KR102007049B1 - Colorant dispersion - Google Patents

Abstract

This invention is made by disperse | distributing a coloring agent, a extender pigment, and a dispersing agent to a solvent,
As a colorant, including dyes and colored pigments,
As a solvent, propylene glycol monomethyl ether acetate is contained, and also
The content of propylene glycol monomethyl ether acetate provides a colorant dispersion having a content of 40% by mass or more and 99% by mass or less with respect to the total amount of the solvent.

Description

Colorant Dispersion {COLORANT DISPERSION}

The present invention relates to colorant dispersions and the like.

Colored curable compositions are used for manufacture of the color filter used for display apparatuses, such as a liquid crystal display device, an electroluminescent display device, and a plasma display. And in the manufacture of such a colored curable composition, it is used for the dispersion liquid which disperse | distributes dye (xanthene dye) and colored pigment which have a xanthene frame | skeleton to propylene glycol monomethyl ether acetate is used, Unexamined-Japanese-Patent No. 2011 38085.

The present invention includes the following inventions.

[1] dispersing a colorant, a extender pigment, and a dispersant in a solvent,

As a colorant, including dyes and colored pigments,

As a solvent, propylene glycol monomethyl ether acetate is contained, and also

The coloring agent dispersion liquid whose content of propylene glycol monomethyl ether acetate is 40 mass% or more and 99 mass% or less with respect to the total amount of a solvent.

[2] The colorant dispersion liquid according to [1], wherein the mass ratio of the total amount of the dye and the total amount of the colored pigment and the extender pigment (total amount of the dye: the total amount of the colored pigment and the extender pigment) is 1:99 to 99: 1.

[3] The dye dispersion according to [1] or [2], wherein the dye is a dye having a xanthene skeleton.

[4] The colorant dispersion liquid according to any one of [1] to [3], further comprising a solvent having a higher polarity than propylene glycol monomethyl ether acetate.

[5] The colorant dispersion according to [4], wherein the solvent having a higher polarity than propylene glycol monomethyl ether acetate is propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone or ethylene glycol monobutyl ether.

[6] The colorant dispersion liquid according to any one of [1] to [5], further containing a resin.

[7] A colored curable composition comprising the colorant dispersion liquid according to any one of [1] to [6], a polymerizable compound, and a polymerization initiator.

[8] A color filter formed from the colored curable composition according to [7].

[9] A display device comprising the color filter according to [8].

1. Colorant Dispersion

The colorant dispersion of the present invention,

It is made by disperse | distributing a coloring agent (A), an extender pigment (A '), and a dispersing agent (D) in a solvent (B),

As a coloring agent (A), it contains dye and a pigment,

As a solvent (B), it contains propylene glycol monomethyl ether acetate,

Content of propylene glycol monomethyl ether acetate is 40 mass% or more and 99 mass% or less with respect to the total amount of a solvent (B).

Colorant dispersion.

Hereinafter, each component of a coloring agent dispersion liquid is demonstrated. In addition, in this specification, the compound illustrated as each component can be used individually or in combination of multiple types unless there is particular notice.

1-1. The colorant (A)

A coloring agent (A) contains dye (A1) and a coloring pigment (A2).

As the dye (A1), a dye having a xanthene skeleton (xanthene dye), a dye having a coumarin skeleton (coumarin dye), a dye having a triphenylmethane skeleton (triphenylmethane dye), a dye having an azo skeleton (azo dye) ), A dye having a phthalocyanine skeleton (phthalocyanine dye), a dye having an anthraquinone skeleton (anthraquinone dye), a dye having a quinophthalone skeleton (quinophthalone dye) and a dye having a cyanine skeleton (cyanine dye) Xanthene dye and coumarin dye are preferable, and xanthene dye is more preferable.

1-1-1. Xanthene dyes

Xanthene dye is dye which has xanthene frame | skeleton in a molecule | numerator. As xanthene dye, C.I. Acid Red 51 (hereinafter, the description of C.I. Acid Red is omitted and only numbers are given. Others are the same.), 52, 87, 92, 94, 289, 388, C.I. Acid violet 9, 30, 102, C.I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. Basic Red 10 (Rhodamine B), 11, C.I. Basic Violet 10, 11, 25, C.I. Solvent Red 218, C.I. Modern Red 27, C.I. Reactive red 36 (rose bengal B), sulforhodamine G, the xanthene dye of Unexamined-Japanese-Patent No. 2010-32999, the xanthene dye of patent 4449760, etc. are mentioned. As xanthene dye, the dye melt | dissolved in the organic solvent is preferable.

As xanthene dye, the compound represented by general formula (1-1)-chemical formula (1-63) is preferable.

In the formula, R ²⁶ and R ⁴⁰ represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, more preferably a 2-ethylhexyl group.

As xanthene dye, C.I. Sulfonamides of acid red 289, C.I. Quaternary ammonium salt of acid red 289, C.I. Sulfonamides of acid violet 102 and C.I. Preferred are quaternary ammonium salts of acid violet 102. As such a compound, the compound etc. which are represented by General formula (1-1)-General formula (1-8), General formula (1-11), and General formula (1-12) are mentioned.

In view of excellent solubility in an organic solvent, a compound represented by any one of formulas (1-24) to (1-33) and (1-37) to (1-63) is also preferable.

Commercially available xanthene dyes (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Chugaikasei Co., Ltd., "Rhodamine 6G" manufactured by Taoka Kagaku Kogyo Co., Ltd.)] Can be used. Moreover, you may synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using commercially available xanthene dye as a starting material.

1-1-2. Colored pigment

As the coloring pigment (A2), a known coloring pigment can be used without particular limitation, and a coloring pigment classified as a pigment in the color index (The Society of Dyers and Colourists) is mentioned.

As a coloring pigment, 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, ;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments such as pigment green 7, 19, 21, 26, 36 and 58; And the like.

As a coloring pigment, C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60; C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.I. Green pigments, such as Pigment Green 7, 36, 58, are preferable, and C.I. Pigment Blue 15: 3, 15: 6, C.I. Pigment violet 23 and C.I. Pigment Green 7, 58 is more preferred, and C.I. Pigment Blue 15: 6 and C.I. Pigment Green 7 is more preferred. By including a coloring pigment, optimization of a transmission spectrum is easy and the light resistance and chemical-resistance of a color filter become favorable.

The colored pigment may be rosin-treated, surface treated with a pigment derivative having an acidic group or basic group introduced therein, graft treatment on the surface of the pigment with a high molecular compound or the like, atomization by sulfuric acid atomization or the like, or removing impurities. The washing treatment by an organic solvent, water, or the like to be removed, the removal treatment by an ion exchange method of ionic impurities, or the like may be performed.

