TWI861335B - Coloring curable composition - Google Patents

Abstract

The purpose of the present invention is to provide a coloring curable composition which can be used to manufacture a color filter with a good pattern shape and has good reflow resistance of the pattern during post-baking. The coloring curable composition of the present invention comprises a coloring agent, an organic solvent, a resin, a polymerizable compound and a polymerization initiator, wherein the coloring agent comprises a compound represented by formula (I), and the polymerizable compound comprises a compound represented by formula (II).

Description

Coloring curable composition

The present invention relates to a coloring curable composition. Specifically, the present invention relates to a coloring curable composition containing a phthalocyanine dye.

Color filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays, and solid-state imaging devices such as CCD (Charge Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor) sensors are made from a coloring curable resin composition. Phthalocyanine dyes are known as coloring agents used in the coloring curable resin composition for forming the color filter (Patent Document 1). [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2011-28236

[The problem the invention is trying to solve]

However, the previously known coloring curable resin composition using phthalocyanine dye as a coloring agent as described in Patent Document 1 cannot fully satisfy the shape of the pattern because the pattern will be reflowed during post-baking. The purpose of the present invention is to provide a coloring curable composition that can be used to manufacture a color filter with a good pattern shape and has better reflow resistance of the pattern during post-baking. [Technical means to solve the problem]

That is, the gist of the present invention is as follows. [1] A coloring curable composition comprising a coloring agent, an organic solvent, a resin, a polymerizable compound and a polymerization initiator, wherein the coloring agent comprises a compound represented by formula (I), the polymerizable compound comprises a compound represented by formula (II), [In formula (I), X represents a hydrogen atom or a monovalent metal atom; ^R1 represents a substituted or unsubstituted amino group or a substituted alkyl group having 1 to 20 carbon atoms; n represents an integer of 1 to 4; m represents an integer of 0 to 4; when formula (I) has a plurality of Xs, Xs may be the same or different from each other, and when formula (I) has a plurality of ^R1s , ^R1s may be the same or different from each other], [In formula (II), ^Ra represents a (q+r)-valent linking group; ^Rb represents an alkanediyl group having 1 to 20 carbon atoms; ^Rc represents an acryloxy group or a methacryloyloxy group; p represents an integer greater than or equal to 0; q represents an integer greater than or equal to 1; r represents an integer greater than or equal to 0; when formula (II) has a plurality of ^Rb , the ^Rb may be the same as or different from each other, when formula (II) has a plurality of ^Rc , the ^Rc may be the same as or different from each other, when formula (II) has a plurality of p, the p may be the same as or different from each other; wherein the total of the integers represented by p in formula (II) is greater than or equal to 2, and the total of the integers represented by q and the integers represented by r is greater than or equal to 3]. [2] The coloring curable composition as described in [1], which comprises at least one selected from the group consisting of CI Direct Blue 86, CI Direct Blue 87, CI Direct Blue 199 and CI Reactive Blue 25 as the compound represented by the above formula (I). [3] The coloring curable composition as described in [1] or [2], wherein in the compound represented by the above formula (II), ^Ra represents a group obtained by removing (q+r) hydrogen atoms from an aliphatic hydrocarbon having 3 to 30 carbon atoms (the methylene group contained in the aliphatic hydrocarbon may be substituted with an oxygen atom to form an ether structure). [4] The coloring curable composition as described in any one of [1] to [3], wherein in the compound represented by the above formula (II), ^Rb represents an alkanediyl group having 1 to 10 carbon atoms. [5] The coloring curable composition as described in any one of [1] to [4], wherein in the compound represented by the above formula (II), r represents an integer of 0 to 6. [6] The coloring curable composition as described in any one of [1] to [5], wherein in the compound represented by the above formula (II), q represents an integer of 2 to 12. [7] The coloring curable composition as described in any one of [1] to [5], wherein in the compound represented by the above formula (II), the total of the integers represented by p in the formula (II) is 2 to 60. [8] The coloring curable composition as described in any one of [1] to [7], wherein the above resin has a structural unit containing a (meth)acryl group in a side chain. [9] A color curable composition as described in any one of [1] to [8], wherein the polymerization initiator comprises an O-acyl oxime compound. [10] A color filter formed from the color curable composition as described in any one of [1] to [9]. [11] A display device comprising the color filter as described in [10]. [12] A solid-state imaging element comprising the color filter as described in [10]. [Effects of the Invention]

According to the present invention, a colored curable composition can be provided, which can be used to manufacture a color filter with good pattern shape, and the pattern has good reflow resistance during post-baking.

The coloring curable composition of the present invention comprises a coloring agent (hereinafter sometimes referred to as coloring agent (A)), an organic solvent (hereinafter sometimes referred to as organic solvent (E)), a resin (hereinafter sometimes referred to as resin (B)), a polymerizable compound (hereinafter sometimes referred to as polymerizable compound (C)) and a polymerization initiator (hereinafter sometimes referred to as polymerization initiator (D)). The coloring agent (A) comprises a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)). The coloring agent (A) may also comprise a coloring agent other than compound (I) (hereinafter sometimes referred to as coloring agent (A1)). The polymerizable compound (C) comprises a compound represented by formula (II) (hereinafter sometimes referred to as compound (II)). The polymerizable compound (C) may also comprise a polymerizable compound other than compound (II) (hereinafter sometimes referred to as polymerizable compound (C1)). The coloring curable composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as a leveling agent (F)). In addition, in this specification, unless otherwise specified, the compounds exemplified as the components may be used alone or in combination of multiple types.

<Coloring agent (A)> The coloring agent (A) contains compound (I).

＜＜Compound (I)＞＞ Compound (I) is a compound represented by the following formula (I).

[In formula (I), X represents a hydrogen atom or a monovalent metal atom; ^R1 represents a substituted or unsubstituted amino group or a substituted alkyl group having 1 to 20 carbon atoms; n represents an integer from 1 to 4; m represents an integer from 0 to 4; when formula (I) has a plurality of Xs, Xs may be the same or different from each other, and when formula (I) has a plurality of ^R1s , ^R1s may be the same or different from each other].

Compound (I) is a compound represented by the following formula (I-0) wherein (n+m) hydrogen atoms contained in the compound are replaced by n -SO ₃ X and m -SO ₂ R ¹ .

n is preferably an integer of 1 to 3, m is preferably an integer of 0 to 3, and the sum of the integer represented by n and the integer represented by m is preferably 1 to 4, and more preferably 1 to 3.

As the monovalent metal atom represented by X, there can be cited alkaline metal atoms such as Na, K, and Li. As X, it is preferably a hydrogen atom, Na, K, or Li, and more preferably a hydrogen atom or Na.

Examples of the substituted or unsubstituted amino group represented by R ¹ include amino groups; amino groups bonded to one or two alkyl groups such as N-methylamino, N-ethylamino, N-anilino, N,N-dimethylamino, and N,N-diethylamino (the alkyl group is preferably a alkyl group having 1 to 15 carbon atoms, and more preferably a alkyl group having 1 to 10 carbon atoms). The substituted or unsubstituted amino group represented by R ¹ is preferably an unsubstituted amino group.

Examples of the alkyl group having 1 to 20 carbon atoms represented by ^R1 include aliphatic alkyl groups and aromatic alkyl groups. The aliphatic alkyl group may be saturated or unsaturated and may be chain or alicyclic.

Examples of the saturated or unsaturated chain alkyl group represented by ^R1 include straight chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; branched chain alkyl groups such as isopropyl, (1-ethyl)propyl, isobutyl, sec-butyl, t-butyl, (1-ethyl)butyl, (2-ethyl)butyl, isopentyl, neopentyl, t-pentyl, (2-methyl)pentyl, isohexyl, (5-methyl)hexyl, and (3-ethyl)heptyl; and alkenyl groups such as vinyl, 1-propenyl, 2-propenyl (allyl), (1-methyl)vinyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, (1-(2-propenyl))vinyl, (1,2-dimethyl)propenyl, and 2-pentenyl. The carbon number of the saturated or unsaturated chain hydrocarbon group is preferably 1-15, more preferably 1-10, and even more preferably 1-8.

