of the present invention is a colored photosensitive resin composition comprising a colorant (a), a binder resin (b), a photopolymerizable compound (c), a photopolymerization initiator (d), and a solvent. In the product, when the amount of the photopolymerizable compound or the epoxy compound (e) is contained, the total amount of the amount of the epoxy compound and the amount of the photopolymerizable compound is based on the solid content of the colored photosensitive resin composition. It is characterized by being in the range of more than 31% by mass and 45% by mass or less.
The colored photosensitive resin composition used for production of the color filter of the present invention contains a colorant (a). The colorant (a) may be a dye or a pigment. When the colorant (a) is a pigment, it may be an organic pigment that is organic or an inorganic pigment that is inorganic. Of these, organic pigments are preferably used because of their excellent heat resistance and color developability.

Specific examples of organic pigments and inorganic pigments 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 (hereinafter, CI Pigment Yellow is omitted and only the numeric part is described. In addition, the same applies to other hues) 3, 12, 13, 14, 15, 16, 17 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 Yellow pigments;
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.

  These organic pigments and inorganic pigments may be used alone or in combination of two or more. For example, in order to form a red pixel, C.I. I. Pigment Red 209 and CI Pigment Red 254 and at least one selected from C.I. I. Pigment Yellow 139 contains C.I. to form a green pixel. I. Pigment Green 36 and C.I. I. Pigment yellow 150 and C.I. I. In order to form a blue pixel by containing at least one selected from the group consisting of CI Pigment Yellow 138, C.I. I. It preferably contains CI Pigment Blue 15: 6 and CI Pigment Violet 23, respectively.

  Among the above pigments, organic pigments are optionally treated with rosin, surface treatment with a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid fine particles, etc. A pulverization process such as an atomization method, a cleaning process using an organic solvent or water for removing impurities, a removal process using an ion exchange method for ionic impurities, or the like may be performed.

  Content of a coloring agent (a) is a mass fraction with respect to the solid content of a coloring photosensitive resin composition, Preferably it is 25 mass% or more and 60 mass% or less, More preferably, it is 27 mass% or more and 55 mass%. %, Particularly preferably 30% by mass or more and 50% by mass or less. When the content of the colorant (a) is in the above range, the color density when it is used as a color filter is sufficient, and a necessary amount of binder resin can be contained in the composition, and the mechanical strength is sufficient. This is preferable because a simple pattern can be formed.

  In the colored photosensitive resin composition of the present invention, the pigment as the colorant preferably has a uniform particle size. The pigment is preferably dispersed uniformly in the solvent. In order to obtain a uniform particle diameter of the pigment, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained by carrying out a dispersion treatment by containing a surfactant as a pigment dispersant.

  Examples of the pigment dispersant include polyesters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, Surfactants such as polyethyleneimines are listed. As pigment dispersants, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (Tochem Products) Co., Ltd.), Mega Fuck (Dainippon Ink Chemical Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (Asahi Glass Co., Ltd.), Solsperse (Geneca Co., Ltd.) , EFKA (manufactured by EFKA CHEMICALS), PB821 (flavor) Made arsenide (Ltd.)), and the like. These pigment dispersants are used alone or in combination of two or more.

  When the pigment dispersant is used, the amount used is preferably 0.05 parts by mass or more and 1 part by mass or less, more preferably 0.05 parts by mass or more and 0.5 parts by mass or less per 1 part by mass of the colorant. . When the amount of the pigment dispersant used is in the above range, it is preferable because the pigment can be uniformly dispersed in the solvent.

  The colored photosensitive resin composition used for production of the color filter of the present invention contains a binder resin (b). The binder resin (b) preferably has a reactive group in its side chain. Here, the reactive group means a group that reacts with light and heat. Examples of the reactive group include a (meth) acryloyl group, an epoxy group, and an oxetanyl group, preferably a (meth) acryloyl group and an epoxy group, and more preferably a (meth) acryloyl group. Can be mentioned. When the binder resin (b) has a reactive group, the coating film hardness tends to increase, which is preferable.

