KR20200040723A - Colored curable resin composition - Google Patents

Abstract

The present invention relates to a colored curable resin composition comprising: a coloring agent (A) including a compound represented by chemical formula (l); a resin (B); a photopolymerization compound (C); and a photopolymerization initiator (D). The resin (B) is an alkali-soluble resin. In the chemical formula (l), X^- represents an anion derived from a dye and Y^+ represents a cation derived from a compound represented by chemical formula (Y). In the chemical formula (Y), n represents an integer of 1-8 and R^40 represents an alkyl group of 1-4 carbon atoms. The present invention can obtain a color filter having excellent heat resistance.

Description

Colored curable resin composition {COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a colored curable resin composition.

The colored curable resin composition is used for the production of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. As a coloring curable resin composition, the coloring curable resin composition containing the following compound is described (Japanese Patent Publication No. 2013-7032).

The present invention provides the following [1] to [7].

[1] A colorant (A) comprising a compound represented by formula (I),

Resin (B),

Photopolymerizable compound (C) and

Photopolymerization initiator (D)

Colored curable resin composition comprising a.

[In the formula (I), X ^- represents an anion derived from a dye, and Y ⁺ represents a cation derived from a compound represented by the formula (Y).

(In the formula (Y), n represents an integer of 1 to 8, and R ⁴⁰ represents an alkyl group having 1 to 4 carbon atoms.)]

[2] The colored curable resin composition according to [1], wherein the anion derived from the dye is an anion derived from an alloy azo dye or a triarylmethane dye.

[3] The colored curable resin composition according to [1] or [2], wherein the anion derived from the dye is an anion derived from the alloy azo dye.

[4] The colored curable resin composition according to [2] or [3], wherein the anion derived from the alloy azo dye is represented by the formula (A0).

[In the formula (A0), R ¹ to R ¹⁸ each independently represent a hydrogen atom, a halogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, a nitro group, or -SO ₂ R ²⁹ .

R ²⁹ represents -OH, -NHR ³⁰ or -R ³² .

R ³⁰ is a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R ³¹ -OR ³³ , -R ³⁴ -CO-OR ³⁵ , -R ^36- O-CO-R ³⁷ or an aralkyl group having 7 to 10 carbon atoms.

R ³¹ , R ³⁴ and R ³⁶ each independently represent a divalent alkanediyl group having 1 to 8 carbon atoms.

R ³² , R ³³ , R ³⁵ and R ³⁷ each independently represent a monovalent alkyl group having 1 to 8 carbon atoms.

R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a methyl group, an ethyl group, or an amino group.

M ¹ represents Cr or Co.]

[5] The coloring curable resin composition according to any one of [1] to [4], wherein the coloring agent (A) further contains a pigment.

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

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

According to the colored curable resin composition of the present invention, a color filter excellent in heat resistance can be obtained.

The colored curable resin composition of the present invention,

A colorant (A) containing a compound represented by the formula (I) (hereinafter sometimes referred to as "compound (I)"),

Resin (B),

Photopolymerizable compound (C) and

It contains a photoinitiator (D).

In the formula (I), X ^- represents an anion derived from a dye,

Y ⁺ represents a cation derived from the compound represented by the formula (Y).

In the formula (Y), n represents an integer of 1 to 8, and R ⁴⁰ represents an alkyl group having 1 to 4 carbon atoms.

Examples of the dyes include alloy azo dyes, triarylmethane dyes, xanthene dyes, and cyanine dyes. Among these, alloy azo dyes and triarylmethane dyes are preferred, and alloy azo dyes are more preferred.

Examples of the anion derived from the alloy azo dye include an anion derived from the following direct yellow 112 or acid blue 158, an anion represented by the following formula (A0), and the like.

Among the anions derived from the alloy azo dye, anions represented by the formula (A0) are preferred.

In the formula (A0), R ¹ to R ¹⁸ each independently represent a hydrogen atom, a halogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, a nitro group, or -SO ₂ R ²⁹ .

R ²⁹ represents -OH, -NHR ³⁰ or -R ³² .

R ³⁰ is a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R ³¹ -OR ³³ , -R ³⁴ -CO-OR ³⁵ , -R ^36- O-CO-R ³⁷ or an aralkyl group having 7 to 10 carbon atoms.

R ³¹ , R ³⁴ and R ³⁶ each independently represent a divalent alkanediyl group having 1 to 8 carbon atoms.

R ³² , R ³³ , R ³⁵ and R ³⁷ each independently represent a monovalent alkyl group having 1 to 8 carbon atoms.

R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, a methyl group, an ethyl group, or an amino group.

M ¹ represents Cr or Co.

In the formula (A0), as the monovalent alkyl group having 1 to 10 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group , n-hexyl group, n-heptyl group, n-octyl group, decyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl group, 1,6- And dimethylheptyl group, 2-ethylhexyl group, and 1,1,5,5-tetramethylhexyl group.

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, and tert-butyl group.

Examples of the aralkyl group having 7 to 10 carbon atoms include a phenylmethyl group, a phenylethyl group, and a phenylpropyl group.

Examples of the divalent alkanediyl group having 1 to 8 carbon atoms include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, butane-1, 3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, etc. are mentioned.

As the monovalent alkyl group having 1 to 8 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n -Heptyl group, n-octyl group, and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom and a chlorine atom are preferable.

As a monovalent alkyl group having 1 to 10 carbon atoms, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group are preferable.

