JP2012159566A - Colored photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition from which a pattern with high resolution and durability can be obtained.SOLUTION: The colored photosensitive resin composition contains the following (A), (B), (C), (D), (E) and (F). They are: (A) a colorant; (B) a resin obtained by reacting (c) described below with a copolymer prepared by copolymerization of (a) and (b) described below, and then reacting (d); (C) a polymerizable compound; (D) a polymerization initiator; (E) a polyfunctional thiol compound; and (F) a solvent. The compounds used to obtain the resin (B) are: (a) a monomer having a 2-4C cyclic ether and an ethylenically unsaturated bond; (b) a monomer having an unsaturated bond copolymerizable with (a) and different from (a); (c) at least one kind selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride; and (d) a polybasic acid anhydride.

Description

  A color filter used in a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel is manufactured using a colored photosensitive resin composition. As such a colored photosensitive resin composition, Patent Document 1 discloses a resin composed of a benzyl methacrylate / methacrylic acid copolymer, 2-benzyl-2-dimethylamino- (4-morpholinophenyl) -butan-1-one, A colored photosensitive resin composition comprising 4,4′-bis (diethylamino) -benzophenone, pentaerythritol tetrakis (3-sulfanylpropionate), a photopolymerizable compound, a solvent, a pigment and a pigment dispersant is described.

JP 2004-83857 A

  In the conventional colored photosensitive resin composition, the resolution and durability of the resulting pattern may not always be satisfactory.

The present invention provides the following [1] to [9].
[1] A colored photosensitive resin composition comprising (A), (B), (C), (D), (E) and (F).
(A) Colorant (B) Resin obtained by reacting (c) and then (d) with a copolymer obtained by copolymerizing the following (a) and (b) (a): Monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b): a monomer having an unsaturated bond copolymerizable with (a) and different from (a) (c ): At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (d): polybasic acid anhydrides (C) polymerizable compounds (D) polymerization initiators (E) polyfunctional thiol compounds (F) Solvent [2] The colored photosensitive resin composition according to [1], wherein (D) is an oxime compound.
[3] The colored photosensitive resin composition according to [1] or [2], further comprising a thioxanthone compound.
[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein (D) comprises an acylphosphine oxide compound or an alkylphenone compound.
[5] Any of [1] to [4], wherein (b) includes a compound having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a tricyclodecene skeleton, and an ethylenically unsaturated bond Or a colored photosensitive resin composition.
[6] The colored photosensitive resin composition according to any one of [1] to [5], wherein (a) is a monomer having an oxiranyl group and an ethylenically unsaturated bond.
[7] A pattern formed using the colored photosensitive resin composition according to any one of [1] to [6].
[8] A color filter including the pattern according to [7] [9] A method for producing a color filter including the steps shown in the following (1) to (3).
(1) Step of obtaining a coating film by applying the colored photosensitive resin composition according to any one of [1] to [6] to a substrate (2) After exposure by exposing the coating film through a mask Step of obtaining a coating film (3) Step of obtaining a pattern by developing the post-exposure coating film with an alkaline developer

  According to the colored photosensitive resin composition of the present invention, a pattern with good resolution and durability can be obtained.

The colored photosensitive resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a polyfunctional thiol compound (E), and a solvent (F). , Resin (B)
It is a resin obtained by reacting (c) with a copolymer obtained by copolymerizing the following (a) and (b), and then reacting (d).
(A): Monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b): A monomer having an unsaturated bond copolymerizable with (a) and different from (a) (C): unsaturated carboxylic acid (d): polybasic acid anhydride

  The colored photosensitive resin composition of the present invention contains a colorant (A). Examples of the colorant (A) include pigments and dyes, but a pigment is preferably included from the viewpoint of heat resistance and light resistance.

Examples of the pigment include organic pigments and inorganic pigments, and compounds classified as pigments by Color Index (published by The Society of Dyers and Colorists).
Specific examples of the organic pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; 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, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

  Among them, C.I. I. Pigment yellow 138, 150, C.I. I. Pigment red 177, 254, C.I. I. Pigment red violet 23, C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Green 36 and 58 are preferable. These pigments may be used alone or in admixture of two or more.