  The binder resin (b) further 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 a mole fraction in the total structural units constituting the binder resin (b), preferably 16 mol% or more and 40 mol% or less, more preferably 18 It is from mol% to 38 mol%. When the content of the structural unit derived from (meth) acrylic acid is within 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 constituent unit of the binder resin other than the constituent unit derived from (meth) acrylic acid include aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, and unsaturated carboxylic acid glycidyl esters. Carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, macros having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain Examples include structural units derived from monomers such as monomers, structural units represented by formula (IV), and structural units represented by formula (VI).

（ＩＶ）

（ＶＩ）

(IV)

(VI)

(In Formula (IV) and Formula (VI), R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

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 the structural unit represented by formula (IV) (wherein, in formula (IV), R ¹ represents a methyl group, R ² Represents a hydrogen atom) / benzyl methacrylate copolymer, methacrylic acid / monomer leading to a structural unit represented by formula (VI) (wherein, in formula (IV), R ¹ represents a methyl group, R ² represents a hydrogen atom.) / benzyl methacrylate copolymer, a structural unit represented by the methacrylic acid / formula (VI) Ku monomer (however, here, in formula (IV), R ¹ represents a methyl group, R ² represents a hydrogen atom.) / Dicyclopentanyl methacrylate / benzyl methacrylate copolymer, methacrylic acid / formula (VI (Wherein, in formula (VI), R ¹ represents a methyl group and R ² represents a hydrogen atom) / styrene copolymer / tricyclodecanyl methacrylate A copolymer or the like is preferred.

  The acid value of binder resin (b) used by this invention is 50-150 normally, Preferably it is 60-135, Most preferably, it is 70-135. 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 acid polymer, and is usually obtained by titration with an aqueous potassium hydroxide solution. it can.

  Content of binder resin (b) is a mass fraction with respect to solid content of a coloring photosensitive resin composition, Preferably it is 16 mass% or more and 45 mass% or less, More preferably, it is 19 mass% or more and 40 mass% or less, Especially preferably, it is 22 mass% or more and 35 mass% or less. When the content of the binder resin (B) is in the above range, a pattern can be formed and the resolution and the remaining film ratio tend to be improved.

Binder resin having a structural component represented by formula (IV), for example, methacrylic acid / monomer leading to a structural unit represented by formula (IV) (wherein, in formula (IV), R ¹ represents a methyl group R ² represents a hydrogen atom.) / 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 formula (v) It can be obtained by reacting the compound represented (wherein, R ² represents a hydrogen atom in formula (V)).

（Ｖ）

(V)

Methacrylic acid / monomer that leads to a structural unit represented by formula (VI) (wherein, in formula (VI), R ¹ represents a methyl group and R ² represents a hydrogen atom) / styrene copolymer The / tricyclodecanyl methacrylate copolymer can be obtained by reacting benzyl methacrylate, methacrylic acid, or a monomethacrylate copolymer having a tricyclodecane skeleton with glycidyl methacrylate.

  The weight average molecular weight in terms of polystyrene of the binder resin is usually 5,000 to 35,000, preferably 6,000 to 30,000, and more 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 used for production of the color filter of the present invention contains a photopolymerizable compound (c). The photopolymerizable compound (c) is a compound capable of initiating polymerization by an active radical generated from a photopolymerization initiator when irradiated with light, for example, a compound having a polymerizable carbon-carbon unsaturated bond Is mentioned. The compound may be a monofunctional photopolymerizable compound or a bifunctional or trifunctional or higher polyfunctional photopolymerizable compound.

  Examples of the monofunctional photopolymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like.

  Examples of the bifunctional photopolymerizable compound include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, and neopentyl glycol diacrylate. Examples thereof include methacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, and 3-methylpentanediol dimethacrylate.

  Examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol. Examples include pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate.

  The photopolymerizable compounds may be used alone or in combination of two or more. Content of a photopolymerizable compound (c) is a mass fraction with respect to solid content of a coloring photosensitive resin composition, Preferably it exceeds 16 mass% and is 45 mass% or less. When the content of the photopolymerizable compound (c) is in the above range, curing is sufficiently performed and the remaining film ratio is improved, which is preferable.