1-2. Extender pigment (A ')

The extender pigment is not particularly limited, and a known extender pigment may be used, and barium sulfate (BaSO ₄ ), barium carbonate (BaCO ₃ ), lime carbonate powder (CaCO ₃ ), silica powder (SiO ₂ ), basic carbonate Extender pigments such as magnesium (MgCO ₃ ), aluminum hydroxide, kaolin clay, and nepheline syenite.

As the extender pigment, barium sulfate (BaSO ₄ ), barium carbonate (BaCO ₃ ), lime carbonate powder (CaCO ₃ ), silica powder (SiO ₂ ), basic magnesium carbonate (MgCO ₃ ) are preferable, and barium sulfate (BaSO ₄₎ ), Lime carbonate powder (CaCO ₃ ) and silica powder (SiO ₂ ) are more preferred. Moreover, among these, it is more preferable that it is high transparency.

The ratio of the content of the dye (A1) to the colored pigment (A2) and the extender pigment (A ') (total amount of the dye: the total amount of the dye and the extender pigment) is preferably 1:99 to 99: 1 by mass. It is more preferable that it is 2: 98-50: 50, and it is still more preferable that it is 3: 97-20: 80. By setting it as such a ratio, the contrast of the colored curable composition manufactured from the coloring agent dispersion liquid of this invention becomes still more favorable.

1-3. Dispersant (D)

As a dispersing agent (D), if it is a dispersing agent used for disperse | distributing a coloring agent, it will not specifically limit, For example, a polymeric dispersing agent and a synergistic dispersing agent are mentioned.

Examples of the polymer dispersant include an acrylic dispersant and a urethane dispersant.

An acrylic block copolymer is mentioned as said acrylic dispersing agent. As an acryl-type block copolymer, the block copolymer which has the block containing a basic group and an acidic group, and the block which does not contain the said basic group or the said acidic group is preferable.

The basic group and the acid group (hereinafter, these groups may be collectively referred to as a "colorant adsorber") each exhibit an action of adsorbing the colorant described above.

As a block containing the said coloring agent adsorption group (henceforth this block may be called a "coloring agent adsorption block"), the block comprised from the monomer which has an acidic group with the monomer which has a basic group is mentioned.

In an acryl-type block copolymer, as a monomer which has a basic group, the monomer which has a primary amino group, a secondary amino group, or a tertiary amino group is mentioned. Specifically, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethyl acrylamide, diethyl acrylamide, dimethylaminopropyl methacrylamide Monomers having glycidyl groups such as acryloyl morpholine, vinylimidazole, 2-vinylpyridine, an amino group and a caprolactone skeleton, and glycidyl (meth) acrylate, and one secondary amino group in the molecule Reactant with a compound having a (meth) acryloylalkylisocyanate compound with 4- (2-aminomethyl) -pyridine, 4- (2-aminoethyl) -pyridine, 4- (2-hydroxyethyl) pyridine, 1- (2-aminoethyl) -piperazine, 2-amino-6-methoxybenzothiazole, 1- (2-hydroxyethylimidazole), N, N-diallylmelamine, N, N-dimethyl And reactants with -1,3-propanediamine.

In an acryl-type block copolymer, the monomer which has an carboxyl group, a sulfonic acid group, and a phosphoric acid group is mentioned as a monomer which has an acidic group.

As a monomer which has a carboxy group, Unsaturated monocarboxylic acid compounds, such as acrylic acid, methacrylic acid, and crotonic acid; Unsaturated dicarboxylic acid compounds such as maleic acid, fumaric acid and itaconic acid, and half esters thereof; And the like.

2-acrylamide-2-methyl-1-propanesulfonic acid, 2-methacrylamide-2-methyl-1-propanesulfonic acid, styrenesulfonic acid, etc. are mentioned as a monomer which has a sulfonic acid group.

As a monomer which has a phosphoric acid group, an acid phosphonyl (meth) acrylate, an acid phosphonyl ethyl (meth) acrylate, etc. are mentioned.

In the acrylic block copolymer, examples of the constituents of the block containing no colorant adsorbent include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and benzyl chloride; Unsaturated carboxylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate; Unsaturated carboxylic acid arylalkyl esters such as benzyl (meth) acrylate; Polycaprolactone containing monomers; Polyalkylene glycol monoester-based monomers; And the like.

The acrylic block copolymer can be obtained by a conventionally known polymerization method such as living anion polymerization.

As for the amine titer of an acryl-type block copolymer, 2-40 mgKOH / g is preferable. In the present specification, the amine titer means the amine titer per 1 g of solid content, and a potentiometric titration method (eg, COMTITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATIONK-900) using 0.1 mol / L hydrochloric acid aqueous solution) is used. , Manufactured by Hiranumasan Co., Ltd.], and then converted into equivalents of potassium hydroxide.

As a commercial item of an acryl-type dispersing agent, "Disperbyk (trademark) -2000 (amine value 4 mgKOH / g)" and "Disperbyk-2001 (amine value 29 mgKOH / g)" etc. which were manufactured by Big Chemi Japan Co., Ltd. are mentioned.

As a urethane type dispersing agent, the urethane type resin which does not have an acidic radical in a molecule | numerator is preferable.

The urethane-based resin can be obtained by reacting a polyisocyanate compound with a compound having at least one hydroxyl group and a basic compound having a functional group capable of reacting with an isocyanate group. The method of obtaining such a urethane type resin is described in Unexamined-Japanese-Patent No. 60-166318.

As a polyisocyanate compound used for preparation of a urethane type resin, the isocyanate compound which has two or more isocyanate groups is mentioned, It is 2, 4- tolylene diisocyanate;

2,6-tolylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'- dimethyl biphenyl-4 Aromatic diisocyanate compounds such as 4'-diisocyanate;

Hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanate methylene) cyclohexane, etc. Aliphatic or alicyclic polyisocyanates;

Polyisocyanates having isocyanuric groups derived from the diisocyanate (polyisocyanates having an isocyanuric group formed by trimming the diisocyanate);

Polyisocyanate obtained by adding diisocyanate to a polyol;

Polyisocyanate obtained by the biuret reaction of a diisocyanate compound;

Dimers of said polyisocyanates;

And the like.

Also in the said polyisocyanate compound, the polyisocyanate which has the isocyanol group derived from diisocyanate is preferable.

As a compound which has one or more hydroxyl groups, a polyether compound, a polyester compound, etc. are mentioned.

Examples of the polyether compound include modified products of polyalkylene glycols, modified products of alkylene glycols, low molecular weight monools, and the like.