  The pigment is optionally treated with rosin, surface treatment using a pigment derivative or pigment dispersant introduced with an acidic group or basic group, graft treatment on the pigment surface with a polymer compound, etc., sulfuric acid atomization Atomization treatment by a method or the like, cleaning treatment with an organic solvent or water for removing impurities, removal treatment by ion exchange method of ionic impurities, or the like may be performed. The pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

  Commercially available surfactants can be used as the pigment dispersant, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, non-ionic, amphoteric, polyester-based, polyamine-based, and acrylic-based. Surfactant etc. are mentioned. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA), Ajisper (manufactured by Ajinomoto Fine Techno Co., Ltd.) ), Disperbyk (manufactured by Big Chemie) and the like. These can be used alone or in combination of two or more.

  When a pigment dispersant is used, the amount used is preferably 100% by mass or less, more preferably 5 to 50% by mass, based on the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion in a uniform dispersion state tends to be obtained.

  Content of a coloring agent (A) becomes like this. Preferably it is 5-60 mass% with respect to solid content of a colored photosensitive resin composition, More preferably, it is 5-45 mass%. When the content of the colorant (A) is in the above range, a desired spectrum and color density can be obtained. Here, solid content in this specification means the total amount of the component remove | excluding the solvent from the coloring photosensitive resin composition.

The colored photosensitive resin composition of the present invention contains a resin (B). The resin (B) is a resin obtained by reacting (c) with a copolymer obtained by copolymerizing the following (a) and (b) and then reacting (d).
(A): a monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b): a monomer having an unsaturated bond copolymerizable with (a) and different from (a) The monomer (c): at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (d): a polybasic acid anhydride

  Examples of (a) include a monomer (a-1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(a-1)”), an oxetanyl group and an ethylenically unsaturated bond. Monomer (a-2) (hereinafter sometimes referred to as “(a-2)”), monomer (a-3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as “(a-3) ) "And so on).

As (a-1), for example, a monomer (a-11) having a structure obtained by epoxidizing a chain olefin and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(a-11)”), And a monomer (a-12) having a structure obtained by epoxidizing a cycloalkene and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(a-12)”).
As (a-1), a monomer having an oxiranyl group and a (meth) acryloyloxy group is preferable, and (a-12) having a (meth) acryloyloxy group is more preferable. Here, in the present specification, the “(meth) acryloyloxy group” represents at least one selected from the group consisting of an acryloyloxy group and a methacryloyloxy group. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Specific examples of (a-11) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinyl. Benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis ( Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris ( Glycidyl oxime Chill) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4, Examples thereof include 6-tris (glycidyloxymethyl) styrene and compounds described in JP-A-7-248625.

  Examples of (a-12) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, cyclone). Mer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), a compound represented by formula (I), formula (II) ) And the like.

[In Formula (I) and Formula (II), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. May be substituted.
X ¹ and X ² each independently represent a single bond, —R ³ —, * —R ³ —O—, * —R ³ —S—, or * —R ³ —NH—.
R ³ represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy-1 -Methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like can be mentioned.
R ¹ and R ² are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— (* represents a bond to O), or * —CH ₂ CH ₂ —O— group. More preferably, a single bond and a * —CH ₂ CH ₂ —O— group are mentioned.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15) The compound represented by either of these is mentioned. More preferably, a compound represented by any one of formula (I-1), formula (I-7), formula (I-9), and formula (I-15) can be mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9), Formula (II-11) to Formula (II-15) The compound represented by either of these is mentioned. More preferably, a compound represented by any one of formula (II-1), formula (II-7), formula (II-9), and formula (II-15) can be mentioned.

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can also be mixed in any ratio. In the case of mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, particularly preferably 20:80 in the formula (I): formula (II). ~ 80: 20.

  (A-2) is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. Examples of (a-2) include 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, and 3-methyl-3- (meth) acryloyloxyethyl. Examples include oxetane and 3-ethyl-3- (meth) acryloyloxyethyl oxetane.

  (A-3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Specific examples of (a-3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Examples of (b) include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate. Alkyl esters;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, dicyclopenta It is said to be nyl (meth) acrylate.
), (Meth) acrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

Aryl (meth) acrylates or aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

  Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2. .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;

  N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;

  Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.

In addition, as (b), a compound (b1) having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a tricyclodecene skeleton and an ethylenically unsaturated bond (hereinafter referred to as “(b1)”) In some cases).
When (b) is (b1), film loss of the pattern due to development can be suppressed.
Here, the “tricyclodecane skeleton” and the “tricyclodecene skeleton” in this specification refer to the following structures (respectively, the bond is an arbitrary position).

