JP2015086380A - Colored curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable resin composition from which a color filter having high lightness and good contrast can be formed.SOLUTION: The colored curable resin composition comprises: a colorant (A) comprising a squarylium dye and at least one compound selected from C.I.Pigment Yellow 138, a green pigment, and a yellow dye; a resin (B); a polymerizable compound (C); a polymerization initiator (D); and a solvent (E). A color filter is formed from the colored curable resin composition.

Description

  The present invention relates to a colored curable resin composition and the like.

The colored curable resin composition is used, for example, for producing a color filter such as a liquid crystal display device.
For color filters, there is a demand for color filters with high transmittance and high brightness for the purpose of reducing power consumption. As green colorants used in such colored curable resin compositions, C . I. Pigment Green 58 is known (Patent Document 1, Non-Patent Document 1).

JP 2003-161827 A (Example 3)

DIC technical review no. 14/2008

  The color filter prepared from the above colored curable resin composition is not sufficiently satisfactory as a color filter of a display device such as a liquid crystal display device in terms of brightness and contrast.

The present invention provides the following [1] to [10].
[1] C.I. I. Pigment Yellow 138, a colorant (A) containing at least one selected from the group consisting of a green pigment and a yellow dye, a squarylium dye, a resin (B), a polymerizable compound (C), and a polymerization initiator ( A colored curable resin composition comprising D) and a solvent (E).
[2] C.I. I. Pigment Yellow 138, at least one selected from the group consisting of green pigments and yellow dyes is C.I. I. The colored curable resin composition according to [1], which is CI Pigment Yellow 138.
[3] C.I. I. The colored curable resin composition according to [1], wherein at least one selected from the group consisting of CI Pigment Yellow 138, a green pigment, and a yellow dye is a yellow dye.
[4] A coating film formed from the colored curable resin composition according to any one of [1] to [3]. [5] A color filter formed from the colored curable resin composition according to any one of [1] to [3].
[6] A display device including the color filter according to [5].

  Since the color filter prepared from the colored curable resin composition of the present invention has high brightness and good contrast, it is excellent as a color filter for a display device such as a liquid crystal display device.

The colored curable resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).
<Colorant (A)>
The colorant (A) includes at least one selected from the group consisting of CI Pigment Yellow 138, a green pigment and a yellow dye, and a squarylium dye.

CI Pigment Yellow 138 is a pigment classified as a pigment by a color index represented by the following formula (published by The Society of Dyers and Colorists).

  As a green pigment, C.I. is classified as a pigment in the color index (published by The Society of Dyers and Colorists). I. Pigment Green 1 (hereinafter, CI Pigment Green is omitted and only the number is described), 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26 36, 45, 48, 50, 51, 54, 55, 58 and the like. Especially, C.I. I. Pigment Green 58 is preferable.

  The yellow dye is C.I. in the Color Index (published by The Society of Dyers and Colorists). I. Solvent Yellow, C.I. I. Acid Yellow, C.I. I. Direct yellow, C.I. I. Examples include compounds classified as modern yellow, coumarin dyes, metal-containing azo dyes, pyridone azo dyes, barbiturazo dyes, quinophthalone dyes, methine dyes, and cyanine dyes.

Specifically, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;
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. 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. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

Examples of the coumarin dye include the following.

Examples of metal-containing azo dyes include the following.

Examples of pyridone azo dyes include the following.

Examples of barbiturazo dyes include the following.

Examples of the quinophthalone dye include the following.

Examples of methine dyes include the following.

Examples of cyanine dyes include the following.

  As the yellow dye, a coumarin dye, a metal-containing azo dye, a pyridone azo dye, a barbiturazo dye, a quinophthalone dye, a methine dye, and a cyanine dye are preferable.

  The colorant (A) contains a squarylium dye. As a squarylium dye used by this invention, it does not specifically limit but a well-known thing can be used, For example, the compound as described in Unexamined-Japanese-Patent No. 2013-76926 etc. are mentioned.

