JP6673204B2 - Colored photosensitive resin composition - Google Patents

Description

  The present invention relates to a colored photosensitive resin composition.

The colored photosensitive resin composition is used for producing a color filter in a display device such as a liquid crystal display panel. In recent years, display displays have been developed to expand the color reproduction range in which display can be performed, and as a part thereof, color filters having a deeper color are required. In order to satisfy the demand, there is a method of increasing the concentration of the coloring material in the color filter. However, when the concentration of the coloring material is increased, the performance as the photosensitive composition may be deteriorated such as deterioration of the pattern shape.
Patent Literature 1 discloses C.I. in order to design a dark green color filter. I. A green photosensitive resin composition containing a colorant containing CI Pigment Green G58, a blue colorant, and a yellow colorant, a resin, a polymerizable monomer, a photopolymerization initiator, and a solvent is described.

JP 2012-247539 A

  An object of the present invention is to obtain a colored photosensitive resin composition having high brightness.

The present invention includes the following inventions.
[1] including a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
As a coloring agent (A), a halogenated zinc phthalocyanine pigment; I. Pigment Yellow 185, C.I. I. Pigment Blue 15: 3 or C.I. I. Pigment Blue 15: 4.
[2] a halogenated zinc phthalocyanine pigment is C. I. Pigment Green 58. The colored photosensitive resin composition according to [1].
[3] C.I. I. Pigment Yellow 185 is the colored photosensitive resin composition according to [1] or [2], wherein the content is 10 to 50 parts by mass with respect to 100 parts by mass of the polymerizable compound (C).
[4] The total amount of the coloring agent (A) is 20 to 50 parts by mass based on 100 parts by mass of the solid content of the colored photosensitive resin composition, and is described in any one of [1] to [3]. Colored photosensitive resin composition.
[5] A color filter formed from the colored photosensitive resin composition according to any one of [1] to [4].

  From the colored photosensitive resin composition of the present invention, a color filter having good brightness can be produced.

FIG. 3 shows a schematic view of a cross-sectional shape of a pattern. FIG. 1 (p1) shows a favorable cross section where cracks and peeling do not easily occur in the inorganic film when the inorganic film is laminated on the coloring pattern, and FIG. 1 (p2) shows cracks and peeling easily occur in the inorganic film. Represents a cross section.

The colored photosensitive resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
The colored photosensitive resin composition of the present invention preferably further contains a solvent (E).
The colored photosensitive resin composition of the present invention may further contain at least one selected from the group consisting of a leveling agent (F) and a thiol compound.
A color filter having high brightness can be produced from the colored photosensitive resin composition of the present invention. Further, the colored photosensitive resin composition hardly generates peeling pieces derived from the colored photosensitive resin composition during the production of a pattern, and can produce a pattern with a good pattern shape.
In the present specification, compounds exemplified as each component can be used alone or in combination of two or more, unless otherwise specified.

<Colorant (A)>
The colored photosensitive resin composition of the present invention contains C.I. I. Pigment Blue 15: 3 or C.I. I. Pigment Blue 15: 4, a zinc halide phthalocyanine pigment and C.I. I. Pigment Yellow 185.
Examples of the halogenated zinc phthalocyanine pigment include C.I. I. Pigment Green 58.

The content of the halogenated zinc phthalocyanine pigment is usually from 10 to 120 parts by mass, preferably from 20 to 110 parts by mass, more preferably from 25 to 70 parts by mass, based on 100 parts by mass of the polymerizable compound (C). It is. When the content of the halogenated zinc phthalocyanine pigment is within the above range, a color filter having particularly good brightness can be obtained.
C. I. Pigment Yellow 185 is generally 10 to 50 parts by mass, preferably 20 to 50 parts by mass, more preferably 25 to 45 parts by mass, based on 100 parts by mass of the polymerizable compound (C). And more preferably 25 to 40 parts by mass. C. I. When the content of CI Pigment Yellow 185 is within the above range, a color filter excellent in brightness and pattern shape can be obtained.
C. I. Pigment Blue 15: 3 and C.I. I. Pigment Blue 15: 4 is generally 1 to 30 parts by mass, preferably 1 to 25 parts by mass, more preferably 5 to 5 parts by mass, based on 100 parts by mass of the polymerizable compound (C). It is 15 parts by mass, more preferably 5 to 9 parts by mass. C. I. Pigment Blue 15: 3 or C.I. I. When the content of Pigment Blue 15: 4 is within the above range, a color filter having particularly excellent pattern shape can be obtained.