Specific examples of the polyalkylene glycols include polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, and the like. Specific examples of alkylene glycols include ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylol propane, pentaerythritol, diglycerol, ditrimethylol propane, Dipentaerythritol and the like. Specific examples of the low molecular monools include methanol and ethanol.

Examples of the modified substances include ethylene oxide modified substances, propylene oxide modified substances, butylene oxide modified substances, tetrahydrofuran modified substances, and the like.

As a polyester compound, Modified products of alkylene glycols and low molecular weight monools;

Polyester polyols such as aliphatic polyester polyols which are esterified products of aliphatic dicarboxylic acids and polyols, and aromatic polyester polyols which are esterified products of aromatic dicarboxylic acids and polyols;

Esterified products of polyhydric hydroxy compound and dicarboxylic acid;

Polyhydric hydroxy group containing compounds, such as monoglyceride obtained by the transesterification reaction of a polyhydric hydroxy group containing compound and a fatty acid ester;

And the like.

As the specific examples of the alkylene glycols and the low molecular monools, the same examples as the alkylene glycols exemplified for the polyether compound can be given with respect to the polyester compound.

Examples of the modified product of alkylene glycols and low molecular weight monools include ε-caprolactone modified substances, γ-butyrolactone modified substances, δ-valerolactone modified substances, methylvalerolactone modified substances, and the like.

Examples of the aliphatic dicarboxylic acids include fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid and dimer acid.

Neopentyl glycol etc. are mentioned as a polyol in polyester polyols.

Terephthalic acid etc. are mentioned as aromatic dicarboxylic acid.

As a polyhydric hydroxy group compound, polycarbonate polyol, an acryl polyol, polytetramethylene hexaglyceryl ether (tetrahydrofuran modified product of hexaglycerin), etc. are mentioned.

As a compound which has one or more said hydroxyl groups, (epsilon) -caprolactone adduct of alcohols (that is, alkylene glycols and low molecular weight monools) is preferable.

As for the number average molecular weight of the compound which has one or more said hydroxyl groups, 300-10,000 are preferable, More preferably, it is 300-6,000. In addition, a number average molecular weight and a weight average molecular weight can be measured by a column chromatography method.

In the urethane-based resin, the basic group-containing compound is not particularly limited, but polythiol having N, N-disubstituted amino group or heterocyclic nitrogen atom, polythiol having N-disubstituted amino group or heterocyclic nitrogen atom, and N It is preferable that it is at least 1 type of nitrogen containing compound chosen from the group which consists of amines which have a di-substituted amino group or a heterocyclic nitrogen atom.

As the nitrogen-containing compound, a compound which is commonly used in the technical field of the dispersant can be used. These compounds have a basic group containing an active hydrogen atom and at least one nitrogen atom of cherevitinov.

Such nitrogen-containing compounds include N, N-dimethyl-1,3-propanediamine, N, N-diethyl 1,4-butanediamine, 2-dimethylaminoethanol, 1- (2-aminoethyl)- Piperazine, 2- (1-pyrrolidyl) -ethylamine, 4-amino-2-methoxypyrimidine, 4- (2-aminoethyl) -pyridine, 1- (2-hydroxyethyl) -piperazine , 4- (2-hydroxyethyl) -morpholine, 2-mercaptopyrimidine, 2-mercaptobenzoimidazole, 2-amino-6-methoxybenzothiazole, N, N-diallyl-melamine , 3-amino-1,2,4-triazole, 1- (2-hydroxyethyl) -imidazole, 3-mercapto-1,2,4-triazole, and the like. Especially, amines which have a heterocyclic nitrogen atom are preferable.

Synthesis of urethane resin is not specifically limited, It can carry out by a conventionally well-known method. The amine titer of the said urethane type dispersion resin becomes like this. Preferably it is 2-90 mgKOH / g, More preferably, it is 5-40 mgKOH / g.

As a commercial item of the urethane type dispersing agent which is a urethane type resin, "Disperbyk-161 (amine value 11 mgKOH / g, acid value 0 mgKOH / g)" manufactured by BIC Chemie Japan, "Disperbyk-162 (amine value 13 mgKOH / g, acid value 0) mgKOH / g) "," Disperbyk-167 (amine value 13 mgKOH / g, acid value 0 mgKOH / g) "," Disperbyk-182 (amine value 13 mgKOH / g, acid value 0 mgKOH / g) ", etc. are mentioned.

As the polymer dispersant, an acrylic dispersant is preferable.

A phthalocyanine derivative is mentioned as a synergy dispersing agent (coloring agent derivative type dispersing agent). Commercially available products of the synergistic dispersant include "Solsperth® 5000 (copper phthalocyanine derivative)" manufactured by Lubriz Corporation.

When it contains a synergistic dispersing agent, 5 mass parts or more are preferable with respect to 100 mass parts of coloring agents (A), More preferably, it is 10 mass parts or more, More preferably, it is 15 mass parts or more, 60 mass parts or less are preferable, More preferably, it is 50 mass parts or less, More preferably, it is 45 mass parts or less.

When using a polymeric dispersing agent and a synergistic dispersing agent together, these mass ratios (polymer dispersing agent / synergistic dispersing agent) have preferable 70 / 30-99 / 1, More preferably, it is 80 / 20-97 / 3, More Preferably it is 85/15-95/5.

1-4. Solvent (B)

The solvent (B) contains 40 mass% or more and 99 mass% or less of propylene glycol monomethyl ether acetate.

Content of propylene glycol monomethyl ether acetate becomes like this. Preferably it is 75 mass% or more and 95 mass% or less, More preferably, it is 80 mass% or more and 95 mass% or less.

If content of a solvent (B) exists in the said range, the storage stability of the colored curable composition manufactured from the coloring agent dispersion liquid of this invention is favorable.

The solvent (B) contains at least one solvent other than propylene glycol monomethyl ether acetate. The solvent other than propylene glycol monomethyl ether acetate is not limited, and a solvent usually used in the field can be used. Examples of solvents other than such propylene glycol monomethyl ether acetate include ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (containing -O- in the molecule, and -COO- Solvent not containing), ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (The solvent which contains OH in a molecule and does not contain -O-, -CO-, and -COO-), an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

As an 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 ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl an Or a brush.

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, 3-methoxy propionate, ethyl 3-methoxy propionate, 3-ethoxy propionic acid Methyl, 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-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate And the like.

As a ketone solvent, 4-hydroxy-4-methyl- 2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- pentanone, Cyclopentanone, cyclohexanone, isophorone, etc. are mentioned.

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

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

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

Among the solvents described above, a solvent having higher polarity than that of propylene glycol monomethyl ether acetate is preferable, and propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone and ethylene glycol monobutyl ether are more preferable. More preferred are propylene glycol monomethyl ether and 4-hydroxy-4-methyl-2-pentanone.

