KR20210012024A - Colored curable resin composition - Google Patents

Abstract

The present invention is to provide a colored curable resin composition comprising: one or more kinds of colorants (A1) selected from the group of C.I. pigment yellow 138, a green pigment and a yellow pigment, a squarylium dye (A2), a resin (B), a polymer compound (C), a polymerization initiator (D) and a solvent (E). A color filter made of the colored curable resin composition of the present invention has high brightness and good contrast.

Description

Colored curable resin composition TECHNICAL FIELD

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

The colored curable resin composition is used, for example, to manufacture a color filter such as a liquid crystal display device.

As a green colorant used in such a colored curable resin composition, C.I. Pigment green 58 and squarylium dye are known (Japanese Patent Laid-Open No. 2003-161827, DIC TECHNICAL REVIEW NO. 14/2008).

Regarding squarylium dyes, Japanese Patent Laid-Open Digestion No. 60-169453 describes a compound represented by the formula (II-0-1), and Japanese Patent Laid-Open Digestion No. 60-248652 discloses a formula (II- The compound represented by 0-2) is described.

The present invention provides the following [1] to [10].

[1] C.I. Pigment Yellow 138, at least one colorant (A1) selected from the group consisting of a green pigment and a yellow dye,

Squarylium dye (A2),

With resin (B),

A polymerizable compound (C),

A polymerization initiator (D),

Solvent (E)

A colored curable resin composition comprising a.

[2] As the colorant (A1), C.I. The colored curable resin composition according to [1] containing Pigment Yellow 138.

[3] The colored curable resin composition according to [1], containing a yellow dye as the coloring agent (A1).

[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 comprising the color filter according to [5].

[7] A compound represented by the formula (II-1).

[In the above formula, R ^1a to R ^4a each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atom or the methyl group contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group It may be done.

R ^5a and R ^6a each independently represent a hydrogen atom or a hydroxy group.

R ^7a and R ^8a each independently represent a monovalent saturated hydrocarbon group having 8 to 20 carbon atoms or a group represented by the formula (i-1).

In the above formula, R ^14a represents a C 1 to C 20 monovalent saturated hydrocarbon group or a C 2 to C 20 monovalent unsaturated hydrocarbon group, and m1 represents an integer of 1 to 5. When m1 is 2 or more, a plurality of R ^14a may be the same or different, respectively. * Represents the number of bonds to a carbon atom.

R ^9a to R ^12a each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by the formula (i-1). The hydrogen atom or the methyl group contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group It can be done.]

[8] A compound represented by the formula (II-2).

[In the above formula, R ^1b to R ^4b each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atom or the methyl group contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group It may be done.

R ^5b to R ^8b each independently represent a hydrogen atom or a hydroxy group.

Ar ^1b and Ar ^2b each independently represent a group represented by the formula (i-2).

In the above formula, R ^12b represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, and m2 represents an integer of 1 to 5. When m2 is 2 or more, a plurality of R ^12b may be the same or different, respectively. * Represents the number of bonds to the nitrogen atom.

R ^9b and R ^10b each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by formula (i-2). The hydrogen atom or the methyl group contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group It can be done.]

[9] A coloring agent containing the compound according to [7] or [8].

[10] A colored curable resin composition containing the compound according to [7] or [8], a resin, a polymerizable compound, a polymerization initiator, and a solvent.

[11] A coating film formed using the colored curable resin composition according to [10].

[12] A color filter formed using the colored curable composition according to [10].

[13] A display device comprising the color filter according to [12].

The colored curable resin composition of the present invention comprises the above coloring agent (A1), squarylium dye (A2), resin (B), polymerizable compound (C), polymerization initiator (D) and solvent (E). Include. Hereinafter, the said colored curable resin composition may be called "colored curable resin composition (1)".

<Coloring agent>

The colored curable resin composition (1), as a coloring agent (A), is C.I. Pigment Yellow 138, at least one colorant selected from the group consisting of a green pigment and a yellow dye (A1), and a squarylium dye (A2).

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

As a green pigment, C.I., classified as a pigment in the Color Index (published by The Society of Dyers and Colorists). Pigment Green 1 (hereinafter, the description of CI Pigment Green is omitted and only the number is indicated), 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45 , 48, 50, 51, 54, 55, 58, etc. are mentioned. Among them, C.I. Pigment Green 58 is preferred.

As a yellow dye, C.I. in the Color Index (published by The Society of Dyers and Colorists). Solvent Yellow, C.I. Acid Yellow, C.I. Direct Yellow, C.I. A compound classified as modern yellow, a coumarin dye, an alloy azo dye, a pyridone azo dye, a barbitur azo dye, a quinophthalone dye, a methine dye, and a cyanine dye are mentioned.

Specifically, C.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; And dyes such as.

Examples of coumarin dyes include the following dyes.

As an alloy azo dye, the following dyes are mentioned, for example.

Examples of the pyridone azo dye include the following dyes.

Barbitur azo dyes include, for example, the following dyes.

Examples of the quinophthalone dye include the following dyes.

Examples of methine dyes include the following dyes.

Examples of cyanine dyes include the following dyes.

As the yellow dye, a coumarin dye, an alloy azo dye, a pyridone azo dye, a barbitur azo dye, a quinophthalone dye, a methine dye and a cyanine dye are preferable, and a coumarin dye, a pyridone azo dye and a quinophthalone dye are more preferable. Do.

The colored curable resin composition (1) contains squarylium dye (A2) as a colorant.

The squarylium dye (A2) is not particularly limited, and a known squarylium dye, a compound represented by the formula (II-1) or formula (II-2) described later, and the like can be mentioned.

As specific examples of the squarylium dye (A2), the compound described in Japanese Patent Application Laid-Open No. 2013-76926, the compound represented by the general formula (AII), and tautomers thereof are mentioned.

(In the above formula, R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a phenyl group which may have a substituent, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

Each of R ⁵ to R ⁸ independently represents a hydrogen atom, a hydroxy group, a mercapto group, an alkoxy group having 1 to 5 carbon atoms, or a trifluoromethyl group.

R ⁹ to R ¹² each independently represent a C 1 to C 20 monovalent saturated hydrocarbon group, and the hydrogen atom contained in the monovalent saturated hydrocarbon group is a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, a hydroxy group, or an amino group. May be substituted with, or an oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the saturated hydrocarbon group.)

[In the above formula, R ^1a to R ^4a each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atom or the methyl group contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group It may be done.

R ^5a and R ^6a each independently represent a hydrogen atom or a hydroxy group.

R ^7a and R ^8a each independently represent a monovalent saturated hydrocarbon group having 8 to 20 carbon atoms or a group represented by the following formula (i-1).

In the above formula, R ^14a represents a C 1 to C 20 monovalent saturated hydrocarbon group or a C 2 to C 20 monovalent unsaturated hydrocarbon group, and m1 represents an integer of 1 to 5. When m1 is 2 or more, a plurality of R ^14a may be the same or different, respectively. * Represents the number of bonds to carbon atoms.

R ^9a to R ^12a each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by the formula (i-1). The hydrogen atom or the methyl group contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group It can be done.]

[In the above formula, R ^1b to R ^4b each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atom or the methyl group contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group It may be done.

R ^5b to R ^8b each independently represent a hydrogen atom or a hydroxy group.

Ar ^1b and Ar ^2b each independently represent a group represented by the following formula (i-2).

In the above formula, R ^12b represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, and m2 represents an integer of 1 to 5. When m2 is 2 or more, a plurality of R ^12b may be the same or different, respectively. * Represents the number of bonds to the nitrogen atom.

R ^9b and R ^10b each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by the formula (i-2). The hydrogen atom or the methyl group contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group. It may be done.]

The squarylium dye (A2) is preferably a compound represented by the general formula (AII). Hereinafter, the compound represented by the formula (AII) will be described in detail.

In the general formula (AII), examples of the halogen atom for R ¹ to R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Examples of the saturated hydrocarbon group for R ¹ to R ⁴ and R ⁹ to R ¹² include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, Straight chain alkyl groups having 1 to 20 carbon atoms such as hexadecyl group and icosyl group;

Branched alkyl groups having 3 to 20 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group;

And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.