Examples of the saturated or unsaturated alicyclic alkyl group represented by ^R1 include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cycloalkenyl groups such as cyclohexenyl (e.g., cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl, cyclooctenyl, and the like, norinyl, adamantyl, bicyclo[2.2.2]octyl, and the like. The saturated or unsaturated alicyclic alkyl group preferably has 3 to 18 carbon atoms, more preferably 3 to 15, and even more preferably 4 to 15 carbon atoms.

Examples of the aromatic hydrocarbon group represented by ^R1 include phenyl, 1-naphthyl, 2-naphthyl, phenanthryl, anthracenyl, pyrenyl, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 18, and even more preferably 6 to 15.

The alkyl group represented by ^R1 may be a group obtained by combining two or more of the above-mentioned chain alkyl groups, alicyclic alkyl groups, and aromatic alkyl groups, as long as the upper limit of the carbon number is 20 or less. Such a group may be, for example, a group obtained by combining an aromatic alkyl group with at least one group selected from chain alkyl groups, alicyclic alkyl groups, and aromatic alkyl groups. In the alkyl group obtained by such combination, the chain alkyl group may be combined in the form of a divalent group (e.g., an alkanediyl group). Examples of the alkyl group obtained by the combination include aralkyl groups such as benzyl, phenethyl, and 1-methyl-1-phenethyl; aralkyl groups such as styryl (phenylvinyl); aralkynyl groups such as phenylethynyl; o-tolyl, m-tolyl, p-tolyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 4-vinylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, 2,5-diisopropylphenyl, and 2,6-diisopropylphenyl. , 2,4,6-triisopropylphenyl, 4-butylphenyl and other alkylaryl groups; 2,3-dihydro-4-indenyl, 1,2,3,5,6,7-hexahydro-4-symmetrical dicyclopentadienylphenyl, 5,6,7,8-tetrahydro-1-naphthyl, 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl and other aryl groups bonded to an alkanediyl group; aryl groups bonded to one or more aryl groups such as biphenyl and terphenyl; cyclohexylmethylphenyl, benzylphenyl, (dimethyl(phenyl)methyl)phenyl and the like. The alkyl group may be a alkyl group obtained by combining a chain alkyl group and an alicyclic alkyl group, and examples thereof include 1-methylcyclopropyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl. , 4-pentylcyclohexyl, 4-octylcyclohexyl and the like; cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, 2-methylcyclohexylmethyl, cyclohexylethyl, adamantylmethyl and the like; and the like. The carbon number of the group obtained by combining two or more of the chain alkyl group, the alicyclic alkyl group and the aromatic alkyl group is preferably 4 to 20, more preferably 6 to 18.

The alkyl group having 1 to 20 carbon atoms represented by R ¹ is preferably an aliphatic alkyl group, and more preferably a saturated chain aliphatic alkyl group.

Examples of the substituents that the alkyl group having 1 to 20 carbon atoms represented by ^R1 may have include: a halogen atom; a nitrile group; a nitro group; an amino group; a hydroxyl group; an alkoxy group having 1 to 15 carbon atoms, such as a methoxy group and an ethoxy group; an aryloxy group having 6 to 20 carbon atoms, such as a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group; a silyl group; an oxyboryl group; an alkylamino group having 1 to 15 carbon atoms, such as a monomethylamino group, a dimethylamino group, a monoethylamino group, and a diethylamino group; and a monophenylamino group, a diphenylamino group. The substituents which the alkyl group having 1 to 20 carbon atoms represented by R ¹ may have are preferably halogen atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferred.

The alkyl group having 1 to 20 carbon atoms represented by R ¹ is preferably a alkyl group having a substituent.

As compound (I), for example, as shown in Table 1 below, there can be exemplified compounds 1 to 80 represented by formula (Ix). Among compounds 1 to 80, when the sum of the integer represented by n, the integer represented by m1, and the integer represented by m2 is 2 or more, _-SO3X , _{-SO2NH2 ,} and/or _-SO2 ( _CH2 ) _rCl are preferably bonded to different benzene rings, respectively.

[Table 1]

Among them, compound (I) is preferably compound 1, compound 11, compound 18, compound 22, compound 23, compound 30, compound 34, compound 35, compound 39, compound 40, compound 53, compound 56, compound 60, and compound 72, and more preferably compound 11, compound 18, compound 23, compound 30, compound 34, compound 35, compound 39, compound 53, compound 56, compound 60, and compound 72.

Specific examples of compound (I) include C.I. Direct Blue 86, C.I. Direct Blue 87, C.I. Direct Blue 199 and C.I. Reactive Blue 25. It is particularly preferred that the compound (I) contains at least one selected from the group consisting of the above dyes.

The method for producing compound (I) is not particularly limited, and the compound (I) can be produced by referring to the synthesis examples described in Japanese Patent Application Laid-Open No. 2011-28236.

As compound (I), it is preferred that the compound (I) is soluble in water and poorly soluble in an organic solvent such as propylene glycol monomethyl ether acetate whose solubility parameter (SP value) is less than 11.0 (cal/cm ³ ) ^1/2 . Furthermore, solubility and poor solubility can be evaluated by the following method. Add 0.1 g of compound (I) to a 20 mL sample vial, and then add water or an organic solvent using a 10 ml full pipette, cover the vial, and treat it by ultrasonication for 3 minutes. The resulting solution is stored in a water bath at 23°C for 60 minutes. Filter 5 ml of the supernatant through a PTFE (Polytetrafluoroethylene) 5 μm membrane filter, and then filter through a 0.25 μm membrane filter to remove insoluble matter. The absorbance spectrum of the obtained filter solution is measured using an ultraviolet-visible spectrophotometer (e.g., UV-2500PC manufactured by Shimadzu Corporation) and a 1 cm unit to determine the absorbance (abs) at the maximum absorption wavelength of compound (I). At this time, if the absorbance (abs) is less than 40% of the upper limit of the measurement (when UV-2500PC manufactured by Shimadzu Corporation is used, the absorbance (abs) is less than 2), it is evaluated as poorly soluble, and if the absorbance (abs) is more than 40% of the upper limit of the measurement, it is evaluated as soluble. Due to such solubility characteristics, compound (I) has excellent solvent resistance and can provide a coloring curable composition in which the pattern will not reflow even when heated at a temperature of 150°C or above.

Since compound (I) is poorly soluble in organic solvents with an SP value of less than 11.0 (cal/cm ³ ) ^1/2 , when the coloring curable composition uses an organic solvent with an SP value of less than 11.0 (cal/cm ³ ) ^1/2 , it is preferred to use a coloring dispersion liquid that is prepared in advance by dispersing the compound (I) in the organic solvent in a uniformly dispersed state by containing a dispersant. The coloring dispersion liquid may contain a part or all of the organic solvent (E) contained in the coloring curable composition. The coloring curable composition may be adjusted using the above-mentioned coloring dispersion liquid.

Examples of the dispersant include surfactants, such as cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants. Specifically, polyester-based, polyamine-based, and acrylic-based surfactants may be used. These dispersants may be used alone or in combination of two or more. Examples of dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), BYK (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), etc. As the dispersant, the resin (B) described below can also be used.

When a dispersant is used, the amount of the dispersant (solid content) used is generally 1 to 500 parts by mass, preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, and further preferably 15 to 180 parts by mass, relative to 100 parts by mass of compound (I). If the amount of the dispersant used is within the above range, a coloring dispersion having a more uniform dispersion state tends to be obtained.

The content of the compound (I) is preferably 50 to 250 parts by mass, more preferably 80 to 200 parts by mass, and even more preferably 100 to 180 parts by mass, based on 100 parts by mass of the resin (B).

The content of the compound (I) in the total amount of the coloring agent (A) is preferably 40 to 100 mass %, more preferably 60 to 100 mass %, and even more preferably 80 to 100 mass %.