1-5. Resin (C)

The coloring agent dispersion liquid of this invention may further contain resin (C).

Although resin (C) is not specifically limited, It is preferable that it is alkali-soluble resin. As resin (C), the following resin [K1]-[K6], etc. are mentioned.

At least one selected from the group consisting of a resin [K1] unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter may be referred to as "(a)"), a cyclic ether structure having 2 to 4 carbon atoms, and Copolymers with a monomer (b) having a ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)");

Resin [K2] (a) and (b), and monomer (c) copolymerizable with (a), but different from (a) and (b) [hereinafter may be called "(c)" Copolymers with;

Copolymer of resin [K3] (a) and (c);

Resin [K4] Resin obtained by making (b) react with the copolymer of (a) and (c);

Resin [K5] Resin obtained by making (a) react with the copolymer of (b) and (c);

Resin [K6] Resin obtained by making (a) react with the copolymer of (b) and (c), and making carboxylic anhydride further react.

Specific examples of (a) include 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, 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;

unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid; And the like.

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

(b) refers to a polymerizable compound having 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) and an ethylenically unsaturated bond. . As for (b), the monomer which has a C2-C4 cyclic ether structure and a (meth) acryloyloxy group is preferable.

In addition, in this specification, "(meth) acrylic acid" represents at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. Quot ;, " (meth) acryloyl ", and " (meth) acrylate "

As (b), the monomer which has an oxiranyl group and ethylenically unsaturated bond, the monomer (b2) which has oxetanyl group and ethylenically unsaturated bond, the monomer (b3) which has tetrahydrofuryl group and ethylenically unsaturated bond, etc. are mentioned. .

As (b), since the reliability of heat resistance, chemical resistance, etc. of the color filter obtained can be made higher, it is preferable that it is a monomer which has an oxiranyl group and ethylenically unsaturated bond.

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 known as "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 [In the technical field, it is a common name as "dicyclo Pentenyl (meth) acrylate], dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, pro (Meth) acrylic acid esters such as pargyl (meth) acrylate, phenyl (meth) 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 itaconic acid;

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-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate 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 them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable in terms of copolymerization reactivity and heat resistance. Do.

As resin (C), 3, 4- epoxycyclohexyl methyl (meth) acrylate / (meth) acrylic acid copolymer, 3, 4- epoxy citricyclo [5.2.1.0 ^2,6 ] decyl acrylate / (meth) acrylic acid Resins such as copolymers [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 ] decylacrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decylacrylate / (meth) acrylic acid / styrene monomer Resins such as copolymers and 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymers; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; Resin which glycidyl (meth) acrylate was added to the benzyl (meth) acrylate / (meth) acrylic acid copolymer, and glycidyl (meth) to the tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin [K4], such as resin which added acrylate, and resin which added glycidyl (meth) acrylate to the tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) 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 Resins [K5] such as resins in which (meth) acrylic acid is reacted with a copolymer; Resin [K6], such as resin which further made tetrahydrophthalic anhydride react with resin which (meth) acrylic acid reacted with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, etc. are mentioned. .

As resin (C), resin [K1] and resin [K2] are preferable.

Resin [K1] is described in, for example, the method described in the document "Experimental Method of Polymer Synthesis" (Oki Takiyuki, Published by Chemical Co., Ltd., First Edition, March 1, 1972). It may be prepared by reference to the cited document.

The weight average molecular weight of polystyrene conversion of resin (C) 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.

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

The acid value of resin (C) becomes like this. Preferably it is 50-170 mgKOH / g, More preferably, it is 60-150 mgKOH / g, More preferably, it is 70-135 mgKOH / g.

The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin. The said acid value can be calculated | required by titration using the potassium hydroxide aqueous solution.

1-6. Process for preparing colorant dispersion

The coloring agent dispersion liquid of this invention is manufactured by disperse | distributing the mixture containing a coloring agent (A), an extender pigment (A ') and a solvent (B), and resin (C) and a pigment dispersing agent (D) as needed.

Dispersion processing means mixing until the particle | grains of a coloring agent (A) become a dispersion state. By this dispersion process, the particle | grains of a coloring agent (A) are grind | pulverized small. A dispersed state means the state in which the particle | grains of the coloring agent (A) contained in a liquid mixture are suspended in the state of microparticles | fine-particles in the solvent (B).

As for content of a coloring agent (A), 5 mass% or more is preferable with respect to the total amount of a coloring agent dispersion liquid, More preferably, it is 10 mass% or more, 30 mass% or less is preferable, and its 20 mass% or less is more preferable.

As for content of a dispersing agent (D), 1 mass% or more is preferable with respect to the total amount of a coloring agent dispersion liquid, More preferably, it is 2 mass% or more, 20 mass% or less is preferable, More preferably, it is 10 mass% or less. . When content of a dispersing agent (D) exists in the said range, there exists a tendency for a dispersed state to stabilize.

When manufacturing the coloring agent dispersion liquid containing resin (C), 1 mass% or more is preferable with respect to the total amount of a coloring agent dispersion, and, as for content of resin (C), More preferably, it is 2 mass% or more, 15 mass% The following is preferable, More preferably, it is 7 mass% or less. When content of resin (C) exists in the said range, there exists a tendency for a dispersed state to stabilize.

As for the temperature at the time of manufacturing a colorant dispersion liquid, 120 degrees C or less is preferable, More preferably, it is 70 degrees C or less. Although the minimum of temperature at the time of dispersing is not specifically limited, Usually, it is 20 degreeC.

0.5 hour or more is preferable, dispersion time is 2 hours or more preferably, 48 hours or less are preferable, More preferably, it is 20 hours or less.

As a device used for dispersion, a roll mill, a high speed stirring apparatus, a bead mill, a ball mill, a sand mill, a paint conditioner, an ultrasonic dispersion machine, a high pressure dispersion machine, etc. are mentioned.

It is preferable to filter the obtained coloring agent dispersion liquid with the filter of about 1.0-5.0 micrometers of pore diameters.

2. Colored Curable Composition

The colored curable composition of this invention contains the above-mentioned coloring agent dispersion liquid, a polymeric compound (E), and a polymerization initiator (F).

The colored curable composition of this invention is obtained by mixing the coloring agent dispersion liquid mentioned above, a polymeric compound (E), and a polymerization initiator (F).

As long as the said colored curable composition is the composition which performed the said mixing, the composition obtained by performing another operation before and after the said mixing may be sufficient.