  Specific examples of (b1) include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. .

  (B) can be used alone or in combination of two or more.

  When (b) is used in combination of two or more, at least one is preferably b1, and the other is aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate in b. (Hereinafter sometimes referred to as “(b2)”)).

In the copolymer obtained by copolymerizing (a), (b1) and (b2), the ratio of the structural units derived from each monomer is copolymerized with (a), (b1) and (b2) It is preferable that it exists in the following ranges with respect to the ratio of the copolymer obtained by making it carry out.
Structural unit derived from (a): 10 to 90 mol% (more preferably 30 to 80 mol%)
Structural unit derived from (b1): 10 to 80 mol% (more preferably 10 to 60 mol%)
Structural unit derived from (b2): 10 to 60 mol% (more preferably 10 to 40 mol%)
However, the sum of (a), (b1) and (b2) is 100 mol% or less. When the component ratio is in the above range, the curability tends to be better.

Specific examples of (c) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of copolymerization reactivity and alkali solubility.

  The added amount of (c) is preferably 10 to 60% by mass, preferably 30 to 40% by mass, based on the copolymer obtained by copolymerizing (a), (b1) and (b2), in terms of charged value. % Is more preferable.

  As (d), known ones can be used, and dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; Examples thereof include polybasic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride or succinic anhydride is preferable from the viewpoint of developability.

  The addition reaction of (d) is performed by a conventional method. The addition amount of (d) is 5 to 100%, preferably 30 to 100%, of the hydroxyl group formed upon introduction of the photosensitive group. When the added amount of (d) is less than 5%, the solubility in a dilute alkali decreases.

The colored photosensitive resin composition of the present invention contains a polymerizable compound (C).
The polymerizable compound (C) is a compound that can be polymerized by active radicals and acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. (Meth) acrylic acid ester compound is mentioned.

  Examples of the polymerizable compound (C) having one ethylenically unsaturated bond include the same compounds as those described above as (a), (b) and (c), and among them, (meth) acrylic acid esters Is preferred.

  Examples of the polymerizable compound (C) having two ethylenically unsaturated bonds include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,6-hexanediol di (meta). ) Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, Bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (me ) Acrylate, 3-methyl-pentanediol di (meth) acrylate.

Examples of the polymerizable compound (C) having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate. , Ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri Pentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaery Ritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, tripenta Erythritol hepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified Pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipenta Lithritol hexa (meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone modified tripentaerythritol penta (meth) acrylate, caprolactone modified tripentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol hepta (meth) Acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride, Examples include caprolactone-modified tripentaerythritol hepta (meth) acrylate and acid anhydrides.
Among these, a tri- or higher functional monomer is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.

  5-50 mass% is preferable with respect to solid content of a coloring photosensitive resin composition, and, as for content of a polymeric compound (C), 10-45 mass% is more preferable. Moreover, Preferably it is 20-80 mass% with respect to the total amount of resin (B) and polymeric compound (C), More preferably, it is 40-60 mass%. When the content of the polymerizable compound (C) is in the above range, sensitivity, pattern strength, smoothness, and reliability tend to be improved.

The colored photosensitive resin composition of the present invention contains a polymerization initiator (D).
The polymerization initiator (D) is not particularly limited as long as it is a compound that generates an active radical and an acid by the action of light and initiates polymerization of the polymerizable compound (C). Can be used.
As the polymerization initiator (D), a biimidazole compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and an oxime compound are preferable. Moreover, you may use the photocationic polymerization initiator (For example, what is comprised from the onium cation and the anion derived from a Lewis acid) described in Unexamined-Japanese-Patent No. 2008-181087. Of these, oxime compounds are preferable in terms of sensitivity.

  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 (see, for example, JP-A-6-75372 and JP-A-6-75373), 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) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913). Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 Examples include 5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

  Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2. -Benzylbutan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, 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-isopropenylphenyl) propan-1-one oligomers and the like Examples thereof include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one. It is done. Commercial products such as Irgacure 369, 907 (above, manufactured by BASF Japan Ltd.) may be used.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-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) Sulfonyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure 819 (manufactured by Ciba Japan) may be used.

  Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one. 2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl- 6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine and the like. Commercial products such as Irgacure OXE-01, OXE-02 (manufactured by BASF Japan), N-1919 (manufactured by ADEKA) may be used.