式（ＡＩＩ）中、Ｒ^１〜Ｒ⁴は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基、置換基を有していてもよいフェニル基又は炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｒ^５〜Ｒ^８は、それぞれ独立に、水素原子、ヒドロキシ基、メルカプト基、炭素数１〜５のアルコキシ基（例えば、メトキシ基、エトキシ基、ブトキシ基等）またはトリフルオロメチル基を表す。
Ｒ^９〜Ｒ^１２は、それぞれ独立に、炭素数１〜２０の１価の飽和炭化水素基を表し、該１価の飽和炭化水素基に含まれる水素原子は、ハロゲン原子、シアノ基、カルバモイル基、スルファモイル基、ヒドロキシ基又はアミノ基で置換されていてもよく、該飽和炭化水素基を構成する炭素原子間に、酸素原子または硫黄原子が挿入されていてもよい。 Specific examples include compounds represented by the following formula.

In formula (AII), R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a phenyl group which may have a substituent, or a monovalent saturated hydrocarbon having 1 to 20 carbon atoms. Represents a group.
R ^{5 to} R ⁸ each independently represents a hydrogen atom, a hydroxy group, a mercapto group, an alkoxy group having 1 to 5 carbon atoms (for example, a methoxy group, an ethoxy group, or a butoxy group) or a trifluoromethyl group.
R ^{9 to} R ¹² each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the monovalent saturated hydrocarbon group is a halogen atom, a cyano group, or a carbamoyl group. , May be substituted with a sulfamoyl group, a hydroxy group or an amino group, and an oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated hydrocarbon group.

で表される基をＸ^１、

で表される基をＸ^２としたとき、Ｘ^１およびＸ^２で表される基としては、例えば、式（Ａ２−１）〜（Ａ２−７）で表される基が挙げられる。＊は、炭素原子との結合の手を表す。

In formula (AII):

A group represented by X ¹ ,

When the group represented by the set to ^{X 2,} the group represented by ^{X 1} and ^{X 2,} for example, groups represented by the formula (A2-1) ~ (A2-7). * Represents a bond to a carbon atom.

Furthermore, group represented by Formula (A3-1)-(A3-6) is mentioned. * Represents a bond to a carbon atom.

  Examples of the compound represented by the formula (AII) include compounds (AII-1) to (AII-14) shown in Table 1 below, but are not limited thereto.

  From the viewpoint of raw material availability, compound (AII-1) to compound (AII-7) are preferable, and compound (AII-2) is more preferable.

  Furthermore, examples of the compound represented by the formula (AII) include compounds (AII-15) to (AII-68) shown in Table 2 and Table 3 below, but are not limited thereto.

  From the viewpoint of raw material availability, the compound (AII-16), the compound (AII-23), the compound (AII-29), and the compound (AII-62) are preferable, and among them, the compound (AII-23) and the compound (AII- 29) is more preferable.

  As a method for producing compound (AII), for example, a method described in JP-A No. 2002-363434, produced by a reaction between an amine derivative and squaric acid (3,4-dihydroxy-3-cyclobutene-1,2dione). can do.

  In the colorant (A), C.I. I. The ratio of at least one selected from the group consisting of CI Pigment Yellow 138, a green pigment and a yellow dye and the content of the squarylium dye is preferably 60:40 to 99.9: 0.1 on a mass basis, and 70: More preferably, it is 30-99: 1. With this ratio, the color filter formed from the colored curable resin composition containing the colorant (A) has high brightness and good contrast.

  Furthermore, in the colorant (A), the content of the squarylium dye is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and more preferably 85 to 100% by mass with respect to the total amount of the dye. % Is more preferable.

  The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and further preferably 10 to 50% by mass with respect to the total amount of the solid content. When the content of the colorant (A) is within the above range, the color density when it is used as a color filter is sufficient, and the resin (B) and the polymerizable compound (C) are contained in a necessary amount in the composition. Therefore, a pattern with sufficient mechanical strength can be formed. Here, the “total amount of solid content” in this specification refers to an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

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

Specific examples of (Ba) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(Bb) is, for example, a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (Bb) 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” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (Bb) include a monomer having an oxiranyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, and a tetrahydrofuryl group and an ethylenically unsaturated bond. And monomers.

  (Bb) is preferably a monomer having an oxiranyl group and an ethylenically unsaturated bond from the viewpoint that the color filter to be obtained can have higher reliability such as heat resistance and chemical resistance. .