<<Colorant (A1)>> The coloring curable composition of the present invention may contain a dye (hereinafter sometimes referred to as dye (A1-1)) and/or a pigment (hereinafter sometimes referred to as pigment (A1-2)) other than compound (I) as colorant (A) (hereinafter sometimes dye (A1-1) and pigment (A1-2) are collectively referred to as colorant (A1)). These may be used alone or in combination of two or more.

The dye (A1-1) is not particularly limited, and known dyes can be used as long as they do not contain compound (I), for example, solvent dyes, acid dyes, direct dyes, mordant dyes, etc. As dyes, for example, compounds classified as dyes in the Dye Index (published by The Society of Dyers and Colourists) and known dyes recorded in the Dyeing Handbook (Sezenshasha) can be cited. In addition, based on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, dibenzopyran dyes, thiazole dyes, thiazolyl dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, methine azo dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and phthalocyanine dyes can be cited.

The pigment (A1-2) is not particularly limited, and known pigments can be used, for example, pigments classified as pigments in the Dye Index (published by The Society of Dyers and Colourists). Examples of pigments classified as pigments include yellow pigments such as 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, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231, etc.; orange pigments such as C.I. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc.; and red pigments such as C.I. pigment red 9, 97, 105, 122, 14 4, 149, 166, 168, 176, 177, 180, 190, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273 and other red pigments; C.I. pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60 and other blue pigments; C.I. pigment purple 1, 19, 23, 32, 36, 38 and other purple pigments; C.I. pigment green 7, 36, 58, 59, 62, 63 and other green pigments; C.I. pigment brown 23, 25 and other brown pigments; C.I. pigment black 1, 7 and other black pigments; etc.

The pigment may be subjected to the following treatments as required: rosin treatment; surface treatment using derivatives that introduce acidic or alkaline groups; grafting treatment on the pigment surface using polymer compounds; micronization treatment using sulfuric acid micronization method; washing treatment using organic solvents or water for removing impurities; removal treatment using ion exchange method for ionic impurities; etc. The particle size of the pigment is preferably roughly uniform. The pigment can be dispersed by containing a dispersant to prepare a pigment dispersion in a uniformly dispersed state in a dispersant solution. When using multiple pigments, they can be dispersed separately or mixed for dispersion. In addition, the pigment can be mixed with the above-mentioned compound (I) for dispersion. As the dispersant, the same dispersants as those mentioned above can be exemplified.

When a dispersant is used, the amount of the dispersant (solid content) used is generally 10 to 200 parts by mass, preferably 15 to 180 parts by mass, and more preferably 20 to 160 parts by mass relative to 100 parts by mass of the pigment. If the amount of the dispersant used is within the above range, a more uniformly dispersed pigment dispersion tends to be obtained.

When the colorant (A) includes the colorant (A1), the content of the colorant (A1) in the total amount of the colorant (A) is preferably 1 to 60 mass %, more preferably 1 to 40 mass %, and even more preferably 1 to 20 mass %.

The content of the colorant (A) relative to the total amount of solid components of the coloring curable composition is preferably 1 to 70 mass%, more preferably 5 to 60 mass%, further preferably 10 to 60 mass%, further preferably 15 to 55 mass%. If the content of the colorant (A) is within the above range, the color concentration when the color filter is made is sufficient, and since the composition can contain the necessary amount of resin (B), a pattern with sufficient mechanical strength can be formed, which is preferred. Among them, the "total amount of solid components" in this specification refers to the amount obtained by subtracting the content of the organic solvent from the total amount of the coloring curable composition. The total amount of solid components and the content of each component relative to the total amount of solid components can be measured by a known analytical method such as liquid chromatography or gas chromatography.

<Resin (B)> The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6], etc. Resin [K1]: A copolymer having structural units derived from at least one (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and structural units derived from monomers (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenic unsaturated bond; Resin [K2]: A copolymer having structural units derived from (a), structural units derived from (b), and structural units derived from monomers (c) copolymerizable with (a) (wherein (a) and (b) are different) (hereinafter sometimes referred to as "(c)"); Resin [K3]; a copolymer having structural units from (a) and structural units from (c); Resin [K4]; a copolymer having structural units obtained by adding (b) to structural units from (a), and structural units from (c); Resin [K5]; a copolymer having structural units obtained by adding (a) to structural units from (b), and structural units from (c); Resin [K6]; a copolymer having structural units obtained by adding (a) to structural units from (b) and further adding polycarboxylic acids and/or carboxylic anhydrides, and structural units from (c).

As (a), specifically, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid, fumaric acid, citric acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1, Unsaturated dicarboxylic acids such as 4-cyclohexenedicarboxylic acid; Methyl-5-northene-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[2.2 .1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; Maleic anhydride, conic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dihydrophthalic anhydride Unsaturated dicarboxylic anhydrides such as carboxybicyclo[2.2.1]hept-2-ene anhydride; Unsaturated mono[(meth)acryloxyalkyl] esters of divalent or higher polycarboxylic acids such as mono[2-(meth)acryloxyethyl] succinate and mono[2-(meth)acryloxyethyl] phthalate; Unsaturated acrylic esters containing hydroxyl and carboxyl groups in the same molecule such as α-(hydroxymethyl) acrylate, etc. Among these, acrylic acid, methacrylic acid, etc. are preferred in terms of copolymerization reactivity or solubility of the resulting resin in alkaline aqueous solution.

(b) refers to, for example, a polymerizable compound having a cyclic ether structure with 2 to 4 carbon atoms (e.g., at least one selected from the group consisting of oxirane ring, cyclohexane ring and tetrahydrofuran ring) and an ethylenic unsaturated bond. (b) Preferably, it is a monomer having a cyclic ether with 2 to 4 carbon atoms and a (meth)acryloyloxy group. Furthermore, in this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. "(Meth)acryloyl" and "(meth)acrylate" also have the same meaning.

Examples of (b) include a monomer (b1) having an ethylene oxide group and an ethylenic unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxycyclobutyl group and an ethylenic unsaturated bond (hereinafter sometimes referred to as "(b2)"), and a monomer (b3) having a tetrahydrofuran group and an ethylenic unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc.

Examples of (b1) include monomers (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon epoxidized structure (hereinafter sometimes referred to as "(b1-1)") and monomers (b1-2) having an alicyclic unsaturated hydrocarbon epoxidized structure (hereinafter sometimes referred to as "(b1-2)").

Examples of (b1-1) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl) 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tri(glycidyloxymethyl)styrene, 2,3,5-tri(glycidyloxymethyl)styrene, 2,3,6-tri(glycidyloxymethyl)styrene, 3,4,5-tri(glycidyloxymethyl)styrene, 2,4,6-tri(glycidyloxymethyl)styrene, and the like.

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Co., Ltd.), compounds represented by formula (BI) and compounds represented by formula (BII).

[In formula (BI) and formula (BII), ^Re and ^Rf represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group; ^Xe and ^Xf represent a single bond, * ^-Rg- , * ^-Rg -O-, * ^-Rg -S- or * ^-Rg -NH-; ^Rg represents an alkanediyl group having 1 to 6 carbon atoms; * represents a bond with O].

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc. Examples of ^Re and ^Rf include preferably a hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, and more preferably a hydrogen atom and methyl.

Examples of the alkanediyl group include methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc. Examples of ^Xe and ^Xf include a single _bond , methylene, ethylidene, * _-CH2 -O-, and * _{-CH2CH2 -} O-, and more preferably a single bond and * _-CH2CH2 -O- (* represents a bond with O).

Examples of the compound represented by formula (BI) include compounds represented by any one of formulas (BI-1) to (BI-15). Among them, preferred are compounds represented by formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9), or formula (BI-11) to formula (BI-15), and more preferred are compounds represented by formula (BI-1), formula (BI-7), formula (BI-9), or formula (BI-15).

Examples of the compound represented by formula (BII) include compounds represented by any one of formulas (BII-1) to (BII-15). Among them, preferred are compounds represented by formula (BII-1), (BII-3), (BII-5), (BII-7), (BII-9) or (BII-11) to (BII-15), and more preferred are compounds represented by formula (BII-1), (BII-7), (BII-9) or (BII-15).