  The colored photosensitive resin composition of the present invention may contain an epoxy compound (e), and preferably contains it. As for an epoxy compound (e), the epoxy compound which can bridge | crosslink binder resin in the heat processing of the coloring pattern after image development is mentioned, for example. Moreover, the epoxy compound which can superpose | polymerize independently by heating may be sufficient. Since the epoxy compound cures the colored pattern by crosslinking the binder resin or polymerizing the epoxy compound itself, the post-baking tends to hardly generate a sublimation from the colored pattern.

Examples of the epoxy compound include aromatic epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, and novolac type epoxy resin;
Epoxy resins such as alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester type resins, glycidyl amine type resins, epoxidation;
Brominated derivatives of said epoxy resins;
Aliphatic compound epoxide, alicyclic compound epoxidized product, aromatic compound epoxy compound, butadiene (co) polymer epoxidized product, isoprene (co) polymer epoxidized product, glycidyl (meth) acrylate (Co) polymer, triglycidyl isocyanurate, etc. are mentioned.

  The content of the epoxy compound (e) is a mass fraction with respect to the solid content of the colored photosensitive resin composition, preferably 0.5% or more and 15% or less, more preferably 1% or more and 15% or less, and particularly preferably. Is from 2% to 12%, more preferably from 3% to 10%. When the content of the epoxy compound is within the above range, curing is sufficiently performed and the remaining film ratio is improved, which is preferable.

  In the colored photosensitive resin composition of the present invention, when the colored photosensitive resin composition does not contain the epoxy compound (e), the amount of the photopolymerizable compound (c) is the same as that of the colored photosensitive resin composition. ), The total amount of (c) and (e) is more than 31% and less than 45%, preferably more than 32%, by mass fraction with respect to the solid content of the colored photosensitive resin composition. It is within 42%, more preferably more than 33% and within 39%. It is preferable that the total amount of the photopolymerizable compound (c) and the epoxy compound (e) is in the above range because the hardness tends to be high and the pixels tend not to wrinkle.

  The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (d). Examples of the photopolymerization initiator (d) include acetophenone compounds, biimidazole compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, oxime compounds, triazine compounds, active radical generators, and acid generators. .

  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, preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and the like. It is done. A plurality of acetophenone-based and other photopolymerization initiators may be used in combination.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2- Chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) bi Imidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) biimidazole, and the phenyl group at the 4,4′5,5′-position are carboalkoxy. Examples thereof include imidazole compounds substituted with a group (for example, see JP-A-7-10913), and preferably 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5 ′. -Tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

  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 (t-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 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, O-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like can be mentioned.

  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 active radical generator 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 and the like 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 And benzoin tosylate.

  Content of a photoinitiator (d) is a mass fraction with respect to the total amount of binder resin (b) and a photopolymerizable compound (c), Preferably it is 0.1 to 30 mass%, From more Preferably they are 1 mass% or more and 25 mass% or less. When the content of the photopolymerization initiator is in the above range, the exposure time is shortened by increasing the sensitivity of the composition, the productivity is improved, and the resolution is lowered due to the sensitivity of the composition being too high. This is preferable because it tends not to occur.

  In the colored photosensitive resin composition of the present invention, a photopolymerization initiation assistant may be used. The photopolymerization initiation assistant may be used in combination with a photopolymerization initiator, and is a compound used to promote polymerization of a photopolymerizable compound that has been polymerized by the photopolymerization initiator. Examples of photopolymerization initiation assistants include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.

  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-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. 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.

The photopolymerization initiation assistant may be used alone or in combination. Moreover, a commercially available thing can also be used as a photoinitiation auxiliary agent, As a commercially available photoinitiation auxiliary agent, a brand name "EAB-F" (made by Hodogaya Chemical Co., Ltd.) etc. are mentioned, for example. .
When using these photopolymerization initiation assistants, the amount used is preferably 0.005 mol or more and 10 mol or less, more preferably 0.01 mol or more and 5 mol or less, per mol of the photopolymerization initiator.

