KR20130121732A - Colored photosensitive resin composition - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition comprising a coloring agent, a resin, a polymerizable compound and a polymerization initiator, wherein the coloring agent includes C.I. pigment green 36 and at least one kind selected from the group consisting of a yellow pigment, a blue pigment, a red pigment, a violet pigment and an orange pigment, and the resin is a copolymer comprising at least one kind selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride and a structure unit having an alicyclic hydrocarbon structure.

Description

Colored photosensitive resin composition {COLORED PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a colored photosensitive resin composition.

The coloring photosensitive resin composition is used for manufacture of the color filter used for display apparatuses, such as a liquid crystal display device, an electro luminescence display device, and a plasma display. As such colored photosensitive resin composition, the composition containing the copolymer of methacrylic acid, methyl methacrylate, n-butyl methacrylate, and 2-hydroxyethyl methacrylate is known (JP2004-309537-A). ).

In the above-mentioned colored photosensitive resin composition, when forming a colored pattern by the photolithographic method, the unexposed part cannot fully be removed by image development, and a residue and a film residue may generate | occur | produce.

The present invention includes the following inventions.

[1] A colored photosensitive resin composition comprising a coloring agent, a resin, a polymerizable compound and a polymerization initiator,

The colorant is C.I. Pigment green 36, a yellow pigment, and at least one selected from the group consisting of a blue pigment, a red pigment, a purple pigment, and an orange pigment,

The colored photosensitive resin composition whose resin is a copolymer containing the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the structural unit which has an alicyclic hydrocarbon structure.

[2] The colored photosensitive resin composition according to [1], wherein the structural unit having an alicyclic hydrocarbon structure is a structural unit derived from a monomer having an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent.

[3] The colored photosensitive resin composition according to [1] or [2], in which the polymerization initiator contains an O-acyl oxime compound.

[4] At least one selected from the group consisting of a blue pigment, a red pigment, a purple pigment, and an orange pigment is C.I. The coloring photosensitive resin composition in any one of [1]-[3] which is Pigment Red 177.

[5] A color filter formed of the colored photosensitive resin composition according to any one of [1] to [4].

[6] A display device comprising the color filter according to [5].

According to the coloring photosensitive resin composition of this invention, developability at the time of forming a coloring pattern by the photolithographic method is excellent.

The coloring photosensitive resin composition of this invention contains a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator (D).

It is preferable that the coloring photosensitive resin composition of this invention further contains at least 1 sort (s) chosen from the group which consists of a solvent (E), a thiol compound (T), a leveling agent (F), and an adhesion promoter (G).

The coloring photosensitive resin composition of this invention may further contain polymerization start adjuvant (D1).

<Coloring agent (A)>

Colorant (A) is C.I. Pigment green 36, a yellow pigment, and at least 1 sort (s) chosen from the group which consists of a blue pigment, a red pigment, a purple pigment, and an orange pigment.

As a yellow pigment, for example, C.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 , 147, 148, 150, 153, 154, 166, 173, 194, 214, etc., Preferably, CI Pigment Yellow 138, 150.

As the blue pigment, for example, C.I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 60, 80 and the like.

As a red pigment, it is C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. And preferably CI. Pigment Red 177.

As a purple pigment, for example, C.I. Pigment violet 1, 19, 23, 29, 32, 36, 38, etc., Preferably, C.I. Pigment Violet 23.

Examples of orange pigments include C.I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc., Preferably, C.I. Pigment Orange 38.

Among at least one selected from the group consisting of blue pigments, red pigments, purple pigments and orange pigments, C.I. Pigment red 177 is preferable at the point that the contrast of the color filter obtained is improved.

The pigment used for the colored photosensitive resin composition of this invention is rosin-treated, surface treatment using the pigment derivative in which an acidic group or a basic group was introduce | transduced, graft treatment to the pigment surface by a high molecular compound, a sulfuric acid atomization method, etc. as needed. May be performed by an organic atomization treatment for removing impurities, or a washing treatment with an organic solvent or water for removing impurities, a removal treatment by an ion exchange method of ionic impurities, or the like. It is preferable that the particle diameter of a pigment is respectively uniform.

These pigments can be made into the pigment dispersion liquid of the state disperse | distributed uniformly in the pigment dispersant solution by containing and disperse | distributing a pigment dispersant. Each pigment may be subjected to dispersion treatment alone, or a plurality of species may be mixed and dispersed treatment.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. You may use these pigment dispersants individually or in combination of 2 or more types. As a pigment dispersant, KP [made by Shin-Etsukagaku Kogyo Co., Ltd.], Floren (manufactured by Kyoeisha Kagaku Co., Ltd.), Solsperth (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF Corporation), Ajisper [ Ajinomoto Fine Techno Co., Ltd.], Disperbyk (Bikkemi company make), etc. are mentioned.

When using a pigment dispersant, the usage-amount is preferably 100 mass parts or less with respect to 100 mass parts of pigments, More preferably, they are 5 mass parts or more and 50 mass parts or less. When the usage-amount of a pigment dispersant exists in the said range, there exists a tendency for the pigment dispersion liquid of a uniform dispersion state to be obtained.

C.I. 20-99 mass% is preferable with respect to the total amount of a coloring agent (A), and, as for content of pigment green 36, 30-95 mass% is more preferable.

0.1-79.9 mass% is preferable with respect to the total amount of a coloring agent (A), and, as for content of a yellow pigment, 4.9-60 mass% is more preferable.

0.1-5 mass% is preferable with respect to the total amount of a coloring agent (A), and, as for at least 1 type of content chosen from the group which consists of a blue pigment, a red pigment, a purple pigment, and an orange pigment, 0.1-3 mass% is more preferable.

The content rate of the coloring agent (A) is preferably 20% by mass or more and 50% by mass or less with respect to the total amount of solids, and more preferably 28% by mass to 45% by mass. In this specification, "total amount of solid content" means the total amount of the component remove | excluding the solvent (E) from the coloring photosensitive resin composition of this invention.