The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone or in combination of two or more. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, the content ratio (compound represented by formula (BI) : compound represented by formula (BII)) is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

As (b2), a monomer having an oxycyclobutyl group and a (meth)acryloyloxy group is more preferred. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxycyclobutane, 3-methyl-3-acryloyloxymethyloxycyclobutane, 3-ethyl-3-methacryloyloxymethyloxycyclobutane, 3-ethyl-3-acryloyloxymethyloxycyclobutane, 3-methyl-3-methacryloyloxyethyloxycyclobutane, 3-methyl-3-acryloyloxyethyloxycyclobutane, 3-ethyl-3-methacryloyloxyethyloxycyclobutane, and 3-ethyl-3-acryloyloxyethyloxycyclobutane.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloyl group is more preferred. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

As (b), (b1) is preferred in terms of further improving the reliability of the obtained color filter in terms of heat resistance, chemical resistance, etc. Furthermore, (b1-2) is more preferred in terms of excellent storage stability of the colored curable composition.

Examples of (c) include (meth)acrylates not having a polycyclic hydrocarbon ring (cf-1) such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-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, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate (cf-1) (hereinafter sometimes referred to as "(cf-1)"); tricyclic (meth)acrylate [5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (which is usually called "dicyclopentanyl (meth)acrylate" in the technical field. It is also sometimes called "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate (which is usually called "dicyclopentenyl (meth)acrylate" in the technical field), dicyclopentyloxyethyl (meth)acrylate, isobutyl (meth)acrylate, adamantyl (meth)acrylate and the like (cf-2) (hereinafter sometimes referred to as "(cf-2)"); (meth)acrylates containing a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxy 5,6-di(2'-hydroxyethyl)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-di(2'-hydroxyethyl) ... [2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2 Bicyclic unsaturated compounds such as 5-(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimidamide; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. Among them, (meth)acrylates are preferred.

In the resin [K1], among all the structural units constituting the resin [K1], the ratio of the structural units from each is as follows: Preferably 2 to 60 mol% of the structural unit from (a) 40 to 98 mol% of the structural unit from (b) More preferably 10 to 50 mol% of the structural unit from (a) 50 to 90 mol% of the structural unit from (b) If the ratio of the structural units of the resin [K1] is within the above range, the storage stability of the coloring curable composition, the developability when forming the coloring pattern, and the solvent resistance of the obtained color filter tend to be excellent.

The resin [K1] can be produced, for example, by referring to the method described in the document "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, Kagaku Dojin, 1st edition, 1st print, issued on March 1, 1972) and the cited documents described in the document.

Specifically, the following method can be cited: a specific amount of (a) and (b), a polymerization initiator and a solvent are placed in a reaction container, and a deoxygenated atmosphere is formed by replacing oxygen with nitrogen, and the mixture is heated and kept warm while being stirred. Furthermore, the polymerization initiator and solvent used here are not particularly limited, and those commonly used in this field can be used. For example, as a polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide, tert-butyl peroxide 2-ethylhexanoate, etc.) can be cited as a solvent that can dissolve each monomer, and the solvents described later as the organic solvent (E) of the coloring curable composition of the present invention can be cited.

Furthermore, the obtained copolymer can be used directly as a solution after the reaction, can be used as a concentrated or diluted solution, or can be used as a solid (powder) obtained by reprecipitation or the like. In particular, by using the solvent contained in the coloring curable composition of the present invention as a solvent during the polymerization, the solution after the reaction can be directly used to prepare the coloring curable composition of the present invention, thereby simplifying the production steps of the coloring curable composition of the present invention.

In the resin [K2], among all the structural units constituting the resin [K2], the ratio of the structural units from each is as follows: Preferably 2 to 45 mol% of the structural unit from (a) 2 to 95 mol% of the structural unit from (b) 1 to 65 mol% of the structural unit from (c) More preferably 5 to 40 mol% of the structural unit from (a) 5 to 80 mol% of the structural unit from (b) 5 to 60 mol% of the structural unit from (c) If the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the coloring curable composition, the developability when forming a coloring pattern, and the solvent resistance, heat resistance and mechanical strength of the obtained color filter tend to be excellent.

The resin [K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

In resin [K3], among all the structural units constituting resin [K3], the ratio of the structural units from each is as follows: Preferably Structural unit from (a); 2-60 mol% Structural unit from (c); 40-98 mol% More preferably Structural unit from (a); 10-50 mol% Structural unit from (c); 50-90 mol% Resin [K3] can be manufactured, for example, in the same manner as the manufacturing method recorded as resin [K1].

Resin [K4] can be produced by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms in (b) to the carboxylic acid and/or carboxylic anhydride in (a). First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that exemplified in resin [K3].

Next, a portion of the carboxylic acid and/or carboxylic anhydride from (a) in the above copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms in (b). After the copolymer of (a) and (c) is produced, the atmosphere in the flask is replaced from nitrogen to air, and (b), a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.) and a polymerization inhibitor (e.g., hydroquinone, etc.) are placed in the flask and reacted at, for example, 60 to 130°C for 1 to 10 hours to produce resin [K4]. The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a). By setting the range, the storage stability of the coloring curable composition, the developability when forming the pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern tend to be good. Since the reactivity of the cyclic ether is high, the unreacted (b) is not easy to remain, so the (b) used as the resin [K4] is preferably (b1), and further preferably (b1-1). The amount of the above-mentioned reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the above-mentioned polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). The reaction conditions such as the addition method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by polymerization. In addition, similarly to the polymerization conditions, the addition method or reaction temperature can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by polymerization.

The first stage of resin [K5] is the same as the manufacturing method of the above-mentioned resin [K1], and a copolymer of (b) and (c) is obtained. As above, the obtained copolymer can be used directly as a solution after the reaction, a concentrated or diluted solution can be used, or a solid (powder) obtained by reprecipitation or the like can be used. The ratio of the structural units from (b) and (c) relative to the total molar number of all structural units constituting the above-mentioned copolymer is as follows: Preferably Structural units from (b); 5-95 mol% Structural units from (c); 5-95 mol% More preferably Structural units from (b); 10-90 mol% Structural units from (c); 10-90 mol%

Furthermore, under the same conditions as the method for producing resin [K4], the cyclic ether from (b) in the copolymer of (b) and (c) is reacted with the carboxylic acid or carboxylic anhydride in (a), thereby obtaining resin [K5]. The amount of (a) used in the above reaction with the copolymer is preferably 5 to 100 mol relative to 100 mol of (b). Since the reactivity of the cyclic ether is high, the unreacted (b) is not likely to remain, so (b1) is preferably used as the resin [K5], and further preferably (b1-1).

Resin [K6] is a resin obtained by reacting resin [K5] with a polycarboxylic acid and/or a carboxylic anhydride. The hydroxyl group produced by the reaction of the cyclic ether from (b) and the carboxylic acid or carboxylic anhydride from (a) is further reacted with a polycarboxylic acid and/or a carboxylic anhydride. Examples of the polycarboxylic acid include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, and triphenylamine formic acid. Examples of the carboxylic anhydride include succinic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. The amount of the polycarboxylic acid and/or carboxylic anhydride used is preferably 0.05 to 1 mol, more preferably 0.1 to 0.5 mol, relative to 1 mol of the amount of (a) used. That is, the resin [K6] preferably also has a structural unit obtained by adding (a) to the structural unit derived from (b) without adding a polycarboxylic acid and/or a carboxylic anhydride to a hydroxyl group generated by the reaction of the cyclic ether derived from (b) and the carboxylic acid or carboxylic anhydride derived from (a).

The resin (B) is preferably a resin containing a structural unit having an ethylenically unsaturated bond in a side chain (resin [K4], resin [K5], or resin [K6]), and more preferably a resin containing a structural unit containing a (meth)acryloyl group in a side chain.