The colorant (A) preferably contains only a zinc phthalocyanine halide pigment as a green pigment. I. More preferably, only Pigment Green 58 is included.
The colorant (A) may contain other known pigments. However, the colored photosensitive resin composition of the present invention contains C.I. I. Pigment Green 58 and C.I. I. Pigment Yellow 185, C.I. I. Pigment Blue 15: 3 or C.I. I. Pigment Blue 15: 4.
The coloring agent (A) further includes C.I. I. Pigment Yellow 138 is preferred.

The total amount of the colorant (A) is usually 20 to 50 parts by mass, preferably 20 to 45 parts by mass, more preferably 20 to 35 parts by mass, based on 100 parts by mass of the solid content of the colored photosensitive resin composition. Parts, more preferably 20 to 30 parts by mass.
Here, the “total amount of solid content” in the present specification refers to an amount obtained by removing the content of the solvent from the total amount of the colored photosensitive resin composition. The total amount of the solid content and the content of each component with respect to the solid content can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1] At least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as “(a)”), and a cyclic ether structure having 2 to 4 carbon atoms And a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”).
Resin [K2] (a) and (b) and monomer (c) copolymerizable with (a) (however, (a) and (b) are different) (hereinafter referred to as “(c)”). In some cases) Copolymer of resin [K3] (a) and (c) Obtained by reacting (b) with a copolymer of resin [K4] (a) and (c) Resin.
Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c).
Resin [K6] A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic anhydride.

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, 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, 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 [2.2.1] bicyclo unsaturated compounds containing a carboxy group such as 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 anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] esters of di- or higher-valent polycarboxylic acids such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate ;
Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

(B) has, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. Refers to a polymerizable compound. (B) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
In this specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  (B) includes a monomer (a1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a monomer having an oxetanyl group and an ethylenically unsaturated bond (B2) (hereinafter sometimes referred to as “(b2)”), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”) and the like. .

  (B1) is, for example, a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon (hereinafter may be referred to as “(b1-1)”), an unsaturated alicyclic hydrocarbon, (B1-2) having an epoxidized structure (hereinafter sometimes referred to as “(b1-2)”).

  (B1-1) includes glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl 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 (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Tris (glycidyloxymethyl) styrene and the like can be mentioned.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate ( For example, cyclomer A400; manufactured by Daicel Chemical Industries, Ltd., 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), and represented by formula (I) And a compound represented by the formula (II).

[In the formulas (I) and (II), R ^a and R ^b 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 ^a and ^{X b} are each independently a single ^{bond, -R c -, * - R} c -O -, * - R c -S -, * - represents the R c -NH-.
R ³ represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

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 in which a hydrogen atom is substituted with hydroxy 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 Examples thereof include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ¹ and R ² preferably include 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 a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane- 1,6-diyl group and the like.
X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, a * -CH ₂ -O- (* represents a bond to O) group, a * -CH ₂ CH ₂ -O- group and the like, more preferably a single _{bond, *} - include CH ₂ CH 2 -O- group.

  Examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (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) ). More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

Examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15). Preferably, formulas (II-1), (II-3), (II-5), (II-7), (II-9), (II-11) to (II-15) ).
More preferably, Formula (II-1), Formula (II-7), Formula (II-9) and Formula (II-15) are mentioned.

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. Also, they can be mixed in any ratio. When mixing, the mixing ratio is a molar ratio, preferably in the formula (I): the formula (II), 5:95 to 95: 5, more preferably 10:90 to 90:10, and further preferably 20:80. ~ 80: 20.

  As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane And 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane.