2-1. Polymerizable Compound (E)

The polymerizable compound (E) is a compound that can be polymerized by an active radical, an acid, or the like generated from the polymerization initiator (F) described later. Examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like. (Meth) acrylic acid ester compound is mentioned.

As the polymerizable compound (E), a polymerizable compound having three or more ethylenically unsaturated bonds (preferably 4 to 10, more preferably 5 to 8) is preferable, and further three or more (preferably 4) An ester of an alcohol (pentaerythritol, a condensate thereof, or a modified product thereof) having an OH group of -10, more preferably 5-8) and (meth) acrylic acid is preferable. As such a polymeric compound, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, and tripentaerythritol hepta (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, caprolactone modified pentaerythritol tetra (Meth) acrylate, caprolactone modified dipentaeryth Tall hexa (meth) acrylate. Especially, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned preferably.

The weight average molecular weight of the polymerizable compound (E) is preferably 150 or more and 2,900 or less, and more preferably 250 to 1,500 or less.

It is preferable that content of a polymeric compound (E) is 7-65 mass% with respect to solid content of a colored curable composition, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When content of the said polymeric compound (E) exists in the said range, since hardening arises enough, the residual film ratio in image development improves, an undercut does not easily arise in a coloring pattern, and since adhesiveness tends to become favorable, it is preferable. .

Here, solid content means the total amount of the component remove | excluding the solvent from the colored curable composition of this invention. Solid content and content of each component with respect to this can be measured by well-known analysis means, such as liquid chromatography or gas chromatography.

2-2. Polymerization initiator (F)

As a polymerization initiator (F), if it is a compound which can generate an active radical, an acid, etc. by the action of light or heat, and can start superposition | polymerization, it will not specifically limit, A well-known polymerization initiator can be used.

As a polymerization initiator (F), the compound which generate | occur | produces an active radical by the effect of light is preferable, and an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an oxime compound, and a biimidazole compound are more preferable.

As the alkylphenone compound, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2- Benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, 2-hydroxy- 2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl Ketones, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one, α, α-diethoxyacetophenone, benzyldimethyl ketal and the like. You may use commercial items, such as Irgacure (trademark) 369, 907, and 379 (above, BASF Corporation make).

In terms of sensitivity, the alkylphenone compounds include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholin). Nophenyl) -2-benzylbutan-1-one is preferred.

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.

As an acyl phosphine oxide compound, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide etc. are mentioned. You may use a commercial item, such as Irgacure (trademark) 819 (made by BASF Corporation).

As an oxime compound, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-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-carbazol-3-yl]- 3-cyclopentyl propane-1-one-2-imine, etc. are mentioned. You may use commercially available products, such as Irgacure (trademark) OXE01, OXE02 (above BASF Corporation make), and N-1919 (ADEKA Corporation make). Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2 -Imines and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imines are preferred. If it is these oxime compounds, when preparing the colored curable composition of this invention as a blue colored curable composition, there exists a tendency for the brightness of the color filter obtained to become high.

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 Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-open 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 imidazole compounds in which the 5'-position phenyl group is substituted with a carboalkoxy group (see JP-A-7-10913, etc.) and the like. Preferred are 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

As a polymerization initiator (F), 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; 10-butyl-2-chloroacridone, benzyl, phenylglyoxylic acid, titanocene compound, etc. are mentioned.

It is preferable to use these in combination with the polymerization start adjuvant (F1) (especially amines) mentioned later.

As an acid generator which generate | occur | produces an acid by light, 4-hydroxyphenyl dimethyl sulfonium p-toluene sulfonate, 4-hydroxyphenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxy phenyl dimethyl sulfonium p Toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p- Onium salts, such as toluene sulfonate and diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylate, benzoin tosylate, etc. are mentioned.

Content of a polymerization initiator (F) is preferably 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (C) and polymeric compound (E) in the colored curable composition of this invention, More preferably, 1 It is -20 mass parts. If content of a polymerization initiator exists in the said range, it will become high sensitivity, shortening an exposure time and improving productivity.

The colored curable composition of this invention may further contain at least 1 sort (s) chosen from the group which consists of a polymerization start adjuvant (F1) and a leveling agent (G).

2-3. Polymerization Initiation Aid (F1)

The colored curable composition of this invention may further contain the polymerization start adjuvant (F1). A polymerization start adjuvant (F1) 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, and is normally used in combination with polymerization initiator (F).

As a polymerization start adjuvant (F1), an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylamino benzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic isoamyl acid, benzoic acid 2-dimethylaminoethyl and 4-dimethyl Aminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4, 4'-bis (ethylmethylamino) benzophenone etc. are mentioned, Especially, 4,4'-bis (diethylamino) benzophenone is preferable. EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) and the like may be used.

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- Dibutoxy anthracene, 2-ethyl-9, 10- dibutoxy anthracene, etc. are mentioned.

As a thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxide Citioxanthone 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, dimethoxysulfanyl 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 a polymerization start adjuvant (F1), the usage-amount is preferably 0.1-30 mass parts, More preferably, with respect to 100 mass parts of total amounts of resin and polymeric compound (E) in the colored curable composition of this invention. It is 1-20 mass parts. If the amount of the polymerization start aid (F1) is within this range, the pattern can be formed with higher sensitivity, and the pattern tends to improve the productivity.

2-4. Leveling agent (G)

Examples of the leveling agent (G) 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 are mentioned. Specifically, Toray Silicon (brand name) DC3PA, Toray Silicon SH7PA, Toray Silicon DC11PA, Toray Silicon SH21PA, Toray Silicon SH28PA, Toray Silicon SH29PA, Toray Silicon SH30PA, Toray Silicon SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsukagaku Kogyo Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (Momentual Performance Materials) Japan Altitude Co., Ltd.) etc. are mentioned.

Examples of the fluorine-based surfactants include surfactants having a fluorocarbon chain. Specifically, Florade (trademark) FC430, Florade FC431 (manufactured by Sumitomo 3M Co., Ltd.), Mega Park (registered trademark) F142D, Mega Park F171, Mega Park F172, Mega Park F173, Mega Park F177, Mega Park F183, Megapak F554, Megapak R30, Megapak RS-718-K (manufactured by DIC Corporation), FTOP® EF301, Ftop EF303, Ftop EF351, Ftop EF352 [Mitsubishi Material Denshika Seijo Co., Ltd.], Supron (registered trademark) S381, Supron S382, Supron SC101, Supron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Co., Ltd.), etc. Can be mentioned.

As silicone type surfactant which has a fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain | strand are mentioned. Specifically, MegaPak (registered trademark) R08, MegaPac BL20, MegaPac F475, MegaPac F477, MegaPac F443 (manufactured by DIC Corporation), and the like.