Examples of the substituents that the phenyl group for R ¹ to R ⁴ may have include a halogen atom, a cyano group, a hydroxy group, and an amino group.

In formula (AII), it is preferable that R ¹ to R ⁴ each independently represent a hydrogen atom.

R ⁵ to R ⁸ are each independently preferably a hydrogen atom, a hydroxy group, or an alkoxy group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a hydroxy group, a methoxy group, or an ethoxy group.

It is preferable that R ⁹ to R ¹² are each independently an alkyl group having 1 to 10 carbon atoms (in the above alkyl group, a hydrogen atom may have a hydroxy group, and an oxygen atom may be inserted between carbon atoms).

In formula (AII),

The group represented by X ¹ ,

When a group represented by a X ^2, X ¹ or a group or groups represented by X ² is, for example represented by the formula (A2-1) ~ formula (A2-7), the formula (A3-1) ~ formula (A3- The group represented by 6) is mentioned. * Represents the number of bonds to carbon atoms.

As compounds represented by the formula (AII), compounds (AII-1) to compounds (AII-14) having substituents shown in Table 1, and compounds (AII-15) to compounds having substituents shown in Tables 2 and 3 Although (AII-68) can be mentioned, it is not limited to these.

[Table 2]

As the compound represented by the formula (AII), since it is easy to obtain raw materials, the compound (AII-1) to the compound (AII-7), the compound (AII-16), the compound (AII-23), and the compound (AII- 29) and compound (AII-62) are preferable, compound (AII-2), compound (AII-23), compound (AII-29) and compound (AII-62) are more preferable, and among them, compound (AII -2), compound (AII-23) and compound (AII-29) are more preferable.

As a method for preparing the compound represented by the formula (AII), for example, the method described in Japanese Patent Laid-Open No. 2002-363434, an amine derivative and a squaric acid (3,4-dihydroxy-3-cyclobutene-1, 2 dione) can be prepared by reaction.

In the colored curable resin composition (1), the ratio of the content of the coloring agent (A1) and the squarylium dye (A2) is preferably 60:40 to 99.9:0.1 by mass, and 70:30 to 99:1 It is more preferable that it is. If it is this ratio, the color filter formed from the colored curable resin composition (1) containing the colorant (A) has high brightness and good contrast.

In addition, in the colored curable resin composition (1), the content of the squarylium dye (A2) is preferably 70 to 100 mass%, more preferably 80 to 100 mass%, based on the total amount of the dye, It is more preferably 85 to 100% by mass.

The content of the colorant (A) is preferably 5 to 60 mass%, more preferably 8 to 55 mass%, and still more preferably 10 to 50 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 used as a color filter is sufficient, and since the required amount of the resin (B) or the polymerizable compound (C) can be contained in the composition, the mechanical strength is increased. A sufficient pattern can be formed. Here, the "total amount of solid content" in this specification means the amount excluding the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid content and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, but it is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1]; At least one (Ba) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "(Ba)"), cyclic ether structures having 2 to 4 carbon atoms, and ethylenically unsaturated bonds A copolymer with a monomer (Bb) (hereinafter sometimes referred to as "(Bb)");

Resin [K2]; A copolymer of (Ba) and (Bb) and a monomer (Bc) copolymerizable with (Ba) [however, it is different from (Ba) and (Bb)] [hereinafter sometimes referred to as "(Bc)"];

Resin [K3]; A copolymer of (Ba) and (Bc);

Resin [K4]; A resin obtained by reacting (Bb) with a copolymer of (Ba) and (Bc);

Resin [K5]; A resin in which (Ba) was reacted with a copolymer of (Bb) and (Bc);

Resin [K6]; A resin in which (Ba) was reacted with a copolymer of (Bb) and (Bc), and a carboxylic anhydride was further reacted.

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 Bicyclo unsaturated compounds containing a carboxyl group such as [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 dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;

Unsaturated mono[(meth)acryloyloxyalkyl] of divalent or more polyvalent carboxylic acids such as succinate mono[2-(meth)acryloyloxyethyl] and phthalate mono[2-(meth)acryloyloxyethyl] ]Esters;

and 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, and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an aqueous alkali solution.

(Bb) refers to a polymerizable compound having, for example, a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. . (Bb) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

In addition, in this specification, "(meth)acrylic acid" represents at least 1 type 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 monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond.

As (Bb), it is preferable that it is a monomer which has an oxiranyl group and ethylenically unsaturated bond from the point that reliability, such as heat resistance and chemical resistance, of the obtained color filter can be improved.

As (Bc), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2- Ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2- Methylcyclohexyl(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl(meth)acrylate (in this technical field, it is called "dicyclopentanyl(meth)acrylate" as a common name. In addition, it may be referred to as "tricyclodecyl(meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl(meth)acrylate (as a common name in the relevant technical field, "dicyclophene Tenyl (meth)acrylate"), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propar (Meth)acrylic acid esters such as gil (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;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxy ratio Cyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2 -Ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept -2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept- 2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxy Cycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxy Bicyclo unsaturated compounds such as cicarbonyl)bicyclo[2.2.1]hept-2-ene;

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

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

Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. are preferable from the viewpoint of copolymerization reactivity and heat resistance. Do.

As resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decylacrylate/(meth) Resins [K1] such as acrylic acid copolymers; 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-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer, etc. [K2]; Resin [K3], such as a benzyl (meth)acrylate/(meth)acrylic acid copolymer and a styrene/(meth)acrylic acid copolymer; A resin obtained by adding glycidyl (meth)acrylate to a benzyl (meth)acrylate/(meth)acrylic acid copolymer, and glycidyl (meth)acrylate in a tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer. ) Resins to which an acrylate was added, resins in which glycidyl (meth)acrylate was added to a tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer [K4]; Tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate resin reacted with (meth) acrylic acid, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin [K5], such as a resin in which (meth)acrylic acid was reacted with a copolymer; And resins [K6], such as a resin in which tetrahydrophthalic anhydride was further reacted with a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate. .

Especially, as resin (B), resin [K1] and resin [K2] are preferable.

For example, resin [K1] is the method described in the document "Experimental method of polymer synthesis" [by Takayuki Otsu, Hakkojo Co., Ltd., first edition, first edition, issued on March 1, 1972] and cited documents described in the document It can be manufactured with reference to.

In addition, as the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or one extracted as a solid (powder) by a method such as reprecipitation may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during polymerization, the solution after the reaction can be used as it is for preparing the colored curable resin composition of the present invention. The manufacturing process of can be simplified.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more 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 rate is high, the solubility in the developer of the unexposed portion 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, 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 required to neutralize 1 g of the resin (B), and can be obtained by titrating, for example, using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass with respect to the total amount of the solid content. When the content of the resin (B) is within the above-described range, a colored pattern can be formed, and the resolution and residual film rate of the colored pattern 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). Examples of the polymerizable compound (C) include compounds having a polymerizable ethylenically unsaturated bond, and a (meth)acrylic acid ester compound is preferable.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more 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, tripentaerythritolhepta (meth)acrylate, tetrapentaerythritol deca (meth)acrylate, tetrapentaerythritol nona (meth)acrylate, tris(2-( Meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, Propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like.

Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

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

The content of the polymerizable compound (C) is preferably 7 to 65 mass%, more preferably 13 to 60 mass%, and still more preferably 17 to 55 mass% with respect to the total amount of the solid content. When the content of the polymerizable compound (C) is within the above-described range, there is a tendency that the residual film rate at the time of forming the colored pattern and the chemical resistance of the color filter are improved.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization of the polymerizable compound (C) by generating active radicals, acids, etc. by the action of light or heat, and a known polymerization initiator can be used. .

As a polymerization initiator generating an active radical, an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound are mentioned, for example.

As the O-acyloxime compound, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane -1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl -6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3 -Dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methyl Benzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3 -Yl]-3-cyclopentylpropan-1-one-2-imine, and the like. Commercial items such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), and N-1919 (made by ADEKA) may be used. Among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) At least one selected from the group consisting of octan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferred, and , N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine is more preferable. With these O-acyloxime compounds, there is a tendency that a color filter with high brightness can be obtained.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 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-hydroxycyclohexyl Phenyl ketone, an oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethylketal. Commercial items such as Irgacure (registered trademark) 369, 907, 379 (above, manufactured by BASF) may be used.