In addition, as a polymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP-T-2002-544205 may be used.
Examples of the polymerization initiator having a group capable of causing the chain transfer include compounds represented by the following formulas (D-1) to (D-6).

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

  The polymerization initiator having a group capable of causing chain transfer can be used as the component (c) constituting the resin (A).

Furthermore, a polymerization initiation assistant (D1) may be included. The polymerization initiation assistant (D1) is used in combination with the polymerization initiator (D), and is a compound or sensitizer used for accelerating the polymerization of a polymerizable compound whose polymerization has been initiated by the polymerization initiator. .
Examples of the polymerization initiation assistant (D1) include amine compounds, thiazoline compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl 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, and 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the thiazoline compound include compounds represented by formula (III-1) to formula (III-3).

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

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

  Carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

  The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is. When the total amount of the polymerization initiator (D) is within this range, a pattern can be formed with high sensitivity, and the chemical resistance, mechanical strength, and surface smoothness of the pattern tend to be good.

  When the polymerization initiation assistant (D1) is used, the amount used is preferably 0.01 to 50 parts by mass, more preferably 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 0.1 to 40 parts by mass. Moreover, it is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, per 1 mol of the polymerization initiator (D). When the amount of the polymerization initiation assistant (D1) is within this range, the pattern can be formed with higher sensitivity, and the productivity of the pattern tends to be improved.

  Moreover, the colored photosensitive resin composition of this invention contains a polyfunctional thiol compound (E). This polyfunctional thiol compound (E) is a compound having two or more sulfanyl groups in the molecule. Especially, it is preferable to use a compound having two or more sulfanyl groups adjacent to the aliphatic hydrocarbon group because a pattern can be formed with high sensitivity.

  As the polyfunctional thiol compound (E), hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl acetate), ethylene Glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), trimethylolpropane tris ( 3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethylate (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanylbutyrate), 1,4-bis (3-sulfanylbutyloxy) butane, among others, pentaerythritol tetrakis (3-sulfanylpropionate) ) Is preferred.

  The content of the polyfunctional thiol compound (E) is preferably 10 to 150 parts by mass, more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the polymerization initiator (D). When the content of the polyfunctional thiol compound (E) is in this range, the sensitivity tends to be high and the developability tends to be good.

  A solvent (F) is not specifically limited, The solvent normally used in the said field | area can be used. For example, ester solvents (solvents containing —COO—), ether solvents other than ester solvents (solvents containing —O—), ether ester solvents (solvents containing —COO— and —O—), ketones other than ester solvents A solvent (solvent containing —CO—), an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like can be selected and used. These solvents may be used alone or in combination of two or more.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  Ether solvents include 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, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and the like methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and the like diethylene glycol monobutyl ether acetate.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. Etc.

  Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.

  Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

  Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. Of these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable.

  Content of a solvent (F) becomes like this. Preferably it is 60-95 mass% with respect to a coloring photosensitive resin composition, More preferably, it is 70-90 mass%. In other words, the solid content of the colored photosensitive resin composition is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. When content of a solvent (F) exists in the said range, there exists a tendency for the flatness at the time of application | coating to become favorable.

  The colored photosensitive resin composition of the present invention preferably contains a surfactant (G). Examples of the surfactant include a silicone surfactant, a fluorine surfactant, a silicone surfactant having a fluorine atom, and the like. By including the surfactant, the flatness during application tends to be good.

Examples of the silicone surfactant include surfactants having a siloxane bond.
Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan GK) Manufactured) and the like.

Examples of the fluorosurfactant include surfactants having a fluorocarbon chain.
Specifically, Florinart (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, R183 (DIC) ), Ftop (registered trademark) EF301, EF303, EF351, EF351, EF352 (manufactured by Mitsubishi Materials Denkasei), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass) And E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

  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 DIC Corporation) and the like can be mentioned. Preferably, MegaFac (registered trademark) F475 is used.

  The surfactant (G) is 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably, based on the colored photosensitive resin composition. Is 0.01 mass% or more and 0.05 mass% or less. By containing the surfactant in this range, the flatness of the coating film can be improved.

  The colored photosensitive resin composition of the present invention may contain various additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, etc., as necessary. May be included.