Examples of -SO ₂ R ²⁹ include a sulfo group represented by -SO ₃ H, a group represented by -SO ₂ NHR ^30, and a group represented by -SO ₂ R ³² .

Examples of the monovalent alkyl group having 1 to 10 carbon atoms represented by R ³⁰ include 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group. A monovalent alkyl group is preferred.

As the cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, cyclohexyl group, 2-methylcyclohexyl group, 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2-isopropylcyclohexyl group, 2-butylcyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4-isopropylcyclohexyl group, 4-butylcyclohexyl group, etc. may be mentioned, and 2 positions A cyclohexyl group having an alkyl group having 1 to 4 carbon atoms is preferable, and a 2-methylcyclohexyl group is preferable.

As -R ³¹ -OR ³³ , methoxymethyl group, ethoxymethyl group, propoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, 2- And an oxo-4-methoxybutyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group, and the like, (C1-C4 alkoxy) methyl group is preferred, Methoxymethyl group and ethoxymethyl group are preferred.

As -R ³⁴ -CO-OR ³⁵ , methoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylmethyl group, ethoxycarbonylethyl group, propoxycarbonylmethyl group, propoxycarbonylethyl group, butoxycarbonyl A methyl group, butoxycarbonyl ethyl group, etc. are mentioned, A methoxycarbonyl methyl group or a methoxycarbonyl ethyl group is preferable.

Examples of -R ³⁶ -O-CO-R ³⁷ include acetyloxymethyl group, acetyloxyethyl group, ethylcarbonyloxymethyl group, ethylcarbonyloxyethyl group, propylcarbonyloxymethyl group, propylcarbonyloxyethyl group, butylcarbonyloxymethyl group, And butylcarbonyloxyethyl groups, and acetyloxymethyl groups and acetyloxyethyl groups are preferred.

As R ³⁰ , a hydrogen atom is preferable.

The group represented by -SO ₂ NHR ³⁰ is N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-iso Butyl sulfamoyl group, N-sec-butyl sulfamoyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethyl Profile) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2 -Methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N -(3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsul Pamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, N- Aliphatic such as allyl sulfamoyl group A sulfamoyl group substituted with a hydrocarbon;

N- (2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N- (3-methoxypropyl) sulfamoyl Diary, N- (3-ethoxypropyl) sulfamoyl group, N- (3-propoxypropyl) sulfamoyl group, N- (3-isopropoxypropyl) sulfamoyl group, N- (3-hexyoxypropyl -R such as sulfamoyl group, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (3-tert-butoxypropyl) sulfamoyl group, N- (4-octyloxybutyl) sulfamoyl group, etc. ^A sulfamoyl group substituted with ³¹ -OR ³³ ;

N- (methoxycarbonylmethyl) sulfamoyl group, N- (methoxycarbonylethyl) sulfamoyl group, N- (ethoxycarbonylmethyl) sulfamoyl group, N- (ethoxycarbonylethyl) sulfamoyl Diary, N- (propoxycarbonylmethyl) sulfamoyl group, N- (propoxycarbonylethyl) sulfamoyl group, N- (butoxycarbonylmethyl) sulfamoyl group, N- (butoxycarbonylethyl) Sulfamoyl groups substituted with -R ³⁴ -CO-OR ^{35 such} as sulfamoyl groups;

N- (acetyloxymethyl) sulfamoyl group, N- (acetyloxyethyl) sulfamoyl group, N- (ethylcarbonyloxymethyl) sulfamoyl group, N- (ethylcarbonyloxyethyl) sulfamoyl group, N- (Propylcarbonyloxymethyl) sulfamoyl group, N- (propylcarbonyloxyethyl) sulfamoyl group, N- (butylcarbonyloxymethyl) sulfamoyl group, N- (butylcarbonyloxyethyl) sulfamoyl group, etc. A sulfamoyl group substituted with -R ³⁶ -O-CO-R ³⁷ of;

N-cyclohexyl sulfamoyl group, N- (2-methylcyclohexyl) sulfamoyl group, N- (3-methylcyclohexyl) sulfamoyl group, N- (4-methylcyclohexyl) sulfamoyl group, N- ( A sulfamoyl group substituted with a cyclohexyl group having a substituent such as 4-butylcyclohexyl) sulfamoyl group;

N-benzyl sulfamoyl group, N- (1-phenylethyl) sulfamoyl group, N- (2-phenylethyl) sulfamoyl group, N- (3-phenylpropyl) sulfamoyl group, N- (4-phenylbutyl ) Sulfamoyl group, N- [2- (2-naphthyl) ethyl] sulfamoyl group, N- [2- (4-methylphenyl) ethyl] sulfamoyl group, N- (3-phenyl-1-propyl) sulfide And sulfamoyl groups substituted with aralkyl groups such as pamoyl group and N- (3-phenyl-1-methylpropyl) sulfamoyl group.

As -SO ₂ NHR ³⁰ , -SO ₂ NH ₂ is preferable.

As -SO ₂ R ³² , methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, Heptylsulfonyl group, octylsulfonyl group, 1-methylbutylsulfonyl group, 1,1,3,3-tetramethylbutylsulfonyl group, 1,5-dimethylhexylsulfonyl group, 1,6-dimethylheptylsulfonyl group, 2-ethyl And hexylsulfonyl groups and 1,1,5,5-tetramethylhexylsulfonyl groups. Especially, a methylsulfonyl group and an ethylsulfonyl group are preferable, and a methylsulfonyl group is more preferable.

