Coloring and curing composition

Abstract

To provide a colored curable composition which is useful for production of a color filter having a good pattern shape, while enabling a pattern to have high reflow resistance during post-baking.SOLUTION: The colored curable composition comprises a coloring agent, an organic solvent, a resin, a polymerizable compound, and a polymerization initiator, where the coloring agent contains a compound represented by formula (I).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a colored curable composition, and more particularly to a colored curable composition containing a phthalocyanine dye. [Background technology]

[0002] Color filters used in displays such as liquid crystal displays, electroluminescent displays, and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors, are produced from colored curable resin compositions. Phthalocyanine dyes are known as colorants used in colored curable resin compositions for forming the color filters (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2011-28236 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, in a conventional colored curable resin composition using a phthalocyanine dye as a colorant as described in Patent Document 1, the pattern reflows during post-baking, and the pattern shape is not fully satisfactory. An object of the present invention is to provide a colored curable composition which is useful for producing a color filter having a good pattern shape and which has high reflow resistance of the pattern during post-baking. [Means for solving the problem]

[0005] That is, the gist of the present invention is as follows. [1] A colorant, an organic solvent, a resin, a polymerizable compound, and a polymerization initiator, The colorant comprises a compound represented by formula (I), The colored curable composition, wherein the polymerizable compound comprises a compound represented by formula (II). [ka] In formula (I), X represents a hydrogen atom or a monovalent metal atom. R 1 represents a substituted or unsubstituted amino group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. n represents an integer of 1 to 4. m represents an integer of 0 to 4. When formula (I) has a plurality of X, X may be the same or different from each other, and when formula (I) has a plurality of R 1 If R 1 may be the same or different.] [ka] [In formula (II), R a represents a (q+r)-valent linking group. R b represents an alkanediyl group having 1 to 20 carbon atoms. R c represents an acryloyloxy group or a methacryloyloxy group. p represents an integer of 0 or greater. q represents an integer of 1 or greater. r represents an integer of 0 or greater. Formula (II) is a compound represented by the formula b If R b may be the same or different, and formula (II) may include multiple R c If R c may be the same as or different from each other, and when formula (II) has a plurality of p's, the p's may be the same as or different from each other. However, the sum of the integers represented by p in formula (II) is 2 or more, and the sum of the integers represented by q and r is 3 or more. [2] The colored curable composition according to [1], comprising 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 formula (I). [3] In the compound represented by formula (II), R a represents a group obtained by removing (q+r) hydrogen atoms from an aliphatic hydrocarbon having 3 to 30 carbon atoms (a methylene group contained in the aliphatic hydrocarbon may be substituted with an oxygen atom to form an ether structure), [4] In the compound represented by formula (II), R b The colored curable composition according to any one of [1] to [3], wherein represents an alkanediyl group having 1 to 10 carbon atoms. [5] The colored curable composition according to any one of [1] to [4], wherein in the compound represented by formula (II), r represents an integer of 0 to 6. [6] The colored curable composition according to any one of [1] to [5], wherein in the compound represented by formula (II), q represents an integer of 2 to 12. [7] The colored curable composition according to any one of [1] to [5], wherein in the compound represented by formula (II), the sum of integers represented by p in formula (II) is 2 to 60. [8] The colored curable composition according to any one of [1] to [7], wherein the resin has a structural unit containing a (meth)acryloyl group in a side chain. [9] The colored curable composition according to any one of [1] to [8], wherein the polymerization initiator comprises an O-acyloxime compound.

[10] A color filter formed from the colored curable composition according to any one of [1] to [9].

[11] A display device comprising the color filter according to

[10] .

[12] A solid-state imaging device comprising the color filter according to

[10] . Effect of the Invention

[0006] According to the present invention, it is possible to provide a colored curable composition which is useful for producing a color filter having a good pattern shape and has high reflow resistance of the pattern during post-baking. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic side view of a colored pattern obtained from a colored curable composition of an Example or Comparative Example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The colored curable composition of the present invention contains a colorant (hereinafter, may be referred to as colorant (A)), an organic solvent (hereinafter, may be referred to as organic solvent (E)), a resin (hereinafter, may be referred to as resin (B)), a polymerizable compound (hereinafter, may be referred to as polymerizable compound (C)), and a polymerization initiator (hereinafter, may be referred to as polymerization initiator (D)). The colorant (A) contains a compound represented by formula (I) (hereinafter, may be referred to as compound (I)). The colorant (A) may contain a colorant other than the compound (I) (hereinafter, may be referred to as colorant (A1)). The polymerizable compound (C) includes a compound represented by formula (II) (hereinafter, may be referred to as compound (II)). The polymerizable compound (C) may contain a polymerizable compound other than the compound (II) (hereinafter, may be referred to as a polymerizable compound (C1)). The colored curable composition of the present invention may contain a leveling agent (hereinafter, may be referred to as leveling agent (F)). In this specification, the compounds exemplified as each component may be used alone or in combination, unless otherwise specified.