Content of a leveling agent (G) is 0.001 mass% or more and 0.2 mass% or less with respect to the total amount of the colored curable composition of this invention, Preferably it is 0.002 mass% or more and 0.1 mass% or less, More preferably, 0.01 It is mass% or more and 0.05 mass% or less. In addition, content of the said pigment dispersant is not contained in this content. If content of a leveling agent (G) exists in the said range, flatness of a color filter can be made favorable.

It is preferable that the colored curable composition of this invention further contains at least 1 sort (s) chosen from the group which consists of a solvent (B ') and resin (C').

2-5. Solvent (B ')

The same thing as a solvent (B) is mentioned as a solvent ["solvent (B ')" used when preparing colored curable composition.

Preferably, from the point of applicability | paintability and dryness, it is an organic solvent whose boiling point in 1 atm is 120 degreeC or more and 180 degrees C or less, More preferably, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, Ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4- Methyl-2-pentanone, N, N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, ethyl lactate, 4-hydroxy-4-methyl-2-pentanone, 3-methoxybutyl Acetate, 3-methoxy-1-butanol and ethyl 3-ethoxypropionate.

Content (the total amount of a solvent (B) and a solvent (B ')) of a solvent in a colored curable composition becomes like this. Preferably it is 70-95 mass% with respect to the total amount of a colored curable composition, More preferably, it is 75-92 Mass%. In other words, solid content of a colored curable composition becomes like this. Preferably it is 5-30 mass%, More preferably, it is 8-25 mass%. When content of a solvent exists in the said range, the 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 a display characteristic to become favorable.

2-6. Resin (C ')

As resin ["resin (C ')" used when preparing colored curable composition, the thing similar to resin (C) is mentioned. Resin (C ') may be the same as resin (C), but may be a different kind.

The content [the total amount of the resin (C) and the resin (C ′)] of the resin is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and more preferably to the total amount of solids. It is 17-55 mass%. When content of resin exists in the said range, there exists a tendency for the resolution of a coloring pattern and the residual film rate of a coloring pattern to improve.

2-7. Colorant (A ")

The colored curable composition may further contain the coloring agent (A ") containing at least 1 sort (s) chosen from another dye and a pigment.

The same thing as a coloring agent (A) is mentioned as a coloring agent ["coloring agent (A") "used when preparing colored curable composition.

Content (the total amount of a coloring agent (A) and a coloring agent (A ")) of a coloring agent becomes like this. Preferably it is 5-60 mass%, More preferably, it is 8-55 mass% with respect to solid content of a colored curable composition, More preferably Preferably it is 10-50 mass%. If content of a coloring agent exists in the said range, since the color density at the time of setting it as a color filter is enough, and a resin and a polymeric compound can be contained in a composition, mechanical strength will be Sufficient patterns can be formed.

2-8. Other components

If necessary, the colored curable composition of the present invention may contain various additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents (hereinafter referred to as "other components"). May be included).

2-9. Method for producing colored curable composition

The coloring curable composition of this invention is a coloring agent dispersion liquid of this invention, a polymeric compound (E), and a polymerization initiator (F), and a polymerization start adjuvant (F1), a leveling agent (G), and other components used as needed. It can prepare by mixing.

When a coloring agent dispersion does not contain resin (C), it is preferable to add resin (C ') when preparing colored curable composition. When a coloring agent dispersion liquid contains resin (C), when preparing colored curable composition, you may add resin (C ') further.

When preparing a colored curable composition, you may add a coloring agent (A ") and / or a solvent (B ') further.

It is preferable to filter the colored curable composition prepared by mixing as mentioned above with the filter of about 0.01-10 micrometers of pore sizes.

3. Manufacturing method of color filter

Color filters formed from the colored curable compositions described above also fall within the scope of the present invention. The said color filter can be obtained by apply | coating a coloring curable composition to a board | substrate, and hardening the obtained composition layer.

As a method of manufacturing the coloring pattern of a color filter with the colored curable 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 colored curable composition to a board | substrate, drying to form a composition layer, exposing the said composition layer through a photomask, and developing. In the photolithographic method, the coloring coating film which is the hardened | cured material of the said composition layer can be formed by not using a photomask at the time of exposure, and / or not developing.

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

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass coated with silica on the surface, resin plates such as polycarbonate, polymethyl methacrylate and polyethylene terephthalate, silicon, and the substrate. What formed aluminum, silver, silver / copper / palladium alloy thin film, etc. is used. On these substrates, other color filter layers, resin layers, transistors, circuits, and the like may be formed.

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

First, a coloring curable composition is apply | coated on a board | substrate, volatile components, such as a solvent, are removed and dried by heat drying (prebaking) and / or drying under reduced pressure, and a smooth 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. As heating time, it is preferable that it is for 10 second-60 minutes, and it is more preferable that it is for 30 seconds-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 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, the composition layer is exposed through a photomask for forming a desired colored pattern. The pattern on the said 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 of around 436 nm, 408 nm, and 365 nm vicinity is used a band pass filter that extracts these wavelength ranges. Alternatively, the extraction may be performed. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

Since it is possible to irradiate parallel light rays uniformly to the entire exposure surface or to accurately position the photomask and the substrate, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.

The coloring pattern is formed on a board | substrate by developing the composition layer after exposure contacting with a developing solution. By development, the unexposed part of a 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, and tetramethylammonium hydroxide, is preferable. 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 puddle 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-bak to the obtained coloring pattern. 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.

The color filter formed from the above-mentioned colored curable composition is useful as a color filter used for a display apparatus (for example, a liquid crystal display device, an organic EL device, etc.), an electronic paper, a solid-state image sensor, etc.

Example

Although an Example is given to the following and this invention was demonstrated more concretely, this invention is not limited by the following Example.

"%" And "part" in each synthesis example, each Example, and each comparative example are mass% and a mass part, unless there is particular notice. In the following synthesis examples, the compound was identified by mass spectrometry (LC; 1200 manufactured by Agilent, MASS; LC / MSD manufactured by Agilent).

Synthesis Example 1

20 parts of the compound represented by the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light shielding conditions, and the resulting solution was stirred at 110 ° C. for 6 hours. After cooling the obtained reaction liquid to room temperature, it added in the liquid mixture of 800 parts of water and 50 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour, and crystal | crystallization precipitated. The precipitated crystals were obtained as a residue of suction filtration and dried to obtain 24 parts of the compound represented by the formula (1-24). The yield was 80%.