Examples of the resin having a structural unit containing a (meth)acryloyl group in the side chain include: using a monomer (ba) having a (meth)acryloyl group such as glycidyl (meth)acrylate, 3,4-epoxyhexylmethyl (meth)acrylate, 3-methyl-3-methacryloyloxymethyloxycyclobutane, tetrahydrofurfuryl acrylate (hereinafter sometimes referred to as "(ba)") as the resin of (b) [K4]; using a monomer (aa) having a (meth)acryloyl group such as acrylic acid, methacrylic acid, succinic acid mono[2-(meth)acryloyloxyethyl] ester (hereinafter sometimes referred to as "(aa)") as the resin of (a) [K5]; or using (aa) as the resin of (a) [K6]. As the resin having a structural unit containing a (meth)acryl group in the side chain, it is preferred to use (aa) as the resin of (a) [K6].

As the resin having a structural unit containing a (meth)acryl group in the side chain, it is more preferred to include a resin [K6] having the following structural units: a structural unit containing a (meth)acryl group in the side chain and a structural unit containing a carboxylic acid group derived from a polycarboxylic acid and/or a carboxylic anhydride (a structural unit obtained by adding (aa) to a structural unit derived from (b) and further adding a polycarboxylic acid and/or a carboxylic anhydride), a structural unit containing a (meth)acryl group in the side chain and not containing a carboxylic acid group derived from The present invention further comprises a resin [K6] comprising a carboxylic acid group derived from a polycarboxylic acid and/or a carboxylic anhydride (a structural unit obtained by adding (aa) to a structural unit derived from (b)), and a structural unit derived from (c); and preferably a resin [K6] comprising a (meth)acryl group in a side chain, a carboxylic acid group derived from a polycarboxylic acid and/or a carboxylic anhydride (a structural unit obtained by adding (aa) to a structural unit derived from (b) and further adding a polycarboxylic acid carboxylic acid and/or carboxylic anhydride), a structural unit containing a (meth)acryloyl group in the side chain and not containing a carboxylic acid group from a polycarboxylic acid and/or carboxylic anhydride (a structural unit obtained by adding (aa) to a structural unit from (b)), and a structural unit from (cf-1) and/or (cf-2); particularly preferably, a resin [K6] containing the following structural units, a structural unit containing a (meth)acryloyl group in the side chain, Structural units derived from carboxylic acid groups of polycarboxylic acids and/or carboxylic anhydrides (structural units obtained by adding (aa) to structural units derived from (b) and further adding polycarboxylic acids and/or carboxylic anhydrides), structural units containing (meth)acryloyl groups in side chains, structural units not containing carboxylic acid groups derived from polycarboxylic acids and/or carboxylic anhydrides (structural units obtained by adding (aa) to structural units derived from (b)), and structural units derived from (cf-1) and (cf-2).

Furthermore, from the viewpoint of improving the residual film ratio, the resin (B) preferably contains the resin [K1] in addition to the resin having a structural unit having an ethylenically unsaturated bond in the side chain (resin [K4], resin [K5], or resin [K6]).

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 4,000 to 50,000, and even more preferably 5,000 to 30,000. If the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is higher, the solubility in the developer of the unexposed part is good, and the resolution of the colored pattern tends to be improved.

The dispersion degree [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

The acid value of the resin (B) is preferably 20 to 170 mg-KOH/g, more preferably 25 to 150 mg-KOH/g, and further preferably 30 to 130 mg-KOH/g when converted to solid content. 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, for example, by titration 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 further preferably 17 to 55% by mass relative to the total solid content of the coloring curable composition. If the content of the resin (B) is within the above range, a coloring pattern can be formed, and the resolution and residual film rate of the coloring pattern tend to be improved.

<Polymerizable compound (C)> The polymerizable compound (C) is a compound that can be polymerized by active free radicals and/or acids generated from a polymerization initiator (D). The polymerizable compound (C) includes compound (II).

＜＜Compound (II)＞＞ Compound (II) is a compound represented by the following formula (II).

[In formula (II), ^Ra represents a (q+r)-valent linking group; ^Rb represents an alkanediyl group having 1 to 20 carbon atoms; ^Rc represents an acryloxy group or a methacryloyloxy group; p represents an integer greater than or equal to 0; q represents an integer greater than or equal to 1; r represents an integer greater than or equal to 0; when formula (II) has a plurality of ^Rb , the ^Rb may be the same as or different from each other, when formula (II) has a plurality of ^Rc , the ^Rc may be the same as or different from each other, when formula (II) has a plurality of p, the p may be the same as or different from each other; wherein the total of the integers represented by p in formula (II) is greater than or equal to 2, and the total of the integers represented by q and the integers represented by r is greater than or equal to 3].

Examples of the (q+r)-valent linking group represented by ^Ra include compounds in which (q+r) hydrogen atoms contained in an aliphatic hydrocarbon having 3 to 30 carbon atoms are removed to form a bonding group, and the methylene group contained in the aliphatic hydrocarbon may be substituted with an oxygen atom to form an ether structure.

The aliphatic hydrocarbons having 3 to 30 carbon atoms may be saturated or unsaturated, preferably saturated. Furthermore, the aliphatic hydrocarbons having 3 to 30 carbon atoms may be chain aliphatic hydrocarbons, alicyclic hydrocarbons, or hydrocarbons obtained by combining chain aliphatic hydrocarbons and alicyclic hydrocarbons, preferably chain aliphatic hydrocarbons.

Examples of the above-mentioned chain aliphatic hydrocarbons include linear aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, and pentadecane; branched aliphatic hydrocarbons such as hydrocarbons represented by the following formulas (ac-1) to (ac-15); and the like.

The carbon number of the chain aliphatic hydrocarbon is preferably 3 to 25, more preferably 4 to 20, and further preferably 6 to 20. In addition, as the chain aliphatic hydrocarbon, a branched chain aliphatic hydrocarbon is preferred, preferably having tertiary or higher carbon atoms, more preferably having quaternary carbon atoms, and further preferably having 2 or more quaternary carbon atoms. Among them, hydrocarbons represented by formula (AC-7) to (AC-15) are preferred, and hydrocarbons represented by formula (AC-7), formula (AC-10), formula (AC-11), and formula (AC-15) are more preferred.

Examples of the alicyclic hydrocarbon include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, and the like; northane, adamantane, and bicyclo[2.2.2]octane, etc. The carbon number of the alicyclic hydrocarbon is preferably 3 to 28, more preferably 5 to 25, and even more preferably 8 to 23.

The alkyl obtained by combining the chain aliphatic hydrocarbon and the alicyclic hydrocarbon may be a alkyl obtained by combining two or more of the chain aliphatic hydrocarbons and the alicyclic hydrocarbons listed above. In the alkyl obtained by the combination, the chain aliphatic hydrocarbon may be combined in the form of a monovalent or divalent group (e.g., an alkyl group, an alkanediyl group). Examples of the alkyl obtained by the combination include methylcyclopropane, 1,3-dimethylcyclobutane, 1,2,4,5-tetramethylcyclohexane, and dicyclohexylmethane. The carbon number of the alkyl obtained by combining the chain aliphatic hydrocarbon and the alicyclic hydrocarbon is preferably 6 to 30, more preferably 6 to 28, and even more preferably 6 to 25.

The methylene group contained in the aliphatic hydrocarbon is preferably substituted with an oxygen atom to form an ether structure, more preferably 1 to 3 ether structures are formed, and even more preferably 1 ether structure is formed.

In the above-mentioned aliphatic hydrocarbon, the site from which a hydrogen atom is removed to form a bonding group is preferably a carbon atom (including a terminal carbon atom) of a -CH ₃ portion contained in the aliphatic hydrocarbon. Furthermore, it is more preferred that only one hydrogen atom is removed from one -CH ₃ portion to form a bonding group.

Examples of the alkanediyl group having 1 to 20 carbon atoms represented by ^Rb include straight-chain alkanediyl groups such as methylene, ethylidene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, and decane-1,10-diyl; and branched-chain alkanediyl groups such as ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, 2-methylpropane-1,2-diyl, 2-methylpropane-1,3-diyl, butane-1,3-diyl, 2-methylbutane-1,4-diyl, and pentane-1,4-diyl; and the like.