<Resin (B)>

Resin (B) is a structural unit derived from at least 1 sort (it may be called "(a)" hereafter) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and an alicyclic hydrocarbon structure. It is a copolymer containing the structural unit which has.

The structural unit having an alicyclic hydrocarbon structure is derived from a monomer having an alicyclic hydrocarbon structure (hereinafter sometimes referred to as "(x)").

Examples of the resin (B) include the following copolymers [K1] to [K5].

Copolymer [K1]; copolymers of (a) with (x);

Copolymer [K2]; Copolymer with (a) and (x) and the monomer (c) copolymerizable with (a), but different from (a) and (x) [Hereinafter, it may be called "(c)"]. ;

Copolymer [K3]; Resin which made the copolymer [K1] or the copolymer [K2] react with the monomer (b) (Hereinafter, it may be called "(b)") which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond;

Copolymer [K4]; Resin which (a) was made to react the copolymer of (b) and (x);

Copolymer [K5]; Resin which further made carboxylic anhydride react with resin which (a) made to react the copolymer of (b) and (x).

(a) include, for example, 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, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- [2.2.1] hept-2-ene, and 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-tetrahydrophthalic anhydride Unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl of a divalent or higher polyhydric carboxylic acid such as succinate mono [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl] ] Esters;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule such as α- (hydroxymethyl) acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable at the point of copolymerization reactivity, or the solubility with respect to the aqueous alkali solution of obtained resin.

(x) is a monomer which has a C3-C18 alicyclic hydrocarbon group which may have a substituent, for example.

As a C3-C18 alicyclic hydrocarbon group, For example, Cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group; Polycyclic alicyclic hydrocarbon groups, such as a tricyclodecyl group, a decahydronaphthyl group, an adamantyl group, and a norbornyl group, etc. are mentioned, Preferably it is a polycyclic alicyclic hydrocarbon group, More preferably, tricyclodecyl It is a practical skill.

As a substituent which these may have, a C1-C18 aliphatic hydrocarbon group, a C6-C18 aromatic hydrocarbon group, a hydroxyl group, a halogen atom, an epoxy group, etc. are mentioned.

Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group.

Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms include phenyl group, naphthyl group, anthryl group, toluyl group, xylyl group, cumenyl group, mesityl group, biphenyl group, and phenanthryl group.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

The monomer having an alicyclic hydrocarbon structure is, for example, a monomer having an alicyclic hydrocarbon structure and an ethylenically unsaturated bond, and preferably a monomer having an alicyclic hydrocarbon structure and a (meth) acryloyloxy group.

In addition, in this specification, "(meth) acryloyl" shows at least 1 sort (s) chosen from the group which consists of acryloyl and methacryloyl. Notation, such as "(meth) acrylic acid" and "(meth) acrylate", has the same meaning.

As (x), for example, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) Acrylate [A common name in the art is called "dicyclopentanyl (meth) acrylate". In addition, it may be called "tricyclodecyl (meth) acrylate", and tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate [Dicyclophene as a conventional name in the technical field in this field. Tenyl (meth) acrylate], dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and an alicyclic hydrocarbon structure such as adamantyl (meth) acrylate (meth) ) Acrylic esters;

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 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- Cyclohexyl [2.2.1] hept-2-ene, 5,6-bis 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like such as bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept- Cyclo-unsaturated compounds; N-substituted maleimides having an alicyclic hydrocarbon structure such as N-cyclohexyl maleimide; And the like.

In addition, (x) is an alicyclic hydrocarbon structure, where two hydrogen atoms respectively bonded to two adjacent carbon atoms of an alicyclic hydrocarbon have a monomer substituted with an epoxy group [hereinafter referred to as "(x ')" Yes] may be used.

Examples of such (x) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane [eg, ceoxide 2000; Daicel Corporation], 3, 4- epoxycyclohexyl methyl acrylate [For example, cyclomer A400; Daicel Corporation], 3, 4- epoxycyclohexyl methyl methacrylate [for example, cyclomer M100; Daicel Co., Ltd.], the compound represented by general formula (I), the compound represented by general formula (II), etc. are mentioned.

[Formula (I) and Formula (II), R ^<a> and R <^b> represent a hydrogen atom or a C1-C4 alkyl group, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.

X ^a and X ^b represent a single bond, -R ^c- , * -R ^c -O-, * -R ^c -S- or * -R ^c -NH-.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents the number of bonds with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and the like.

As an alkyl group in which a hydrogen atom was substituted by hydroxy, it is a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

As R ^<a> and R <^b> , Preferably a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group is mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

Examples of the alkanediyl group are 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-1, 6-diyl group etc. are mentioned.

X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, and more preferably a single bond, *- CH ₂ CH ₂ —O— (* indicates the number of bonds with O).

As a compound represented by general formula (I), the compound etc. which are represented by either of general formula (I-1)-general formula (I-15) are mentioned. Among them, general formula (I-1), general formula (I-3), general formula (I-5), general formula (I-7), general formula (I-9) or general formula (I-11) to general formula (I-15) The compound represented by) is preferable, and the compound represented by general formula (I-1), general formula (I-7), general formula (I-9), or general formula (I-15) is more preferable.

As a compound represented by general formula (II), the compound etc. which are represented by either of general formula (II-1)-general formula (II-15) are mentioned. Among them, the formulas (II-1), (II-3), (II-5), (II-7), (II-9) or (II-11) to (II-15) The compound represented by) is preferable, and the compound represented by general formula (II-1), general formula (II-7), general formula (II-9), or general formula (II-15) is more preferable.

The compound represented by general formula (I) and the compound represented by general formula (II) may be used independently, respectively, and may use together the compound represented by general formula (I) and the compound represented by general formula (II). When using these together, the content rate of the compound represented by general formula (I) and the compound represented by general formula (II) is based on molar basis, Preferably it is 5: 95-95: 5, More preferably, it is 10: 90-90. : 10, More preferably, it is 20: 80-80: 20.

(c) is copolymerizable with (a) and will not be specifically limited if it is a monomer different from (a) and (x).