Identification of Compounds Represented by Formula (1-24)

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 603.4

                        Exact Mass: 602.2

[Synthesis Example 2]

A compound represented by the formula (1-32) was obtained in the same manner as in Synthesis example 1 except that N-propyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

Identification of the compound represented by the formula (1-32)

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 659.9

                        Exact Mass: 658.9

[Synthesis Example 3]

Nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace with a nitrogen atmosphere, 300 parts of diethylene glycol ethylmethyl ether was added, and the mixture was heated to 85 ° C while stirring.

54 parts of methacrylic 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 -The mixed solution which melt | dissolved 306 parts of mixtures of monoacrylate and 24 parts of 2, 2- azobis (2, 4- dimethylvaleronitrile) in 316 parts of diethylene glycol ethyl methyl ether was dripped over 5 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours, cooled to room temperature, and measured by a B-type viscometer (23 ° C.). Hereinafter, it is called "resin C1 solution."

The produced copolymer (resin C1) was a weight average molecular weight (Mw) 7500 and molecular weight distribution 1.93.

[Synthesis Example 4]

Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was injected at 0.02 L / min to make a nitrogen atmosphere, 220 parts of diethylene glycol methylethyl ether was added, and heated to 70 ° C while stirring.

Subsequently, 75 parts of methacrylic acid, 110 parts of vinyltoluene, and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ² 315 parts of a mixture of ^{, 6} ] decane-9-ylacrylate was dissolved in 140 parts of diethylene glycol methylethyl ether to prepare a solution. This solution was dripped in the flask kept at 70 degreeC over 4 hours using the dropping funnel.

On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 95 parts of diethylene glycol methyl ethyl ether was put into the flask over 4 hours using the other dropping funnel. It dripped. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature, whereby the weight average molecular weight (Mw) was 10.7 × 10 ³ , the molecular weight distribution was 2.04, the solid content was 37.7%, the solution A resin C2 solution having an acid value of 43 mgKOH / g (an acid value in terms of solid content is 115 mgKOH / g) was obtained.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of resin obtained by the synthesis example 3 and the synthesis example 4 was performed on condition of the following using GPC method.

Device; K2479 [manufactured by Shimadzu Seisakusho Corporation]

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

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.

≪ Example 1 >

[Preparation of Colorant Dispersion Liquid 1]

Dyes (A1); 0.48 parts of a compound represented by the formula (1-32)

Colored pigment (A2); C.I. Pigment Blue 15: 6

Extender pigments (A '); Barium sulfate 2.88 parts

Acrylic dispersants [Disperbyk® 2000; Big Chemistry Co.] 3.84

Resin C2 Part 2.88

Solvent (B-1); Propylene glycol monomethyl ether acetate 55.04 parts

Solvent (B-2); 4-hydroxy-4-methyl-2-pentanone 5.76 parts

And 360 parts of 0.2 mm diameter zirconia beads were placed in a 140 ml mayonnaise bottle, kneaded at 60 ° C. for 10 hours with a paint conditioner, and dispersed. Thereafter, zirconia beads were removed and a dispersion was obtained. The dispersion was filtered with a membrane filter having a pore size of 1.0 μm to obtain a colorant dispersion 1.

<Example 2>

[Preparation of Colored Curable Composition]

The following components were mixed and the colored curable composition was obtained.

Colorant dispersion 1 196.6 parts

Resin (C '); Resin C1 50 parts

Polymerizable compound (E); Dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 50 parts

Polymerization initiator (F); 2-methyl-2-morpholino-1- (4-methylsulfanylfe

Nil) propane-1-one [Irgacure® 907; Manufactured by BASF Corporation; Alkylphenone Compound] 5 parts

Polymerization initiator (F); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure® OXE01; Manufactured by BASF Corporation; Oxime compound] 10 parts

Polymerization initiation aid (F1); 2,4-diethyl thioxanthone [KAYACURE® DETX; Nihon Kayaku Co., Ltd. product; Thioxanthone compound] 2 parts

Leveling agent (G); Polyether modified silicone oils [Toray Silicone SH8400; Toray Dow Corning Co., Ltd.] 0.2 parts

Solvent (B '); Propylene glycol monomethyl ether acetate 498 parts

&Lt; Comparative Example 1 &

[Preparation of Colorant Dispersion Liquid 2]

Dyes (A1); 0.48 parts of a compound represented by the formula (1-32)

Colored pigment (A2); C.I. Pigment Blue 15: 6 (pigment) 9.12

Acrylic dispersants [Disperbyk® 2000; Big Chemistry Co.] 3.84

Resin C2 Part 2.88

Solvent (B-1); Propylene glycol monomethyl ether acetate 49.28 parts

Solvent (B-2); 4-hydroxy-4-methyl-2-pentanone14.40part

And 360 parts of 0.2 mm diameter zirconia beads were placed in a 140 ml mayonnaise bottle, and kneaded at 60 ° C. for 10 hours with a paint conditioner to carry out dispersion treatment. Thereafter, zirconia beads were removed and a dispersion was obtained. The dispersion was filtered with a membrane filter having a pore size of 1.0 μm to obtain a colorant dispersion 2.

Comparative Example 2

[Preparation of Colored Curable Composition]

The following components were mixed and the colored curable composition was obtained.

Colorant dispersion 2 185.4 parts

Resin (C '); Resin C1 50 parts

Polymerizable compound (E); Dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 50 parts

Polymerization initiator (F); 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one [Irgacure® 907; Manufactured by BASF Corporation; Alkylphenone Compound] 5 parts

Polymerization initiator (F); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure® OXE01; Manufactured by BASF Corporation; Oxime compound] 10 parts

Polymerization initiation aid (F1); 2,4-diethyl thioxanthone [KAYACURE® DETX; Nihon Kayaku Co., Ltd. product; Thioxanthone compound] 2 parts

Leveling agent (G); Polyether modified silicone oils [Toray Silicone SH8400; Toray Dow Corning Co., Ltd.] 0.2 parts

Solvent (B '); Propylene glycol monomethyl ether acetate 455 parts

&Lt; Comparative Example 3 &

[Preparation of Colored Curable Composition]

The following components were mixed and the colored curable composition was obtained.

Colorant dispersion 2 212.5 parts

Sieving Pigment Dispersion 23.9Parts

Resin (C '); Resin C1 50 parts

Polymerizable compound (E); Dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 50 parts

Polymerization initiator (F); 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one [Irgacure® 907; Manufactured by BASF Corporation; Alkylphenone Compound] 5 parts

Polymerization initiator (F); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure® OXE01; Manufactured by BASF Corporation; Oxime compound] 10 parts

Polymerization initiation aid (F1); 2,4-diethyl thioxanthone [KAYACURE® DETX; Nihon Kayaku Co., Ltd. product; Thioxanthone compound] 2 parts

Leveling agent (G); Polyether modified silicone oils [Toray Silicone SH8400; Toray Dow Corning Co., Ltd.] 0.2 parts

Solvent (B '); Propylene glycol monomethyl ether acetate 490 parts

&Lt; Comparative Example 4 &

[Preparation of Colored Curable Composition]

The following components were mixed and the colored curable composition was obtained.