The carbon number of the alkanediyl group represented by R ^b is preferably 1-10, more preferably 1-8, further preferably 1-5, further preferably 2-4.

R ^c is preferably an acryloyloxy group.

As p, it is preferably an integer of 0 to 15, more preferably an integer of 1 to 10, further preferably an integer of 1 to 8, further preferably an integer of 1 to 6, further preferably an integer of 1 to 4, and particularly preferably an integer of 2 to 3. The total of the integers represented by p in formula (II) is 2 or more, and the sum is preferably 2 to 60, more preferably 4 to 50, further preferably 4 to 40, further preferably 5 to 30, and particularly preferably 8 to 20. By containing the compound (II) in which the total of the integers represented by p is within the above range as a polymerizable compound, a coloring curable composition can be provided in which the pattern does not reflow even when heated at a temperature of 150° C. or more.

q is preferably an integer of 1 to 12, more preferably an integer of 2 to 10, and still more preferably an integer of 4 to 8.

As r, an integer of 0 to 6 is preferred, an integer of 0 to 4 is more preferred, an integer of 0 to 2 is further preferred, an integer of 0 to 1 is further preferred, and 0 is particularly preferred.

The sum of the integer represented by q and the integer represented by r is 3 or more, preferably 3-12, more preferably 4-10, further preferably 5-10, further more preferably 6-10.

As compound (II), as shown in Tables 2 to 4, the most preferred are compounds II-1 to II-240 represented by formula (II-x).

[Table 2]

[Table 3]

[Table 4]

In Tables 2 to 4, Ax-1 and Ax-2 respectively refer to the groups represented by the following formula (Ax-1) and formula (Ax-2), Bx-1 refers to ethylidene, Bx-2 refers to propane-1,2-diyl, Cx-1 refers to acryloxy, Cx-2 refers to methacryloxy, and tPx refers to the total number of integers represented by px in formula (II-x). In the following formula (Ax-1) and formula (Ax-2), * represents a bond.

Among them, as compound (II), preferred are compounds II-1 to II-120, more preferred are compounds II-1 to II-96, further preferred are compounds II-1 to II-48, further preferred are compounds II-13 to II-36, further preferred are compounds II-13, compound II-14, compound II-17, compound II-18, compound II-21, compound II-22, compound II-25, compound II-26, compound II-29, compound II-30, compound II-33, and compound II-34, and particularly preferred are compounds II-21, compound II-22, compound II-33, and compound II-34.

As compound (II), commercially available products can be used, for example, A-DPH6E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., number of ethylene oxide chains: 6), A-DPH12E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., number of ethylene oxide chains: 12), A-DPH18E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., number of ethylene oxide chains: 18), A-DPH24E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., number of ethylene oxide chains: 24), A-DPH48E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., number of ethylene oxide chains: 48), A-DPH6PO (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., number of propylene oxide chains: 6), etc. Furthermore, the above-mentioned ethylene oxide chain is equivalent to a group (chain) in which R ^b of "-OR ^b -" in compound (II) is an ethylene group, and the propylene oxide chain is equivalent to a group (chain) in which R ^b of "-OR ^b -" in compound (II) is a propylene group. The number of ethylene oxide chains or propylene oxide chains is equivalent to the total number of the integer represented by p in compound (II).

The content of the compound (II) in the total amount of the polymerizable compound (C) is preferably 50 to 100 mass %, more preferably 60 to 100 mass %, and even more preferably 80 to 100 mass %.

＜＜Polymerizable compound (C1)＞＞ The coloring curable composition of the present invention may contain a polymerizable compound (polymerizable compound (C1)) other than compound (II) as polymerizable compound (C). The polymerizable compound (C1) is a compound that can be polymerized by active free radicals and/or acids generated from a polymerization initiator (D), for example, a polymerizable compound having ethylenic unsaturated bonds other than compound (II), preferably a (meth)acrylate compound other than compound (II).

Among them, the polymerizable compound (C1) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compound (C1) include trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

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

The content of the polymerizable compound (C) is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass, based on the total solid content of the coloring curable composition.

<Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active free radicals, acids, etc. by the action of light or heat to initiate polymerization, and a known polymerization initiator can be used. Examples of polymerization initiators that generate active free radicals include phenanone compounds, trioxane compounds, acylphosphine oxide compounds, O-acyl oxime compounds, and biimidazole compounds.

The above-mentioned O-acyl oxime compound is a compound having a partial structure represented by the following formula (d1): Hereinafter, * represents a bond.

Examples of the O-acyl oxime compound include N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-{2-methyl-4- [0063] (3,3-dimethyl-2,4-dioxolanylmethoxy)benzyl}-9H-carbazol-3-yl]ethane-1-imide, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imide, N-benzyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imide, N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imide, etc. Commercially available products such as Irgacure OXE01, OXE02 (both manufactured by BASF) and N-1919 (manufactured by ADEKA) can be used. Among them, the O-acyl oxime compound is preferably at least one selected from the group consisting of N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine and N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, and more preferably N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine and N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine. In the case of these O-acyl oxime compounds, there is a tendency to obtain a color filter with high brightness.

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

Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) can be used.

Examples of compounds having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzoyl dimethyl ketal. In terms of sensitivity, the benzophenone compound is preferably a compound having a partial structure represented by formula (d2).

Examples of the tris(iodine) compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris(iodine), 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tris(iodine), 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tris(iodine), 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris(iodine), 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris(iodine), [2-(5-methylfuran-2-yl)vinyl]-1,3,5-trisin, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-trisin, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-trisin, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-trisin, and the like.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can be used.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Laid-Open No. 6-75372 and Japanese Patent Laid-Open No. 6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, Biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with alkoxycarbonyl groups (for example, see Japanese Patent Publication No. 7-10913, etc.).

Further, as the polymerization initiator (D), there can be exemplified: benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, diphenylethanedione, methyl phenylglyoxylate, and titaniumocene compounds, etc. These are preferably used in combination with the polymerization initiator aid (D1) (particularly amines) described later.

Examples of the polymerization initiator that generates an acid include onium salts such as 4-hydroxyphenyldimethylzincium p-toluenesulfonate, 4-hydroxyphenyldimethylzincium hexafluoroanticorate, 4-acetoxyphenyldimethylzincium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylzincium hexafluoroanticorate, triphenylzincium p-toluenesulfonate, triphenylzincium hexafluoroanticorate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroanticorate, nitrobenzyl toluenesulfonates, and benzoin toluenesulfonates.

The polymerization initiator (D) is preferably a polymerization initiator comprising at least one selected from the group consisting of a phenanone compound, a trioxane compound, an acylphosphine oxide compound, an O-acyl oxime compound and a biimidazole compound, and more preferably a polymerization initiator comprising an O-acyl oxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the content of the polymerization initiator (D) is within the above range, there is a tendency for high sensitivity and shortened exposure time, thereby improving the productivity of the optical filter.

＜Polymerization initiator (D1)＞ The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound that starts polymerization by the polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiator (D1) include 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethyl-9-thiothionate, , N-phenylglycine, etc.

When the polymerization initiator (D1) is used, its content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the amount of the polymerization initiator (D1) is within this range, a colored pattern can be formed with higher sensitivity, and there is a tendency that the productivity of the color filter is improved.

<Organic solvent (E)> The organic solvent (E) is not particularly limited, and any organic solvent commonly used in the field can be used. For example, ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH but not -O-, -CO- and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. can be cited.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, cyclohexyl acetate, and γ-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, and methyl anisole.

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

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone.

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 1,3,5-trimethylbenzene.

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

The organic solvent (E) preferably includes one or more selected from the group consisting of ether solvents, ether ester solvents and ketone solvents, more preferably includes ether ester solvents and ketone solvents, and further preferably includes propylene glycol monomethyl ether acetate and 4-hydroxy-4-methyl-2-pentanone.

