JP2009276756A - Colored photosensitive resin composition, and pattern and color filter formed using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition which is less liable to dry and is easily redissolved when it dries. <P>SOLUTION: The colored photosensitive resin composition includes a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent. The solvent consists of at least one solvent (A) selected from the group consisting of dipropylene glycol monoalkyl ethers having a 1-4C alkyl group and dipropylene glycol monoalkyl ether esters having a 1-4C alkyl group and a solvent (B) different from the solvent (A), a content of the solvent (A) is 5-40 mass% relative to the total amount of the solvents, and a content of the solvent (B) is 60-95 mass% relative to the total amount of the solvents. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

In recent years, a liquid-saving coater typified by a slit-and-spin method and a spinless method has been used as a coating apparatus used for manufacturing a color filter (Patent Document 1). This liquid-saving coater is superior in cost because it can be applied to a substrate with a small amount of a colored photosensitive resin composition as compared with a conventional spin coater.
However, in this liquid-saving coater, the colored photosensitive resin composition is dried to become a foreign substance at the periphery of the slit where the colored photosensitive resin composition is brought into contact with the base material, falls on the base material, and the yield of the color filter is reduced. May cause decline. In order to avoid this, a cleaning operation around the slit is required, and improvement in productivity has been desired.
On the other hand, it is generally considered that drying is prevented by using a solvent having a high boiling point for the colored photosensitive resin composition. However, when a solvent having a high boiling point is used excessively, there is a problem that workability of a pre-bake process, which is a process for removing the solvent by volatilization before the exposure process, is lowered.

  An object of the present invention is to provide a colored photosensitive resin composition that is difficult to dry and can be easily redissolved when dried.

As a result of intensive studies, the present inventors have found that the above-described problems can be solved by using a specific amount of a specific solvent, and have completed the present invention.
That is, the colored photosensitive resin composition of the present invention is
A colored photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The solvent is at least one solvent (A) selected from the group consisting of dialkylene glycol monoalkyl ethers having 1 to 4 carbon atoms in the alkyl group and dipropylene glycol monoalkyl ether esters having 1 to 4 carbon atoms in the alkyl group; Comprising a solvent (B) different from (A),
The content of the solvent (A) is 5% by mass or more and 40% by mass or less based on the total amount of the solvent,
The content of the solvent (B) is 60% by mass or more and 95% by mass or less based on the total amount of the solvent.

Moreover, it is preferable that a solvent (B) is a solvent which has a boiling point of 121 to 171 degreeC.
The solvent (A) may be a C1-C4 dipropylene glycol monoalkyl ether of an alkyl group, and is particularly preferably dipropylene glycol monomethyl ether.
Furthermore, the solvent (B) is preferably propylene glycol methyl ether acetate.

Moreover, the pattern of this invention is formed using the colored photosensitive resin composition mentioned above, It is characterized by the above-mentioned.
Furthermore, the color filter of the present invention includes the above pattern.

  According to the colored photosensitive resin composition of the present invention, the colored photosensitive resin composition is hard to solidify around the slit, and even if partially solidified, it is re-dissolved by the solvent in the colored photosensitive resin composition. Since it is easy, the production | generation of the foreign material on a color filter can be suppressed. Further, productivity can be improved by reducing the frequency of slit cleaning or securing the productivity of the pre-baking process.

The colored photosensitive resin composition of the present invention mainly contains a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
The colorant used in the present invention may be an organic pigment or an inorganic pigment. A dye may also be used. Of these, organic pigments are preferably used because of their excellent heat resistance and color developability.

Examples of the organic pigments and inorganic pigments include compounds classified as pigments by Color Index (published by The Society of Dyers and Colorists).
Specifically, C.I. I. Pigment Yellow 1 (hereinafter, CI Pigment Yellow is omitted and only the number is described. Other hues are also described in the same manner) 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, etc. ;
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, 264, 265;

C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; 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, to form a red pixel, C.I. I. Pigment red 254 and C.I. I. Pigment red 177 or C.I. I. Pigment Yellow 139 is preferably contained, and C.I. I. Pigment green 36 and C.I. I. Pigment yellow 150 and C.I. I. It is preferable to contain at least one selected from the group consisting of CI Pigment Yellow 138. I. Pigment blue 15: 6 and C.I. I. Pigment violet 23 is preferably contained.