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

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

As the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) )-4,4',5,5'-tetraphenylbiimidazole (refer to Japanese Patent Laid-Open Hei 6-75372, Japanese Patent Laid-Open Hei 6-75373, etc.), 2,2'-bis ( 2-Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)- 4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (refer to Japanese Patent Publication No. 48-38403, Japanese Patent Laid-Open No. 62-174204, etc.), 4,4', Imidazole compounds in which the phenyl group at the 5,5'-position is substituted by a carboalkoxy group (refer to Japanese Laid-Open Patent Publication No. 7-10913, etc.), and the like.

Examples of the acid-generating polymerization initiator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylsulfonium p- Toluenesulfonate, 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluene Onium salts, such as sulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoyl methylbenzoate, 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-ethylanthraquinone, and campaquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds, and the like.

As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound and a biimidazole compound is preferable, and O -A polymerization initiator containing an acyloxime compound is more preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above-described range, since there is a tendency that the sensitivity is increased and the exposure time is shortened, the productivity of the color filter is improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent commonly used in the field can be used. For example, an ester solvent (a solvent that contains -COO- in the molecule and does not contain -O-), an ether solvent (a solvent that contains -O- in the molecule and does not contain -COO-), 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 (containing OH in the molecule, -O- , A solvent not containing -CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

As ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyisobutanoate methyl, 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.

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 methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl and methylani And a brush.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and 3-ethoxypropionic acid Methyl, 3-ethoxy ethyl propionate, 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-methoxy propyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-methoxy-2 -Methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

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

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

As an aromatic hydrocarbon solvent, benzene, toluene, xylene, mesitylene, etc. are mentioned.

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

Among the above-described solvents, organic solvents having a boiling point at 1 atm of 120°C or more and 210°C or less are preferable from the viewpoint of coating properties and drying properties. As a solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethylpropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydre Roxy-4-methyl-2-pentanone and N,N-dimethylformamide are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N,N-dimethylformamide, N-methylpyrrolidone and Ethyl 3-ethoxypropionate is more preferred.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. 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 application is improved, and the color density is not insufficient when the color filter is formed, so that the display characteristics tend to be improved.

<Other ingredients>

The colored curable resin composition of the present invention may contain other dyes and pigments.

Other dyes include oil-soluble dyes, acid dyes, amine salts of acid dyes or sulfonamide derivatives of acid dyes. For example, dyes from The Society of Dyers and Colorists The compounds classified as and known dyes described in the dyeing notes (Shikisensha) are mentioned. These dyes may be used alone or in combination of two or more.

Specifically, C.I. Solvent Orange 2, 7, 11, 15, 26, 56, etc. 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. Acid dyes;

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

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

The pigment is not particularly limited, and a known pigment may be used, and examples thereof include pigments classified as pigments in the color index (published by The Society of Dyers and Colorists).

Specifically, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 139, 147 , 148, 150, 153, 154, 166, 173, 194, 214 and the like yellow pigments;

C.I. Orange pigments, such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, are mentioned.

Pigments, if necessary, rosin treatment; Surface treatment using a pigment derivative into which an acidic group or a basic group has been introduced; Graft treatment on the pigment surface with a polymer compound or the like; Atomization treatment by sulfuric acid atomization method or the like; Or washing treatment with an organic solvent or water to remove impurities; Removal treatment of ionic impurities by an ion exchange method or the like; The back may be done.

It is preferable that the pigment has a uniform particle size. By containing the pigment dispersant and performing the dispersion treatment, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

As the above-described pigment dispersant, surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic are mentioned. 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.], Solspurs [manufactured by Zeneka Co., Ltd.], EFKA (registered trademark) (BASF Co., Ltd.) Manufacturing), Azispur (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Vicchemy), and the like.

The colored curable resin composition of the present invention, if necessary, may contain additives known in the art, such as polymerization initiation aids, leveling agents, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc. good.

<Production method of colored curable resin composition>

The colored curable resin composition (1) of the present invention is a colorant (A1), a squarylium dye (A2), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and required According to the above, it can be prepared by mixing other components such as a leveling agent (F) and a polymerization initiation aid.

The dye may be previously dissolved in a part or all of the solvent (E) to prepare a solution. It is preferable to filter the solution with a filter having a pore diameter of about 0.01 to 1 µm.

The pigment is preferably mixed with a part or all of the solvent (E) in advance, and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 µm or less. At this time, if necessary, some or all of the pigment dispersant and the resin (B) may be blended. A desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion liquid thus obtained to a predetermined concentration.

It is preferable to filter the colored curable resin composition after mixing with a filter having a pore diameter of about 0.1 to 10 µm.

<Method of manufacturing color filters, etc.>

The coating film formed from the above-described colored curable resin composition, and the color filter formed from the above-described colored curable resin composition also fall within the scope of the present invention. A display device including the color filter also falls within the scope of the present invention.

As a method of producing a colored pattern from the colored curable resin composition (1), a photolithography method, an inkjet method, a printing method, and the like can be mentioned. Among them, the photolithography method is preferred. The photolithography 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 to develop. In the photolithography method, by not using a photomask at the time of exposure and/or not developing, a colored coating film that is a cured product of the colored composition layer can be formed. The colored pattern or colored coating film formed in this way is the color filter.

The film thickness of the color filter to be produced is not particularly limited, and can be appropriately adjusted according to the purpose or use, and is, for example, 0.1 to 30 µm, preferably 0.1 to 20 µm, and more preferably 0.5 to 6 µm.

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

The formation of each color pixel by the photolithography method can be performed with known or commonly used devices and conditions. For example, it can be manufactured as follows.

First, a colored curable resin composition is applied onto a substrate, followed by drying by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent and drying to obtain a smooth colored composition layer.

Examples of the coating method include a spin coating method, a slit coating method, and a slit and spin coating method.

The temperature in the case of heating and drying is preferably 30°C to 120°C, and more preferably 50°C to 110°C. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

In the case of drying under reduced pressure, it is preferable to carry out in a temperature range of 20°C to 25°C under a pressure of 50 to 150 Pa.

The film thickness of the colored composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the colored composition layer is exposed through a photomask for forming a desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.

As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light of less than 350 nm can be cut using a filter that cuts this wavelength region, or light in the vicinity of 436 nm, 408 nm, or 365 nm is extracted using a band pass filter that extracts these wavelength regions. It may be selectively extracted. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

It is preferable to use an exposure apparatus such as a mask aligner and a stepper because it is possible to uniformly irradiate parallel light rays on the entire exposure surface or to accurately align the photomask with the substrate on which the colored composition layer is formed.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By development, the unexposed part of the colored composition layer is dissolved in the developer and removed. As the developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or 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. In addition, the developer may contain a surfactant.

The developing method may be any of a puddle method, a dipping method, and a spray method. Further, the substrate may be tilted at an arbitrary angle during development.

After image development, it is preferable to wash with water.

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

According to the colored curable resin composition (1), a color filter having particularly excellent brightness can be produced. The color filter is useful as a color filter used in a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

<Compound represented by Formula (II-1)>

The compound represented by the formula (II-1) is a novel compound.

R ^1a to R ^4a each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atom or the methyl group contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group It may be done.

R ^5a and R ^6a each independently represent a hydrogen atom or a hydroxy group.

R ^7a and R ^8a each independently represent a monovalent saturated hydrocarbon group having 8 to 20 carbon atoms or a group represented by formula (i-1).

In the above formula, R ^14a represents a C 1 to C 20 monovalent saturated hydrocarbon group or a C 2 to C 20 monovalent unsaturated hydrocarbon group, and m1 represents an integer of 1 to 5. When m1 is 2 or more, a plurality of R ^14a may be the same or different, respectively. * Represents the number of bonds to carbon atoms.

R ^9a to R ^12a each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by the formula (i-1). The hydrogen atom or the methyl group contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group It can be done.]

In the present specification, formula (II-1) and formula (II-2) to be described later are each a concept including a tautomer.

Examples of the halogen atom for R ^1a to R ^4a include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

* Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^1a to R ^4a , R ^9a to R ^12a and R ^14a include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group , A linear alkyl group having 1 to 20 carbon atoms such as an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group and an icosyl group;

Branched alkyl groups having 3 to 20 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group;

And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.