  Examples of the combination of a photopolymerization initiator and a photopolymerization initiation assistant that can be used in the colored photosensitive resin composition of the present invention include 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-phenylpropan-1-one / 4,4'- Bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4 4'-bis (diethylamino) benzophenone, 1-hydroxycyclohexyl fe Luketone / 4,4′-bis (diethylamino) benzophenone, oligomer of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one / 4,4′-bis (diethylamino) ) Benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, and the like, preferably 2-methyl-2 A combination of -morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone is mentioned.

  The colored photosensitive resin composition used for production of the color filter of the present invention contains a solvent (f). Examples of the solvent 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.
Among the above solvents, ethyl 3-ethoxypropionate and propylene glycol monomethyl ether acetate are preferably used.

  These solvents can be used alone or in combination of two or more. Content of a solvent is a mass fraction with respect to a coloring photosensitive resin composition, Preferably it is 70 to 95 mass%, More preferably, it is 75 to 90 mass%. When the content of the solvent is in the above range, the flatness at the time of coating is good, and the display characteristics are good when a color filter is formed, which is preferable.

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

  As the surfactant, at least one selected from the group consisting of silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms can be used.

  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 (trade name: manufactured by Torresilicone Co., Ltd.), KP321, KP322, KP323 , KP324, KP326, KP340, KP341 (made by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (made by GE Toshiba Silicone Co., Ltd.).

  Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Fluorinert (trade name) FC430, FC431 (Sumitomo 3M Co., Ltd.), Megafuck (trade name) F142D, F171, F172, F173, F177, F183, R183 (large) Nippon Ink Chemical Co., Ltd.), Ftop (trade name) EF301, EF303, EF351, EF352, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Surflon (tradename) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (all trade names: manufactured by BM Chemie) and the like.

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by Dainippon Ink & Chemicals, Inc.) and the like can be mentioned.

These surfactants can be used alone or in combination of two or more.
When the surfactant is contained, the content is a mass fraction with respect to the colored photosensitive resin composition, preferably 0.0005% by mass to 0.6% by mass, more preferably 0.001% by mass. It is 0.5 mass% or less. When the content of the surfactant is in the above range, the variation in the film thickness in the coating substrate surface tends to be small, which is preferable.

  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-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Examples include ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  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-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4-octyloxybenzophenone, and the like. Benzophenone series, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and other benzoate series, 2- (4,6-diphenyl-1,3,5-triazine And triazines such as -2-yl) -5-hexyloxyphenol.

  Examples of the aggregation preventing agent include sodium polyacrylate.

Examples of the organic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, and caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid;
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid are listed.

Examples of the organic amino compound include n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, and n-heptylamine. Monoalkylamines such as n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-butylamine, disec-butylamine, di-t-butylamine, di dialkylamines such as 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, tri-i-propylamine, tri-n-butylamine, tri trialkylamines such as i-butylamine, trisec-butylamine, tri-t-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, di-i-propanolamine, di-n-butanolamine, dii-butanolamine, di-n-pentanolamine, di-n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, 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 , 2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, aminoalkanediols such as 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, pi-propylaniline, pn-butylaniline, pt-butylaniline, Aromatic amines such as 1-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.

  As said hardening | curing agent, the compound which can react with the carboxyl group in binder resin and can bridge | crosslink binder resin by heating is mentioned, for example. Moreover, the compound which can superpose | polymerize independently and can harden a colored pattern is also mentioned. Examples of the compound include oxetane compounds.

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

  When the colored photosensitive composition of the present invention contains an oxetane compound or the like as a curing agent, it may contain a compound capable of ring-opening polymerization of the oxetane skeleton of the oxetane compound. 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, 3,3 Aromatic polycarboxylic acids such as', 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 polyvalent carboxylic acids such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride. Acid 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.

  The said hardening | curing agent can be used individually or in combination of 2 types or more, respectively.

  As a method for forming the color filter of the present invention, specifically, a colored photosensitive resin composition of one color of R, G, B is formed on a substrate or a substrate in advance. It is applied onto a photosensitive resin composition layer (hereinafter sometimes referred to as a substrate or the like), volatile components such as a solvent are removed from the applied colored photosensitive resin composition layer, and the volatile components are passed through a photomask. After the layer having been removed is exposed, it is developed with a developer such as an alkaline aqueous solution and post-baked to form one step, which is repeated using a colored photosensitive resin composition containing the other two colors, and finally The method of forming the color filter which has three colors of RGB is mentioned.