The colored photosensitive resin composition of the present invention can be prepared, for example, as follows.
First, the pigment of the colorant (A) is preliminarily mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a pigment dispersant and some or all of resin (B) as needed. In the obtained pigment dispersion, the rest of the resin (B), the polymerizable compound (C) and the polymerization initiator (D), other components used as necessary, and further an additional solvent if necessary The desired colored photosensitive resin composition can be obtained.

  Examples of the method for obtaining the pattern include a photolithography method, an ink jet method, and a printing method. Of these, the photolithography method is preferable. The photolithographic method is a method for obtaining a pattern by applying the colored photosensitive resin composition to a substrate, drying, exposing through a photomask, and developing.

Examples of the substrate include glass, metal, plastic, and the like, and may be plate-shaped or film-shaped.
Examples of the plastic include polyolefins such as polyethylene, polypropylene, norbornene-based polymers, polyvinyl alcohol, polyethylene terephthalate, polyethylene naphthalate, poly (meth) acrylate, cellulose ester, polycarbonate, polysulfone, polyethersulfone, polyetherketone, Examples include polyphenylene sulfide and polyphenylene oxide. Here, (meth) acrylic acid means at least one selected from the group consisting of acrylic acid and methacrylic acid. Structures such as a color filter, various insulating or conductive films, and a drive circuit may be formed on these substrates.
According to the colored photosensitive resin composition of the present invention, a pattern cured at a lower temperature can be formed, which is particularly useful when forming a pattern on a plastic substrate.

  Examples of the coating method on the substrate include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Apply using a coating device such as a dip coater, roll coater, bar coater, spin coater, slit & spin coater, slit coater (sometimes called a die coater, curtain flow coater, or spinless coater) or inkjet. Also good. Especially, it is preferable to apply using a slit coater, a spin coater, a roll coater or the like.

Examples of the method for drying the film applied to the substrate include methods such as heat drying, natural drying, ventilation drying, and vacuum drying. A plurality of methods may be combined.
As drying temperature, 10-120 degreeC is preferable and 25-100 degreeC is more preferable. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
The vacuum drying is preferably performed at a temperature of 20 to 25 ° C. under a pressure of 50 to 150 Pa.
The film thickness of the coating film after drying is not particularly limited and can be appropriately adjusted depending on the material used, application, etc., and is, for example, 0.1 to 20 μm, preferably 1 to 6 μm.

The coating film after drying is exposed through a photomask for forming a target pattern. The pattern shape on the photomask at this time is not particularly limited, and a pattern shape corresponding to the intended application is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
It is preferable to use an apparatus such as a mask aligner or a stepper because the entire exposed surface can be irradiated with parallel light rays uniformly or the mask and the substrate can be accurately aligned.

After exposure, the coating film is brought into contact with a developer to dissolve a predetermined portion, for example, an unexposed portion, and developed, whereby a pattern can be obtained. As the developer, an organic solvent can be used, but it is preferable to use an aqueous solution of an alkaline compound because the exposed portion of the coating film is hardly dissolved or swollen by the developer and a pattern having a good shape can be obtained. .
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

Examples of the 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, sodium carbonate, Inorganic alkaline compounds such as potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia; tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, mono Examples include organic alkaline compounds such as ethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Of these, potassium hydroxide, sodium hydrogen carbonate and tetramethylammonium hydroxide are preferable.
The density | concentration in the aqueous solution of these inorganic and organic alkaline compounds becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%.

The aqueous solution of the alkaline compound may contain a surfactant.
Surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters , Nonionic surfactants such as polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine;
Anionic surfactants such as sodium lauryl alcohol sulfate, sodium oleyl alcohol sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate;
And cationic surfactants such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
The concentration of the surfactant in the aqueous solution of the alkaline compound is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and particularly preferably 0.1 to 5% by mass.

  By further baking the pattern obtained as described above, a cured pattern can be obtained. The baking temperature is 25 ° C. or higher and 230 ° C. or lower, preferably 25 ° C. or higher and 200 ° C. or lower, more preferably 25 ° C. or higher and 160 ° C. or lower, and further preferably 25 ° C. or higher and 120 ° C. or lower. The baking time is 1 to 300 minutes, preferably 1 to 180 minutes, and more preferably 1 to 60 minutes.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