As (c), for example, 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, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) (Meth) acrylic acid esters such as acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

N-phenylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate Dicarbonyl imide derivatives such as N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Among these, styrene, vinyltoluene, benzyl (meth) acrylate, N-phenylmaleimide, N-benzyl maleimide, etc. are preferable at the point of copolymerization reactivity and heat resistance.

In addition, in (c), the monomer which has a C2-C4 cyclic ether structure (for example, at least 1 sort (s) chosen from the group which consists of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) [hereinafter "(c ')" May be referred to as, for example, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and o-vinyl. Benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyl Oxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene , 2,3,6-tris Oxyranyl groups such as (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene, and ethylenically unsaturated bonds Monomer having;

3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3- Acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl ox Monomers having an oxetanyl group and an ethylenically unsaturated bond such as cetane and 3-ethyl-3-acryloyloxyethyl oxetane;

Monomers having an ethylenically unsaturated bond with a tetrahydrofuryl group such as tetrahydrofurfuryl acrylate [for example, biscoat V # 150, manufactured by Osaka Yuki Chemical Co., Ltd.], tetrahydrofurfuryl methacrylate; And the like.

In copolymer [K1], the ratio of the structural unit derived from each is in the all the structural units which comprise copolymer [K1],

structural unit derived from (a); 2 ~ 60 mol%

structural unit derived from (x); It is preferable that it is 40-98 mol%,

structural unit derived from (a); 10-50 mol%

structural unit derived from (x); It is more preferable that it is 50-90 mol%.

When the ratio of the structural unit of copolymer [K1] exists in the said range, there exists a tendency for the developability at the time of forming a coloring pattern and the solvent resistance of the color filter obtained to be excellent.

Copolymer [K1] is, for example, the method described in the document "Experimental method of polymer synthesis" [Oka Takayuki Publishing Co., Ltd. 1st edition first edition issued March 1, 1972], and the citations described in this document. It can be prepared with reference to.

Specifically, a predetermined amount of (a) and (x), a polymerization initiator, a solvent, and the like are put in a reaction vessel, and a method of heating and keeping warm while stirring, for example, by replacing oxygen with nitrogen to make a deoxygen atmosphere. . In addition, the polymerization initiator, solvent, etc. which are used here are not specifically limited, What is normally used in the said field | area can be used. For example, an azo compound [2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.] and an organic peroxide (benzoyl peroxide etc.) are mentioned as a polymerization initiator. As a solvent, what is necessary is just to melt | dissolve each monomer, and the solvent etc. which are mentioned later as a solvent (E) of the coloring photosensitive resin composition of this invention are mentioned.

In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was extracted as solid (powder) by methods, such as reprecipitation. In particular, by using the solvent contained in the coloring photosensitive resin composition of this invention as a solvent at the time of this superposition | polymerization, since the solution after reaction can be used for preparation of the coloring photosensitive resin composition of this invention as it is, of the coloring photosensitive resin composition of this invention The manufacturing process can be simplified.

In copolymer [K2], the ratio of the structural unit derived from each is in the all the structural units which comprise copolymer [K2],

structural unit derived from (a); 2 ~ 45 mol%

structural unit derived from (x); 2 ~ 95 mol%

structural unit derived from (c); It is preferable that it is 1-65 mol%,

structural unit derived from (a); 5-40 mol%

structural unit derived from (x); 5 ~ 80 mol%

structural unit derived from (c); It is more preferable that it is 5-60 mol%.

When the ratio of the structural unit of copolymer [K2] exists in the above-mentioned range, there exists a tendency which is excellent in the developability at the time of forming a coloring pattern, and the solvent resistance, heat resistance, and mechanical strength of the color filter obtained.

Copolymer [K3] can be manufactured by adding (b) to copolymer [K1] or copolymer [K2]. As (b), the above-mentioned (c ') and (x') are mentioned. It is preferable that copolymer [K1] and copolymer [K2] used for manufacture of copolymer [K3] do not have a structural unit derived from (x '), and a structural unit derived from (c').

The number of carbon atoms which (b) has in the copolymer [K1] or the copolymer [K2] produced as described above in a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer React cyclic ether of ˜4.

Following the preparation of copolymer [K1] or copolymer [K2], the atmosphere in the flask is replaced with nitrogen to air and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride with a cyclic ether [eg Tris ( Dimethylaminomethyl) phenol and the like] and a polymerization inhibitor (such as hydroquinone) and the like can be put in a flask and reacted at, for example, 60 ° C. to 130 ° C. for 1 to 10 hours to produce a copolymer [K3].

As for the usage-amount of (b), 5-80 mol is preferable with respect to 100 mol of (a), More preferably, it is 10-75 mol. By setting it as this range, there exists a tendency for the balance of the storage stability of a coloring photosensitive resin composition, the developability at the time of forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and the sensitivity of the pattern obtained to become favorable. Since the reactivity of cyclic ether is high and unreacted (b) hardly remains, the monomer which has an oxiranyl group and ethylenically unsaturated bond is preferable as (b) used for manufacture of copolymer [K3].

As for the usage-amount of the said reaction catalyst, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of all the monomers used for manufacture of copolymer [K1] or copolymer [K2], and (b). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of all the monomers used for manufacture of copolymer [K1] or copolymer [K2], and (b).

Reaction conditions, such as an injection | throwing-in method, reaction temperature, and time, can be adjusted suitably in consideration of heat generation amount by a manufacturing facility, superposition | polymerization, etc. In addition, as in the case of the polymerization conditions, the injection method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production facility or polymerization.

Copolymer [K4] is a 1st step and obtains the copolymer of (b) and (x) similarly to the manufacturing method of copolymer [K1] mentioned above. As mentioned above, the obtained copolymer may use the solution after reaction as it is, the concentrated or diluted solution may be used, and what was extracted as solid (powder) by methods, such as reprecipitation, may be used. As (b) used for manufacture of copolymer [K4], the monomer which has an oxiranyl group and ethylenically unsaturated bond is preferable.