Examples of (Bc) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) ) (In the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) Cyclo [5.2.1.0 ^{2, 6]} decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
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, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance. preferable.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6. ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- ( Resin [K2] such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / Glycidyl (meth) acrylate was added to resin [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer such as (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer Resin, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic Resins such as resins obtained by adding glycidyl (meth) acrylate to an acid copolymer [K4]; resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid , Tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin [K5] such as a resin obtained by reacting a copolymer with (meth) acrylic acid; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid Furthermore, resin [K6] such as a resin obtained by reacting tetrahydrophthalic anhydride may be used.
Especially, as resin (B), resin [K1] and resin [K2] are preferable.

For example, the resin [K1] is a method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the document. Can be produced with reference to the cited references described in 1.
Yes.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction is used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern 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 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and still more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

  Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to the total amount of solid content, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the remaining film rate tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Is a (meth) acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, 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 dipentaerythritol hexa (meth) acrylate, etc. Is mentioned.
Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

  The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, more preferably from 250 to 1,500.

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of the solid content. is there. When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.
<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator that generates an active radical include an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound.

  Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among these, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. When these O-acyloxime compounds are used, a color filter with high brightness tends to be obtained.

  Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane. -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-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl -1- (4-Isopropenylphenyl) propan-1-one oligomer, α, α-diethoxyacetophenone, benzyldi And methyl ketal. Commercial products such as Irgacure (registered trademark) 369, 907, 379 (above, manufactured by BASF) may be used.

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

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trial Xylphenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), a phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913).

  Examples of the polymerization initiator that generates an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxy Onium salts such as phenyl, methyl, benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl Tosylate, benzoin tosylate and the like can be mentioned.

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.

  The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an O-acyl oxime compound, an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, and a biimidazole compound. More preferred is a polymerization initiator containing a sulfur compound.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter is improved.
<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- A solvent not containing CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

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

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

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

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

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

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

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

  Among the above solvents, an organic solvent having a boiling point of 120 ° C. or more and 210 ° C. or less at 1 atm is preferable from the viewpoints of coating properties and drying properties. Solvents include 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, 4-hydroxy-4-methyl-2-pentanone And N, N-dimethylformamide is preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N, N-dimethylformamide, N-methylpyrrolidone, and ethyl 3-ethoxypropionate are more preferred.

  Content of a solvent (E) becomes like this. Preferably it is 70-95 mass% with respect to the total amount of the colored curable resin composition of this invention, More preferably, it is 75-92 mass%. In other words, the total amount of 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 range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. .

<Other ingredients>
The colored curable resin composition of the present invention may contain other dyes and pigments in the colorant (A).

Other dyes include dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes and sulfonamides of acid dyes, and are classified as dyes by the Color Index (published by The Society of Dyers and Colorists), for example. And known dyes described in Dyeing Notes (Color Dyeing). These dyes may be used alone or in combination of two or more.
Specifically, C.I. I. Solvent Orange 2, 7, 11, 15, 26, 56, etc. I. Solvent dyes;
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, etc. I. Acid dyes;
C. I. Direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, etc. I. Direct dyes; C.I. 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, etc. I. Modern dyes may be mentioned.

The pigment is not particularly limited, and a known pigment can be used. Examples thereof include pigments classified as pigments according to a color index (published by The Society of Dyers and Colorists).
Specifically, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 139, 147, Yellow pigments such as 148, 150, 153, 154, 166, 173, 194, 214;
C. I. And orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73.

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

  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.), Solsperse (manufactured by Geneca Corporation), EFKA (registered trademark) (manufactured by BASF), Examples include Ajisper (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemie).

  The colored curable resin composition of the present invention, if necessary, a polymerization initiation aid, leveling agent, filler, other polymer compound, adhesion promoter, antioxidant, light stabilizer, chain transfer agent, etc. Additives known in the art may be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and a leveling agent as necessary. It can be prepared by mixing (F) and other components such as a polymerization initiation aid.
The dye may be previously dissolved in part or all of the solvent (E) to prepare a solution.
The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.
The pigment is preferably mixed in advance with part or all of the solvent (E) and dispersed using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.1 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited, and can be adjusted as appropriate according to the purpose and application. ~ 6 μm.