[0009] <Colorant (A)> The colorant (A) comprises a compound (I).

[0010] <<Compound (I)>> Compound (I) is a compound represented by the following formula (I).

[0011] [ka] In formula (I), X represents a hydrogen atom or a monovalent metal atom. R 1 represents a substituted or unsubstituted amino group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. n represents an integer of 1 to 4. m represents an integer of 0 to 4. When formula (I) has a plurality of X, X may be the same or different from each other, and when formula (I) has a plurality of R 1 If R 1 may be the same or different.]

[0012] Compound (I) is a compound represented by the following formula (I-0), in which (n+m) hydrogen atoms are replaced by n -SO 3 x and m -SO 2 R 1 represents a compound substituted with

[0013] [ka]

[0014] 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.

[0015] Examples of the monovalent metal atom represented by X include alkali metal atoms such as Na, K, and Li. X is preferably any one of a hydrogen atom, Na, K, and Li, and more preferably a hydrogen atom or Na.

[0016] R 1Examples of the substituted or unsubstituted amino group represented by the formula (I) include an amino group; an amino group having one or two hydrocarbon groups bonded thereto, such as an N-methylamino group, an N-ethylamino group, an N-phenylamino group, an N,N-dimethylamino group, or an N,N-diethylamino group (the hydrocarbon group preferably has 1 to 15 carbon atoms, and more preferably has 1 to 10 carbon atoms). 1 As the substituted or unsubstituted amino group represented by the following formula:

[0017] R 1 Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by the formula (1) include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or alicyclic.

[0018] R 1 Examples of the saturated or unsaturated chain hydrocarbon group represented by the formula (I) include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; an isopropyl group, a (1-ethyl)propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a (1-ethyl)butyl group, a (2-ethyl)butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, and Examples of such alkyl groups include branched alkyl groups such as (2-methyl)pentyl, isohexyl, (5-methyl)hexyl, and (3-ethyl)heptyl; and alkenyl groups such as vinyl, 1-propenyl, 2-propenyl (allyl), (1-methyl)ethenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, (1-(2-propenyl))ethenyl, (1,2-dimethyl)propenyl, and 2-pentenyl. The number of carbon atoms in the saturated or unsaturated chain hydrocarbon group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 8.

[0019] R 1Examples of the saturated or unsaturated alicyclic hydrocarbon group represented by the formula (1) include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; cycloalkenyl groups such as cyclohexenyl group (e.g., cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl group, and cyclooctenyl group; norbornyl group, adamantyl group, and bicyclo[2.2.2]octyl group. The number of carbon atoms in the saturated or unsaturated alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 15, and further preferably 4 to 15.

[0020] R 1 Examples of the aromatic hydrocarbon group represented by the formula (I) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenanthryl group, an anthryl group, a pyrenyl group, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 18, and further preferably 6 to 15.

[0021] R 1The hydrocarbon group represented by the formula (I) may be a group obtained by combining two or more of the chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups listed above, so long as the upper limit of the carbon number is not more than 20. Such a group may be, for example, a group obtained by combining an aromatic hydrocarbon group with at least one group selected from a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and in such a combined hydrocarbon group, the chain hydrocarbon group may be combined as a divalent group (for example, an alkanediyl group). Examples of the combined hydrocarbon groups include aralkyl groups such as benzyl, phenethyl, and 1-methyl-1-phenylethyl; arylalkenyl groups such as phenylethenyl (phenylvinyl); arylalkynyl 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, 2,6-diisopropylphenyl, and the like. alkylaryl groups such as arylphenyl, 2,4,6-triisopropylphenyl, and 4-butylphenyl; aryl groups to which an alkanediyl group is bonded, such as a 2,3-dihydro-4-indenyl group, a 1,2,3,5,6,7-hexahydro-4-s-indacenyl group, a 5,6,7,8-tetrahydro-1-naphthyl group, and a 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl group; aryl groups to which one or more aryl groups are bonded, such as a biphenylyl group and a terphenylyl group; a cyclohexylmethylphenyl group, a benzylphenyl group, and a (dimethyl(phenyl)methyl)phenyl group.The hydrocarbon group may be, for example, a hydrocarbon group formed by a combination of a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of such groups include alicyclic hydrocarbon groups having one or more alkyl groups bonded thereto, such as a 1-methylcyclopropyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, a 1,2-dimethylcyclohexyl group, a 1,3-dimethylcyclohexyl group, a 2,4,6-trimethylcyclohexyl group, a 2,2,6,6-tetramethylcyclohexyl group, a 4-pentylcyclohexyl group, or a 4-octylcyclohexyl group; and alkyl groups having one or more alicyclic hydrocarbon groups bonded thereto, such as a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a 2-methylcyclohexylmethyl group, a cyclohexylethyl group, or an adamantylmethyl group. The chain hydrocarbon group, the alicyclic hydrocarbon group, and the group obtained by combining two or more aromatic hydrocarbon groups preferably have 4 to 20 carbon atoms, and more preferably 6 to 18 carbon atoms.