The ratio of the structural unit derived from (b) and (x) is respectively with respect to the total number of moles of all the structural units which comprise the said copolymer.

structural unit derived from (b); 5 ~ 95 mol%

structural unit derived from (x); It is preferable that it is 5-95 mol%,

structural unit derived from (b); 10 to 90 mol%

structural unit derived from (x); It is more preferable that it is 10-90 mol%.

Moreover, the carboxylic acid or carboxylic anhydride which (a) has in the cyclic ether derived from (b) which the copolymer of (b) and (x) has on the same conditions as the manufacturing method of copolymer [K4]. The copolymer [K4] can be obtained by reacting.

As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b).

Copolymer [K5] is resin which made carboxylic anhydride further react with copolymer [K4]. The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic anhydride.

As carboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 -Tetrahydrophthalic anhydride, dimethyl tetrahydrophthalic anhydride, 5, 6- dicarboxy bicyclo [2.2.1] hept-2-ene anhydride, etc. are mentioned. As for the usage-amount of carboxylic anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / Copolymers such as (meth) acrylic acid copolymer and tricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid copolymer [K1];

3,4-Epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth Copolymers such as) acrylate / (meth) acrylic acid / vinyltoluene copolymer and tricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid copolymer / benzyl (meth) acrylate;

Resin which added glycidyl (meth) acrylate to the tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) Copolymers [K3] such as a resin obtained by adding glycidyl (meth) acrylate to an acrylic acid copolymer;

Of resin, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate which made (meth) acrylic acid react with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate Copolymers [K4] such as resins in which (meth) acrylic acid is reacted with a copolymer;

And copolymers such as resin [K5] such as resin in which tetrahydrophthalic anhydride is further reacted with a resin in which (meth) acrylic acid is reacted with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate. have.

Resin (B), Preferably, it is 1 type chosen from the group which consists of a copolymer [K1] and a copolymer [K2]. If it is these resin, colored photosensitive resin composition is excellent in developability. The copolymer [K2] is more preferable from the viewpoint of adhesion between the coloring pattern and the substrate.

The weight average molecular weight of polystyrene conversion of resin (B) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When the molecular weight is in the above-described range, the coating film hardness is improved, the residual film ratio is also high, the solubility in the developer of the unexposed part is good, and the resolution of the coloring pattern tends to be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of resin (B) becomes like this. Preferably it is 50-170 mg-KOH / g, More preferably, it is 60-150 mg-KOH / g, More preferably, it is 70-135 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to the total amount of solid content, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When content of resin (B) exists in the said range, there exists a tendency for the resolution and residual film rate of a coloring pattern to improve.

<Polymeric Compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D). Examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like. It is a (meth) acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth ) Acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritolhepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth Acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene Glycol-modified dipentaerythritol hexa (meth) acrylate And caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like.

Especially, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

Preferably the weight average molecular weight of a polymeric compound (C) is 150 or more and 2,900 or less, More preferably, it is 250-1,500 or less.

It is preferable that content of a polymeric compound (C) is 7-65 mass% with respect to the total amount of solid content, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%.

The content ratio [resin (B): polymerizable compound (C)] of the resin (B) and the polymerizable compound (C) is preferably 20:80 to 80:20, more preferably on a mass basis. It is 35: 65-80: 20, More preferably, it is 50: 50-75: 25, Especially preferably, it is 55: 50-70: 30.

When content of a polymeric compound (C) exists in the said range, there exists a tendency for the chemical film resistance of the residual film rate at the time of a coloring pattern formation, and a color filter to improve.

<Polymerization Initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid, or the like by the action of light or heat and can initiate polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds, biimidazole compounds and the like.

The O-acyloxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond number.

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-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-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, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl ) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- And the like] -3-cyclopentylpropane-1-one-2-imine. You may use commercially available products, such as Irgacure OXE01, OXE02 (above BASF Corporation), and N-1919 (ADEKA Corporation). Among them, the O-acyl oxime compound is N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane At least one selected from the group consisting of -1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferable, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferred.

The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). Of these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-morpholinyl) phenyl] butane-1-one, 2- (dimethylamino) -1-one. You may use commercial items, such as Irgacure 369, 907, 379 (above, BASF Corporation make).

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy- -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan- ?,? - diethoxyacetophenone, and benzyl dimethyl ketal.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

The biimidazole compound is, for example, a compound represented by the formula (d5).

[In formula (d5), R <^3> -R <^8> represents the C6-C10 aryl group which may have a substituent.]

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, toluyl group, xylyl group, ethylphenyl group, naphthyl group, and the like, and preferably a phenyl group.

As a substituent, a halogen atom, a C1-C4 alkoxy group, etc. are mentioned, for example. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, for example, Preferably it is a chlorine atom. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, butoxy group etc. are mentioned, for example, Preferably it is a methoxy group.

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 eg JPH06-75372-A, JPH06-75373-A, etc.), 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 (trialkoxyphenyl) biimidazole (see, eg, JPS48-38403-B, JPS62-174204-A, etc.), imidazole in which the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group A compound (for example, JPH07-10913-A etc.) is mentioned. Especially, the compound represented by the following formula and its mixture are preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloro Rhomethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2 , 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and the like. You may use commercial items, such as Lucirin (trademark) TPO (made by BASF Corporation) and Irgacure (registered trademark) 819 (made by BASF Corporation).

Moreover, as a 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-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, and campquinone; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiator (D1) (particularly amines) to be described later.

Content of a polymerization initiator (D) becomes like this. Preferably it is 1-30 mass% with respect to the total amount of solid content, More preferably, it is 5-20 mass%.

Moreover, content of a polymerization initiator (D) becomes like this. Preferably it is 1-50 mass parts with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), More preferably, it is 10-45 mass parts, Preferably it is 20-40 mass parts.

<Polymerization start preparation (D1)>

A polymerization start adjuvant (D1) is a compound or sensitizer used in order to accelerate superposition | polymerization of the polymeric compound in which superposition | polymerization was started with a polymerization initiator. When including a polymerization start adjuvant (D1), it is normally used in combination with a polymerization initiator (D).

An amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned as a polymerization start adjuvant (D1).

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate and 4-dimethylamino 2-ethylhexyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4 '-Bis (ethylmethylamino) benzophenone and the like can be cited, and among these, 4,4'-bis (diethylamino) benzophenone is preferable. You may use a commercial item, such as EAB-F (made by Hodogaya Kagaku Kogyo Co., Ltd.).

Examples of the alkoxy anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibu Methoxy anthracene, 2-ethyl-9, 10-dibutoxy anthracene, etc. are mentioned.

As the thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy city Orcanthone etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid and chloro Phenyl sulfanyl acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthyl thioacetic acid, N-naphthyl glycine, naphthoxy acetic acid, etc. are mentioned.

When using these polymerization start adjuvant (D1), the content becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), More preferably, it is 1-20 mass It is wealth. When the amount of the polymerization initiator (D1) is within this range, the coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Thiol compound (T)>

Thiol compound (T) is a compound which has -SH in a molecule | numerator.

Examples of the compound having one -SH in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzooxazole, 2 Sulfanylnicotinic acid, 2-sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino -6-hydroxy-2-sulfanylpyrimidine, 4-amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy- 2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propylpyrimidine, 2-sulfanyl- 4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2 Sulfanyl Sol, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5-sulfanyl-1,2, 4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-sulfanyl-1H- 1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl) methanethiol, 2-sulfanyl-5-thiazolidone, 2-sulfanylthiazoline, 2-sulfanyl- 4 (3H) -quinazolinone, 1-phenyl-1H-tetrazol-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2-sulfanyl-5-nitrobenzimidazole , 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthoimidazole, 2-sulfanylnaphthooxazole, 3-sulfanyl-1,2,4-triazole, 4-amino-6-sulfanylpyrazolo [2,4-d] pyridine, 2-amino-6-purinthiol, 6- Purine isoquinoline, and the like can be mentioned 4-sulfanyl -1H- pyrazolo [2,4-d] pyrimidine.

Examples of the compound having two or more -SH in the molecule include hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediolbis (3-sulfanylpropionate), and butanediolbis (3-sulfanyl Acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylol propane tris (3-sulfanylpropionate ), Trimethylol propane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyl tris (3-sulfanyl) Propionate), pentaerythritol tetrakis (3-sulfanylbutylate), 1,4-bis (3-sulfanylbutyloxy) butane and the like.

As a thiol compound (T), the compound which has one -SH in a molecule | numerator is preferable.

Content of a thiol compound (T) becomes like this. Preferably it is 0.5-20 mass parts, More preferably, it is 1-15 mass parts with respect to 100 mass parts of polymerization initiators (D). When content of a thiol compound (T) exists in this range, there exists a tendency for a sensitivity to become high and developability becomes favorable.

&Lt; Solvent (E) >

The solvent (E) is not particularly limited, and a solvent commonly used in the field can be used. For example, an ester solvent (solvent containing -COO- in a molecule and no -O-), an ether solvent (solvent containing -O- in a molecule and not containing -COO-), an ether ester solvent ( A solvent containing -COO- and -O- in a molecule, a ketone solvent (a solvent containing -CO- in a molecule and no -COO-), an alcoholic solvent (containing OH in a molecule, -O- , -CO- and -COO- free solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyric acid Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, gamma -butyrolactone, and the like.

As the ether solvent, 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, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl anisole, etc. Can be mentioned.

Examples of the ether ester solvents include methyl methoxy acetate, ethyl methoxy acetate, butyl acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate and methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methyl Methyl propionate, 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 Bit, di, and the like ethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate.

As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopenta Paddy fields, cyclohexanone, isophorone, etc. are mentioned.

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

Benzene, toluene, xylene, mesitylene etc. are mentioned as an aromatic hydrocarbon solvent.

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

These solvents may be used independently and may use 2 or more types together.

Among the solvents described above, organic solvents having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm are preferable in view of coatability and dryness. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl 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, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-ethoxypropionate, and the like are more preferable. .

Content of a solvent (E) becomes like this. Preferably it is 70-95 mass% with respect to the total amount of a coloring photosensitive resin composition, More preferably, it is 75-92 mass%. In other words, solid content of a coloring photosensitive resin composition becomes like this. Preferably it is 5-30 mass%, More preferably, it is 8-25 mass%.

When content of a solvent (E) exists in the said range, flatness at the time of application | coating becomes favorable, and since a color density does not run short when a color filter is formed, there exists a tendency for display characteristics to become favorable.

<Leveling agent (F)>

Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymeric group in a side chain.

As silicone type surfactant, surfactant etc. which have a siloxane bond in a molecule | numerator are mentioned. Specifically, doyle silicon DC3PA, doyle silicon SH7PA, doyle silicon DC11PA, doyle silicon SH21PA, doyle silicon SH28PA, doyle silicon SH29PA, doyle silicon SH30PA, doyle silicon SH8400 [brand name: doray silicon Dow Corning ( Manufacture), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsukagaku Kogyo Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (Momental performance) Materials Japan Kogyo Co., Ltd.) etc. are mentioned.

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned in a molecule | numerator. Specifically, Fluoride (RT) FC430, Fluoride FC431 (manufactured by Sumitomo 3M Co., Ltd.), Mega Pack (F) D142, Mega Pack F171, Mega Pack F172, Mega Pack F173, Mega Pack F177, Mega Pack F183 , Megapack F554, Megapack R30, Megapack RS-718-K (manufactured by DIC Corporation), FTop® EF301, Ftop EF303, Ftop EF351, Ftop EF352 [Mitsubishi Material Denshi Kasei Ltd.], Supron (registered trademark) S381, Supron S382, Supron SC101, Supron SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Co., Ltd.) Can be mentioned.

As silicone type surfactant which has the said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain | strand are mentioned in a molecule | numerator. Specific examples thereof include Mega Pack (R) R08, Mega Pack BL20, Mega Pack F475, Mega Pack F477, and Mega Pack F443 (manufactured by DIC Corporation).