  The dye is not particularly limited as long as it is a dye that is soluble in an organic solvent. From the viewpoint of chemical structure, triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo as the organic solvent-soluble dye. , Etc. can be used. Particularly preferred are pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes, anthraquinone dyes and anthrapyridone dyes.

Among these, specific examples of acid dyes and direct dyes include the following.
acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112,113,120,129,138,147,150,158,171,182,192,210,242,243,256,259,267,278,280,285,290,296,315,324: 1, 335, 340;
acid chroma violet K;
acid Fuchsin;
acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251

Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;
Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3;
And derivatives of these dyes.
A derivative obtained by amidating a sulfonic acid group with an amine is preferably used.

  The content of the colorant is preferably 25% by mass or more and 60% by mass or less, more preferably 27% by mass or more and 55% by mass or less, in terms of mass fraction with respect to the solid content of the photosensitive resin composition. Preferably they are 30 mass% or more and 50 mass% or less. When the content of the colorant is in the above range, the color density when it is used as a color filter is sufficient, and since a necessary amount of binder resin can be contained in the composition, a pattern having excellent mechanical strength. Can be formed.

  If necessary, the pigment may be treated by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid atomization method, etc. Atomization treatment, cleaning treatment with an organic solvent or water for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like may be performed.

In the colored photosensitive resin composition obtained in the present invention, the pigment preferably has a uniform particle size.
In order to make the pigment have a uniform particle diameter, a dispersion liquid containing a surfactant is performed to obtain a pigment dispersion in which the pigment is uniformly dispersed in the solution.
Examples of the surfactant include cationic, anionic, nonionic, and amphoteric surfactants, and each is used alone or in combination of two or more.
When a surfactant is used during the preparation of the pigment dispersion, the amount used is usually 1 part by mass or less, preferably 0.05 parts by mass or more and 0.5 parts by mass or less per 1 part by mass of the pigment. When the amount of the surfactant used is in the above range, a pigment having a uniform particle size tends to be obtained.

  The colored photosensitive resin composition of the present invention contains a binder resin. As the binder resin, an acrylic copolymer can be used. Examples of the acrylic copolymer include a copolymer of a carboxyl group-containing monomer such as (meth) acrylic acid and another monomer copolymerizable with this monomer. In this specification, (meth) acrylic acid represents at least one selected from the group consisting of acrylic acid and methacrylic acid. The same applies to (meth) acrylate.

Examples of the carboxyl group-containing monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated polycarboxylic acids such as unsaturated tricarboxylic acids, and the like, and unsaturated monomers having at least one carboxyl group in the molecule. Carboxylic acid is mentioned.
Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

  The unsaturated polyvalent carboxylic acid may be its acid anhydride, specifically maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester such as succinic acid mono (2-acryloyloxyethyl) or succinic acid mono (2-methacryloyloxy). Ethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends thereof, and may be, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, or the like. These carboxyl group-containing monomers can be used alone or in admixture of two or more.

Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include a monomer having an ethylenically unsaturated bond and / or a monomer capable of addition polymerization.
For example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether Aromatic vinyl compounds such as m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, indene;

  Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl Methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl Acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy Tyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, Toxipropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy- Unsaturated carboxylic esters such as 3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate;

2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl Unsaturated carboxylic acid aminoalkyl esters such as methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;

Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether;
Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide;
Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples include macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane. Can do.
These monomers can be used alone or in admixture of two or more.

  The content of the carboxyl group-containing monomer unit in the copolymer is preferably 5% to 45%, more preferably 10% to 40%, based on the total number of moles of all the structural units of the copolymer. Yes, particularly preferably 15% to 35%. When the content of the carboxyl group-containing monomer unit is in the above range, the solubility in the developer is good and the pattern tends to be formed accurately during development.

  Examples of the acrylic polymer include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxy. Ethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl (meth) Acrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, ( (Meth) acrylic acid / 2-hydroxye (Meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer , (Meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / benzyl (meth) acrylate / N -Phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer (meth) acrylic acid / benzyl (meth) Acrylate / N-phenylmale De / styrene / glycerol mono (meth) acrylate copolymer, and the like.

Among them, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl (meth) acrylate copolymer, (Meth) acrylic acid / methyl (meth) acrylate / styrene copolymer is preferred.
These can be used alone or in admixture of two or more.