The content of the organic solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, relative to the total amount of the coloring curable composition of the present invention. In other words, the solid content of the coloring curable composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. If the content of the organic solvent (E) is within the above range, the flatness during coating becomes good, and since the color concentration is sufficient when forming a color filter, there is a tendency that the display characteristics become good.

<Leveling agent (F)> As the leveling agent (F), silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms can be cited. These surfactants may have polymerizable groups in the side chains. As silicone-based surfactants, surfactants having siloxane bonds in the molecule can be cited. Specifically, there can be mentioned Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Maitu Advanced Materials Japan Co., Ltd.), etc.

Examples of the fluorine-based surfactant include surfactants having a fluorine-carbon chain in the molecule. Specifically, there are Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC Co., Ltd.), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Corporation), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by AGC Co., Ltd. (formerly Asahi Glass Co., Ltd.)) and E5844 (manufactured by Daikin Fine Chemicals Laboratories Co., Ltd.), etc.

Examples of the silicone-based surfactant having fluorine atoms include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, etc. Specifically, examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Corporation).

When the leveling agent (F) is included, the content of the leveling agent (F) is preferably 0.001 to 0.2 mass%, more preferably 0.002 to 0.1 mass%, relative to the total amount of the coloring curable composition. In addition, the content does not include the content of the above-mentioned pigment dispersant. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients> The coloring curable composition of the present invention may contain fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., as well as additives known in the art, as needed.

<Method for producing a coloring curable composition> The coloring curable composition of the present invention can be prepared, for example, by mixing a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and an organic solvent (E), and a leveling agent (F) and other components as needed. The coloring agent (A) can be prepared using the above-mentioned coloring dispersion or pigment dispersion. By mixing the residual components in the coloring dispersion or pigment dispersion in a manner to obtain a specific concentration, the target coloring curable composition can be prepared. When the dye (A1-1) is included, the dye (A1-1) can be dissolved in part or all of the organic solvent (E) to prepare a solution. It is preferred to filter the solution using a filter having a pore size of about 0.01 to 1 μm. Furthermore, the mixed colored curable composition is preferably filtered through a filter having a pore size of about 0.01 to 10 μm.

<Method for manufacturing color filter> As a method for manufacturing a coloring pattern from the coloring curable composition of the present invention, photolithography, inkjet method, printing method, etc. can be cited. Among them, photolithography is preferred. Photolithography is a method of applying the above-mentioned coloring curable composition on a substrate and drying it to form a coloring composition layer, and exposing and developing the coloring composition layer through a photomask. In the photolithography method, since no photomask is used during exposure and/or no development is performed, a cured product of the above-mentioned coloring composition layer, i.e., a coloring film, can be formed. The coloring pattern or coloring film formed in this way is the color filter of the present invention.

As the substrate, the following glass plates can be used: quartz glass, borosilicate glass, alumina silicate glass, sodium calcium glass coated with silicon dioxide, etc.; resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc.; silicon; aluminum, silver, silver/copper/palladium alloy thin films formed on the above substrates. Other color filter layers, resin layers, transistors, circuits, etc. can be formed on these substrates.

The formation of pixels of various colors by photolithography can be performed by known or conventional devices or conditions. For example, it can be produced as follows. First, the coloring curable composition is applied to the substrate, and heat drying (pre-baking) and/or reduced pressure drying are performed to remove volatile components such as solvents, thereby obtaining a smooth coloring composition layer. As coating methods, spin coating, slit coating, slit-spin coating, etc. can be cited. The temperature when heating and drying is preferably 30 to 120°C, and more preferably 50 to 110°C. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. When performing reduced pressure drying, it is preferably performed at a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C. The film thickness of the coloring composition layer is not particularly limited and can be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a mask for forming a target coloring pattern. The pattern on the mask is not particularly limited, and a pattern corresponding to the target use can be used. As a light source used for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferred. For example, a filter that cuts off the wavelength region can be used to cut off light that does not reach 350 nm, or a bandpass filter that extracts the wavelength region can be used to selectively extract light near 436 nm, near 408 nm, and near 365 nm. Specifically, as a light source, mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, etc. can be cited. In order to uniformly irradiate the entire exposure surface with parallel light or to accurately align the photomask with the substrate on which the colored composition layer is formed, it is preferred to use an exposure device such as a photomask alignment exposure machine and a stepper exposure machine.

The exposed coloring composition layer is brought into contact with a developer for development, thereby forming a coloring pattern on the substrate. By developing, the unexposed portion of the coloring composition layer is dissolved in the developer and removed. As a developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, etc. is preferred. The concentration of the alkaline compound in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Furthermore, the developer may also contain a surfactant. The developing method may be any one of a coating method, an immersion method, and a spray method. Furthermore, the substrate may be tilted at any angle during development. After development, it is preferred to perform water washing.

Furthermore, it is preferred to post-bake the obtained colored pattern. The post-bake temperature is preferably 150-250° C., more preferably 170-245° C., and further preferably 180-240° C. The post-bake time is preferably 1-120 minutes, and more preferably 5-60 minutes.

The thickness of the coating after post-baking is preferably 3 μm or less, more preferably 2.0 μm or less. The lower limit of the coating thickness is not particularly limited, but is usually 0.3 μm or more, and may be 0.5 μm or more.

According to the coloring curable composition of the present invention, a coloring curable composition can be provided, which can be used to manufacture a color filter with good pattern shape, and the pattern has good reflow resistance during post-baking. The color filter can be used as a filter for display devices (such as liquid crystal display devices, organic EL (electroluminescence) devices, electronic paper, etc.) and solid-state imaging devices. [Example]

Hereinafter, the present invention will be described in more detail with reference to the following embodiments, however, the present invention is not limited to the following embodiments. In the examples, unless otherwise specified, "parts" means "parts by mass", and "%" means "% by mass".

(Synthesis Example 1) A suitable amount of nitrogen gas was flowed into a flask equipped with a reflux cooler, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80°C while stirring. Next, a solution prepared by dissolving 38 parts of acrylic acid, 289 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl acrylate (content ratio of 1:1) in 125 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over about 5 hours using a dropping pump. On the other hand, using another drop pump, a solution obtained by dissolving 33 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator in 235 parts of propylene glycol monomethyl ether acetate was dripped into the flask over a period of about 6 hours. After the dripping was completed, the solution was kept at 80°C for 4 hours and then cooled to room temperature to obtain a polymer (resin (B-1)) solution having a polymer solid content of 35.1%. The weight average molecular weight Mw of the resulting copolymer (polymer; resin (B-1)) was 9200, the degree of dispersion was 2.08, and the acid value when converted to solid content was 77 mg-KOH/g. The resulting copolymer had the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin are determined using the GPC method (Gel Permeation Chromatography) under the following conditions. Apparatus: K2479 (manufactured by Shimadzu Corporation) Column: SHIMADZU Shim-pack GPC-80M Column temperature: 40°C Solvent: THF (tetrahydrofuran) Flow rate: 1.0 mL/min Detector: RI (refractive index detector) Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation) The ratio of the weight average molecular weight and the number average molecular weight (Mw/Mn) obtained above in terms of polystyrene conversion was taken as the dispersion degree.

(Synthesis Example 2) 276.8 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while replacing the atmosphere with nitrogen, and the temperature was raised to 120°C. Next, 35.3 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator) was added to a monomer mixture containing 92.4 g of 2-ethylhexyl acrylate, 184.9 g of glycidyl methacrylate, and 12.3 g of dicyclopentyl methacrylate, and the mixture was dripped from the dropping funnel into the above flask over 2 hours. After the dripping was completed, the mixture was further stirred at 120°C for 30 minutes to carry out a copolymerization reaction, thereby generating an addition copolymer. Afterwards, the flask was replaced with air, and 93.7 g of acrylic acid, 1.5 g of triphenylphosphine (catalyst), and 0.8 g of p-methoxyphenol (polymerization inhibitor) were added to the above-mentioned addition copolymer solution, and the reaction was continued at 110°C for 10 hours. The epoxy groups from glycidyl methacrylate reacted with acrylic acid to cleave the epoxy groups, and at the same time, polymerizable unsaturated bonds were introduced into the side chains of the polymer. Next, 24.2 g of succinic anhydride was added to the reaction system, and the reaction was continued at 110°C for 1 hour. The hydroxyl groups generated by the cleavage of the epoxy groups reacted with succinic anhydride, and carboxyl groups were introduced into the side chains to obtain a polymer. Finally, 383.3 g of propylene glycol monomethyl ether acetate was added to the reaction solution to obtain a polymer (resin (B-2)) solution having a polymer solid content of 40%. The weight average molecular weight Mw of the resulting copolymer (polymer; resin (B-2)) was 6.3×10 ³ , and the acid value when converted to solid content was 34 mg-KOH/g.