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less with respect to the total amount of the colored photosensitive resin composition, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.005% by mass or more and 0.05. It is mass% or less. If content of a leveling agent (F) exists in the said range, flatness of a color filter can be made favorable.

<Adhesive Promoter (G)>

Examples of the adhesion promoter (G) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, and 3-glycidoxypropylmethyl. Dimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxy Silane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatepropyltrie Methoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3- Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxy Cysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, and the like.

Content of adhesion promoter (G) becomes like this. Preferably it is 0.1 mass% or more and 5 mass% or less with respect to the total amount of solid content, Preferably it is 0.2 mass% or more and 2 mass% or less. If content of adhesion promoter (G) exists in the said range, adhesiveness with a board | substrate can be made favorable.

&Lt; Other components >

The coloring photosensitive resin composition of this invention may contain additives known in the art, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, a light stabilizer, a chain transfer agent, as needed.

<The manufacturing method of a coloring photosensitive resin composition>

The coloring photosensitive resin composition of this invention is a coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), and the solvent (E) and thiol compound (T) used as needed, for example. ), A leveling agent (F), a polymerization start aid (D1), an adhesion promoter (G), and other components can be prepared.

It is preferable to mix a pigment previously with a part or all of the solvent (E), and to disperse | distribute using a bead mill etc. until the average particle diameter of a pigment becomes about 0.2 micrometer or less. At this time, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The target coloring photosensitive resin composition can be prepared by mixing the remaining components with the pigment dispersion liquid thus obtained so as to have a predetermined concentration.

It is preferable to filter the coloring photosensitive resin composition after mixing with the filter of about 0.1-10 micrometers of pore diameters.

<Manufacturing Method of Color Filter>

As a method of manufacturing a coloring patterned coating film from the coloring photosensitive resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Especially, the photolithographic method is preferable. The photolithographic method is a method of apply | coating the said coloring photosensitive resin composition to a board | substrate, drying to form a coloring composition layer, and exposing and developing the said coloring composition layer through a photomask. In the photolithographic method, the colored coating film which is the hardened | cured material of the said coloring composition layer can be formed by not using a photomask at the time of exposure, and / or not developing. The coloring patterning coating film and coloring coating film which were formed in this way are the color filter of this invention.

The film thickness of the produced color filter is not specifically limited, It can adjust suitably according to the objective, a use, etc., for example, 0.1-30 micrometers, Preferably it is 0.1-20 micrometers, More preferably, it is 0.5-6 micrometers.

As a board | substrate, glass plates, such as quartz glass, borosilicate glass, alumina silicate glass, and the soda-lime glass which silica-coated the surface, resin plates, such as polycarbonate, polymethyl methacrylate, and a polyethylene terephthalate, silicon, aluminum on the said board | substrate, Silver and the thing which formed the silver / copper / palladium alloy thin film etc. are used. Separate color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

Formation of each color pixel by the photolithographic method can be performed by a well-known or usual apparatus and conditions. For example, it can produce as follows.

First, a coloring photosensitive resin composition is apply | coated on a board | substrate, and volatile components, such as a solvent, are removed and dried by heat-drying (prebaking) and / or drying under reduced pressure, and a smooth coloring composition layer is obtained.

As a coating method, a spin coat method, the slit coat method, the slit and spin coat method, etc. are mentioned.

30 degreeC-120 degreeC is preferable, and, as for the temperature at the time of heat-drying, 50 degreeC-110 degreeC is more preferable. Moreover, as heating time, it is preferable that it is for 10 second-60 minutes, and it is more preferable that it is for 30 second-30 minutes.

When drying under reduced pressure, it is preferable to carry out in the temperature range of 20 degreeC-25 degreeC under the pressure of 50-150 Pa.

The film thickness of a coloring composition layer is not specifically limited, What is necessary is just to select suitably according to the film thickness of the target color filter.

Next, a coloring composition layer is exposed through a photomask in order to form the target coloring patterned coating film. The pattern on this photomask is not specifically limited, The pattern according to the intended use is used.

As a light source used for exposure, the light source which produces the light of 250-450 nm wavelength is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm is selected using a band pass filter that extracts these wavelength ranges. May be taken out. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

It is preferable to use exposure apparatuses, such as a mask aligner and a stepper, since the parallel light beam can be irradiated uniformly to the whole exposure surface or the exact alignment of a photomask and the board | substrate with a coloring composition layer can be performed.

A colored patterned coating film is formed on a board | substrate by developing the coloring composition layer after exposure contacting with a developing solution. By development, the unexposed part of a coloring composition layer melt | dissolves in a developing solution and is removed.

As a developing solution, aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide, is preferable, for example. The density | concentration in the aqueous solution of these alkaline compounds becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%. In addition, the developing solution may contain surfactant.

The developing method may be any of a paddle method, a dipping method, a spray method, and the like. In addition, you may tilt the board | substrate at arbitrary angles at the time of image development.

It is preferable to wash with water after image development.

Moreover, it is preferable to post-bake to the obtained colored patterned coating film. 150 degreeC-250 degreeC is preferable, and, as for post-baking temperature, 160 degreeC-235 degreeC is more preferable. 1-120 minutes are preferable and, as for post-baking time, 10 to 60 minutes are more preferable.

According to the coloring photosensitive resin composition of this invention, since the generation | occurrence | production of a residue and a film residue is especially small, the color filter with few defects can be manufactured. This color filter is useful as a color filter used for a display apparatus (for example, a liquid crystal display device, an organic electroluminescent apparatus, an electronic paper, etc.) and a solid-state image sensor.

Example

Next, an Example is given and this invention is demonstrated further more concretely. In the examples, &quot;% &quot; and &quot; part &quot; are parts by mass and parts by mass unless otherwise specified.

Synthesis Example 1

In a flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 257 parts by mass of propylene glycol monomethyl ether acetate was added and heated to 70 ° C while stirring. Subsequently, 8 parts of acrylic acid, 70 parts of N-cyclohexylmaleimide, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] 32 parts by mass of a mixture of decan-9-yl acrylate (containing 50:50 in molar ratio) was dissolved in 140 parts by mass of propylene glycol monomethyl ether acetate to prepare a solution, and the solution was added to the dropping funnel. It was dripped in the flask heated to 70 degreeC over 4 hours.