The polystyrene-reduced weight average molecular weight of the binder resin is preferably 5,000 to 50,000, more preferably 7,000 to 40,000, and particularly preferably 8,000 to 35,000. When the molecular weight of the binder resin is within the above range, the coating film hardness is improved, the remaining film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution tends to be improved.
The acid value of the binder resin is preferably 50 to 150, more preferably 60 to 140, and particularly preferably 70 to 130. 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. There is.
Here, the acid value is a value measured as an amount (mg) of potassium hydroxide necessary to neutralize 1 g of a resin having a group such as carboxylic acid, and usually an aqueous potassium hydroxide solution having a known concentration is used. Can be obtained by titration.

  The content of the binder resin is a mass fraction with respect to the solid content of the colored photosensitive resin composition, preferably 5% by mass to 30% by mass, more preferably 10% by mass to 28% by mass, and particularly preferably. It is 15 mass% or more and 26 mass% or less. When the content of the binder resin is in the above range, a pattern can be formed, and the resolution and the remaining film ratio tend to be improved.

  The colored photosensitive resin composition of the present invention contains a photopolymerizable compound. A photopolymerizable compound is a compound that can be polymerized by an active radical, an acid, or the like generated from a photopolymerization initiator when irradiated with light, such as a compound having a polymerizable carbon-carbon unsaturated bond. Can be mentioned.

The photopolymerizable compound 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. These can be used alone or in combination of two or more.
The content is a mass fraction of the colored photosensitive resin composition, preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and particularly preferably 20% by mass to 70% by mass. It is as follows. When the content of the photopolymerizable compound is 5% by mass or more and 90% by mass or less, the curing is sufficiently performed and the remaining film rate is improved, the pattern is less likely to be undercut, and the adhesion is improved. Tend.

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

  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.

  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 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) ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  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 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.
These can be used alone or in combination of two or more.

  Content of a photoinitiator is a mass fraction with respect to the total amount of binder resin and a photopolymerizable compound, Preferably it is 0.1 to 20 mass%, More preferably, it is 1 to 15 mass% It is as follows. When the content of the photopolymerization initiator is within the above range, the sensitivity is increased and the exposure time is shortened and the productivity is improved. On the other hand, the sensitivity is too high and the resolution does not tend to be poor.

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 further accelerate the polymerization of a photopolymerizable compound that has been polymerized by the photopolymerization initiator.
Examples of the 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, 4′-bis (ethylmethylamino) benzophenone and the like can be mentioned. Of 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, 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.

Moreover, a commercially available thing can also be used as a photoinitiator auxiliary agent, and as a commercially available photoinitiator auxiliary agent, brand name "EAB-F" (made by Hodogaya Chemical Co., Ltd.) etc. are mentioned, for example. .
The photopolymerization initiation assistants can be used alone or in combination of two or more.

  Examples of the combination of the photopolymerization initiator and the photopolymerization initiation assistant 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 Benzyl dimethyl 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 phenyl ketone / 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- Examples thereof include a combination of 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone. Of these, a combination of 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone is preferable.

  When using these photopolymerization initiation assistants, the amount used is preferably 10 mol or less, more preferably 0.01 mol or more and 5 mol or less, per mol of the photopolymerization initiator.

The solvent used in the colored photosensitive resin composition of the present invention is a group consisting of an alkyl group having 1 to 4 carbon atoms dipropylene glycol monoalkyl ether and an alkyl group having 1 to 4 carbon atoms dipropylene glycol monoalkyl ether ester. At least one solvent (A) selected from (hereinafter sometimes referred to as “solvent (A)”).
Here, the dipropylene glycol monoalkyl ether ester refers to a compound in which one hydroxyl group of dipropylene glycol forms an ether bond and the other hydroxyl group is acylated into an ester.
As an alkyl group, any of methyl, ethyl, propyl, n-butyl, t-butyl, and i-butyl may be used. Of these, those having 1 or 2 carbon atoms and more preferably 1 carbon atoms are preferred.