It is preferable that at least one of R ¹ to R ¹⁸ is a nitro group, because the heat resistance tends to be able to form more excellent patterns and the like.

Further, it is preferable that at least one of R ¹ to R ⁵ and at least one of R ⁶ to R ^{10 be} -SO ₂ R ²⁹ . When having a plurality of -SO ₂ R ²⁹ , a plurality of R ²⁹ may be the same or different from each other.

As -SO ₂ R ²⁹ , -SO ₂ R ³² is preferable, and a methylsulfonyl group is more preferable.

If the anion represented by the formula (A0) having a -SO ₂ R ^32, R ¹¹ ~R at least one of R and at least one of ^{14 15} ~R ¹⁸ it is more preferably -SO ₂ R ^32. In the case of having a plurality of -SO ₂ R ³² , a plurality of R ³² may be the same as or different from each other.

R ¹⁹ and As R ²⁰ , a methyl group, an ethyl group and an amino group are preferable, and a methyl group is more preferable.

Preferable examples of the anion represented by the formula (A0) include anions represented by the formulas (1-b1) to (1-b60).

A method for synthesizing an anion represented by the formula (A0) will be described taking an anion represented by the formula (A01).

(In the above formula, R ¹ to R ⁵ , R ¹¹ to R ¹⁴ , R ¹⁹ and M ¹ represent the same meaning as in the above.)

The anion reacts the compound represented by the formula (d) with the chromium compound in an aqueous solvent (N, N-dimethylformamide, N-methylpyrrolidone, etc.) at 70 ° C to 150 ° C for 3 to 10 hours. Can be produced.

(In the above formula, R ¹ to R ⁵ , R ¹¹ to R ¹⁴ and R ¹⁹ represent the same meanings as above.)

Examples of the chromium compound include chromium formate, chromium acetate, chromium chloride, chromium fluoride, ammonium chromium sulfate, and preferably chromic formate, ammonium chromium sulfate, and the like.

It is preferable that the usage-amount of a chromium compound is 0.5-1 mol with respect to 1 mol of compounds represented by general formula (d).

The compound represented by the formula (d) can be produced by diazo coupling the diazonium salt represented by the formula (a2) and the compound represented by the formula (b1) in an aqueous solvent.

The diazonium salt represented by the formula (a2) can be obtained, for example, by diazotizing the amine represented by the formula (a1) with nitrous acid, nitrite or nitrite ester.

[In the formula (a1) and the formula (a2), R ¹¹ to R ¹⁴ have the same meaning as described above. A ¹ represents an inorganic or organic anion.

In the formula (b1), R ¹ to R ⁴ and R ¹⁹ have the same meaning as above.]

Examples of the inorganic anions include fluoride ions, chloride ions, bromide ions, iodide ions, perchlorate ions, hypochlorite ions, and the like.

Examples of the organic anion include CH ₃ COO-, PhCOO-, and the like.

As A ¹ , preferably, chloride ions, bromide ions, CH ₃ COO-, and the like are listed.

In the diazo coupling reaction, the reaction temperature is preferably -5 ° C to 60 ° C, and more preferably 0 ° C to 30 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 1 hour to 4 hours. N-methylpyrrolidone etc. are mentioned as said aqueous solvent.

In order to promote the reaction, an inorganic base can be coexisted.

Examples of the inorganic base include sodium hydroxide, calcium hydroxide, sodium carbonate, calcium carbonate, sodium acetate, and calcium acetate, preferably sodium carbonate, sodium acetate, and the like.

An anion derived from a triarylmethane dye is an anion having a triarylmethane skeleton and anionic groups such as sulfo groups.

Specific examples of the anion derived from the triarylmethane dye include anions represented by the formulas (2-b1) to (2-b3).

The xanthene dye is a dye having a xanthene skeleton in a molecule.

The cyanine dye is a dye having a cyanine skeleton in the molecule.

Y ⁺ in formula (I) represents a cation derived from the compound represented by formula (Y).

n represents an integer of 1 to 8, and R ⁴⁰ represents an alkyl group having 1 to 4 carbon atoms.

In the formula (Y), n is preferably an integer of 1 to 3. As R ⁴⁰ , a methyl group and an ethyl group are preferable.

Specific examples of the cation derived from the compound represented by the formula (Y) include those represented by the formulas (3-b1) to (3-b9).

As a compound represented by general formula (I), the compound shown below is preferable.

Next, a method for producing the compound represented by the formula (I) (hereinafter, the compound is referred to as compound (I)) will be described.

As a method for producing compound (I), it can be produced by mixing a salt of an anion derived from a dye with a metal cation and a compound represented by formula (Y) in a solvent.

The salt of the anion derived from the dye and the metal cation can be obtained by dissolving the dye in an aqueous solution containing a halide of the metal cation or the like.

Examples of the salt-forming metal cation include alkali metal cations such as lithium cations, sodium cations, and potassium cations.

As the compound represented by the formula (Y), commercially available compounds can be used.

As a solvent, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran , Dioxane, water and chloroform.

Among them, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, methanol, ethanol, isopropanol and water are preferable.

When the solvent is water, an acid such as acetic acid or hydrochloric acid may be added.