  Examples of the substrate include flat substrates such as a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, an Al substrate, and a GaAs substrate. These substrates may be subjected to pretreatment such as chemical treatment with chemicals such as a silane coupling agent, plasma treatment, ion plating treatment, sputtering treatment, gas phase reaction treatment, and vacuum deposition treatment. When a glass substrate or a silicon substrate is used as the substrate, a TFT or the like may be formed in advance on the surface of the substrate.

  In order to apply the colored photosensitive resin composition on the substrate, for example, the colored photosensitive resin composition of the present invention can be applied by spin coating (spin coating), casting coating, roll coating, slit & What is necessary is just to apply | coat on a board | substrate etc. by normal coating methods, such as a spin coat method and a slit coat method, and to volatilize volatile components, such as a solvent, by heating then. In this way, a layer made of the solid content of the colored photosensitive resin composition is formed on the substrate or the like.

  Next, a layer composed of a solid content of the colored photosensitive resin composition (hereinafter, this may be referred to as a colored photosensitive resin composition layer) is exposed. For exposure, for example, light may be irradiated through a photomask. As light rays, ultraviolet rays called g-line (wavelength 436 nm) and i-line (wavelength 365 nm) are usually used. The light beam is irradiated through a photomask. Here, for example, the photomask is provided with a light shielding layer that shields the light beam on the surface of a glass plate. The portion of the glass plate where the light-shielding layer is not provided is a light-transmitting portion that transmits light, and the colored photosensitive resin composition layer is exposed in a pattern according to the pattern of the light-transmitting portion, so that the light is transmitted. An unirradiated area that has not been irradiated and an irradiated area that has been irradiated with the light beam are generated. The irradiation amount of light in the irradiation region is the weight average molecular weight of the binder resin contained in the colored photosensitive resin composition, the ratio of the constituent units constituting the binder resin, the content of the binder resin, the type and content of the photopolymerizable compound. It is appropriately selected depending on the amount, the type and content of the photopolymerization initiator, the type and content of the photopolymerization initiation assistant, and the like.

  Develop after exposure. In order to develop, for example, the colored photosensitive resin composition layer after exposure may be brought into contact with a developer. Specifically, a substrate having a colored photosensitive resin composition layer formed on the surface thereof may be used. What is necessary is just to immerse in a developing solution. Examples of the developer include aqueous solutions of alkaline compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide. By the development, an unirradiated region that has not been irradiated with light rays in the colored photosensitive resin composition layer is removed. On the other hand, the light irradiation area remains as it is to form a pattern.

  After development, the desired pattern can be obtained usually by washing with water and drying. After developing and drying, post baking is performed in an apparatus such as a baking furnace. The post-baking tends to improve the mechanical strength of the pattern, and when a colored photosensitive resin composition further containing a curing agent is used, the colored pattern is further cured to increase the mechanical strength. It can be improved further. The post-baking temperature is preferably 180 ° C. or higher and 250 ° C. or lower, more preferably 200 ° C. or higher and 230 ° C. or lower. When the post-baking temperature is within the above range, curing is sufficiently caused, which is preferable. Further, the post-bake time is preferably 5 to 40 minutes, more preferably 10 to 36 minutes, and particularly preferably 15 to 30 minutes. When the post-bake time is in the above range, curing is sufficiently caused, which is preferable.

  In this way, the target colored pattern is formed, but the color of the colorant contained in the colored photosensitive resin composition is changed, and the colored photosensitive resin composition layer is again formed on the substrate in the same manner as described above. After the layer is exposed, it can be developed and then post-baked to further form a colored pattern. By repeating the above operation while changing the color of the colorant contained in the colored photosensitive resin composition, a colored pattern can be further formed, and a target color filter can be produced.

  Next, an ITO film is usually formed on the obtained color filter by sputtering. The film forming conditions for the ITO film can be appropriately selected from the conditions generally used industrially.

  The color filter thus obtained contains a pattern, and a suitable liquid crystal display device can be obtained by using the color filter.