Specific examples of the dipropylene glycol monoalkyl ether having 1 to 4 carbon atoms in the alkyl group include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. . Preferred are dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether, and more preferred are dipropylene glycol monomethyl ether.
Examples of the dipropylene glycol monoalkyl ether ester having 1 to 4 carbon atoms in the alkyl group include dipropylene glycol monomethyl ether acetate.
Especially, it is preferable that a solvent (A) is a C1-C4 dipropylene glycol monoalkyl ether of an alkyl group, and it is more preferable that it is a dipropylene glycol monomethyl ether.

  Content of a solvent (A) is 5 to 40 mass% with respect to the total amount of solvent. In particular, the content is preferably 10% to 40%, and more preferably 10% to 30%. As a result, it is possible to prevent the colored photosensitive resin composition from solidifying at the slit portion of the slit coater and generating foreign matter on the color filter. Further, the pre-bake time before exposure can be shortened to improve productivity. Further, in some cases, the solvent is condensed in a pre-baking furnace, the condensed solvent falls on the substrate, and the yield of the unevenness is caused in the part where the solvent is dropped on the substrate obtained after the development. However, by setting the above-mentioned range, this can be effectively prevented.

  In addition, the solvent of the present invention preferably has an appropriate boiling point in combination with properties such as the chemical structure of the specific solvent described above from another viewpoint. For example, the boiling point is preferably about 172 ° C. or higher, about 180 ° C. or higher, and more preferably about 230 ° C. or lower and 220 ° C. or lower. By using a solvent having a boiling point in such a range, in the colored photosensitive resin composition, a balance between prevention of drying and volatilization of the solvent is achieved by combination with the type and amount of other solvent and further with other components. be able to.

  Moreover, as a solvent, the solvent (B) different from a solvent (A) other than the solvent (A) mentioned above is included. Examples of the solvent (B) include ethers excluding dipropylene glycol ethers and dipropylene glycol ether esters, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like.

Examples of the ethers include
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and diethylene glycol dibutyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monobutyl ether;
Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol dimethyl ether acetate, methoxybutyl acetate and methoxypentyl acetate;
Alkyl ether acetates such as methoxybutyl acetate and methoxypentyl acetate;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;
Other examples include ethyl carbitol acetate, butyl carbitol acetate, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, phenetole, and methylanisole.

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, glycerin, diacetone alcohol, and 3-methyl-3-methoxy-1-butanol.

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.
In particular, ether solvents are preferred, among which alkylene glycol alkyl ether acetates are more preferred, and propylene glycol methyl ether acetate is particularly preferred.

Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.
Examples of other solvents include N-methylpyrrolidone and dimethyl sulfoxide.
These can be used alone or in combination of two or more.

  Content of a solvent (B) is 60 to 95 mass% with respect to the total amount of solvent. In particular, the content is preferably 60% or more and 90% or less, and more preferably 70% or more and 90% or less. As a result, it is possible to prevent the colored photosensitive resin composition from solidifying at the slit portion of the slit coater and generating foreign matter on the color filter. Further, the pre-bake time before exposure can be shortened to improve productivity. Further, in some cases, the solvent is condensed in a pre-baking furnace, the condensed solvent falls on the substrate, and the yield of the unevenness is caused in the part where the solvent is dropped on the substrate obtained after the development. However, by setting the above-mentioned range, this can be effectively prevented.

  In addition, the solvent (B) of the present invention preferably has an appropriate boiling point in combination with properties such as the chemical structure of the specific solvent (A) as described above from another viewpoint. For example, the boiling point is preferably 171 ° C. or lower and 121 ° C. or higher. By using a solvent having a boiling point in such a range, in the colored photosensitive resin composition, a balance between prevention of drying and volatilization of the solvent is achieved by combination with the type and amount of other solvent and further with other components. It has been confirmed that the yield can be improved and the occurrence of unevenness on the surface after development is suppressed.

  The combination of the solvent (A) and the solvent (B) is preferably a combination of the solvent (A) and an alkylene glycol alkyl ether acetate (solvent (B)), or the solvent (A) and propylene glycol monomethyl ether. A combination of acetate (solvent (B)), a solvent (solvent (A)) selected from one or more types of C1-C4 dipropylene glycol monoalkyl ethers and propylene glycol monomethyl ether acetate (solvent (B )).

The colored photosensitive resin composition of the present invention may contain a surfactant. Examples of the surfactant include silicone surfactants, fluorine surfactants, and silicone surfactants 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, Examples thereof include KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by GE Toshiba Silicone).