On the other hand, the solution which melt | dissolved 15 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of propylene glycol monomethyl ether acetates was put into the flask over 4 hours using another dropping funnel. It dripped. After dripping of the solution of a polymerization initiator was complete | finished, it maintained at 70 degreeC for 4 hours, and cooled to room temperature after that, and obtained the resin B1 solution of 26.7 mass% of solid content. The weight average molecular weight of resin B1 was 6.8x10 <^3> , molecular weight distribution was 2.23, and the acid value of conversion of solid content was 114 mg-KOH / g. Resin B1 has the following structural units.

Synthesis Example 2

A proper amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace with a nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C while stirring. 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-yl The mixed solution prepared by dissolving 225 parts of acrylate mixtures (content: molar ratio 50:50) and 81 parts of vinyltoluene (isomer mixture) in 80 parts of propylene glycol monomethyl ether acetate was dripped in the flask over 4 hours.

On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition of the initiator solution, the mixture was kept at 85 ° C for 4 hours and then cooled to room temperature to obtain a copolymer solution. This copolymer is referred to as resin B2. Solid content of resin B2 solution measured by 37.5% and the Brookfield viscometer (23 degreeC) was 246 mPa * s. The weight average molecular weight of resin B2 was 1.06x10 <^4> , the molecular weight distribution was 2.01, and the acid value of conversion of solid content was 115 mg-KOH / g. Resin B2 has the following structural units.

Synthesis Example 3

200 parts of propylene glycol monomethyl ether acetate were introduce | transduced into the flask provided with the stirrer, the thermometer, the reflux cooling tube, the dropping funnel, and the gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. After heating the solution in a flask to 70 degreeC, 144 parts of benzyl methacrylate, 30 parts of tricyclo [5.2.1.0 ^2.6 ] decyl methacrylate, 35 parts of methacrylic acid, 5.2 parts of azobisisobutyronitrile, and propylene glycol The mixture consisting of 213 parts of monomethyl ether acetate was added dropwise into the flask over 2 hours using a dropping funnel, and further stirred at 100 ° C. for 5 hours after completion of dropping. After dripping of the solution of a polymerization initiator was complete | finished, it maintained at 70 degreeC for 4 hours, and cooled to room temperature after that, and obtained the resin B3 solution of 33.6% of solid content. The weight average molecular weight of resin B3 was 1.03x10 <^4> , the molecular weight distribution was 2.16, and the acid value of conversion of solid content was 110.4 mg-KOH / g. Resin B3 has the following structural units.

Synthesis Example 4

200 parts of propylene glycol monomethyl ether acetate were introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. After heating the solution in a flask to 70 degreeC, 144 parts of benzyl methacrylate, 30 parts of tricyclo [5.2.1.0 ^2.6 ] decyl methacrylate, 42 parts of acrylic acid, 5.2 parts of azobisisobutyronitrile, and propylene glycol monomethyl The mixture consisting of 213 parts of ether acetate was added dropwise into the flask over 2 hours using a dropping funnel, and further stirred at 100 ° C. for 5 hours after completion of dropping. After dripping of the solution of a polymerization initiator was complete | finished, it maintained at 70 degreeC for 4 hours, and cooled to room temperature after that, and obtained the resin B4 solution of 34.1% of solid content. The weight average molecular weight of resin B4 was 1.13x10 <^4> , the molecular weight distribution was 2.18, and the acid value of conversion of solid content was 108.5 mg-KOH / g. Resin B4 has the following structural units.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of polystyrene conversion of resin was performed on condition of the following by GPC method.

Device; HLC-8120 GPC [manufactured by Tosoh Corporation]

column; TSK-GELG2000HXL

Column temperature; 40 ℃

menstruum; THF

Flow rate; 1.0 ml / min

Test liquid solids concentration; 0.001-0.01 mass%

Dose; 50 μl

Detector; RI

Calibration standards; TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight of polystyrene conversion obtained above was made into molecular weight distribution.

[Preparation of Pigment Dispersion A1]

C.I. Pigment Green 36 Part 15.0

3.0 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 78.0 parts

Was mixed and the pigment dispersion A1 was obtained by fully disperse | distributing a pigment using the bead mill.

[Preparation of Pigment Dispersion A2]

C.I. Pigment Yellow 150 Part 11.9

5.4 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 77.3 parts

Was mixed and the pigment dispersion A2 was obtained by fully disperse | distributing a pigment using the bead mill.

[Preparation of Pigment Dispersion A3]

C.I. Pigment Yellow 139 Part 15.0

4.5 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 80.6 parts

Was mixed and the pigment dispersion A3 was obtained by fully disperse | distributing a pigment using the bead mill.

[Preparation of Pigment Dispersion A4]

C.I. Pigment Red 177 Part 14.2

2.8 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 77.3 parts

Was mixed and the pigment dispersion A4 was obtained by fully disperse | distributing a pigment using the bead mill.

[Preparation of Pigment Dispersion A5]

C.I. Pigment Red 254 Part 11.1

6.4 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 80.0 parts

Was mixed and the pigment dispersion A5 was obtained by fully disperse | distributing a pigment using the bead mill.

Examples 1-7 and Comparative Example 1

[Preparation of colored photosensitive resin composition]

The component of Table 1 was mixed and the coloring photosensitive resin composition was obtained.

In Table 1, the "resin (B)" column shows content (part) by conversion of solid content.

The coloring agent (A) produced the pigment dispersion liquids A1-A5 previously, and was used for mixing. The "coloring agent (A)" column of Table 1 shows content (part) of the coloring agent contained in the used pigment dispersion liquid.

The "acrylic dispersant" column represents the total amount (part) of the acrylic dispersant contained in the used pigment dispersion.

The "solvent (E)" column shows the total amount (part) of each solvent contained in the colored photosensitive resin composition.