<Synthesis of Resin Solution B1>
Synthesis example 1
In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube,
571 parts of propylene glycol monomethyl ether acetate was introduced, the atmosphere in the flask was changed from air to nitrogen, the temperature was raised to 110 ° C., 17.6 parts of benzyl methacrylate, 113.7 parts of glycidyl methacrylate, and monocyclodecane skeleton mono To a monomer mixture consisting of 22.0 parts of methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.)
A solution obtained by adding 3.6 parts of azobisisobutyronitrile to 153 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask from the dropping funnel over 2 hours, and further stirred at 100 ° C. for 2 hours. Next, the atmosphere in the flask is changed from nitrogen to air, 57.7 parts of acrylic acid, 0.9 part of trisdimethylaminomethylphenol and 0.145 part of hydroquinone are put into the flask, and the reaction is continued at 110 ° C. for 6 hours. The reaction was terminated when the solid content acid value reached 1 mgKOH / g.
Next, 53.3 parts of tetrahydrophthalic anhydride and 0.8 part of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a solid content of 37.7% and an acid value of 66.8 mgKOH / g (in terms of solid content). Resin solution B1 was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 8,700.

<Synthesis of Resin Solution B2>
Synthesis example 2
In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube,
After introducing 593 parts of propylene glycol monomethyl ether acetate and changing the atmosphere in the flask from air to nitrogen,
After raising the temperature to 110 ° C., 88.1 parts of benzyl methacrylate, 56.9 parts of glycidyl methacrylate,
And a monomer mixture consisting of 22.0 parts of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.)
A solution obtained by adding 3.6 parts of azobisisobutyronitrile to 153 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask from the dropping funnel over 2 hours, and further stirred at 100 ° C. for 2 hours. Next, the atmosphere in the flask is changed from nitrogen to air,
28.8 parts of acrylic acid, 0.9 part of trisdimethylaminomethylphenol and 0.145 part of hydroquinone were charged into the flask,
The reaction was continued at 110 ° C. for 6 hours, and the reaction was terminated when the solid content acid value reached 1 mgKOH / g.
Next, 47.2 g of tetrahydrophthalic anhydride and 0.8 part of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a solid content of 36.5% and an acid value of 71.8 mgKOH / g (in terms of solid content). Resin solution B2 was obtained.
The weight average molecular weight in terms of polystyrene measured by GPC was 8,600.

<Synthesis of Resin Solution B3>
Synthesis example 3
In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube,
After introducing 591 parts of propylene glycol monomethyl ether acetate and changing the atmosphere in the flask from air to nitrogen,
After raising the temperature to 110 ° C., 17.6 parts of benzyl methacrylate, 113.7 parts of glycidyl methacrylate,
And a monomer mixture consisting of 22.0 parts of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.)
A solution obtained by adding 3.6 parts of azobisisobutyronitrile to 153 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask from the dropping funnel over 2 hours, and further stirred at 100 ° C. for 2 hours. Next, the atmosphere in the flask is changed from nitrogen to air,
68.9 parts of methacrylic acid, 0.9 g of trisdimethylaminomethylphenol and 0.145 part of hydroquinone were charged into the flask,
The reaction was continued at 110 ° C. for 6 hours, and the reaction was terminated when the solid content acid value reached 1 mgKOH / g.
Next, 53.3 parts of tetrahydrophthalic anhydride and 0.8 part of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a solid content of 37.9% and an acid value of 68.6 mgKOH / g (in terms of solid content). Resin solution B3 was obtained.
The weight average molecular weight in terms of polystyrene measured by GPC was 7,900.

<Synthesis of Resin Solution B4>
Synthesis example 4
In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube,
After introducing 505 parts of propylene glycol monomethyl ether acetate and changing the atmosphere in the flask from air to nitrogen,
After raising the temperature to 110 ° C., 88.1 parts of benzyl methacrylate, 56.9 parts of glycidyl methacrylate,
And a monomer mixture consisting of 22.0 parts of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.)
A solution obtained by adding 3.6 parts of azobisisobutyronitrile to 153 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask from the dropping funnel over 2 hours, and further stirred at 100 ° C. for 2 hours. Next, the atmosphere in the flask is changed from nitrogen to air,
34.4 parts of acrylic acid, 0.9 part of trisdimethylaminomethylphenol and 0.145 part of hydroquinone were charged into the flask,
The reaction was continued at 110 ° C. for 6 hours, and the reaction was terminated when the solid content acid value reached 1 mgKOH / g.
Next, 47.2 parts of tetrahydrophthalic anhydride and 0.8 part of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a solid content of 37.1% and an acid value of 72.2 mgKOH / g (in terms of solid content). Resin solution B4 was obtained.
The weight average molecular weight in terms of polystyrene measured by GPC was 8,900.