Examples of the fluorosurfactant 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 (trade name) 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 these surfactants are used, the content is 0.0005% by mass or more and 0.6% by mass or less, preferably 0.001% by mass or more and 0.000% by mass or less, based on the colored photosensitive resin composition. 5% by mass or less. When the content of the surfactant is in the above range, the flatness of the obtained coating film tends to be improved.

  The colored photosensitive resin composition of the present invention comprises 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 amine compound, a curing agent, and the like. An agent 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-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Examples include methoxysilane, 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, and benzophenones such as 2-hydroxy-4-octyloxybenzophenone. Benzoate series such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazine-2 -Yl) -5-hexyloxyphenol and other triazine-based ultraviolet absorbers.

Examples of the aggregation inhibitor 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;
And aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid and pyromellitic acid.

Examples of the organic amine compound include n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-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;
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 thereof include aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid.

  As a hardening | curing agent, the compound which can react with the carboxyl group in a binder polymer by heating and can bridge | crosslink a binder polymer 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 an epoxy compound and an oxetane compound.

  Examples of the epoxy compound include bisphenol A-based epoxy resins, hydrogenated bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, novolac-type epoxy resins, other aromatic epoxy resins, and alicyclic rings. Epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oil, brominated derivatives of these epoxy resins, aliphatics other than epoxy resins and brominated derivatives thereof, Alicyclic or aromatic epoxy compounds, epoxidized products of butadiene (co) polymers, epoxidized products of isoprene (co) polymers, (co) polymers of glycidyl (meth) acrylate, triglycidyl isocyanurate, etc. Can be mentioned.

  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 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. . 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 glycerine tristrimellitic anhydride.

As the carboxylic acid anhydrides, those commercially available as an epoxy resin curing agent may be used. Examples of the epoxy resin curing agent include a trade name “Adeka Hardener EH-700” (manufactured by Asahi Denka Kogyo Co., Ltd.), a trade name “Licacid HH” (manufactured by Shin Nippon Rika Co., Ltd.), and a trade name “MH”. -700 "(manufactured by Shin Nippon Rika Co., Ltd.).
The said hardening | curing agent can be used individually or in combination of 2 types or more, respectively.

  As a method for forming a pattern using the colored photosensitive resin composition of the present invention, specifically, the colored photosensitive resin composition of the present invention is formed on a substrate or a solid colored photosensitive resin previously formed on the substrate. The volatile component such as a solvent is removed from the applied colored photosensitive resin composition layer by coating on the photosensitive resin composition layer (hereinafter sometimes referred to as a substrate), and the volatile component is passed through a photomask. And a method of developing after exposing the layer from which is removed.

  Examples of the substrate include a glass substrate; a plastic substrate such as polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide; a metal or alloy substrate such as Al; a semiconductor substrate such as silicon; and a surface of a compound semiconductor substrate such as GaAs. A flat substrate may be mentioned. These substrates may be subjected to pretreatment such as chemical treatment with a chemical such as a silane coupling agent, plasma treatment, ion plating treatment, sputtering treatment, gas phase reaction treatment, and vacuum deposition treatment. When a substrate such as a semiconductor or a compound semiconductor is used as the substrate, a charge coupled device (CCD), a thin film transistor (TFT), or the like may be formed on the surface of the silicon substrate or the like.

  In order to apply the colored photosensitive resin composition on the substrate, it is applied on the substrate using a spin coater, a liquid-saving coater, especially a slit coater, and then a volatile component such as a solvent is heated. It only has to be volatilized. In this way, a layer made of the solid content of the colored photosensitive resin composition is formed on the substrate or the like with good flatness. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target image. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so that parallel light rays are uniformly irradiated on the entire exposure unit and accurate alignment between the mask and the substrate is performed. Thereafter, the cured film is brought into contact with an alkaline aqueous solution to dissolve the non-exposed portion and developed, whereby a target image is obtained. After the development, post-baking can be performed at 150 to 230 ° C. for about 10 to 60 minutes as necessary.

The developer used for development after patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant.
The alkaline compound may be an inorganic or organic alkaline compound.
Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, and carbonic acid. Sodium, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like can be mentioned.
Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. It is done.
These inorganic and organic alkaline compounds can be used alone or in combination of two or more.
The preferable density | concentration of the alkaline compound in an alkali developing solution is 0.01-10 mass%, More preferably, it is 0.03-5 mass%.