Examples of the group in which the hydrogen atom or the methyl group contained in these saturated hydrocarbon groups is substituted with a halogen atom, a hydroxy group, or an alkylamino group having 1 to 8 carbon atoms include groups represented by the following formulas.

Examples of the alkylamino group having 1 to 8 carbon atoms include methylamino group, ethylamino group, n-propylamino group, n-butylamino group, n-pentylamino group, dimethylamino group, diethylamino group, and dibutylamino group.

(In each formula, * represents a binding site.)

As a group in which an oxygen atom or a sulfur atom is inserted between carbon atoms constituting these saturated hydrocarbon groups, a group represented by the following formula is exemplified.

(In each formula, * represents a binding site.)

In R ^7a and R ^8a , examples of the monovalent saturated hydrocarbon group having 8 to 20 carbon atoms include linear alkyl groups having 8 to 20 carbon atoms such as octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, and icosyl group;

2-methylheptyl group, 2-methyloctyl group, 2-methylnonyl group, 2-methyldecyl group, 2-methyldodecyl group, 2-methylhexadecyl group, 2-methylnonadecyl group, 2-ethylhexyl group, 2-ethylheptyl group, 2-ethyloctyl group, 2-ethylnonyl group, 2-ethyldecyl group, 2-ethyldodecyl group, 2-ethylpentadecyl group, 2-ethyloctadecyl group, 2-propylhexyl group, 2-propylheptyl group, 2-propyloctyl group, 2-propylnonyl group, 2-propyldecyl group, 2-propyldodecyl group, 2-propylheptadecyl group, 2-butylhexyl group, 2-pentylheptyl group, 2 -Hexyloctyl group, 2-heptylnonyl group, 2-octyldecyl group, 2-nonyldodecyl group, 3-methylheptyl group, 3-methyloctyl group, 3-methylnonyl group, 3-methyldecyl group, 3-methyl Dodecyl group, 3-methylhexadecyl group, 3-methylnonadecyl group, 3-ethylhexyl group, 3-ethylheptyl group, 3-ethyloctyl group, 3-ethylnonyl group, 3-ethyldecyl group, 3-ethyl Dodecyl group, 3-ethylpentadecyl group, 3-ethyloctadecyl group, 3-propylhexyl group, 3-propylheptyl group, 3-propyloctyl group, 3-propylnonyl group, 3-propyldecyl group, 3-propyl Dodecyl group, 3-propylheptadecyl group, 3-butylheptyl group, 3-pentyloctyl group, 3-hexylnonyl group, 3-heptyldecyl group, 3-octyldodecyl group, 2,2-dimethylhexyl group, 2, Branched alkyl groups having 8 to 20 carbon atoms such as 2-methylethylheptyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, and 2,5-dimethylhexyl group; Methylcyclooctyl group,

Cycloalkyl groups having 8 to 20 carbon atoms, such as an ethylcyclohexyl group, a propylcyclopentyl group, a butylcyclobutyl group, a pentylcyclopropyl group, and an adamantyl group; may be mentioned.

In R ^14a , examples of the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms include vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, and decenyl group. .

Examples of the group represented by the general formula (i-1) include the following groups. * Represents the number of bonds to carbon atoms.

As R ^1a to R ^4a , a hydrogen atom, a hydroxy group and a methyl group are preferable, and a hydrogen atom is more preferable.

As R ^7a and R ^8a , a linear alkyl group having 8 to 12 carbon atoms, a branched alkyl group having 8 to 16 carbon atoms, and a group represented by the formula (i-1) are preferable, and an octyl group, a nonyl group, a decyl group, a dodecyl group, a carbon number A branched alkyl group of 8 to 16 (especially a 2-ethylhexyl group) and a group represented by the formula (i-1) are more preferred, and a 2-ethylhexyl group and a group represented by the formula (i-1) are still more preferred. From the viewpoint of good solubility in a solvent, each of R ^7a and R ^8a is preferably a branched alkyl group having 8 to 16 carbon atoms.

As R ^9a to R ^12a , a C2-C20 alkyl group and a group represented by the formula (i-1) are preferable, and a C2-C8 alkyl group and a group represented by the formula (i-1) are more preferable.

As R ^14a , a C1-C4 alkyl group is preferable, and a methyl group and an ethyl group are more preferable.

In formula (II-1),

The group represented by X ^1a ,

When the group represented by X ^2a to, groups represented by X ^1a and X ^2a is, for example there may be mentioned a group represented by the formula (A2-1-1) ~ formula (A2-1-7). * Represents the number of bonds to carbon atoms.

In formula (II-1),

The group represented by Y ¹ ,

When the group represented by Y ^{2 is defined} as Y ² , examples of the group represented by Y ¹ or Y ² include groups represented by the general formulas (A3-1-1) to (A3-1-6). * Represents the number of bonds to carbon atoms.

Examples of the compound represented by the general formula (II-1) include compounds (AII-1-1) to (AII-1-21) shown in Table 4.

As the compound represented by the formula (II-1), since raw materials are readily available, compounds (AII-1-1) to (AII-1-7) are preferable, and compounds (AII-1-5) and Compound (AII-1-6) is more preferable.

The compound represented by formula (II-1) is, for example, reacting a compound represented by formula (IV-1) with squaric acid (3,4-dihydroxy-3-cyclobutene-1,2dione). It can be manufactured by a method.

[In the above formula, R ^1a , R ^2a , R ^5a , R ^7a , R ^9a and R ^10a each represent the same meaning as above.]

The amount of squaric acid used is preferably 0.5 mol or more and 0.8 mol or less, and more preferably 0.55 mol or more and 0.6 mol or less per 1 mol of the compound represented by the formula (IV-I).

The reaction temperature is preferably 30°C to 180°C, and more preferably 80°C to 140°C. The reaction time is preferably 1 to 12 hours, more preferably 3 to 8 hours.

It is preferable to perform the reaction in an organic solvent from the viewpoint of a yield. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; Alcohol solvents such as methanol, ethanol, isopropanol, and butanol; Nitrohydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; Amide solvents such as 1-methyl-2-pyrrolidone; Etc. are mentioned, and these may be mixed and used for them. Among them, a mixed solvent of butanol and toluene is preferable. The amount of the organic solvent used is preferably 30 parts by mass or more and 200 parts by mass or less, and more preferably 50 parts by mass or more and 150 parts by mass or less, based on 1 part by mass of the compound represented by the formula (IV-I).

The method for obtaining the compound represented by the formula (II-1) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, after cooling, a method of filtering the precipitated crystals is mentioned. It is preferable to wash the crystal|crystallization taken by filtration with water etc., and to dry continuously. Further, if necessary, further purification may be performed by a known method such as recrystallization.

The compound represented by formula (IV-I) can be synthesized by reacting a compound represented by formula (IV-2) with a compound represented by formula (IV-3).

[In each formula, R ^1a , R ^2a , R ^5a , R ^7a , R ^9a and R ^10a each represent the same meaning as above.]

<Compound represented by Formula (II-2)>

The compound represented by the formula (II-2) is a novel compound. Such compounds are also within the scope of this application.

[In the above formula, R ^1b to R ^4b each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atom or the methyl group contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group It may be done.

R ^5b to R ^8b each independently represent a hydrogen atom or a hydroxy group.

Ar ^1b and Ar ^2b each independently represent a group represented by the formula (i-2).

In the above formula, R ^12b represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, and m2 represents an integer of 1 to 5. When m2 is 2 or more, a plurality of R ^12b may be the same or different, respectively. * Represents the number of bonds to the nitrogen atom.

R ^9b and R ^10b each independently represent a C 1 to C 20 monovalent saturated hydrocarbon group or a group represented by the formula (i-2). The hydrogen atom or the methyl group contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group It can be done.]

Examples of the halogen atom for R ^1b to R ^4b include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the groups represented by R ^1b to R ^4b , R ^9b , R ^10b and R ^12b include groups exemplified as R ^1a to R ^4a in formula (II-1).

Examples of the saturated hydrocarbon group for R ^9b , R ^10b and R ^12b include groups exemplified as the saturated hydrocarbon group represented by R ^1a to R ^4a in formula (II-1).