The mixing temperature of the salt of the anion derived from the dye and the metal cation and the compound represented by the formula (Y) is preferably 0 ° C to 150 ° C, more preferably 10 ° C to 120 ° C, and even more preferably 20 ° C to 100 ° C. The mixing time is preferably 1 hour to 72 hours, more preferably 2 hours to 48 hours, and even more preferably 3 hours to 24 hours.

When a solvent compatible with water is used, a mixed solution of a salt of an anion derived from a dye with a metal cation and a compound represented by the formula (Y) is further stirred for 1 to 3 hours as necessary, after which , The compound represented by the formula (I) can be extracted as a solid by obtaining by filtration.

When a solvent that is not compatible with water is used, water is added to a reaction solution of a salt of an anion derived from a dye and a metal cation and a compound represented by the formula (Y) to precipitate crystals, and then filtered. By doing so, the compound represented by the formula (I) can be extracted as a solid.

<Colorant (A)>

The coloring agent (A) may contain dyes different from the compound (I) together. Examples of the dye include dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes, sulfonamide derivatives of acid dyes, and the like, for example, color index (published by The Society of Dyers and Colourists). Compounds classified as, and known dyes described in dyeing notes (Shikisensha) are exemplified.

Specifically, C.I. Solvent yellow 4 (hereinafter, C.I. solvent yellow is omitted, only numbers are described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. Solvent red 45, 49, 125, 130;

C.I. Solvent orange 2, 7, 11, 15, 26, 56; C.I. Solvent dyes,

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. Acid violet 6B, 7, 9, 17, 19; C.I. Acid Dye,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; C.I. Direct dyes,

C.I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Modern red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C.I. Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C.I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; C.I. And modern dyes.

The coloring agent (A) may also contain a pigment together.

As a pigment, an organic pigment, C.I. Violet pigments such as pigment violet 1, 19, 23, 29, 32, 36, 38;

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 , Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;

C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73;

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 And the like.

Among them, C.I. Pigment Yellow 138, 139, 150, C.I. It is preferable to contain at least 1 sort (s) selected from pigment red 177, 242, 254. By including the above-mentioned pigment, optimization of the transmission spectrum is easy, and chemical resistance becomes good.

These pigments may be used alone or in combination of two or more.

If necessary, the organic pigments are subjected to rosin treatment, surface treatment using an acidic or basic group-derived pigment derivative, graft treatment on a pigment surface with a polymer compound, atomization treatment using a sulfuric acid atomization method, or removal of impurities. Washing treatment with an organic solvent, water, or the like, and removal treatment with an ion exchange method of ionic impurities may be performed.

It is preferable that the organic pigment has a uniform particle size. A pigment dispersion liquid in which a pigment is uniformly dispersed in a solution can be obtained by subjecting the pigment dispersant to dispersion treatment.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solspers [manufactured by Geneca Co., Ltd.], EFKA (manufactured by BASF), Aji Spas (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by BIC Chemie), and the like.

When a pigment dispersant is used, the amount used is preferably 100% by mass, more preferably 5% by mass or more and 50% by mass or less with respect to the pigment. When the amount of the pigment dispersant used is in the above-mentioned range, a pigment dispersion liquid in a uniform dispersion state tends to be obtained.

The content of the compound (I) is preferably 3 to 100% by mass, more preferably 5 to 90% by mass, and even more preferably 10 to 80% by mass with respect to the colorant (A).

The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and even more preferably 10 to 50% by mass, based on the solid content in the colored curable resin composition. Here, solid content means the sum of the components except a solvent in a colored curable resin composition. When the content of the colorant (A) is within the above-mentioned range, the color concentration when the color filter is used is sufficient, and since a desired amount of the binder polymer can be contained in the composition, a pattern with sufficient mechanical strength can be formed.

<Resin (B)>

The coloring curable resin composition of this invention contains resin (B). Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin.

Examples of the resin (B) include resins [K1] to [K4] below.

[K1] A group consisting of a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (a) (hereinafter sometimes referred to as "(a)"), and an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. A copolymer with at least one selected from (b) (hereinafter sometimes referred to as "(b)").

[K2] With (a) and (b), and (a) a copolymerizable monomer (c) (but different from (a) and (b)) [hereinafter sometimes referred to as "(c)"] Copolymer

[K3] Copolymer of (b) and (c)

[K4] A resin obtained by reacting (a) with a copolymer of (b) and (c).

By including the structural unit derived from (a), the resin (B) can further increase the reliability of the obtained colored pattern, such as heat resistance and chemical resistance.

(a) is, for example, a cyclic ether structure having 2 to 4 carbon atoms (eg, 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. It refers to a polymerizable compound having a. (a) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, "(meth) acrylic acid" refers to 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.

Examples of the monomer (a) include a monomer having an oxiranyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond, and the like.

As (a), it is preferable that it is a monomer which has an oxiranyl group and an ethylenically unsaturated bond from the viewpoint that reliability, such as heat resistance and chemical resistance, of the obtained coloring pattern can be raised more.

As (b), specifically, unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene , 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo A bicyclo unsaturated compound containing a carboxyl group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic 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 (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl of divalent or higher polyvalent carboxylic acids such as mono succinate [2- (meth) acryloyloxyethyl], phthalate mono [2- (meth) acryloyloxyethyl] ]ester;

and unsaturated acrylates containing hydroxy groups and carboxy groups in the same molecule, such as α- (hydroxymethyl) acrylic acid.