The surfactant in the alkaline developer may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene Examples include ethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

Examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and dodecyl. And alkylaryl sulfonates such as sodium naphthalene sulfonate.
Examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
These surfactants may be used alone or in combination of two or more.
The concentration of the surfactant in the alkali developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass, based on mass.

  The pixels corresponding to the color of the coloring material in the colored photosensitive resin composition are obtained through the operations of applying the colored photosensitive resin composition as described above, drying, patterning exposure to the resulting dried coating film, and development. Further, by repeating these operations for the number of colors required for the color filter, a color filter is obtained. The thickness of the color filter is not particularly limited, and can be appropriately adjusted depending on the type and amount of the colorant used, the type and amount of the binder resin and solvent used, and the like.

  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 further includes meanings 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. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

<Synthesis of binder resin>
150 g of propylene glycol monomethyl ether acetate was introduced into a 1 L 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. Subsequently, the temperature of the solution in the flask was raised to 100 ° C., 130.4 g (0.74 mol) of benzyl methacrylate, 31.0 g (0.26 mol) of methacrylic acid, 2.6 g of azobisisobutyronitrile and propylene. A mixture consisting of 163 g of glycol monomethyl ether acetate was 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. A resin having a solid content of 34% by mass and an acid value of 100 mgKOH / g 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 weight average molecular weight of polystyrene conversion measured by GPC method of the following conditions of the obtained binder resin was 25,000.
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)

<Example 1>
14.6 parts of binder resin (methacrylic acid / benzyl methacrylate copolymer) obtained as described above, 3.3 parts of photopolymerizable compound (dipentaerythritol hexaacrylate), photopolymerization initiator (Irgacure 907) 0.5 part, 0.5 part of photopolymerization initiation assistant (2,4-diethylthioxanthone), 10 parts of propylene glycol monomethyl ether acetate and 35.4 parts of dipropylene glycol monomethyl ether as a solvent were mixed. Further, 10.2 parts of a colorant (CI Pigment Red 254), 3 parts of a dispersant (Ajisper PB821; acid value 17 mg (KOH) / g; manufactured by Ajinomoto Fine Techno Co., Ltd.) and propylene glycol monomethyl ether acetate 63 What was mixed and dispersed in advance was added and stirred to obtain a colored photosensitive resin composition.
Next, a glass substrate (# 1737; manufactured by Corning Japan Co., Ltd.) having a chromium film patterned in a lattice pattern was washed successively with a neutral detergent, water and alcohol and then dried.

On this glass substrate, the obtained colored photosensitive resin composition was applied with a coater equipped with a slit nozzle so that the post-baking chromaticity x = 0.655 (CIE1931 color system) and dried under reduced pressure. In the apparatus, the solvent was distilled off by maintaining at 1 torr and 70 ° C. for 60 seconds. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the photomask made of quartz glass having a stripe pattern is set to 150 μm, and an exposure amount of 100 mJ / cm ^{2 in} an air atmosphere using an ultrahigh pressure mercury lamp ( The light was irradiated at 365 nm standard).
Thereafter, development is performed by spraying a developer, which is an aqueous solution containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide, through the shower nozzle at 23 ° C. for 80 seconds. went. After washing with water, post-baking was performed at 220 ° C. for 20 minutes to form a pattern.

<Evaluation>
The obtained pattern substrate was observed for unevenness under a sodium lamp. In the vacuum drying apparatus used, the pins that support the substrate are arranged at a certain position. However, if unevenness can be confirmed at a position on the substrate corresponding to the position of this pin, the substrate is determined to be defective due to pin unevenness. The When such pin unevenness was observed in a number exceeding 30% of the charged substrate, “x” was written in the pin uneven column of Table 1. In the case of 30% or less, it was described as “◯”.
In addition, when unevenness is observed at a location that does not correspond to the position of the pin, the location is observed with an optical microscope, and the same color as the colored photosensitive resin composition, that is, a colored photosensitive resin composition of red is used. Then, when a red foreign material was confirmed, the number of substrates was recorded as a defective substrate due to the foreign material.
When the difference between the total number of substrates introduced and the total number of defective substrates due to foreign matter is 95% or more of the total number of substrates introduced, “Y” is indicated in the yield column of Table 1. When it was less than 95%, it was described as x.