Examples 1-7
Of the components listed in Table 1, the total amount of pigment and pigment dispersant and propylene glycol monomethyl ether acetate as a solvent were mixed in advance. At this time, propylene glycol monomethyl ether acetate was mixed so that the total amount of the pigment and the pigment dispersant was 20% by mass with respect to the mixture. Using a bead mill, the pigment in the mixture was sufficiently dispersed, and the remaining components including the remaining amount of propylene glycol monomethyl ether acetate were added to the mixture and further mixed to obtain a photosensitive resin composition. .

Comparative Example 1
The same operation as in Example 1 except that the resin B1 is changed to the resin B5 (benzyl methacrylate / methacrylic acid copolymer (mass composition ratio 80/20, polystyrene-equivalent weight average molecular weight 35,000)) in Example 1. Went.

Ａ１：Ｃ．Ｉ．ピグメントグリーン ３６
Ａ２：Ｃ．Ｉ．ピグメントイエロー １５０
Ａ３：Ｃ．Ｉ．ピグメントグリーン ５８
Ａ４：Ｃ．Ｉ．ピグメントイエロー １３８
Ａ５：Ｃ．Ｉ．ピグメントレッド １７７
Ａ６：Ｃ．Ｉ．ピグメントレッド ２５４
Ａ７：Ｃ．Ｉ．ピグメントブルー １５：６
Ａ８：Ｃ．Ｉ．ピグメントバイオレット ２３
Ｂ５：ベンジルメタクリレート／メタクリル酸共重合体（質量組成比 ８０／２０、ポリスチレン換算重量平均分子量 ３５，０００）Ｃ１：ジペンタエリスリトールヘキサアクリレート（ＫＡＹＡＲＡＤ ＤＰＨＡ；日本化薬（株）製）
Ｄ１：２−ベンジル−２−ジメチルアミノ−（４−モルホリノフェニル）−ブタン−１−オン（ＩＲＧＡＣＵＲＥ ３６９；ＢＡＳＦジャパン社製）
Ｄ２：４，４’−ビス（ジエチルアミノ）−ベンゾフェノン（ＥＡＢ−Ｆ；保土ヶ谷化学（株）製）
Ｄ３：Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン（ＯＸＥ−０１；ＢＡＳＦジャパン社製）
Ｄ４：ビス（２，４，６−トリメチルベンゾイル）フェニルフォスフィンオキサイド（イルガキュア８１９；ＢＡＳＦ・ジャパン社製）
Ｄ５：２−メチル−２−モルホリノ（４−メチルスルファニルフェニル）−プロパン−１−オン（イルガキュア９０７；ＢＡＳＦ・ジャパン社製）
Ｄ６：ジエチルチオキサントン（ＫＡＹＡＣＵＲＥ ＤＥＴＸ；日本化薬（株）製）
Ｅ１：ペンタエリスリトールテトラキス（３−スルファニルプロピオネート）（ＰＥＭＰ；ＳＣ有機化学（株）製）
Ｆ１：プロピレングリコールモノメチルエーテルアセテート
Ｆ２：３−エトキシプロピオン酸エチル
Ｇ１：顔料分散剤（ポリエステル系）
Ｇ２：顔料分散剤（アクリル系）
Ｇ３：ＳＵＭＩ−ＥＰＯＸＹ ＥＳＣＮ−１９５ＸＬ
Ｇ４：界面活性剤：ポリエーテル変性シリコーンオイル
（トーレシリコーンＳＨ８４００；東レダウコーニング（株）製）