Examples of the unsaturated hydrocarbon group for R ^12b include vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, and decenyl group.

Examples of the group represented by the general formula (i-2) include groups exemplified as the group represented by the aforementioned general formula (i-1).

As R ^1b to R ^4b , a hydrogen atom, a hydroxy group and a methyl group are preferable, and a hydrogen atom is more preferable.

As R ^9b and R ^10b , a linear alkyl group having 8 to 12 carbon atoms, a branched alkyl group having 8 to 16 carbon atoms, and a group represented by formula (i-2) are preferable, and octyl group, nonyl group, decyl group, dodecyl group, carbon number 8 to 16 branched alkyl groups (especially 2-ethylhexyl groups) and groups represented by formula (i-2) are more preferable, and C 8 to 16 branched alkyl groups (especially 2-ethylhexyl groups) are more preferable. .

As R ^12b , a C1-C4 alkyl group is preferable, and a methyl group and an ethyl group are more preferable.

In formula (II-2),

The group represented by X ^1b ,

When the group represented by X ^2b is used as the group represented by X ^1b or X ^2b , groups represented by the general formulas (A2-2-1) to (A2-2-7) are mentioned. In each group, * represents the number of bonds to carbon atoms.

Examples of the compound represented by the formula (II-2) include compounds (AII-2-1) to (AII-2-21) shown in Table 5.

From the viewpoint of availability of raw materials, compound (AII-2-8) to compound (AII-2-14) are more preferable, and among them, compound (AII-2-8) is more preferable.

The compound represented by formula (II-2) is, for example, a compound represented by formula (IV-2-1) and squaric acid (3,4-dihydroxy-3-cyclobutene-1,2dione). It can be produced by a method of reacting.

In the formula (IV-1), R ^1b , R ^2b , R ^5b , R ^6b , R ^9b and Ar ¹ each represent the same meaning as above. The amount of squaric acid used is preferably 0.5 mol or more and 0.8 mol or less, and more preferably 0.55 mol or more and 0.6 mol or less per 1 mol of the compound represented by the formula (IV-2-I).

The reaction temperature is preferably 30°C to 180°C, and more preferably 80°C to 140°C. The reaction time is preferably 1 to 12 hours, more preferably 3 to 8 hours.

It is preferable to perform the reaction in an organic solvent from the viewpoint of a yield. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; Alcohol solvents such as methanol, ethanol, isopropanol, and butanol; Nitrohydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; Amide solvents such as 1-methyl-2-pyrrolidone; Etc. are mentioned, and these may be mixed and used for them. Among them, a mixed solvent of butanol and toluene is preferable. The amount of the organic solvent used is preferably 30 parts by mass or more and 200 parts by mass or less, more preferably 50 parts by mass or more and 150 parts by mass or less, based on 1 part by mass of the compound represented by the formula (IV-2-I). .

The method of obtaining the compound represented by the formula (II-2) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, after cooling, a method of filtering the precipitated crystals is mentioned. It is preferable to wash the crystal|crystallization taken by filtration with water etc., and to dry continuously. Further, if necessary, further purification may be performed by a known method such as recrystallization.

The compound represented by the formula (VI-2-1) can be prepared by reacting a compound represented by the formula (IV-2-4) with a compound represented by the formula (IV-2-5). The compound represented by the formula (IV-2-4) can be prepared by reacting a compound represented by the formula (IV-2-2) with a compound represented by the formula (IV-2-3).

In each formula, R ^1b , R ^2b , R ^5b , R ^6b , R ^9b , R ^12b and m2 each represent the same meaning as above.

As a method for preparing the compound represented by the formula (IV-2-1) from the compound represented by the formula (IV-2-4) and the compound represented by the formula (IV-2-5), various known methods For example, the method described in J. Polymer Sciene Science Part A: Polymer Chemistry 2012, 50, 3788-3796 can be mentioned.

As a method for preparing the compound represented by the formula (IV-2-4) from the compound represented by the formula (IV-2-2) and the compound represented by the formula (IV-2-3), various known methods , Eg, Eur. J. Org. Chem. The method described in 2012, 3105-3111. is mentioned.

A colorant including the compound represented by the formula (II-1) or the compound represented by the formula (II-2) is also one of the present invention.

In the present specification, unless otherwise specified, the compound represented by the formula (II-1) and the compound represented by the formula (II-2) are collectively referred to as "the compound of the present invention".

The colorant of the present invention may contain a dye other than the compound of the present invention (hereinafter, this dye is referred to as "dye (A-1)") or a pigment.

Examples of the dye (A-1) include dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes, sulfonamide derivatives of acid dyes, etc., for example, dyes from The Society of Dyers and Colorists. The compounds classified and known dyes described in the dyeing notes (Shikisensha) can be mentioned.

As the dye (A-1), according to the chemical structure, according to the chemical structure, coumarin dye, alloy azo dye, pyridone azo dye, barbitur azo dye, quinophthalone dye, methine dye, cyanine dye, anthraquinone dye, triphenylmethane dye, And xanthene dyes and phthalocyanine dyes. These dyes may be used alone or in combination of two or more.

Specifically, C.I. Solvent dye, C.I. Acid dye, C.I. Direct dye, C.I. And modern dyes.

C.I. As a solvent dye, C.I. Solvent Orange 2, 7, 11, 15, 26, 56, or C.I. Solvent yellow is mentioned.

C.I. As an acid dye, 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, or C.I. Acid yellow is mentioned.

C.I. As a direct dye, C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, or C.I. Direct yellow is mentioned.

C.I. As a modern dye, C.I. Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 CI Modern yellow and the like.

As the dye (A-1), a yellow dye is preferable, and a yellow dye which is a coumarin dye, an alloy azo dye, a pyridone azo dye, a barbitur azo dye, a quinophthalone dye, a methine dye or a cyanine dye is preferable.

The pigment is not particularly limited, and a known pigment may be used, and examples thereof include pigments classified as pigments by the color index (published by The Society of Dyers and Colorists).

As a specific example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194, 214 and the like yellow pigments;

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

C.I. Green pigments, such as a pigment green pigment, are mentioned.

As a pigment, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 139, 147 , 148, 150, 153, 154, 166, 173, 185, 194, 214 and the like yellow pigments; C.I. Green pigments such as Pigment Green 7, 36, and 58 are preferable, and C.I. Pigment Yellow 138, 150, 185 and C.I. Pigment Green 58 is more preferable, and C.I. Pigment Yellow 138 and C.I. Pigment Green 58 is more preferred. By including the above pigment, it is easy to optimize the transmission spectrum.

The content of the compound represented by the general formula (II-1) is usually 3 to 100 mass%, preferably 4 to 50 mass%, and more preferably 5 to 30 mass% with respect to the total amount of the colorant.

The content of the compound represented by the formula (II-2) is usually 3 to 100% by mass, preferably 4 to 50% by mass, and more preferably 5 to 30% by mass, based on the total amount of the colorant.

When the content of the compound of the present invention is within the above ranges, since a color filter having high brightness can be easily obtained, it is preferable.

A colored curable resin composition comprising a compound represented by formula (II-1) or formula (II-2), resin (B), polymerizable compound (C), polymerization initiator (D) and solvent (E) (hereinafter, This colored curable resin composition is also referred to as "colored curable resin composition (A)") is also one of the present invention.

The colored curable resin composition (A) contains at least one compound of the present invention as a colorant. The colored curable resin composition may further contain the above-described dye (A-1) or pigment as a colorant.

In the colored curable resin composition (A), the total content of the colorant is preferably 5 to 60 mass%, more preferably 8 to 55 mass%, and still more preferably 10 to 50 with respect to the total amount of the solid content. It is mass%. If the total content of the colorant is within the above range, the color density when used as a color filter is sufficient, and since the required amount of the resin (B) or the polymerizable compound (C) can be contained in the composition, a pattern having sufficient mechanical strength Can be formed. Here, the "total amount of solid content" in this specification means the amount excluding the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid content and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, but it is preferably an alkali-soluble resin. Examples of the resin (B) include resins [K1] to [K6] described above.

Specific examples and preferred examples of the resin (B) are the same as those of the colored curable resin composition (1) described above.