As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable.
Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (c), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] decane-8-yl (meth) acrylate (commonly known in the art as "dicyclopentanyl (meth) acrylate"; sometimes referred to as "tricyclodecyl (meth) acrylate") .), Tricyclo [ .2.1.0 ^2,6] (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) Decene-8-yl (meth) acrylate, dicyclopentenyl oxyethyl (Meth) acrylates such as (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate ) Acrylate esters;
Hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

  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 -maleimidopropionate, N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, 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.
Among them, benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2. 2.1] Hept-2-ene and the like are preferred. Benzyl (meth) acrylate and tricyclodecyl (meth) acrylate are more preferred because of their excellent developability during pattern formation.

In the resin [K1], the ratio of the structural units derived therefrom is preferably in the following range among all the structural units constituting the resin [K1].
Structural unit derived from (a); 2 to 50 mol% (more preferably 10 to 45 mol%)
Structural unit derived from (b); 50 to 98 mol% (more preferably 55 to 90 mol%)
When the ratio of the structural unit of the resin [K1] is in the above range, storage stability, developability, and solvent resistance of the obtained pattern tend to be excellent.

  The resin [K1] can be obtained, for example, by the method described in the document "Experimental Method for Polymer Synthesis" (published by Takayuki Otsu, published by Kagaku Dojin, 1st Edition, 1st edition, March 1, 1972) and the literature. And can be produced with reference to the references described in the above.

  Specifically, there is a method in which predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and the mixture is stirred, heated, and kept warm under a deoxygenated atmosphere. The polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those commonly used in the art can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (benzoyl peroxide and the like) Any solvent can be used as long as it dissolves each monomer, and a solvent (E) described below or the like can be used as a solvent for the colored photosensitive resin composition.

  As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or one obtained as a solid (powder) by reprecipitation or the like may be used. May be used. In particular, by using a solvent (E) described below as a solvent during this polymerization, the solution after the reaction can be used as it is, and the production process can be simplified.

In the resin [K2], the ratio of the structural units derived therefrom is preferably in the following range among all the structural units constituting the resin [K2].
Structural unit derived from (a); 4 to 45 mol% (more preferably 10 to 30 mol%)
Structural unit derived from (b); 2 to 95 mol% (more preferably 5 to 80 mol%)
Structural unit derived from (c); 1 to 65 mol% (more preferably 5 to 60 mol%)
When the ratio of the structural unit of the resin [K2] is in the above range, storage stability, developability, solvent resistance, heat resistance, and mechanical strength of the obtained pattern tend to be excellent.

The resin [K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].
Specifically, there is a method in which predetermined amounts of (a), (b) and (c), a polymerization initiator and a solvent are charged in a reaction vessel, and the mixture is stirred, heated and kept warm under a deoxygenated atmosphere. As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or one obtained as a solid (powder) by a method such as reprecipitation may be used. May be used.

In the resin [K3], the ratio of the structural units derived therefrom is preferably in the following range among all the structural units constituting the resin [K3].
(A) 2-55 mol%, more preferably 10-50 mol%
(C) 45-98 mol%, more preferably 50-90 mol%
The resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (b) has a cyclic ether having 2 to 4 carbon atoms and (a) has a carboxylic acid and / or carboxylic anhydride. Can be produced by adding
First, a copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing the resin [K1]. In this case, the ratio of the structural units derived therefrom is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).
(A) 5 to 50 mol%, more preferably 10 to 45 mol%
(C) 50-95 mol%, more preferably 55-90 mol%

Next, the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer is partially reacted with the cyclic ether having 2 to 4 carbon atoms of (b).
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask was replaced with air from nitrogen, and (b), a catalyst for the reaction of carboxylic acid or carboxylic anhydride with cyclic ether (tris (dimethyl) A resin [K4] can be obtained by placing an aminomethyl) phenol or the like and a polymerization inhibitor (hydroquinone or the like) in a flask and reacting the mixture at, for example, 60 to 130 ° C. for 1 to 10 hours.
(B) is preferably used in an amount of 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). Within this range, the balance among storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be good. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used in the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5% by mass based on the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by mass based on the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. As in the case of the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