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. EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.
<Synthesis of Resin (b-1)>
333 g of propylene glycol monomethyl ether acetate was introduced into a 1 L flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and 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 completion of the stirring, air was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was changed to air, and then 35.5 g of glycidyl methacrylate [corresponding to 0.25 mol, methacrylic acid used in this reaction] 50 mol% relative to the molar ratio], 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, the reaction was continued at 110 ° C. for 6 hours, and the solid content, acid value of 80 mgKOH / g of resin b-1 was obtained.
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 b-1 had a polystyrene-reduced weight average molecular weight of 9,000 as measured by GPC method.

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 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 Blue 15: 6
(A-2) Colorant: C.I. I. Pigment Violet 23
(B-1) Resin

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate (d) photopolymerization initiator; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (g) photopolymerization initiator Agent: 4,4′-bis (diethylamino) benzophenone (e) epoxy compound [orthocresol novolac type epoxy resin, “Sumiepoxy ESCN-195XL-80” (manufactured by Sumitomo Chemical Co., Ltd.)]
(F) Solvent: Propylene glycol monomethyl ether acetate

Example 1
[Preparation of colored photosensitive resin composition 1]
(A-1) 2.301 parts by mass (a-2) 1.239 parts by mass Acrylic pigment dispersant 1.772 parts by mass (b-1) 6.495 parts by mass (c) 6.495 parts by mass (d ) 0.779 parts by mass (g) 0.260 parts by mass (e) 0.650 parts by mass (f) 79.910 parts by mass were mixed to obtain a colored photosensitive resin composition 1. In the colored photosensitive resin composition 1, the total amount of the photopolymerizable compound (c) and the epoxy compound (e) was 35.7% with respect to the solid content of the colored photosensitive resin composition.

(Formation of colored layer)
On the surface of a glass substrate (# 1737; manufactured by Corning), the colored photosensitive resin composition 1 obtained above is applied by spin coating, and then heated at 100 ° C. for 3 minutes to volatilize volatile components and color. A photosensitive resin composition layer was formed. After cooling, the colored photosensitive resin composition layer was irradiated with i-line [wavelength 365 nm] using a photomask. An ultra-high pressure mercury lamp (HB-75105AA OP1 type; manufactured by USHIO INC.) was used as the i-line light source, and the amount of irradiation light was 150 mJ / cm ² . Next, the film was developed by immersing in a developer (an aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate by mass fraction) for 80 seconds, washed with pure water, and then glass. A colored layer formed over the entire surface of the substrate was obtained. Thereafter, heat treatment (post-bake) was performed at 220 ° C. for 20 minutes to obtain a pixel.

[Undissolved substance evaluation]
After being immersed in the developer for 80 seconds (time when the unexposed portion was dissolved: 30 seconds), using a spectrophotometer (model number: OSP-SP200; manufactured by Olympus Co., Ltd.), unexposed with the colored layer removed by development When the transmittance of the part was measured, the average transmittance at a wavelength of 380 nm to 780 nm was 99% or more, and no undissolved product was found.

[Pencil hardness evaluation]
In accordance with the test method described in JIS K 5400, the pencil hardness was measured five times with a pencil “Mitsubishi High Uni” using a pencil “Mitsubishi High Uni” and a load of 9.8 N was applied. The highest hardness that does not stick is defined as pencil hardness.
The pencil hardness after post-baking was no problem at 5H or higher.
[ITO deposition evaluation]
What was sputtered at 120 ° C. using a vapor deposition apparatus (SPS-530H type; manufactured by Anelva) on the obtained color filter was subjected to ITO vapor deposition under an annealing condition at 230 ° C. for 30 minutes under 1500 ° C. When this film was formed, no wrinkles on the pixel and disconnection of the ITO film were observed.