In the colored curable resin composition (A), the content of the resin (B) is preferably 7 to 65 mass%, more preferably 13 to 60 mass%, and still more preferably 17 with respect to the total amount of the solid content. It is -55 mass%. When the content of the resin (B) is within the above-described range, a colored pattern can be formed, and the resolution and residual film rate of the colored pattern 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). Examples of the polymerizable compound (C) include compounds having a polymerizable ethylenically unsaturated bond, and a (meth)acrylic acid ester compound is preferable.

Specific examples and preferred examples of the polymerizable compound (C) are the same as those of the colored curable resin composition (1) described above.

In the colored curable resin composition (A), the content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably based on the total amount of the solid content. Is 17 to 55% by mass. When the content of the polymerizable compound (C) is within the above-described range, there is a tendency that the residual film rate at the time of forming the colored pattern and the chemical resistance of the color filter are improved.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization of the polymerizable compound (C) by generating active radicals, acids, etc. by the action of light or heat, and a known polymerization initiator can be used. .

Specific examples and preferable examples of the polymerization initiator (D) are the same as those of the colored curable resin composition (1) described above.

In the colored curable resin composition (A), the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is 1 to 20 parts by mass. When the content of the polymerization initiator (D) is within the above-described range, since there is a tendency that the sensitivity is increased and the exposure time is shortened, the productivity of the color filter is improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent commonly used in the field can be used.

Specific examples and preferred examples of the solvent (E) are the same as those of the colored curable resin composition (1) described above.

In the colored curable resin composition (A), the content of the solvent (E) is preferably 70 to 95 mass%, and more preferably 75 to 92 mass% with respect to the total amount of the composition. When the content of the solvent (E) is within the above range, the flatness at the time of application is improved, and the color density is not insufficient when the color filter is formed, so that the display characteristics tend to be improved.

<Other ingredients>

The colored curable resin composition (A) of the present invention may contain additives known in the art, such as polymerization initiation aids, leveling agents, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and the like, if necessary. You may include it.

<Production method of colored curable resin composition (A)>

The colored curable resin composition (A) is a compound represented by formula (II-1) or formula (II-2), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), And it can be prepared by mixing a leveling agent, a polymerization initiation aid, and other components used as needed.

The pigment (P) is preferably mixed with a part or all of the solvent (E) in advance, and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 µm or less. At this time, if necessary, some or all of the pigment dispersant and the resin (B) may be blended. A desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion liquid thus obtained to a predetermined concentration.

The dye may be previously dissolved in a part or all of the solvent (E) to prepare a solution. It is preferable to filter the solution with a filter having a pore diameter of about 0.01 to 1 µm.

It is preferable to filter the colored curable resin composition after mixing with a filter having a pore diameter of about 0.1 to 10 µm.

<Method of manufacturing color filters, etc.>

The coating film and the color filter formed from the colored curable resin composition (A) also fall into the scope of the present invention. A display device including the color filter also falls within the scope of the present invention.

The color filter means a film obtained by curing the colored curable resin composition (A), and a cured film having a specific pattern. The said coating film means a film obtained by coating and drying the said color filter or a board|substrate.

The film thickness of the color filter is not particularly limited, and can be appropriately adjusted according to the purpose or use, and is, for example, 0.1 to 30 µm, preferably 0.1 to 20 µm, and more preferably 0.5 to 6 µm.

As the substrate, the substrate illustrated for the color filter obtained from the colored curable resin composition (A) is used. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

The method of manufacturing the coating film and the color filter is not particularly limited. The coating film or the color filter can be formed in the same manner as the coating film or color filter formed from the colored curable resin composition 1 described above, for example.

According to the colored curable resin composition (A), a color filter having particularly excellent brightness can be produced. The color filter is useful as a color filter used in a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Example

Hereinafter, the present invention has been described in more detail by examples, but the present invention is not limited by these examples. In the examples,% and parts indicating content to amount used are based on mass unless otherwise noted.

In the following synthesis examples, the compound was identified by NMR (JNM-EX-270; [manufactured by Nihon Denshi Co., Ltd.]).

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

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

¹ H-NMR (270MHz, δ value (ppm, based on TMS), 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 a compound represented by Formula (AII-23)

N,N-dibutyl-3-aminophenol [Tokyo Case High School Co., Ltd. product] 5.4 parts, 3,4-dihydroxy-3-cyclobutene-1,2-dione [Tokyo Case High School Co., Ltd. product] 1.7 parts, 200.7 parts of 1-butanol and 134.1 parts of toluene were mixed. While removing the generated water using a Dean-Stark tube, the obtained mixture was stirred at 125° C. for 5 hours. After completion of the reaction, the solvent was distilled off, a small amount of toluene was added, and then 100 parts of water was added to discard the aqueous layer. After repeating the operation of washing the obtained organic layer with water twice, 50 parts of hexane was added, and the precipitated solid was collected by filtration. The solid obtained by filtration was dispersed in 5 parts of tetrahydrofuran, filtered, and then the solid was washed with 10 parts of tetrahydrofuran and then 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 (270MHz, δ value (ppm, based on TMS) of the compound represented by the formula (AII-23), CDCl ₃ )

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 a compound represented by the formula (AII-62)

3-ethoxy-N,N-diethylaniline [manufactured by Tokyo Case High School Co., Ltd.] 2.5 parts, 3,4-dihydroxy-3-cyclobutene-1,2-dione [manufactured by Tokyo Case High School Co., Ltd.] ] 0.7 parts, 1-butanol 103.7 parts, and toluene 55.7 parts were mixed. While removing the generated water using a Dean-Stark tube, the obtained mixture was stirred at 125° C. for 5 hours. After completion of the reaction, the solvent was distilled off, a small amount of toluene was added, and then 50 parts of water was added to discard the aqueous layer. After repeating the operation of washing the obtained organic layer with water twice, hexane was added 25 parts, and the precipitated solid was filtered and taken out. The solid obtained by filtration was dispersed in 3 parts of tetrahydrofuran, 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 parts of a compound represented by the formula (AII-62).

¹ H-NMR (270 MHz, δ value (ppm, based on TMS) of the compound represented by the formula (AII-62), 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, a thermometer, a reflux condenser, a dropping funnel, and a gas introduction tube, nitrogen was flowed at 0.02 L/min to obtain a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate were added and heated to 70°C while stirring. . Subsequently, 36 parts of acrylic acid; And 4,5-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-ylacrylate {that is, the monomer represented by the formula (BI-1)} and 3,4-epoxytricyclo[5.2.1.0 ^{2 ,6} ] a mixture of decane-8-ylacrylate {that is, a monomer represented by the formula (BII-1)} {molar ratio of each monomer in the mixture = 50:50} 264 parts; 140 parts of propylene glycol monomethyl ether acetate To prepare a monomer solution. The monomer solution was dropped into a flask kept warm at 70°C over 4 hours using a dropping funnel. On the other hand, a polymerization initiator solution obtained by dissolving 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of propylene glycol monomethyl ether acetate was added in 4 hours using a separate dropping funnel. It was dripped into the flask over. After the dropping of the polymerization initiator solution was completed, it was maintained at 70° C. for 4 hours, and then cooled to room temperature, and the weight average molecular weight Mw: 9000, molecular weight distribution: 2.0, solid content 33%, solid content acid value 90 mg-KOH/g The resin B1 solution was obtained.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin was performed under the following conditions using the GPC method.

Device; K2479 [manufactured by Shimadzu 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 in terms of polystyrene obtained above was taken as the molecular weight distribution.

Examples 1 to 6, Comparative Examples 1 and 2

<Preparation of a colored curable resin composition>

Each component was mixed so that it might become the composition shown in Table 6, and the colored curable resin composition was obtained.

^{1) The} pigment was mixed with a pigment dispersant and propylene glycol monomethyl ether acetate in the amount described in the column ³⁾ E-1, and dispersed in advance.

²⁾ E-1 ²⁾ represents the sum of the content of propylene glycol monomethyl ether acetate.

In addition, in Table 6, each component shows the following. In addition, resin (B) showed a mass part in terms of solid content.