Colorant dispersion 2 212.5 parts

Sieving pigment dispersion 47.8parts

Resin (C '); Resin C1 50 parts

Polymerizable compound (E); Dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 50 parts

Polymerization initiator (F); 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one [Irgacure® 907; Manufactured by BASF Corporation; Alkylphenone Compound] 5 parts

Polymerization initiator (F); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure® OXE01; Manufactured by BASF Corporation; Oxime compound] 10 parts

Polymerization initiation aid (F1); 2,4-diethyl thioxanthone [KAYACURE® DETX; Nihon Kayaku Co., Ltd. product; Thioxanthone compound] 2 parts

Leveling agent (G); Polyether modified silicone oils [Toray Silicone SH8400; Toray Dow Corning Co., Ltd.] 0.2 parts

Solvent (B '); Propylene glycol monomethyl ether acetate 481 parts

However, the extender pigment dispersion was prepared as follows.

(Preparation of extender pigment dispersion)

Extender pigments (A '); Barium sulfate 12.8 parts

Acrylic dispersants [Disperbyk® 2000; Big Chem Co., Ltd.] 4.48

Resin C2 part 3.58

Solvent (B-1); Propylene glycol monomethyl ether acetate 47.14 parts

Solvent (B-2); 4-hydroxy-4-methyl-2-pentanone12.0parts

The mixed pigment dispersion was obtained by mixing and dispersing the pigment sufficiently using a bead mill.

&Lt; Comparative Example 5 &

[Preparation of Colorant Dispersion Liquid 3]

Dyes (A1); 0.48 parts of a compound represented by the formula (1-32)

Colored pigment (A2); C.I. Pigment Blue 15: 6 (pigment) 9.12

Acrylic dispersants [Disperbyk® 2000; Big Chemistry Co., Ltd.] 3.84

Resin C2 Part 2.88

Solvent (B-1); Propylene glycol monomethyl ether acetate 63.68 parts

And 360 parts of 0.2 mm diameter zirconia beads were placed in a 140 ml mayonnaise bottle, kneaded at 60 ° C. for 10 hours as a paint conditioner, and dispersed. Thereafter, zirconia beads were removed and a dispersion was obtained. This dispersion liquid was filtered with the membrane filter of 1.0 micrometer of pore diameters, and the coloring agent dispersion liquid 3 was obtained.

Since the obtained coloring agent dispersion 3 had bad fluidity | liquidity and viscosity stability was not ensured, preparation of the colored curable composition was impossible.

[Production of Color Filter (Coloring Pattern)]

After apply | coating a colored curable resin composition by the spin coat method on the square glass substrate (Eagle XG; Corning Corporation make) one side is 2 inches, it prebaked at 100 degreeC for 3 minutes, and formed the composition layer. After cooling, the interval between the composition layer on the substrate and the quartz glass photomask having the pattern was set to 100 m, and an exposure machine [TME-150RSK; Topcon Co., Ltd.] was irradiated with light at an exposure dose (365 nm standard) of 40 mJ / cm 2 under an air atmosphere. In addition, as a photomask, the mask in which the line-and-space pattern of 100 micrometers of line widths was formed was used.

After light irradiation, the obtained coating film was immersed and developed for 25 seconds at 25 degreeC for 70 second in the aqueous developing solution containing 0.12% of nonionic surfactant and 2% of sodium carbonate, and after water washing, it post-baked at 230 degreeC for 20 minutes in an oven, and color A filter was obtained.

[Film thickness measurement]

For the color filter formed on the glass substrate, the film thickness was measured by a film thickness measuring apparatus [DEKTAK3; Nippon Shinkujuju Co., Ltd. product] was used for the measurement. The results are shown in Table 1.

[Color evaluation]

For a color filter formed on a glass substrate, a colorimeter [OSP-SP-200; Spectrophotometry was measured using Olympus Co., Ltd., and the xy chromaticity coordinates (x, y) and tristimulus values (Y) in the XYZ colorimeter of CIE were measured using the isochromat function of the C light source. The larger the value of Y, the higher the brightness. The results are shown in Table 1.

[Contrast Evaluation]

Except not exposing and using a photomask, except having not developed, the operation similar to manufacture of a color filter (coloring pattern) was performed, and the color filter (color coating film) was produced on the glass substrate. About the color filter (color coating film) on the obtained glass substrate, a blank value was set to 30000 using the contrast colorimeter (CT-1; Tsubasaka Denki Co., Ltd. detector, BM-5A, light source; F-10). Contrast was measured. What sandwiched the colored coating film on a glass substrate between polarizing films (POLAX-38S; Lukeo Co., Ltd.) was used as the measurement sample. The results are shown in Table 1.

From the above result, it was confirmed that the color filter formed from the colored curable composition obtained from the coloring agent dispersion liquid of this invention is excellent in brightness and contrast.

The color filter (comparative example 2) formed from the colored curable composition which does not contain a extender pigment has a low contrast, and even if it contains a extender pigment, the coating film formed from the colored curable composition obtained without using the coloring agent dispersion liquid of this invention ( In Comparative Example 3 and Comparative Example 4), both contrast and lightness were low.

By the colored curable composition obtained from the coloring agent dispersion liquid of this invention, a high contrast color filter can be manufactured.

Claims (9)

It is made by disperse | distributing a coloring agent, a sieving pigment, and a dispersing agent to a solvent,
As a colorant, including dyes and colored pigments,
As the solvent, a solvent having higher polarity than propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, and the content of the propylene glycol monomethyl ether acetate is 40% by mass or more and 99% by mass with respect to the total amount of the solvent. Is less than
The coloring agent dispersion liquid which is higher polar solvent than the said propylene glycol monomethyl ether acetate is 4-hydroxy-4-methyl- 2-pentanone. The coloring agent dispersion liquid of Claim 1 whose mass ratio (total amount of dye: total amount of a coloring pigment and a sieving pigment) of the total amount of dye and the total amount of a coloring pigment and an extender pigment is 1: 99-99: 1. The colorant dispersion liquid according to claim 1 or 2, wherein the dye is a dye having a xanthene skeleton. delete delete The colorant dispersion according to claim 1 or 2, further comprising a resin. The coloring curable composition containing the coloring agent dispersion liquid of Claim 1 or 2, a polymeric compound, and a polymerization initiator. The color filter formed from the colored curable composition of Claim 7. The display apparatus containing the color filter of Claim 8.