A1: C.I. I. Pigment Green 36
A2: C.I. I. Pigment Yellow 150
A3: C.I. I. Pigment Green 58
A4: C.I. I. Pigment Yellow 138
A5: C.I. I. Pigment Red 177
A6: C.I. I. Pigment Red 254
A7: C.I. I. Pigment Blue 15: 6
A8: C.I. I. Pigment Violet 23
B5: benzyl methacrylate / methacrylic acid copolymer (mass composition ratio 80/20, polystyrene-equivalent weight average molecular weight 35,000) C1: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
D1: 2-benzyl-2-dimethylamino- (4-morpholinophenyl) -butan-1-one (IRGACURE 369; manufactured by BASF Japan Ltd.)
D2: 4,4′-bis (diethylamino) -benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.)
D3: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (OXE-01; manufactured by BASF Japan)
D4: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure 819; manufactured by BASF Japan Ltd.)
D5: 2-methyl-2-morpholino (4-methylsulfanylphenyl) -propan-1-one (Irgacure 907; manufactured by BASF Japan Ltd.)
D6: Diethylthioxanthone (KAYACURE DETX; manufactured by Nippon Kayaku Co., Ltd.)
E1: Pentaerythritol tetrakis (3-sulfanylpropionate) (PEMP; manufactured by SC Organic Chemical Co., Ltd.)
F1: Propylene glycol monomethyl ether acetate
F2: Ethyl 3-ethoxypropionate G1: Pigment dispersant (polyester)
G2: Pigment dispersant (acrylic)
G3: SUMI-EPOXY ESCN-195XL
G4: Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Solvent resistance evaluation>
The colored photosensitive compositions 1 to 8 are applied by spin coating on a substrate obtained by laminating a PET film (Toray Lumirror 75-T60) on a 2-inch square glass plate. Pre-baked for a minute.
After standing to cool, light exposure was performed using an exposure machine (TME-150RSK; manufactured by Topcon Corporation) at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. After light irradiation, it was developed by immersing in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 ° C. for 50 seconds, washed pure, and then at 60 ° C. Heated for 5 minutes to form a colored pattern. The film thickness of the obtained pattern was 2 μm when measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).
The chromaticity is a value measured using a microspectrophotometer (OSP-SP200 manufactured by OLYMPUS). A C light source was used as a light source for chromaticity measurement.
1 ml of propylene glycol monomethyl ether acetate was dropped on the coating film after the measurement, and after standing still for 30 s with a paddle, it was shaken off for 10 s at a rotation speed of 1000 rpm.
Thereafter, the film thickness and chromaticity were measured by the same method as described above. The rate of change in film thickness before and after contact measurement with propylene glycol monomethyl ether acetate was calculated according to the formula described below.
Film thickness retention rate (%) = film thickness after contact / film thickness before contact × 100
Moreover, the color difference was calculated from chromaticity before and after the contact measurement of JIS Z 8730 and propylene glycol monomethyl ether acetate.
The higher the film thickness retention rate and the smaller the color difference, the better the solvent resistance, and color mixing can be prevented when forming a color filter.

<Resolution evaluation>
The previously formed pattern was observed with a laser microscope (manufactured by Axio Imager MAT Carl Zeiss), and the minimum dimension resolved was taken as the resolution. The resolution is excellent in workability as fine patterns can be formed.

  According to the colored photosensitive resin composition of the present invention, a pattern having excellent resolution and durability can be obtained.

Claims (9)

A colored photosensitive resin composition comprising (A), (B), (C), (D), (E) and (F).
(A) Colorant (B) Resin obtained by reacting (c) and then (d) with a copolymer obtained by copolymerizing the following (a) and (b) (a): Monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b): a monomer having an unsaturated bond copolymerizable with (a) and different from (a) (c ): At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (d): polybasic acid anhydrides (C) polymerizable compounds (D) polymerization initiators (E) polyfunctional thiol compounds (F) Solvent   The colored photosensitive resin composition according to claim 1, wherein (D) is an oxime compound.   Furthermore, the coloring photosensitive resin composition of Claim 1 or 2 containing a thioxanthone compound.   The colored photosensitive resin composition according to any one of claims 1 to 3, wherein (D) comprises an acylphosphine oxide compound or an alkylphenone compound.   5. The colored photosensitive composition according to claim 1, wherein (b) includes a compound having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a tricyclodecene skeleton, and an ethylenically unsaturated bond. Resin composition.   The colored photosensitive resin composition according to claim 1, wherein (a) is a monomer having an oxiranyl group and an ethylenically unsaturated bond.   The pattern formed using the colored photosensitive resin composition in any one of Claims 1-6.   A color filter comprising the pattern according to claim 7. The manufacturing method of a color filter including the process shown by following (1)-(3).
(1) The process of obtaining a coating film by apply | coating the colored photosensitive resin composition in any one of Claims 1-6 to a board | substrate (2) The coating film after exposure by exposing to a coating film through a mask (3) Step of obtaining a pattern by developing the post-exposure coating film with an alkaline developer