As (b), acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

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-methylcyclo Hexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, it is commonly called dicyclopentanyl (meth) acrylate), dicyclo Fentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, Naphthyl (meth) acrylate, benzyl (meth) acrylate (Meth) acrylic acid esters such as;

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 itaconic acid;

Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxy ratio Cyclo [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 [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methyl Bicyclo [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-phenoxy Cycarbonylbicyclo [2.2.1] hept-2-ene, 5,6- Ratios such as su (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Cyclo unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimidebutylate, N-succinimidyl Dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

As (c), from the viewpoint of copolymerization reactivity and heat resistance, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene, and the like are preferable. .

Resin (B) is a method described in the literature "Experiment of Polymer Synthesis" (Otaka Takayuki Hakjo Co., Ltd. First Edition, First Printing, Issued March 1, 1972) and cited literatures described in the document. It can be prepared for reference.

Moreover, the obtained copolymer may use the solution after reaction as it is, the concentrated or diluted solution may be used, and the thing extracted as solid (powder) by methods, such as reprecipitation, may be used. In particular, by using the solvent (E) described later as a solvent at the time of polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

As the resin (B), 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxycitricyclo [5.2.1.0 ^2.6 ] decylacrylate / (meth) acrylic acid copolymer Resins such as [K1]; 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 ] resins such as decylacrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer [K3]; A glycidyl (meth) acrylate resin is added to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, and a tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer is glycidyl (meth) Resin [K4] etc., such as resin which added acrylate, resin which added glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, etc. Can be mentioned.

Especially, resin [K1] and resin [K2] are preferable, resin [K1] is more preferable, and 3,4-epoxycitricyclo [5.2.1.0 ^2.6 ] decylacrylate / (meth) acrylic acid copolymer is further desirable.

The weight average molecular weight in terms of polystyrene in the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, further preferably 5,000 to 35,000, particularly preferably 6,000 to 30,000, and particularly preferably It is 7,000-28,000. When the molecular weight is in the above-mentioned range, the coating film hardness is improved, the residual film rate is also high, the solubility in the developing solution of the unexposed portion is good, and the resolution tends to be improved.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 150 mg-KOH / g, more preferably 60 to 135 mg-KOH / g, more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of the resin (B), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass with respect to the solid content of the colored curable resin composition. When the content of the resin (B) is within the above range, a pattern can be formed, and the resolution and the residual film rate tend to be improved.

<Photopolymerizable compound (C)>

The colored curable resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is a compound capable of polymerizing with active radicals and acids generated from the photopolymerization initiator (D) by irradiating light, and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and the like. (Meth) acrylic acid ester compound is mentioned.

The photopolymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds. As such a photopolymerizable compound, for example, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacryl Rate etc. are mentioned. The photopolymerizable compound (C) may be used alone or in combination of two or more.

The content of the photopolymerizable compound (C) is preferably 7 to 65 mass%, more preferably 13 to 60 mass%, still more preferably 17 to 55 mass%, based on the solid content of the colored curable resin composition. . When the content of the photopolymerizable compound (C) is in the above-mentioned range, curing is sufficiently performed, the film thickness ratio before and after development is improved, and undercuts are unlikely to occur in the pattern, and adhesion is likely to be improved, which is preferable. .

<Photopolymerization initiator (D)>

The colored curable resin composition of the present invention contains a photopolymerization initiator (D).

The photopolymerization initiator (D) is not particularly limited as long as it is a compound that generates active radicals, acids, and the like by the action of light and initiates polymerization, and a known polymerization initiator can be used.

As the photopolymerization initiator (D), a compound that generates an active radical by the action of light is preferred, and at least 1 selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, oxime compounds, and biimidazole compounds The photopolymerization initiator containing a species is more preferable, and the photopolymerization initiator containing an oxime compound is more preferable.

Examples of the alkylphenone compound include diethoxy acetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, and 2-dimethylamino-1- (4-morpholino Phenyl) -2-benzylbutan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, 2-hydroxy-2-methyl -1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl And oligomers of phenyl ketone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one. Preferably, 2-methyl-2-morpholino -1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and the like. You may use commercial items, such as Irgacure (registered trademark) 369, 907 (above, manufactured by BASF).

As the triazine compound, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (triclo Romethyl) -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)- And 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned as an acylphosphine oxide compound. You may use commercial items, such as Irgacure (trademark) 819 (made by BASF Corporation).

As an oxime compound, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one -2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethan-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. You can. You may use commercial items, such as Irgacure (trademark) OXE-01, OXE-02 (above, BASF company make), and N-1919 (made by ADEKA company).

As the biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see Japanese Patent Laid-Open Publication No. 6-75372, Japanese Patent Publication Laid-Open Publication No. 6-75373, etc.), 2,2'-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) ratio Imidazole, 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 Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), 4,4', 5 And an imidazole compound in which the phenyl group at the 5'-position is substituted by a carboalkoxy group (see Japanese Unexamined Patent Publication No. Hei 7-10913, etc.). Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 And ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

Examples of the acid generator that generates acid by light include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylsulfonium p -Toluenesulfonate, 4-acetoxyphenyl · methyl · benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p- And onium salts such as toluene sulfonate and diphenyl iodonium hexafluoroantimonate; and nitrobenzyl tosylate and benzointosylate.

The photopolymerization initiator (D) may be a compound that simultaneously generates an active radical and an acid by light, such as a triazine compound.