As the resin [K5], as a first step, a copolymer of (b) and (c) is obtained in the same manner as in the method for producing the resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, as a concentrated or diluted solution, or as a solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is preferably in the following range with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5 to 95 mol% (more preferably 10 to 90 mol%)
Structural unit derived from (c); 5 to 95 mol% (more preferably 10 to 90 mol%)

Further, under the same conditions as in the method for producing the resin [K4], the carboxylic acid or carboxylic anhydride of (a) is added to the cyclic ether derived from (b) of the copolymer of (b) and (c). By reacting the product, resin [K5] can be obtained.
The amount of (a) used to react with the copolymer is preferably 5 to 80 mol per 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferably used as (b) used in the resin [K5], and more preferably (b1-1).

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5].
A carboxylic anhydride is reacted with a hydroxy group generated by a reaction between a cyclic ether and a carboxylic acid or a carboxylic anhydride.
Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride) and the like. Can be

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] Resin [K1] such as decyl acrylate / (meth) acrylic acid copolymer; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- ( Resin [K2] such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / Resins [K3] such as (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer; benzyl Glycidyl (meth) acrylate is added to (meth) acrylate / (meth) acrylic acid copolymer and glycidyl (meth) acrylate is added to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer. Resin [K4] such as a resin in which glycidyl (meth) acrylate is added to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; tricyclodecyl (meth) ) Acrylate / glycidyl (meth) acrylate copolymer with (meth) acrylic acid Resin [K5] such as a resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate; tricyclodecyl (meth) acrylate / Resins [K6] such as a resin obtained by reacting a copolymer of glycidyl (meth) acrylate with (meth) acrylic acid and further reacting tetrahydrophthalic anhydride with a resin.
These resins may be used alone or in combination of two or more.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, and still more preferably from 5,000 to 30,000. . When the molecular weight is in the above range, the solubility of the unexposed portion in a developing solution tends to be high, and the residual film ratio and hardness of the obtained pattern tend to be high.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, and more preferably from 1.2 to 4.
The acid value of the resin (B) is preferably from 50 to 180 mg-KOH / g, and more preferably from 60 to 150 mg-KOH / g.
Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined, for example, by titration using an aqueous solution of potassium hydroxide.

  The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the solid content of the colored photosensitive resin composition. %, Particularly preferably 17 to 40% by mass. When the content of the resin (B) is in the above range, the solubility of the unexposed portion in the developer tends to be high.

<Polymerizable compound (C)>
The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less. The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical or the like generated from the polymerization initiator (D) upon irradiation with light. And the like.

The polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate Pentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol La (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate And caprolactone-modified dipentaerythritol hexa (meth) acrylate. Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned.
The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass with respect to 100 parts by mass of the resin (B) in the colored photosensitive resin composition.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it generates an active radical under the action of light or heat and can initiate polymerization of the polymerizable compound (C). Can be used.
As the polymerization initiator (D), a compound that generates an active radical by the action of light is preferable, and an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an oxime compound, and a biimidazole compound are more preferable. Initiators are more preferred.
Examples of the O-acyl oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-. On-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. Commercial products such as Irgacure OXE01, OXE02 (all manufactured by BASF) and N-1919 (ADEKA) may be used.

The colored photosensitive resin composition of the present invention may contain a polymerization initiation assistant (D1). When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D). The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D).
Examples of the polymerization initiator (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxylic acid compound, and a thiol compound, and a thiol compound is preferable. These polymerization initiation aids may be used alone or in combination of two or more.

The content of the polymerization initiator (D) is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and still more preferably 3 to 10% by mass, based on the solid content of the colored photosensitive resin composition. is there.
When the polymerization initiator (D1) is used, its content is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, per 1 mol of the polymerization initiator (D).
The total content of the polymerization initiator (D) and the polymerization initiation assistant (D1) is preferably 1 to 35% by mass, more preferably 1 to 25% by mass, based on the solid content of the colored photosensitive resin composition. And more preferably 1 to 20% by mass, particularly preferably 5 to 20% by mass.

  The colored photosensitive resin composition of the present invention preferably contains a solvent (E). The solvent (E) is not particularly limited, and a solvent usually used in the art 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 used.