A-1-1: compound represented by formula (AII-16)

A-1-2: compound represented by formula (AII-23)

A-1-3: compound represented by the formula (AII-62)

A-2-1: C.I. Pigment Yellow 138

A-2-2: C.I. Pigment Green 58 [FASTOGEN (registered trademark) Green A110; DIC Co., Ltd. manufacture]

A-2-3: Pigment Yellow 150

Resin (B): Resin B1

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

Polymerization initiator (D): N-1919 (manufactured by ADEKA; O-acyloxime compound)

E-1: Propylene glycol monomethyl ether acetate

E-2: N-methylpyrrolidone

Leveling agent (F): Polyether-modified silicone oil [Toray Silicone SH8400; Toray Dow Corning Co., Ltd.]

<Preparation of colored coating film>

On a square glass substrate (Eagle XG; manufactured by Corning) having a side of 5 cm, a colored curable resin composition was applied by a spin coating method so that the film thickness after post-baking became 2.2 µm, and then prebaked at 100°C for 3 minutes. I did. After cooling, exposure machine [TME-150RSK; Using Topcon Co., Ltd.], light irradiation was performed at an exposure amount of 60 mJ/cm 2 (based on 365 nm) in an air atmosphere. After light irradiation, in an oven, post-baking was performed at 160°C for 20 minutes to obtain a colored coating film (hereinafter, this colored coating film is referred to as “coating film”).

<Measurement of film thickness>

For the obtained coating film, a film thickness measuring device [DEKTAK3; The thickness of the film was measured using [Nippon Shinkugi Jutsu Co., Ltd. product]. Table 7 shows the results.

<chromaticity evaluation>

About the obtained coating film, a colorimeter [OSP-SP-200; Olympus Co., Ltd.] was used to measure spectroscopy, and xy chromaticity coordinates (x, y) and tristimulus values (Y) in the XYZ color system of CIE were measured using the characteristic function of the C light source. The larger the value of Y, the higher the brightness. Table 7 shows the results.

<Contrast measurement>

The glass substrate on which the coating film was formed was sandwiched between a polarizing film (POLAX-38S; manufactured by Lukeo) as a measurement sample.

For the obtained coating film, the contrast was measured using a contrast colorimeter (CT-1; manufactured by Tsubosaka Denki, detector; BM-5A, light source; F-10) with a blank value of 30000. Table 7 shows the results.

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 was found that by using the colored pattern formed from the colored curable resin composition (1) as a color filter, it was possible to manufacture a display device having excellent color performance.

Example 7: Synthesis of a compound represented by the formula (AII-1-5)

5.0 parts of 3'-(diethylamino)acetanilide [manufactured by Wako Pure Chemical Industries, Ltd.] and 50 parts of 10% sulfuric acid were mixed. The resulting mixture was stirred at 90° C. for 5 hours. After completion of the reaction, 20 parts of water were added, neutralized with 15% caustic soda water, and 100 parts of chloroform was added to discard the aqueous layer. After repeating the operation of washing the obtained organic layer with water twice, the solvent was distilled off. The obtained oil was dried under reduced pressure at 60° C. for 24 hours to obtain 4.8 parts of the compound represented by the formula (d1-1).

¹ H-NMR (270MHz, δ value (ppm, based on TMS) of the compound represented by the formula (d1-1), CDCl ₃ )

δ 1.16 (t, 6H), 3.32 (q, 8H), 3.56 (br, 2H), 6.04 (m, 2H), 6.16 (m, 1H), 7.01 (t, 1H)

3.0 parts of the compound represented by the formula (d1-1) and 7.6 parts of pyridine were mixed and cooled at 4°C. A mixed solution of 3.2 parts of 2-ethylhexyl chloride [Tokyo Chemical Industry Co., Ltd.] and 2.5 parts of pyridine was added dropwise to the obtained mixture over 1 hour, followed by stirring at 4°C for 7 hours. 30 parts of water and 100 parts of 3% hydrochloric acid were added, and 100 parts of chloroform was added to discard the aqueous layer. After repeating the operation of washing with water twice, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: chloroform/toluene=1/1), and the obtained oil was dried under reduced pressure at 60° C. for 24 hours to obtain 3.3 parts of the compound represented by the formula (d1-2).

¹ H-NMR (270MHz, δ value (ppm, based on TMS) of the compound represented by the formula (d1-2), CDCl3)

δ 0.91 (m, 6H), 1.11 (t, 6H), 1.27 (m, 4H), 1.60 (m, 4H), 2.66 (m, 1H), 3.28 (q, 4H), 3.99 (br, 1H), 6.16(q, 1H), 6.70(m, 1H), 7.21(m, 1H), 7.31(m, 1H)

2.1 parts of a compound represented by the formula (d1-2), 3,4-dihydroxy-3-cyclobutene-1,2-dione [manufactured by Tokyo Chemical Industry Co., Ltd.] 0.6 parts, 1-butanol 87.9 parts, and toluene 62.3 parts were mixed. While removing the generated water using a Dean-Stark tube, the obtained mixture was stirred at 125° C. for 5 hours. After completion of the reaction, the solvent was distilled off, a small amount of toluene was added, and then 100 parts of water was added to discard the aqueous layer. After repeating the operation of washing the obtained organic layer with water twice, 50 parts of hexane was added, and the precipitated solid was collected by filtration. The solid obtained by filtration was dispersed in 5 parts of tetrahydrofuran, and after filtration, the solid was washed with 10 parts of tetrahydrofuran and then 25 parts of hexane. The obtained solid was dried under reduced pressure at 60° C. for 24 hours to obtain 0.2 parts of a compound represented by the formula (AII-1-5).

¹ H-NMR (270MHz, δ value (ppm, based on TMS) of the compound represented by the formula (AII-1-5), CDCl ₃ )

δ 0.87 (t, 6H), 0.97 (t, 6H), 1.29 (t, 12H), 1.33 (m, 8H), 1.55 (m, 4H), 1.73 (m, 4H), 2.65 (m, 2H), 3.53(q, 8H), 6.46(m, 2H), 8.36(d, 2H), 8.50(m, 2H), 12.00(d, 2H)

Example 8: Synthesis of a compound represented by the formula (AII-2-8)

2,4-dimethylaniline [manufactured by Tokyo Case High School Co., Ltd.] 10.0 parts, 2-ethylhexane bromide [manufactured by Tokyo Case High School Corporation] 17.0 parts, tetrabutylammonium bromide [manufactured by Wako Pure Chemical Industries, Ltd.] 44.0 The parts were mixed. The resulting mixture was stirred at 90° C. for 8 hours. After completion of the reaction, 50 parts of 10% sodium bicarbonate were added, followed by addition of 100 parts of ethyl acetate, and the aqueous layer was discarded. After repeating the operation of washing the obtained organic layer with water and 10% hydrochloric acid twice, the solvent was distilled off. The obtained oil was dried under reduced pressure at 60° C. for 24 hours to obtain 9.3 parts of a compound represented by the following formula (d2-1).

¹ H-NMR (270MHz, δ value (ppm, based on TMS), DMSO-d6) of the compound represented by the formula (d2-1)

δ 0.85 (m, 6H), 1.23-1.42 (br, 8H), 1.59 (br, 1H), 2.04 (s, 3H), 2.12 (s, 3H), 2.91 (d, 2H), 4.37 (br, 1H) ), 6.38(d, 1H), 6.75(s, 1H), 6.77(d, 1H)

3.0 parts of the compound represented by the formula (d2-1), 3-bromophenol [manufactured by Tokyo Case High School Co., Ltd.] 2.2 parts, palladium acetate 0.015 parts, tert-butoxy sodium [manufactured by Tokyo Case High School Corporation] 3.2 Part, tri tert-butylphosphine [manufactured by Tokyo Case High School Co., Ltd.] 0.055 parts and 25.6 parts of toluene were mixed, and stirred at 100°C for 15 hours. To the obtained mixture, 30 parts of ethyl acetate and 100 parts of water were added, and the aqueous layer was discarded. After repeating the operation of washing the obtained organic layer with water twice, the solvent was distilled off. The residue was purified by silica gel chromatography (chloroform/hexane=1/1), and the obtained oil was dried under reduced pressure at 60° C. for 24 hours to obtain 1.9 parts of a compound represented by the following formula (d2-2).