Examples of the photopolymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone , 2,4,6-trimethylbenzophenone and other benzophenone compounds; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and campaquinone; And 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. It is preferable to use these in combination with the photoinitiator (D1) (amine etc.) mentioned later.

The content of the photopolymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the photopolymerizable compound (C). When the content of the photopolymerization initiator is in the above-described range, the sensitivity is increased, the exposure time is shortened, and productivity is improved.

<Photopolymerization start adjuvant (D1)>

The photocuring initiation aid (D1) may further be included in the colored curable resin composition of the present invention. The photopolymerization initiation aid (D1) is usually used in combination with the photopolymerization initiator (D), and is a compound or sensitizer used to accelerate polymerization of the photopolymerizable compound in which polymerization is initiated by the photopolymerization initiator.

Examples of the photopolymerization initiation aid (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

As the amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoate methyl, 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoic acid isoamyl, benzoic acid 2-dimethylaminoethyl, 4-dimethyl Aminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as healer ketone), 4,4'-bis (diethylamino) benzophenone, 4, And 4'-bis (ethylmethylamino) benzophenone. Among them, 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

As the alkoxy anthracene compound, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10- And dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

As the thioxanthone compound, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxy And city oak xanthone.

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 and dimethoxyphenylsulfanyl acetic acid, And chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The photopolymerization initiation aid (D1) may be used alone or in combination of two or more.

When using these photopolymerization start adjuvants (D1), the use amount thereof is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is the mass part. Moreover, with respect to 1 mol of a photoinitiator (D), it is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol. When the amount of the polymerization initiation aid (D1) is in this range, the pattern can be formed with higher sensitivity, and the productivity of the pattern tends to be improved.

<Solvent (E)>

The colored curable resin composition of the present invention may contain a solvent (E).

The solvent (E) is not particularly limited, and a solvent commonly used in the field can be used. As the solvent (E), an ester solvent (a solvent containing -COO-), an ether solvent other than an ester solvent (a solvent containing -O-), and an ether ester solvent (a solvent containing -COO- and -O-) , Ketone solvents other than ester solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

As an ester solvent, 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, 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, phenitol, methylani And brushes.

As the ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, butyl butyl acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl, 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-methyl propionate, 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 , Di, and the like ethylene glycol monobutyl ether acetate.

As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, And cyclopentanone, cyclohexanone, and isophorone.

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 solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

These solvents may be used alone or in combination of two or more.

Among the above-mentioned solvents, from the viewpoints of coatability and dryness, organic solvents having a boiling point of 1 atm of 120 ° C or more and 180 ° C or less are preferable. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionate ethyl, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy Preference is given to -4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone, etc., propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, 3-ethoxypropionic acid Ethyl and the like are more preferable. When these solvents are included, the flatness at the time of coating is excellent.

The content of the solvent (E) in the colored curable resin composition is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, with respect to the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above-mentioned range, the flatness at the time of application becomes good, and when the color filter is formed, the color density is not insufficient, so the display characteristics tend to be improved.

The colored curable resin composition of the present invention may contain various additives such as surfactants, fillers, other polymer compounds, adhesion promoters, antioxidants, leveling agents, ultraviolet absorbers, light stabilizers, and chain transfer agents, if necessary.

The color filter formed by the above-mentioned colored curable composition also falls within the scope of the present invention. The color filter comprises a step of applying a colored curable composition to a substrate and drying it to form a colored layer (sometimes referred to as a "composition layer"), and further curing the obtained colored layer. Can be obtained by method.

A photolithography method, an inkjet method, a printing method, etc. are mentioned as a method of manufacturing the colored pattern of a color filter from the colored curable composition of this invention. Especially, the photolithography method is preferable. In the photolithography method, a colored curable resin composition is applied onto a substrate or another resin layer (for example, another colored curable resin composition layer first formed on a substrate, etc.), and volatile components such as a solvent are removed by drying or the like to remove the colored layer. It is a method of forming and exposing the colored layer through a photomask to develop. In the photolithography method, a coating film that is a cured product of the colored layer can be formed by not using and / or not developing a photomask during exposure.

The film thickness of the coating film in this case is not particularly limited, and can be appropriately adjusted depending on the material, application, and the like, and is usually 0.1 to 30 μm, preferably 1 to 20 μm, and more preferably 1 to 6 μm.

Extrusion coating method, direct gravure coating method, reverse gravure coating method, CAP coating method, die coating method etc. are mentioned as a coating method of a coloring curable resin composition. You may apply using a coater such as a dip coater, bar coater, spin coater, slit & spin coater, and slit coater (sometimes referred to as a die coater, curtain flow coater, or spinless coater).

The removal / drying of the solvent can be performed by natural drying, air drying, vacuum drying, heat drying, or the like. The specific drying temperature is preferably 10 ° C to 120 ° C, and more preferably 25 ° C to 100 ° C.

The drying time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

The drying under reduced pressure is preferably performed in a range of 20 ° C to 25 ° C under a pressure of 50 to 150 Pa.

The coated film after drying is exposed through a photomask for forming a desired 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.

The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, and the like may be used, and the filter may be cut using a filter that cuts a specific wavelength region, or selectively extracted using a band pass filter that extracts a specific wavelength region. May be exposed.

It is preferable to use a device such as a mask aligner, a stepper, etc., because it is possible to uniformly irradiate parallel light beams over the entire exposed surface or to accurately align the mask with the substrate.