  As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern 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. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed.
As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

  Furthermore, it is preferable to post-bake the obtained colored pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

  According to the colored curable resin composition of the present invention, a color filter having particularly excellent brightness can be produced. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.
In the following synthesis examples, the compound was identified by NMR (JNM-EX-270; manufactured by JEOL Ltd.).

Synthesis Example 1: Synthesis of compound represented by formula (AII-16)

18.7 parts of N, N-dibutylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.6 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.), 1 -542.3 parts of butanol and 362.6 parts of toluene were mixed. The resulting mixture was stirred at 125 ° C. for 5 hours while removing water produced using a Dean-Stark tube. After completion of the reaction, the solvent was distilled off, a small amount of toluene was added, 200 parts of water was added, and the aqueous layer was discarded. The operation of washing with water was repeated twice, 100 parts of hexane was added, and the precipitated solid was collected by filtration. The solid collected by filtration was dispersed in 10 parts of tetrahydrofuran and filtered, and then the solid was washed with 20 parts of tetrahydrofuran and then with 50 parts of hexane. The obtained solid was dried under reduced pressure at 60 ° C. for 24 hours to obtain 3.94 parts of a compound represented by the formula (AII-16).

¹ H-NMR (270 MHz, δ value (ppm, TMS standard), CDCl ₃ ) of the compound represented by the formula (AII-16)
δ 0.98 (t, 12H), 1.40 (m, 8H), 1.61 (m, 8H), 3.44 (t, 8H), 6.70 (d, 2H), 8.35 ( d, 2H)

Synthesis Example 2: Synthesis of compound represented by formula (AII-23)

5.4 parts of N, N-dibutyl-3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.) 7 parts, 200.7 parts of 1-butanol and 134.1 parts of toluene were mixed. The resulting mixture was stirred at 125 ° C. for 5 hours while removing water produced using a Dean-Stark tube.
After completion of the reaction, the solvent was distilled off, a small amount of toluene was added, 100 parts of water was added, and the aqueous layer was discarded. The operation of washing with water was repeated twice, 50 parts of hexane was added, and the precipitated solid was collected by filtration. The solid collected by filtration was dispersed in 5 parts of tetrahydrofuran and filtered, and then the solid was washed with 10 parts of tetrahydrofuran and then with 25 parts of hexane. The obtained solid was dried under reduced pressure at 60 ° C. for 24 hours to obtain 3.23 parts of a compound represented by the formula (AII-23).

¹ H-NMR (270 MHz, δ value (ppm, TMS standard), CDCl ₃ ) of the compound represented by the formula (AII-23)
δ 0.96 (t, 12H), 1.35 (m, 8H), 1.61 (m, 8H), 3.37 (t, 8H), 6.10 (d, 2H), 6.30 ( dd, 2H), 7.86 (d, 2H), 12.07 (s, 2H)

Synthesis Example 3: Synthesis of compound represented by formula (AII-62)

2.5 parts of 3-ethoxy-N, N-diethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.) 0. 7 parts, 10-parts of 1-butanol and 55.7 parts of toluene were mixed. The resulting mixture was stirred at 125 ° C. for 5 hours while removing water produced using a Dean-Stark tube. After completion of the reaction, the solvent was distilled off, a small amount of toluene was added, 50 parts of water was added, and the aqueous layer was discarded. The operation of washing with water was repeated twice, 25 parts of hexane was added, and the precipitated solid was collected by filtration.
The solid collected by filtration was dispersed in 3 parts of tetrahydrofuran and filtered, and then the solid was washed with 4 parts of tetrahydrofuran and then 10 parts of hexane. The obtained solid was dried under reduced pressure at 60 ° C. for 24 hours to obtain 0.95 part of a compound represented by the formula (AII-62).