<Examples 2-7, Comparative Examples 1-5>
The solvent described in Example 1 was changed to that shown in Table 1, and a colored photosensitive resin composition was prepared in the same manner, and applied, exposed, and developed to obtain a pattern substrate.
The evaluation results described above are shown in Table 1.

The numbers next to the solvent names represent the mass fraction of each solvent relative to the entire solvent.
PGMEA; propylene glycol monomethyl ether acetate (boiling point 146 ° C)
PGME; propylene glycol monomethyl ether (boiling point 121 ° C)
EEP; ethoxyethyl propionate (boiling point 165 ° C)
MFDG: Dipropylene glycol monomethyl ether (boiling point 190 ° C)
MBA; methoxybutyl acetate (boiling point 171 ° C.)
CHN; cyclohexanone (boiling point 156 ° C.)

  According to Table 1, in this example, the yield was good and almost no pin unevenness was observed.

Creation of Green Pixel The colorant described in Example 1 is C.I. I. Pigment Green 36 (7.1 parts) and C.I. I. A green colored photosensitive composition was prepared in the same manner except that it was changed to CI Pigment Yellow 150 (3.1 parts), and the above-described substrate on which the Red pixel was formed was similarly applied, exposed, developed, and post-baked. Green pixels were created. However, the coating was performed so that the chromaticity after Green post-baking was y = 0.590 (CIE 1931 color system).

Preparation of Blue Pixel The colorant described in Example 1 is C.I. I. Pigment Blue 15: 6 (7 parts) and C.I. I. A blue-colored photosensitive composition was prepared in the same manner except that it was changed to CI Pigment Violet 23 (0.5 part). Similarly, coating, exposure, development, and post-baking were performed on the substrate on which the green pixel was created, and a blue pixel was obtained. And a color filter having an RGB pattern was created. However, the coating was performed so that the chromaticity after blue post-baking was y = 0.100 (CIE 1931 color system).

Example 8 Production of Black Matrix [Preparation of Binder Resin]
In a four-necked flask with a volume of 300 mL, 46.3 g of bisphenol fluorenediglycidyl ether, 8.7 g of itaconic acid, 0.09 g of triethylbenzylammonium chloride, 0.18 g of tetraethylammonium bromide, 0.02 g of methoquinone, and propylene glycol monomethyl ether Acetate 55g was charged and reacted at 120 ° C. for 4 hours under heating and stirring to obtain a transparent light yellow viscous liquid. To the obtained viscous liquid, 4.8 g of propylene glycol monomethyl ether acetate and 4.8 g of acrylic acid were further added and reacted at 120 ° C. for 8 hours. This is designated Compound A.
Next, 55 g of Compound A, 10.2 g of tetrahydrophthalic anhydride, and 10.2 g of propylene glycol monomethyl ether acetate were charged and reacted at 120 ° C. with heating and stirring for 2 hours to obtain a pale yellow transparent unsaturated group-containing carboxyl. An acid compound solution A1 was obtained.

[Production of colored photosensitive resin composition]
52 parts by weight of a colorant [mixture of 40 parts by weight of a black pigment (CI Pigment Black 7) having an average particle size of 0.03 μm and 12 parts by weight of a dispersant]
Binder resin (resin solution A1 obtained above) 33 parts by mass (in terms of solid content),
10 parts by mass of an addition-polymerizable compound having an ethylenically unsaturated bond [dipentaerythritol hexaacrylate],
Photopolymerization initiator [2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine] 5.0 parts by mass and solvent [propylene glycol monomethyl ether acetate] 252 parts by mass and [dipropylene glycol monomethyl Ether] 122 parts by mass were mixed to obtain a colored photosensitive resin composition (black).