After exposure, a pattern can be obtained by contacting a developer and dissolving and developing a predetermined portion (such as an unexposed portion). Examples of the developing solution include an aqueous solution of an alkaline compound (potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide, etc.). This developer may contain a surfactant.

The developing method may be any of a puddle method, a dipping method, and a spray method. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.

Further, if necessary, post-baking may be performed. The post-baking, for example, is preferably in the range of 150 ° C to 230 ° C and 10 to 240 minutes.

According to the colored curable resin composition of the present invention, it is possible to obtain a coating film having good brightness and contrast, a pattern, and a high-quality color filter. These color filters or patterns can be used in a manner known to all of the devices associated with various colored images, such as display devices provided as part of their constituent parts, such as known liquid crystal display devices, organic EL devices, and solid-state imaging devices. .

Next, the present invention will be described in more detail with reference to Examples. In the examples,% and parts indicating the content to the amount used are based on mass unless otherwise specified.

In the following, the structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

[Synthesis Example 1]

After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No. 101861-04-5), 1.3 parts of sodium hydroxide was added to dissolve it. Under ice-cooling, 6.1 parts of an aqueous 35% sodium nitrite solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and then 19.4 parts of 35% hydrochloric acid was gradually added to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt. . Subsequently, an aqueous solution in which 5.6 parts of amide sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 26 parts of water was slowly added to inactivate excess sodium nitrite.

Subsequently, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 70 parts of water, and the pH was adjusted to 8.0 using sodium hydroxide. To this, the suspension containing the diazonium salt was added dropwise over 15 minutes while adding a 10% sodium hydroxide solution appropriately so that the pH was in the range of 7 to 7.5. After completion of the dropwise addition, yellow suspension was obtained by further stirring for 30 minutes. Stir for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C. to obtain 11.7 parts of a compound represented by the formula (p-2) (yield 87%).

10 parts of the compound of formula (p-2) is dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved, and ammonium chromium (III) sulfate hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 3.1 parts, After adding 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), the mixture was refluxed for 4 hours and 30 minutes. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline, and the red-orange solid obtained after filtration was dried at 60 ° C. to obtain 13.6 parts of a compound represented by the formula (z-2A) (yield 63%). .

[Synthesis Example 2]

A solution (d-1) was prepared by dissolving 9.1 parts of the compound represented by the formula (z-2A) in 100 parts of water. To the liquid (d-1), 2.2 parts of 3-aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added over 1 hour, and then stirred for 24 hours. The resulting precipitate was filtered, washed with 1000 parts of water, and dried under reduced pressure at 60 ° C. for 24 hours to obtain 1.0 part of the compound represented by formula (z-3).

[Synthesis Example 3]

In a flask equipped with a stirrer, a thermometer, a reflux cooler, and a dropping funnel, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was added and heated to 70 ° C while stirring.

Subsequently, 60 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate [a compound represented by the formula (I-1) and a compound represented by the formula (II-1), in molar ratio, 50:50 mixture] 440 parts were dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a solution, and this solution was added dropwise into a flask kept at 70 ° C over 4 hours using a dropping funnel.

Meanwhile, a solution in which 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts of propylene glycol monomethyl ether acetate was added dropwise into the flask over 4 hours using another dropping funnel. . After the dropping of the polymerization initiator solution is completed, the temperature is maintained at 70 ° C. for 4 hours, and then cooled to room temperature, so that the weight average molecular weight (Mw) is 9.1 × 10 ³ , molecular weight distribution is 2.16, solid content is 34.8%, acid in terms of solid content. A thin B1 solution of 81 mg-KOH / g was obtained. Resin B1 has a structural unit shown below.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured under the following conditions using the GPC method.

Device; K2479 [manufactured by Shimadzu Seisakusho Co., Ltd.]

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Detector; RI

Standard materials for calibration; 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 in terms of polystyrene obtained above was used as the molecular weight distribution.

<Example 1>

A colored photosensitive resin composition was prepared by mixing each of the following components.

Compound (A): 5.1 parts of compound represented by formula (z-3)

Pigment: C.I. Pigment Red 254 part 40.1

Resin (B): Resin B1 15.0 parts

Photopolymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD (registered trademark) DPHA; Nihon Kayaku Co., Ltd.] 52.1 copies

Photopolymerization initiator (D): 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one [Irgacure® 369; BASF Corporation] 2.0 copies

Photopolymerization initiator (D): Irgacure (registered trademark) OXE01 (manufactured by BASF)

                                                        Section 8.5

Photopolymerization initiation adjuvant (D1): 2,4-diethylthioxanthone [KAYACURE® DETX-S; Nihon Kayaku Co., Ltd.] 2.1 copies

Solvent (E): 690.1 parts of propylene glycol monomethyl ether acetate

Solvent (E): 62.1 parts of propylene glycol monomethyl ether

<Example 2>

A colored photosensitive resin composition was prepared by mixing each of the following components.

Compound (A): Compound 7.3 represented by formula (z-3)

Resin (B): Resin B1 12.0 parts

Photopolymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD (registered trademark) DPHA; Nihon Kayaku Co., Ltd.] 52.1 copies

Photopolymerization initiator (D): 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one [Irgacure® 369; BASF Corporation] 2.0 copies

Photopolymerization initiator (D): Irgacure (registered trademark) OXE01 (manufactured by BASF)

                                                        Section 8.5

Photopolymerization initiation adjuvant (D1): 2,4-diethylthioxanthone [KAYACURE® DETX-S; Nihon Kayaku Co., Ltd.] 2.1 copies

Solvent (E): 895.1 parts of propylene glycol monomethyl ether acetate

Solvent (E): 73.2 parts of propylene glycol monomethyl ether

<Comparative Example 1>

A colored resin composition was prepared by mixing the following components.