¹ H-NMR of compound represented by formula (AII-62) (270 MHz, δ value (ppm, TMS standard), DMSO-d8)
δ 1.16 (t, 12H), 1.42 (t, 6H), 3.52 (q, 8H), 4.12 (q, 4H), 6.15 (s, 2H), 6.48 ( dd, 2H), 8.54 (d, 2H)

Synthesis example 4
In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and gas introduction tube, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was added while stirring. Heated to ° C. Then 36 parts of acrylic acid; and 4,5-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate {ie monomer (BI-1)} and 3,4-epoxytri Cyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate {ie monomer (BII-1)} mixture {monomer (BI-1) in mixture: monomer (BII -1) molar ratio = 50: 50} 264 parts; was dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a monomer solution. The monomer solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel. On the other hand, a polymerization initiator solution in which 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts of propylene glycol monomethyl ether acetate was added for 4 hours using another dropping funnel. And dropped into the flask. After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours, and then cooled to room temperature, weight average molecular weight Mw: 9000, molecular weight distribution: 2.0, solid content 33%, solid content acid value 90 mg. A resin B1 solution of -KOH / g was obtained.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Examples 1-6, Comparative Examples 1 and 2
<Preparation of colored photosensitive resin composition>
Each component was mixed so that it might become a composition shown in Table 4, and the colored photosensitive resin composition was obtained.

In Table 4, each component represents the following. Moreover, resin (B) showed the mass part of solid content conversion.
Dye: A-1-1: Compound represented by formula (AII-16) Dye: A-1-2: Compound represented by formula (AII-23) Dye: A-1-3: Formula (AII-) 62) Pigment: A-2-1: C.I. I. Pigment Yellow 138
Pigment: A-2-2: C.I. I. Pigment Green 58 (FASTOGEN (registered trademark) Green A110; manufactured by DIC Corporation)
Pigment: A-2-3: Pigment Yellow 150
Resin (B): Resin B1
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): N-1919 (manufactured by ADEKA; O-acyloxime compound)
Solvent (E): E-1: Propylene glycol monomethyl ether acetate Solvent (E): E-2: N-methylpyrrolidone Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.) Made)

<Preparation of colored coating film>
On a 5 cm square glass substrate (Eagle XG; manufactured by Corning), the colored curable resin composition was applied by spin coating so that the film thickness after post-baking was 2.2 μm, and then 3 ° C. at 100 ° C. Pre-baked for a minute. After standing to cool, light exposure was performed using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) in an air atmosphere at an exposure amount of 60 mJ / cm ² (based on 365 nm). After light irradiation, post-baking was performed in an oven at 160 ° C. for 20 minutes to obtain a colored coating film.

<Film thickness measurement>
About the obtained colored coating film, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Table 2.

<Chromaticity evaluation>
About the obtained colored coating film, spectrum was measured using a colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity in the XYZ color system of CIE using the characteristic function of the C light source. The coordinates (x, y) and the tristimulus value Y were measured. The larger the value of Y, the higher the brightness.
The results are shown in Table 5.

<Contrast measurement>
About the obtained colored coating film, contrast was measured by using a contrast colorimeter (CT-1; manufactured by Aisaka Electric Co., Ltd .; detector: BM-5A, light source: F-10) with a blank value of 30000. A measurement sample was obtained by sandwiching the glass substrate on which the coating film was formed with a polarizing film (POLAX-38S; manufactured by Luceo Co., Ltd.). The results are shown in Table 5.

  From the above results, it was confirmed that the colored pattern formed from the colored curable resin composition of the present invention was excellent in brightness and contrast. From this, it is understood that a display device having excellent color performance can be produced by using a color pattern formed from the colored curable resin composition of the present invention as a color filter.

  The colored curable resin composition of the present invention is excellent as a colored curable resin composition used for a color filter of a display device such as a liquid crystal display device, because the color filter prepared therefrom has high brightness and good contrast.

Claims (6)

  C. I. Pigment Yellow 138, a colorant (A) containing at least one selected from the group consisting of a green pigment and a yellow dye, a squarylium dye, a resin (B), a polymerizable compound (C), and a polymerization initiator (D ) And a solvent (E).   C. I. At least one selected from the group consisting of CI Pigment Yellow 138, a green pigment and a yellow dye; I. The colored curable resin composition according to claim 1, which is CI Pigment Yellow 138.   C. I. The colored curable resin composition according to claim 1, wherein at least one selected from the group consisting of CI Pigment Yellow 138, a green pigment, and a yellow dye is a yellow dye.   The coating film formed from the colored curable resin composition in any one of Claims 1-3.   The color filter formed from the colored curable resin composition in any one of Claims 1-3.   A display device comprising the color filter according to claim 5.