[Formation of black pattern]
An optical density after post-baking of the black photosensitive resin composition obtained on a glass substrate (# 1737; manufactured by Corning Japan Co., Ltd.) which has been washed with a neutral detergent, water and alcohol in sequence and then dried is 3 .1 was applied with a coater equipped with a slit nozzle.
Next, the solvent was distilled off by maintaining at 1 torr and 70 ° C. for 60 seconds in a vacuum drying apparatus. After cooling, a substrate coated with this colored photosensitive resin composition and a quartz glass photomask (having a light transmission part with a width of 30 μm and a light shielding part having a rectangular lattice pattern with sides of 80 μm and 40 μm) And an ultra high pressure mercury lamp was used to irradiate with light at an exposure amount of 200 mJ / cm ² (based on 365 nm) using an ultra high pressure mercury lamp.
Thereafter, development is performed by spraying a developer, which is an aqueous solution containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide, through the shower nozzle at 23 ° C. for 80 seconds. It was. After washing with water, post-baking was performed at 220 ° C. for 20 minutes to form a black matrix.
Similarly, a total of 451 black matrix substrates were observed with an optical microscope under a sodium lamp, the presence or absence of black foreign matter was observed, and the number was accumulated. By dividing the result by the total number of sheets 451, the number of black foreign matters observed per sheet was calculated. The results are shown in Table 2.

Comparative Example 6
Instead of 252 parts by mass of the solvent [propylene glycol monomethyl ether acetate] and 122 parts by mass of [dipropylene glycol monomethyl ether] used in [Production of colored photosensitive resin composition] in Example 6, the solvent [propylene glycol monomethyl ether acetate] The same operation was performed except that a colored photosensitive resin composition (black) was prepared using 377 parts by mass, and 235 black matrix substrates were prepared.
The obtained substrate was further observed with an optical microscope under a sodium lamp, the presence or absence of black foreign matters was observed, and the number was accumulated. By dividing the result by the total number of sheets 235, the number of black foreign matters observed per sheet (370 mm × 470 mm) was calculated. The results are shown in Table 2.

As described above, in Comparative Examples 1 to 5, the yield is less than 95%, while in Examples 1 to 7 using the colored photosensitive resin composition of the present invention, the yield is as high as 95% or more, and the production is high. It turns out that it is excellent in property. Since the comparative example 4 has many defects by pin nonuniformity, productivity is inferior.
In addition, when Example 8 and Comparative Example 6 are compared, Example 8 using the colored photosensitive resin composition of the present invention has less foreign matter per sheet, that is, a defective substrate. It can be seen that the rate of occurrence is low and the productivity is excellent.

<Examples 9 to 12>
The solvent described in Example 1 is changed to that shown in Table 3, and a colored photosensitive resin composition is similarly prepared, applied, exposed, and developed to obtain a pattern substrate. In either case, good results are obtained as in Example 1.

The numbers next to the solvent names represent the mass fraction of each solvent relative to the entire solvent.
PGMEA; propylene glycol monomethyl ether acetate (boiling point 146 ° C)
MFDG: Dipropylene glycol monomethyl ether (boiling point 190 ° C)
DPMA: Dipropylene glycol monomethyl ether acetate (boiling point 209 ° C)

  The colored photosensitive resin composition of the present invention can be used to improve productivity in the production of a color filter, and has various optical properties or various light shielding properties. It can be applied for forming filters, membranes, layers and the like.

JP-A-2002-23352, page 2, right column, lines 11-22

Claims (7)

A colored photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The solvent is at least one solvent (A) selected from the group consisting of dialkylene glycol monoalkyl ethers having 1 to 4 carbon atoms in the alkyl group and dipropylene glycol monoalkyl ether esters having 1 to 4 carbon atoms in the alkyl group; Comprising a solvent (B) different from (A),
The content of the solvent (A) is 5% by mass or more and 40% by mass or less with respect to the total solvent amount,
The colored photosensitive resin composition whose content of a solvent (B) is 60 to 95 mass% with respect to the total amount of solvent.   The colored photosensitive resin composition according to claim 1, wherein the solvent (B) is a solvent having a boiling point of 121 ° C. or higher and 171 ° C. or lower.   The colored photosensitive resin composition according to claim 1 or 2, wherein the solvent (A) is a C1-C4 dipropylene glycol monoalkyl ether of an alkyl group.   The colored photosensitive resin composition according to any one of claims 1 to 3, wherein the solvent (A) is dipropylene glycol monomethyl ether.   The colored photosensitive resin composition according to any one of claims 1 to 4, wherein the solvent (B) is propylene glycol methyl ether acetate.   The pattern formed using the colored photosensitive resin composition as described in any one of Claims 1-5.   A color filter comprising the pattern according to claim 6.