  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.

  Examples of the ether solvent 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, and 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, and 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, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl 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. And the like.

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.

These solvents may be used alone or in combination of two or more.
Among the above-mentioned solvents, an organic solvent having a boiling point of 120 ° C. or more and 180 ° C. or less at 1 atm is preferable from the viewpoint of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol , 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and the like are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-Methoxy-1-butanol, ethyl 3-ethoxypropionate and the like are more preferred.

The content of the solvent (E) is preferably from 70 to 95% by mass, more preferably from 75 to 92% by mass, based on the colored photosensitive resin composition. In other words, the solid content of the colored photosensitive resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass.
When the content of the solvent (E) is in the above range, the flatness at the time of coating is improved, and the display characteristics tend to be improved because the color density is not insufficient when a color filter is formed.

<Leveling agent (F)>
Examples of the leveling agent (F) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone-based surfactant include a surfactant having a siloxane bond in a molecule. Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Dow Corning Toray 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 and TSF4460 (manufactured by Momentive Performance Materials Japan GK). No.

  Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in a molecule. Specifically, Florad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554 R30, RS-718-K (manufactured by DIC Corporation), EFTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals, Inc.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

  The content of the leveling agent (F) is preferably from 0.001% by mass to 0.2% by mass, and more preferably from 0.002% by mass to 0.1% by mass, based on the total amount of the colored photosensitive resin composition. %, More preferably 0.01 to 0.05% by mass. This content does not include the content of the pigment dispersant.

  The colored photosensitive resin composition of the present invention contains, if necessary, additives such as a filler, another polymer compound, an adhesion promoter, an antioxidant, an ultraviolet absorber, a light stabilizer, and a chain transfer agent. May be.

The colored photosensitive resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and if necessary, a solvent (E) and a leveling agent (F). And other additives can be manufactured by stirring and mixing by a conventionally known method.
After mixing, it is preferable to filter with a filter having a pore size of about 0.05 to 5.0 μm.
C. contained as a coloring agent (A) I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, a zinc halide phthalocyanine pigment and C.I. I. Pigment Yellow 185 is preferably mixed with other components as a pigment dispersion.
Each pigment dispersion can be prepared by dispersing any of the above pigments in a solvent (E) containing a pigment dispersant.
The pigment dispersants may be used alone or in combination of two or more.
Examples of the pigment dispersant include known pigment dispersants such as an acrylic surfactant, and KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) ) (Manufactured by Abisia), EFKA (registered trademark) (manufactured by BASF), Azispar (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BIC Chemie), and the like.
The amount of the pigment dispersant used is preferably from 1% by mass to 100% by mass, more preferably from 5% by mass to 50% by mass, based on the pigment. When the amount of the pigment dispersant is within the above range, a pigment dispersion in a uniform dispersion state can be obtained.
When dispersing the pigment in the solvent (E), a known disperser such as a bead mill may be used.

The colored photosensitive resin composition of the present invention is useful as a material for a coating film such as a color filter (hereinafter, a coating film in which any shape is resolved may be referred to as a “pattern”). The color filter obtained from the colored photosensitive resin composition has a good pattern shape.
Examples of a method for forming a pattern from the colored photosensitive resin composition of the present invention include a photolithographic method, an inkjet method, a printing method, and the like. Among them, the photolithographic method is preferred.
The photolithographic method is a method in which the colored photosensitive resin composition is applied to a substrate, dried, exposed through a photomask, and developed to obtain a pattern.

Examples of the substrate include glass, metal, and plastic, and may be in the form of a plate or a film. On these substrates, structures such as color filters, various insulating or conductive films, and driving circuits may be formed.
The coating on the substrate can be performed by using a coating apparatus such as a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater, a curtain flow coater, or a spinless coater), an ink jet or the like.

  Examples of the method of drying the colored photosensitive resin composition applied to the substrate include methods such as heat drying, natural drying, ventilation drying, and drying under reduced pressure. A plurality of methods may be combined. The drying temperature is preferably from 10 to 120C, more preferably from 50 to 100C. The heating time is preferably from 10 seconds to 60 minutes, and more preferably from 30 seconds to 10 minutes. The drying under reduced pressure is preferably performed in a temperature range of 20 to 25 ° C. under a pressure of 50 to 150 Pa.