In Table 1, each component is as follows.

Colorant (A); A1; C.I. Pigment Green 36 (pigment dispersion A1)

Colorant (A); A2; C.I. Pigment Yellow 150 (pigment dispersion A2)

Colorant (A); A3; C.I. Pigment Yellow 139 (pigment dispersion A3)

Colorant (A); A4; C.I. Pigment Red 177 (pigment dispersion A4)

Colorant (A); A5; C.I. Pigment Red 254 (pigment dispersion A5)

Resin (B); B1; Resin B1

Resin (B); B2; Resin B2

Resin (B); B3; Resin B3

Resin (B); B4; Resin B4

Resin (B); B5; Methacrylic acid / Methyl methacrylate / n-butyl methacrylate / 2-hydroxy methacrylate copolymer [Copolymerization ratio is 20/10/55/15 on a mass basis, weight average molecular weight: about 40000, Japanese patent publication Synthesis according to the embodiment of the 2004-309537 publication]

Polymerizable compound (C); C1; Dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.]

Polymerizable compound (C); C2; Trimethylolpropane acrylate (NK ester ATMPT; manufactured by Shin-Nakamura Kagaku Co., Ltd.)

Polymerization initiator (D); D1; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure® OXE01; Manufactured by BASF Corporation; O-acyl oxime compound]

Polymerization initiator (D); D2; 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one [Irgacure® 907; Manufactured by BASF Corporation; Alkylphenone Compound]

Polymerization initiator (D); D3; A mixture of compounds represented by the following formula (CHEMCURE-TCDM; manufactured by Cambridge; Biimidazole Compound)

Polymerization initiation aid (D1); 4,4'-bis (diethylamino) benzophenone [EAB-F; Hodogaya Kagaku Kogyo Co., Ltd.]

Thiol compound (T); D1a; 2-sulfanylbenzothiazole [Soxinol® M; Sumitomo Chemical Co., Ltd. manufacture: Compound represented by the following formula]

Adhesion promoter (G); D1b; 3-methacryloyloxypropyltrimethoxysilane [KBM-503; Shin-Etsukagaku Kogyo Co., Ltd. product]

Solvent (E); E1; Propylene glycol monomethyl ether acetate

Solvent (E); E2; Ethyl lactate

Solvent (E); E3; Cyclohexanone

Surfactant (F); Polyether modified silicone oil [manufactured by Toray Dow Corning Co., Ltd .; SH8400]

[Production of Patterned Coating Film]

After apply | coating the coloring photosensitive resin composition by the spin coat method on the square glass substrate (Eagle XG; the Corning company make) one side is 2 inches, it prebaked at 100 degreeC for 3 minutes, and formed the coloring composition layer. After cooling, the interval between the substrate on which the coloring composition layer was formed and the photomask made of quartz glass was set to 100 µm, and the exposure machine [TME-150RSK; Topcon Co., Ltd.] was irradiated with an exposure amount (365 nm standard) of 30 mJ / cm <2> in air | atmosphere. As a photomask, what provided the 50 micrometer line and space pattern was used. After light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 24 ° C. for 60 seconds, washed with water, and then post-baked at 230 ° C. for 30 minutes in an oven. A colored patterned coating film was obtained.

[Developability evaluation]

The glass substrate in which the coloring patterning coating film was formed was observed with the optical microscope, and it was set as (circle), and when it confirmed, if a residue and a film residue were not recognized in an unexposed part. The results are shown in Table 2.

[Evaluation of adhesion]

When the coloring patterned coating film was observed with an optical microscope and peeling was not confirmed, when (circle) and peeling was confirmed in a part of colored patterning coating film, (triangle | delta) and all coloring patterning coating films were made into x. The results are shown in Table 2.

[Film thickness measurement]

About the obtained coloring patterned coating film, film thickness measuring apparatus [DEKTAK3; Nihon Shinkugi Jutsu Co., Ltd.] was used to measure the film thickness. The results are shown in Table 2.

[Color evaluation]

About the obtained coloring patterned coating film, a colorimetric machine [OSP-SP-200; (X, y) and a tristimulus value Y in an XYZ colorimetric system of CIE were measured using a characteristic function of a C light source. The larger the value of Y, the higher the brightness. The results are shown in Table 2.

[Contrast Evaluation]

Except not using a photomask at the time of exposure, the same operation as the preparation of a coloring patterned coating film was performed, and the coloring patterning coating film was created. Contrast system [CT-1; Tsubosaka Denki Co., Ltd., color colorimeter BM-5A; Manufacture of Topcon, Light Source; F-10, polarizing film; The contrast was measured using the Tsubosaka Denki Co., Ltd. make blank value 30000. The results are shown in Table 2. When coloring agent A1 and coloring agent A4 are used together, there exists a tendency for contrast of colored patterned coating film to become high.

According to the coloring photosensitive resin composition of this invention, developability at the time of coloring patterning coating film formation is excellent.

Claims (6)

As a coloring photosensitive resin composition containing a coloring agent, resin, a polymeric compound, and a polymerization initiator,
A colorant contains CI pigment green 36, a yellow pigment, and at least 1 sort (s) chosen from the group which consists of a blue pigment, a red pigment, a purple pigment, and an orange pigment,
The colored photosensitive resin composition whose resin is a copolymer containing the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the structural unit which has an alicyclic hydrocarbon structure. The coloring photosensitive resin composition of Claim 1 whose structural unit which has an alicyclic hydrocarbon structure is a structural unit derived from the monomer which has a C3-C18 alicyclic hydrocarbon group which may have a substituent. The coloring photosensitive resin composition of Claim 1 or 2 in which a polymerization initiator contains an O-acyl oxime compound. The C.I. compound according to any one of claims 1 to 3, wherein at least one selected from the group consisting of a blue pigment, a red pigment, a purple pigment, and an orange pigment. Colored photosensitive resin composition which is Pigment Red 177. The color filter formed with the coloring photosensitive resin composition in any one of Claims 1-4. The display apparatus containing the color filter of Claim 5.