Compound (A): Compound 10.3 parts represented by chemical formula (z-2)

Pigment: C.I. Pigment Red 254 Part 80.1

Resin (B): Resin B1 31.1 parts

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD (registered trademark) DPHA; Nihon Kayaku Co., Ltd.] 50.0 copies

Photopolymerization initiator (D): 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one [Irgacure® 369; BASF Corporation] 11.4 copies

Polymerization initiator (D): Irgacure (registered trademark) OXE01 (manufactured by BASF)

                                                        Section 8.5

Polymerization initiation aid (D1): 2,4-diethylthioxanthone [KAYACURE® DETX-S; Nihon Kayaku Co., Ltd.] 2.1 copies

Solvent (E): 1120.8 parts of propylene glycol monomethyl ether acetate

Solvent (E): 12.5 parts of propylene glycol monomethyl ether

Solvent (E): 180.2 parts of diacetone alcohol

<Test Example>

[Production of colored patterns]

After coating the composition obtained in Example 1, Example 2 or Comparative Example 1 on a square glass substrate (Egle XG; manufactured by Corning) having a side of 2 inches by spin coating, pre-baking at 100 ° C. for 3 minutes to obtain a thickness. A 2.5 µm composition layer was formed.

After cooling, the distance between the photomask made of quartz glass having a pattern and the composition layer was set to 100 µm [TME-150RSK; Topcon Co., Ltd.], and irradiated with light at an exposure amount of 150 mJ / cm 2 (based on 365 nm) in an atmospheric atmosphere.

As a photomask, a mask having a 100 µm line and space pattern was used. After light irradiation, the obtained coating film was developed by immersing it in an aqueous developing solution (alkali aqueous developing solution) containing 0.12% of nonionic surfactant and 2% of sodium carbonate at 23 ° C for 80 seconds, and after washing with water to 230 ° C in an oven. Post-baking was performed for 20 minutes to obtain a colored pattern.

[Heat resistance evaluation]

A coating layer having a thickness of 2.5 µm was formed by applying a composition obtained in Example 1, Example 2 or Comparative Example 1 on a square glass substrate (Egle XG; manufactured by Corning) having a side of 2 inches by spin coating. Further, the coating film was heated at 230 ° C for 20 minutes, and the color difference (ΔEab *) before and after heating of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS).

When the coating films obtained by the compositions of Examples 1 and 2 were evaluated for heat resistance, the color difference (ΔEab *) was 4.2 and 4.8, respectively.

When the heat resistance evaluation was similarly performed on the coating film obtained from the composition of Comparative Example 1, it was found that the color difference (ΔEab *) was 5.1, and the colored photosensitive resin composition of the present application was excellent in heat resistance.

When the colored curable resin composition of the present invention is used, a color filter excellent in heat resistance can be provided. The color filter is useful as a color filter used in display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Claims (9)

Coloring agent (A) comprising a compound represented by formula (I),
Resin (B),
Photopolymerizable compound (C) and
It includes a photopolymerization initiator (D),
The resin (B) is an alkali-soluble resin colored curable resin composition:

[In the formula (I), X ⁻ represents an anion derived from a dye, and Y ⁺ represents a cation derived from a compound represented by the formula (Y):

(In the formula (Y), n represents an integer of 1 to 8, and R ⁴⁰ represents an alkyl group having 1 to 4 carbon atoms.)] The colored curable resin composition according to claim 1, wherein the anion derived from the dye is an anion derived from an alloy azo dye or a triarylmethane dye. The colored curable resin composition according to claim 1 or 2, wherein the anion derived from the dye is an anion derived from the alloy azo dye. The colored curable resin composition according to claim 2, wherein the anion derived from the alloy azo dye is represented by the formula (A0).

[In the formula (A0), R ¹ to R ¹⁸ each independently represent a hydrogen atom, a halogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, a nitro group, or -SO ₂ R ²⁹ .
R ²⁹ represents -OH, -NHR ³⁰ or -R ³² .
R ³⁰ is a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R ³¹ -OR ³³ , -R ³⁴ -CO-OR ³⁵ , -R ^36- O-CO-R ³⁷ or an aralkyl group having 7 to 10 carbon atoms.
R ³¹ , R ³⁴ and R ³⁶ each independently represent a divalent alkanediyl group having 1 to 8 carbon atoms.
R ³² , R ³³ , R ³⁵ and R ³⁷ each independently represent a monovalent alkyl group having 1 to 8 carbon atoms.
R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a methyl group, an ethyl group, or an amino group.
M ¹ represents Cr or Co.] The colored curable resin composition according to claim 1 or 2, wherein the colorant (A) further comprises a pigment. The colored curable resin composition according to claim 1 or 2, wherein the resin (B) has an acid value of 50 to 150 mg-KOH / g. The colored curable resin composition according to claim 1 or 2, wherein the colored curable resin composition is for pattern production using a photolithography method. A color filter formed by the colored curable resin composition according to claim 1 or 2. A display device comprising the color filter according to claim 8.