The film obtained by 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 according to the intended use is used.
As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, and light of about 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps and the like can be mentioned.
It is preferable to use a device such as a mask aligner or a stepper because the entire exposure surface can be uniformly irradiated with parallel rays or the mask and the substrate can be accurately positioned.

After exposure, development is performed by contacting with a developing solution to dissolve unexposed portions. A pattern can be obtained by the development. As the developing solution, an organic solvent can be used. However, an aqueous solution of a basic compound is preferable because the developing solution hardly dissolves or swells the exposed portion of the coating film and obtains a pattern having a good shape.
The developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be inclined at an arbitrary angle during development.
After development, it is preferable to wash with water.

Examples of the basic 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 sodium carbonate. , Potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia and other inorganic basic compounds; tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine And organic basic compounds such as monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine and ethanolamine. Among them, potassium hydroxide, sodium hydrogen carbonate and tetramethylammonium hydroxide are preferred.
The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass.

The aqueous solution of the basic compound may contain a surfactant.
Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester Nonionic surfactants such as polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine;
Anionic surfactants such as sodium lauryl alcohol sulfate, sodium oleyl alcohol sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate;
Examples include cationic surfactants such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
The concentration of the surfactant in the aqueous solution of the basic 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.

  Further, post baking may be performed as necessary. Post-baking is preferably performed at 150 to 250 ° C. for 1 to 240 minutes.

  The thickness of the coating film after the post-baking can be appropriately adjusted, but is preferably 0.5 to 5 μm, particularly preferably 0.5 to 3 μm.

The pattern obtained by using the colored photosensitive resin composition of the present invention is useful as a color filter.
The color filter can be used in a known manner in a device related to various colored images such as a display device (a liquid crystal display device, an organic EL device, etc.), a solid-state imaging device, and electronic paper.

  Next, the present invention will be described more specifically with reference to examples. “%” And “parts” in Examples and Comparative Examples are “% by mass” and “parts by mass” unless otherwise specified.

Synthesis Example 1
An appropriate amount of nitrogen was flowed into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was replaced with a nitrogen atmosphere. Then, 280 parts by weight of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C. with stirring. Then, 38 parts by weight of acrylic acid, 289 parts by weight of a mixture of 3,4-epoxytricyclo [5.2.1.02,6] decane-8 or / and 9-yl acrylate, and 125 parts by weight of propylene glycol monomethyl ether acetate Was added dropwise over 5 hours. On the other hand, a mixed solution of 33 parts by weight of 2,2-azobis (2,4-dimethylvaleronitrile) dissolved in 235 parts by weight of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature. A solution of a copolymer having a B-type viscosity (23 ° C.) of 125 mPas, a solid content of 37.0% by weight, and a solution acid value of 27 mg-KOH / g (Resin B-1 solution) was obtained. The weight average molecular weight Mw of the obtained copolymer (resin B-1) was 9,200, and the degree of dispersion was 2.08.

The measurement of the polystyrene-equivalent weight average molecular weight Mw and the number average molecular weight Mn of the resin obtained in the above synthesis example was performed using GPC under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature; 40 ° C
Solvent: tetrahydrofuran [THF]
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Tosoh Corporation)

[Preparation of pigment dispersion 1]
C. I. Pigment Green 58 13.0 parts Acrylic pigment dispersant 2.0 parts Propylene glycol monomethyl ether acetate 85.0 parts are mixed, and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid (A-1). I got

[Preparation of Pigment Dispersion Liquid 2]
C. I. Pigment Yellow 185 5.0 parts Acrylic pigment dispersant 3.5 parts Propylene glycol monomethyl ether acetate 91.5 parts are mixed, and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-2). I got

[Preparation of pigment dispersion 3]
C. I. Pigment Blue 15: 3 12.0 parts Acrylic pigment dispersant 4.0 parts Propylene glycol monomethyl ether acetate 84.0 parts are mixed and sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-3). I got