¹ H-NMR (270MHz, δ value (ppm, based on TMS) of the compound represented by the formula (d2-2), DMSO-d6) 0.85 (m, 6H), 1.23-1.42 (br, 8H), 1.55 (br) , 1H), 1.94(s, 3H), 2.27(s, 3H), 2.90(d, 2H), 6.37(d, 1H), 6.75(s, 1H), 6.76(d, 1H), 6.92-7.14( m, 4H), 8.93 (s, 1H)

4.4 parts of a compound represented by the formula (d2-2), 3,4-dihydroxy-3-cyclobutene-1,2-dione [manufactured by Tokyo Chemical Industry Co., Ltd.] 0.8 parts, 1-butanol 90.0 parts and toluene 60.0 parts were mixed. While removing the generated water using a Dean-Stark tube, the resulting mixture was stirred at 125° C. for 3 hours. After completion of the reaction, the solvent was distilled off, 15 parts of acetic acid was added, and then it was dripped at 100 parts of 18% saline, and the precipitated solid was collected by filtration. The solid obtained by filtration was washed with hexane. The obtained solid was dried under reduced pressure at 60° C. for 24 hours to obtain 4.9 parts of a compound represented by the formula (AII-2-8).

¹ H-NMR (270MHz, δ value (ppm, based on TMS) of the compound represented by the formula (AII-2-8), DMSO-d6) 0.87 (m, 12H), 1.21-1.57 (m, 16H), 1.72 (br, 2H), 2.05(s, 6H), 2.36(s, 6H), 3.37(br, 2H), 3.78(br, 2H), 6.00(br, 4H), 6.97-7.12(m, 6H), 7.77-7.95(m, 2H), 11.35(s, 1H), 12.06(s, 1H)

Test Example 1 and Test Example 2, Comparative Test Example 1 and Comparative Test Example 2

For the compound represented by the formula (AII-1-5) and the compound represented by the formula (AII-2-8), propylene glycol monomethyl ether (hereinafter referred to as PGME) and ethyl lactate (hereinafter referred to as EL), respectively. ), and the solubility in propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) was determined as follows.

<Solubility of dye>

In a 50 ml sample tube, the compound and the solvent were mixed in the following ratios, respectively, and then the sample tube was sealed, and the mixture was vibrated with an ultrasonic vibrator at 30°C for 3 minutes. Subsequently, the obtained mixture was allowed to stand at room temperature for 30 minutes, followed by suction filtration, and the residue (ie, insoluble matter) was visually observed. When insoluble matters were not confirmed, the solubility was judged to be good and set as ○. When insoluble matters were confirmed, the solubility was judged to be poor and set as x.

Test Example 1: Using a compound represented by the formula (AII-1-5).

-0.05 g of the compound is dissolved in 1 g of solvent (EL).

Dissolve 0.03 g of the compound per 1 g of solvent (PGME)

Dissolve 0.01 g of the compound per 1 g of solvent (PGMEA)

Test Example 2: Using a compound represented by the formula (AII-2-8).

-0.1 g of the compound is dissolved per 1 g of solvent (PGME).

-0.15 g of the compound is dissolved with respect to 1 g of the solvent (EL).

-0.01 g of the compound is dissolved in 1 g of a solvent (PGMEA).

Separately, the solubility of the compound represented by Formula (II-0-1) as Comparative Test Example 1 and the solubility of the compound represented by Formula (II-0-2) as Comparative Test Example 2 were measured in Test Example 1 and Test, respectively. It was obtained in the same manner as in Example 2.

The results are shown in Tables 8 and 9.

Synthesis Example 7

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was allowed to flow in an appropriate amount to obtain a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added and heated to 85°C while stirring. Subsequently, in the flask, 19 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 ] A mixture of decane-9-yl acrylate (the content ratio is 50:50 in a molar ratio) (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) 171 parts of a solution dissolved in 40 parts of propylene glycol monomethyl ether acetate was added to a dropping pump. It was dripped over about 5 hours. On the other hand, a solution in which 26 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 120 parts of propylene glycol monomethyl ether acetate was added dropwise into the flask over about 5 hours using a separate dropping pump. I did. After the dropping of the polymerization initiator was completed, it was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (B-1)) having a solid content of 43.5%. The weight average molecular weight of the obtained resin (B-1) was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mg-KOH/g.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin in terms of polystyrene was performed under the following conditions by the GPC method.

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

column; TSK-GELG2000HXL

Column temperature; 40℃

menstruum; THF

Flow rate; 1.0 ml/min

Solid content concentration in the test solution; 0.001 to 0.01 mass%

Injection volume; 50 μl

Detector; RI

Calibration standards; TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500 [manufactured by Tosoh Corporation]

The ratio (Mw/Mn) of the weight average molecular weight and number average amount in terms of polystyrene obtained above was taken as the molecular weight distribution.

Example 9, Example 10 and Comparative Example 3

<Preparation of a colored curable resin composition>

Each component was mixed so that it might become the composition shown in Table 10, and the colored curable resin composition was obtained.

^{1) The} pigment was mixed with a pigment dispersant and propylene glycol monomethyl ether acetate in the amount described in the column ³⁾ E-1, and dispersed in advance.

2) E-1 ²⁾ represents the total content of propylene glycol monomethyl ether acetate.

In addition, in Table 10, each component shows the following. In addition, resin (B-1) showed a mass part in terms of solid content.

AII-1-5: Compound represented by the formula (AII-1-5)

AII-2-8: Compound represented by formula (AII-2-8)

A-2-3: C.I. Pigment Yellow 150

A-2-2: C.I. Pigment Green 58 [FASTOGEN (registered trademark) Green A110; DIC Co., Ltd. manufacture]

Resin (B): Resin B1

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

*Polymerization initiator (D): N-1919 (manufactured by ADEKA; O-acyloxime compound)

E-1: Propylene glycol monomethyl ether acetate

E-2: N-methylpyrrolidone

Leveling agent (F): Polyether-modified silicone oil [Toray Silicone SH8400; Toray Dow Corning Co., Ltd.]

<Production of coating film>

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

<Measurement of film thickness>

For the obtained coating film, a film thickness measuring device [DEKTAK3; The film thickness was measured using the Nippon Shinkugi Jutsu Co., Ltd. product. Table 10 shows the results.

<chromaticity evaluation>

About the obtained coating film, a colorimeter [OSP-SP-200; Olympus Co., Ltd.] was used to measure spectroscopy, and xy chromaticity coordinates (x, y) and tristimulus values (Y) in the XYZ color system of CIE were measured using the characteristic function of the C light source. The larger the value of Y, the higher the brightness. Table 10 shows the results.

<Contrast measurement>

The glass substrate on which the coating film was formed was sandwiched between a polarizing film (POLAX-38S; manufactured by Lukeo) as a measurement sample.

For the obtained colored coating film, the contrast was measured using a contrast colorimeter (CT-1; manufactured by Tsubosaka Denki, detector; BM-5A, light source; F-10) with a blank value of 30000. Table 10 shows the results.

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 was found that it was possible to manufacture a display device excellent in color performance by using the colored pattern formed from the colored curable resin composition (A) 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 because the color filter produced by this has high brightness and good contrast.

The compound of the present invention is excellent in solubility in an organic solvent. Therefore, when a colored curable resin composition containing a colorant containing the compound of the present invention is used, generation of foreign matter is small, and a high-quality color filter can be produced.

Claims (6)

A compound represented by formula (II-2).

[In the above formula, R ^1b to R ^4b each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atom or the methyl group contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group It may be done.
R ^5b to R ^8b each independently represent a hydrogen atom or a hydroxy group.
Ar ^1b and Ar ^2b each independently represent a group represented by the formula (i-2).

In the above formula, R ^12b represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, and m2 represents an integer of 1 to 5. When m2 is 2 or more, a plurality of R ^12b may be the same or different, respectively. * Represents the number of bonds to the nitrogen atom.
R ^9b and R ^10b each independently represent a C 1 to C 20 monovalent saturated hydrocarbon group or a group represented by the formula (i-2). The hydrogen atom or the methyl group contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group It can be done.] A coloring agent containing the compound according to claim 1. A colored curable resin composition comprising the compound according to claim 1, a resin, a polymerizable compound, a polymerization initiator, and a solvent. A coating film formed using the colored curable resin composition according to claim 3. A color filter formed using the colored curable composition according to claim 3. A display device comprising the color filter according to claim 5.