(Mass reduction)
On the surface of a glass substrate (# 1737; manufactured by Corning), the colored photosensitive resin composition 1 obtained above is applied by spin coating, and then heated at 100 ° C. for 3 minutes to volatilize volatile components and color. A photosensitive resin composition layer was formed. After cooling, this colored photosensitive resin composition layer was irradiated with i-line (wavelength 365 nm) over the entire surface without passing through a photomask. An ultra-high pressure mercury lamp was used as the i-line light source, and the irradiation light quantity was 150 mJ / cm ² . Next, after immersing and developing in a developing solution (aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate by mass fraction), washing with pure water, A blue colored layer formed over the entire surface was obtained. The colored layer formed above is scraped from the glass substrate, its mass (M ₀ ) is measured at 23 ° C., then heated at 220 ° C. for 85 minutes, cooled to 23 ° C., and its mass (M ₁ ) is measured. The mass reduction rate (ΔM) was calculated by the formula (III) and found to be 0.07. Here, the smaller the mass reduction rate (ΔM), the smaller the amount of sublimation produced by heating after development. It is preferable that the amount of generated sublimation is small because the contamination in the baking furnace is small, and the interval for stopping the apparatus for maintenance to remove the sublimation can be increased.

ΔM = (M ₀ −M ₁ ) / M ₀ (III)

Example 2
[Preparation of colored photosensitive resin composition 2]
(A-1) 2.301 parts by mass (a-2) 1.239 parts by mass Acrylic pigment dispersant 1.772 parts by mass (b-1) 4.676 parts by mass (c) 8.313 parts by mass (d ) 0.779 parts by mass (g) 0.260 parts by mass (e) 0.650 parts by mass (f) 79.910 parts by mass were mixed to obtain a colored photosensitive resin composition 2. In the colored photosensitive resin composition 2, the total amount of the photopolymerizable compound (c) and the epoxy compound (e) was 44.8% with respect to the solid content of the colored photosensitive resin composition.

(Formation of colored layer)
A pixel was formed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was replaced with the colored photosensitive resin composition 2.
[Undissolved substance evaluation]
After immersing in the developer for 80 seconds (time when the unexposed portion was dissolved: 10 seconds), the transmittance on the glass substrate was measured. The average transmittance at a wavelength of 380 nm to 780 nm was 99% or more. I couldn't see it.

[Pencil hardness evaluation]
As a result of measuring the pencil hardness in the same manner as in Example 1, there was no problem at 5H or higher.

[ITO deposition evaluation]
When the obtained color filter was subjected to ITO vapor deposition treatment in the same manner as in Example 1, no wrinkles on the pixel and no disconnection of the ITO film were observed.
(Mass reduction)
The mass reduction rate (ΔM) was calculated in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was replaced with the colored photosensitive resin composition 2, and was 0.06. .

Example 3
[Preparation of colored photosensitive resin composition 2]
(A-1) 2.301 parts by mass (a-2) 1.239 parts by mass Acrylic pigment dispersant 1.772 parts by mass (b-1) 6.795 parts by mass (c) 6.795 parts by mass (d 0.816 parts by mass (g) 0.272 parts by mass (e) 0.000 parts by mass (f) 79.910 parts by mass were mixed to obtain a colored photosensitive resin composition 3. In the colored photosensitive resin composition 3, the total amount of the photopolymerizable compound (c) and the epoxy compound (e) was 34.0% with respect to the solid content of the colored photosensitive resin composition.

(Formation of colored layer)
A color filter was formed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was replaced with the colored photosensitive resin composition 3.
[Undissolved substance evaluation]
When the transmittance on the glass substrate was measured after the development step (film removal rate: 30 seconds), the average transmittance at a wavelength of 380 nm to 780 nm was 99% or more, and no undissolved material was observed.

[Pencil hardness evaluation]
As a result of measuring the pencil hardness in the same manner as in Example 1, there was no problem at 5H or higher.
[ITO deposition evaluation]
When the obtained color filter was subjected to ITO vapor deposition treatment in the same manner as in Example 1, no wrinkles on the pixel and no disconnection of the ITO film were observed.

(Mass reduction)
The mass reduction rate (ΔM) was calculated in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was replaced with the colored photosensitive resin composition 3, and was 0.08. .