[Preparation of pigment dispersion 4]
C. I. Pigment Yellow 138 15.0 parts Acrylic pigment dispersant 4.5 parts Propylene glycol monomethyl ether acetate 80.5 parts are mixed, and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid (A-4). I got

[Preparation of Pigment Dispersion 5]
C. I. Pigment Green 7 11.0 parts Acrylic pigment dispersant 3.0 parts 86.0 parts of propylene glycol monomethyl ether acetate are mixed, and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid (A-5). I got

Examples 1-6 and Comparative Examples 1-2
(Preparation of colored photosensitive resin composition)
The components shown in Table 1 were mixed to obtain a colored photosensitive resin composition. Propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored photosensitive resin composition became “solid content (%)” in Table 1.

In Table 1, each component is as follows.
Coloring dispersant (A1); pigment dispersion (A-1)
Coloring dispersant (A2); pigment dispersion (A-2)
Coloring dispersant (A3); Pigment dispersion (A-3)
Coloring dispersant (A4); Pigment dispersion (A-4)
Coloring dispersant (A5); Pigment dispersion (A-5)
Resin (B1); Resin B-1 solution Polymerizable compound (C1); Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator D1; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; O-acyl oxime compound)

[Preparation of pattern]
The colored photosensitive resin composition was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning Incorporated) by spin coating, and then prebaked at 100 ° C. for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the photomask made of quartz glass having a pattern was set to 100 μm, and exposed to air using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Irradiation was performed at an exposure amount of 150 mJ / cm ² (based on 365 nm). As the photomask, a mask having a line and space pattern with a line width of 50 μm (pitch: 50 μm) was used. After the light irradiation, the coating film was immersed and developed in an aqueous developer solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds. For 30 minutes to obtain a pattern.

(Thickness measurement)
About the obtained pattern, the film thickness was measured using the film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Engineering Co., Ltd.). Table 2 shows the results.

[Chromaticity evaluation]
The obtained pattern is measured for its spectrum using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates (in the CIE XYZ color system) using the characteristic function of the C light source. x, y) and lightness Y were measured. Table 2 shows the results.

[Pattern shape]
About the cross section of the obtained pattern, the shape was observed using the scanning electron microscope (S-4000; manufactured by Hitachi High-Technologies Corporation). The shape shown in FIG. 1 (p1) was evaluated as ○, and the shape shown in FIG. 1 (p2) was evaluated as ×. With the shape shown in FIG. 1 (p1), when the inorganic film is laminated on the pattern, the inorganic film tends not to crack or peel. Table 2 shows the results.

(Observation of peeled pieces)
In the preparation of the pattern, the developing solution after the development was visually observed. When no peeling strip derived from the colored photosensitive resin composition was observed in the developing solution, it was evaluated as ○, and when peeling was observed, it was evaluated as ×. It is not preferable that a peeled strip derived from the colored photosensitive resin composition is observed in the developer, because the strip may adhere to the pattern as a foreign substance and cause a defect. Table 2 shows the results.

注：表２において、着色剤濃度は、固形分全量を１００％として換算した濃度である。

Note: In Table 2, the colorant concentration is a concentration calculated assuming that the total solid content is 100%.

  A color filter having high brightness can be produced from the colored photosensitive resin composition of the present invention.

Claims (5)

A colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
As a coloring agent (A), a halogenated zinc phthalocyanine pigment; I. Pigment Yellow 185, C.I. I. Pigment Blue 15: 3 or C.I. I. Pigment Blue 15: 4. Halogenated zinc phthalocyanine pigment is C. I. The colored photosensitive resin composition according to claim 1, which is Pigment Green 58.   C. I. The colored photosensitive resin composition according to claim 1, wherein the content of Pigment Yellow 185 is 10 to 50 parts by mass based on 100 parts by mass of the polymerizable compound (C).   The colored photosensitive resin composition according to claim 1, wherein the total amount of the coloring agent (A) is 20 to 50 parts by mass based on 100 parts by mass of the solid content of the colored photosensitive resin composition.   A color filter formed from the colored photosensitive resin composition according to claim 1.

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