(Preparation of Dispersion 1) 14 parts of CI Direct Blue 86, 4.1 parts of dispersant (BYK LPN-6919 manufactured by BYK), 2.8 parts of resin (B-1) (converted to solid content), and 79.1 parts of propylene glycol monomethyl ether acetate were mixed, 300 parts of 0.4 mm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain Dispersion 1.

(Preparation of Dispersion 2) 14 parts of C.I. Direct Blue 199, 4.1 parts of dispersant (BYK LPN-6919 manufactured by BYK), 2.8 parts of resin (B-1) (converted to solid content), and 79.1 parts of propylene glycol monomethyl ether acetate were mixed, 300 parts of 0.4 mm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain Dispersion 2.

[Examples 1 to 4, Comparative Examples 1 to 2] (Preparation of coloring curable composition) The components shown in Table 5 were mixed to obtain each coloring curable composition.

[Table 5] Unit: (piece) Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparison Example 1 Comparison Example 2 Dispersion 1 480 480 480 480 Dispersion 2 480 Compound (z) 57 Resin (B) 47 47 47 47 60 47 Polymerizable compound (C-1) 40 40 Polymerizable compound (C-2) 40 Polymerizable compound (C-3) 40 40 Polymerizable compound (C-4) 40 Polymerization initiator (D) 5 5 5 5 5 5 Organic solvent (E-1) 458 Organic solvent (E-2) 708 708 708 708 458 708

In Table 5, the components are as follows. Compound (z): a compound represented by the following formula (z)

Resin (B): Resin (B-2) (solid content conversion) Polymerizable compound (C-1): Dipentaerythritol polyacrylate ("A9550" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., solid content conversion) Polymerizable compound (C-2): Ethylene oxide-modified dipentaerythritol hexaacrylate ("A-DPH6E" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., number of ethylene oxide chains: 6, solid content conversion) Polymerizable compound (C-3): Ethylene oxide-modified dipentaerythritol hexaacrylate ("A-DPH12E" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., number of ethylene oxide chains: 12, solid content conversion) Polymerizable compound (C-4): Ethylene oxide-modified dipentaerythritol hexaacrylate ("A-DPH48E" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., number of ethylene oxide chains: 48, solid content conversion) Polymerization initiator (D): N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine Organic solvent (E-1): 4-Hydroxy-4-methyl-2-pentanone Organic solvent (E-2): Propylene glycol monomethyl ether acetate

(Production of Colored Patterns) On a 4-inch silicon substrate, a colored curable composition was applied by spin coating in such a manner that the film thickness after post-baking became 0.8 μm, and then pre-baked at 80°C for 2 minutes to obtain a colored composition layer. After cooling, the substrate formed with the colored composition layer was irradiated with light using an exposure machine (NSR-1755i7A; manufactured by Nikon Corporation) with an exposure amount of 300 mJ/ ^cm2 (365 nm reference). A dot pattern of 1.0 μm square was used as a photomask. The colored composition layer after light irradiation was immersed in an aqueous developer containing tetramethylammonium hydroxide at 23°C for 30 seconds, and after washing with water, a colored pattern I after development (before post-baking) was obtained. Furthermore, the substrate formed with the colored pattern I was post-baked at 230° C. for 10 minutes to obtain a post-baked colored pattern II.

(Evaluation of reflow resistance of colored patterns) For the silicon wafer substrate having the colored pattern I or the colored pattern II obtained above, the formed colored pattern was observed using an electron microscope (S-4100, manufactured by Hitachi High-Tech Corporation) at a magnification of 30,000 times. When the colored pattern was viewed from the side (refer to Figure 1), the width lc (width represented by lc in Figure 1) of the colored pattern at a height hb (height represented by hb in Figure 1) of 90% of the film thickness la (length represented by la in Figure 1) was measured, and the change rate of lc before and after post-baking was calculated (lc of colored pattern II/lc of colored pattern I×100(%)), and the evaluation was performed according to the following judgment criteria. The results are shown in Table 6. ○: The change rate of lc before and after post-baking is more than 90% △: The change rate of lc before and after post-baking is more than 70% and less than 90% ×: The change rate of lc before and after post-baking is less than 70%

[Table 6] Reflow resistance Embodiment 1 ○ Embodiment 2 ○ Embodiment 3 ○ Embodiment 4 ○ Comparison Example 1 × Comparison Example 2 △

la: film thickness lc: width hb: height

FIG. 1 is a schematic side view of a colored pattern obtained from the colored curable composition of the embodiment or comparative example.

Claims (11)

A coloring curable composition comprises a coloring agent, an organic solvent, a resin, a polymerizable compound and a polymerization initiator, wherein the coloring agent comprises a compound represented by formula (I), the polymerizable compound comprises a compound represented by formula (II),

[In formula (I), X represents a hydrogen atom or a monovalent metal atom; ^R1 represents a substituted or unsubstituted amino group or a substituted alkyl group having 1 to 20 carbon atoms; n represents an integer of 1 to 4; m represents an integer of 0 to 4; when formula (I) has a plurality of Xs, Xs may be the same or different from each other; when formula (I) has a plurality of ^R1s , ^R1s may be the same or different from each other],

[In formula (II), ^Ra represents a (q+r)-valent linking group; ^Rb represents an alkanediyl group having 1 to 20 carbon atoms; ^Rc represents an acryloxy group or a methacryloyloxy group; p represents an integer greater than or equal to 0; q represents an integer greater than or equal to 1; and r represents an integer greater than or equal to 0; when formula (II) has a plurality of ^Rb , the ^Rb may be the same as or different from each other, when formula (II) has a plurality of ^Rc , the ^Rc may be the same as or different from each other, and when formula (II) has a plurality of p, the p may be the same as or different from each other; wherein the total of the integers represented by p in formula (II) is 8 to 60, and the total of the integers represented by q and the integers represented by r is 3 or greater]. The colored curable composition of claim 1 comprises at least one compound selected from the group consisting of C.I. Direct Blue 86, C.I. Direct Blue 87, C.I. Direct Blue 199 and C.I. Reactive Blue 25 as the compound represented by the above formula (I). The colored curable composition of claim 1 or 2, wherein in the compound represented by the above formula (II), ^Ra represents a group obtained by removing (q+r) hydrogen atoms from an aliphatic hydrocarbon having 3 to 30 carbon atoms, and the methylene group contained in the aliphatic hydrocarbon may be substituted with an oxygen atom to form an ether structure. The colored curable composition of claim 1 or 2, wherein in the compound represented by the above formula (II), R ^b represents an alkanediyl group having 1 to 10 carbon atoms. The colored curable composition of claim 1 or 2, wherein in the compound represented by the above formula (II), r represents an integer of 0 to 6. The colored curable composition of claim 1 or 2, wherein in the compound represented by the above formula (II), q represents an integer of 2 to 12. A colored curable composition as claimed in claim 1 or 2, wherein the resin has a structural unit containing a (meth)acryl group in the side chain. The colored curable composition of claim 1 or 2, wherein the polymerization initiator comprises an O-acyl oxime compound. A color filter formed by a colored curable composition as described in any one of claims 1 to 8. A display device comprising a color filter as claimed in claim 9. A solid-state imaging element comprising a color filter as claimed in claim 9.