Comparative Example 1
[Preparation of colored photosensitive resin composition 4]
(A-1) 2.301 parts by mass (a-2) 1.239 parts by mass Acrylic pigment dispersant 1.772 parts by mass (b-1) 4.546 parts by mass (c) 8.443 parts by mass (d ) 0.779 parts by mass (g) 0.260 parts by mass (e) 0.650 parts by mass (f) 79.910 parts by mass were mixed to obtain a colored photosensitive resin composition 4. In the colored photosensitive resin composition 4, the total amount of the photopolymerizable compound (c) and the epoxy compound (e) was 45.5% with respect to the solid content of the colored photosensitive resin composition.

(Formation of colored layer)
A color filter was formed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was replaced with the colored photosensitive resin composition 4.
[Undissolved substance evaluation]
When the development process was performed, an unexposed portion remained, and the transmittance on the glass substrate was measured, and the average transmittance at a wavelength of 380 nm to 780 nm was 95% or less.

[Pencil hardness evaluation]
As a result of measuring the pencil hardness in the same manner as in Example 1, there was no problem at 5H or higher.
[ITO deposition evaluation]
When the obtained color filter was subjected to ITO vapor deposition treatment in the same manner as in Example 1, no wrinkles on the pixel and no disconnection of the ITO film were observed.
(Mass reduction)

  The mass reduction rate (ΔM) was calculated in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was replaced with the colored photosensitive resin composition 4, and was 0.06. .

Comparative Example 2
[Preparation of colored photosensitive resin composition 5]
(A-1) 2.301 parts by mass (a-2) 1.239 parts by mass Acrylic pigment dispersant 1.772 parts by mass (b-1) 7.534 parts by mass (c) 5.456 parts by mass (d ) 0.779 parts by mass (g) 0.260 parts by mass (e) 0.650 parts by mass (f) 79.910 parts by mass were mixed to obtain a colored photosensitive resin composition 5. In the colored photosensitive resin composition 5, the total amount of the photopolymerizable compound (c) and the epoxy compound (e) was 30.5% with respect to the solid content of the colored photosensitive resin composition.

(Formation of colored layer)
A color filter was formed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was replaced with the colored photosensitive resin composition 5.
[Undissolved substance evaluation]
During the development, the developing speed of the coating film is slow, and after the developing step (film removal speed: 60 seconds), the transmittance on the glass substrate is measured, and the average transmittance at a wavelength of 380 nm to 780 nm is 95% or less, Undissolved material was seen.

[Pencil hardness evaluation]
As a result of measuring the pencil hardness in the same manner as in Example 1, there was no problem at 5H or higher.
[ITO deposition evaluation]
When the obtained color filter was subjected to ITO vapor deposition treatment in the same manner as in Example 1, no wrinkles on the pixel and no disconnection of the ITO film were observed.

(Mass reduction)
The mass reduction rate (ΔM) was calculated in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was replaced with the colored photosensitive resin composition 5, and it was 0.10. .

Claims (8)

In a colored photosensitive resin composition comprising a colorant (a), a binder resin (b), a photopolymerizable compound (c), a photopolymerization initiator (d), an epoxy compound (e), and a solvent (f) The total amount of (c) and (e) is a mass fraction with respect to the solid content of the colored photosensitive resin composition, exceeding 31% and within 45%, and the polystyrene equivalent weight of the binder resin (b) The average molecular weight is 5000 to 35000, the acid value of the binder resin (b) is 50 to 150 mg-KOH / g, the photopolymerizable compound (c) is dipentaerystol hexaacrylate, and photopolymerization is performed. A colored photosensitive resin composition, wherein the initiator (d) is an acetophenone compound and the epoxy compound (e) is a novolac type epoxy resin.   The colored photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (d) is a photopolymerization initiator containing 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one. .   The colored photosensitive resin composition according to claim 1 or 2, wherein the binder resin (b) has a reactive group.   The colored photosensitive resin composition according to claim 3, wherein the reactive group is a (meth) acryloyl group, an epoxy group, or an oxetanyl group.   The colored photosensitive resin composition according to claim 3, wherein the reactive group is a (meth) acryloyl group.   A color filter formed using the colored photosensitive resin composition according to claim 1.   The color filter according to claim 6, wherein the pixel does not have an overcoat.   A liquid crystal display device comprising the color filter according to claim 6.