[0022] R 1 The hydrocarbon group having 1 to 20 carbon atoms represented by the following formula is preferably an aliphatic hydrocarbon group, more preferably a saturated chain aliphatic hydrocarbon group.

[0023] R 1Examples of the substituent that the hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) may have include a halogen atom, a nitrile group, a nitro group, an amino group, a hydroxy group, an alkoxy group having 1 to 15 carbon atoms, such as a methoxy group or an ethoxy group, an aryloxy group having 6 to 20 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group or a 2-naphthyloxy group, a silyl group, a boryl group, an alkylamino group having 1 to 15 carbon atoms, such as a monomethylamino group, a dimethylamino group, a monoethylamino group or a diethylamino group, and an arylamino group having 6 to 20 carbon atoms, such as a monophenylamino group or a diphenylamino group. aralkylamino groups having 7 to 20 carbon atoms, such as a benzylamino group; a carboxy group; a carbamoyl group; an alkylcarbonyl group having 2 to 15 carbon atoms, such as an acetyl group or a propionyl group; an arylcarbonyl group having 7 to 20 carbon atoms, such as a benzoyl group, a 1-naphthylcarbonyl group or a 2-naphthylcarbonyl group; an alkoxycarbonyl group having 2 to 15 carbon atoms, such as a methoxycarbonyl group or an ethoxycarbonyl group; and an aryloxycarbonyl group having 7 to 20 carbon atoms, such as a phenyloxycarbonyl group, a 1-naphthyloxycarbonyl group or a 2-naphthyloxycarbonyl group. R 1 The substituent that the hydrocarbon group having 1 to 20 carbon atoms represented by the following formula may have is preferably a halogen atom.

[0024] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a chlorine atom being preferred.

[0025] R 1 The hydrocarbon group having 1 to 20 carbon atoms represented by the following formula is preferably a hydrocarbon group having a substituent.

[0026] Examples of Compound (I) include Compounds 1 to 80 represented by formula (Ix), as shown in Table 1 below. 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, -SO 3 X, -SO 2 NH 2 , and / or -SO 2 (CH 2 ) rIt is preferable that each Cl is bonded to a different benzene ring.

[0027] [ka]

[0028] [Table 1]

[0029] Among them, as compound (I), 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 are preferable, and compound 11, compound 18, compound 23, compound 30, compound 34, compound 35, compound 39, compound 53, compound 56, compound 60, and compound 72 are more preferable.

[0030] Specific examples of compound (I) include CI Direct Blue 86, CI Direct Blue 87, CI Direct Blue 199, and CI Reactive Blue 25, and it is particularly preferable to contain at least one selected from the group consisting of the above dyes.

[0031] The method for producing compound (I) is not particularly limited, but compound (I) can be produced by referring to the synthesis examples described in JP-A-2011-28236.

[0032] Compound (I) is soluble in water and has a solubility parameter (SP value) of 11.0 (cal / cm) such as propylene glycol monomethyl ether acetate. 3 ) 1 / 2 It is preferable that the polymer is poorly soluble in an organic solvent having a melting point of less than 1000 nm. The solubility and poor solubility can be evaluated by the following method. Compound (I) (0.1 g) is added to a 20 mL sample vial, water or an organic solvent is added using a 10 mL volumetric pipette, the vial is closed, and the vial is treated with ultrasonic waves for 3 minutes. The obtained liquid is left to stand in a water bath at 23°C for 60 minutes. 5 mL of the supernatant is filtered through a PTFE 5 μm membrane filter, and then filtered through a 0.25 μm membrane filter to remove insoluble matter. The absorption spectrum of the obtained filtrate is measured using a UV-visible spectrophotometer (e.g., Shimadzu UV-2500PC) using a 1 cm cell, and the absorbance (abs) at the maximum absorption wavelength of Compound (I) is obtained. At this time, if the absorbance (abs) is less than 40% of the upper measurement limit (in the case of Shimadzu UV-2500PC, the absorbance (abs) is less than 2), it is evaluated as being poorly soluble, and if it is 40% or more of the upper measurement limit, it is evaluated as being soluble. By virtue of having such solubility characteristics, compound (I) has excellent solvent resistance, and it is possible to provide a colored curable composition which does not cause pattern reflow even when heated at 150° C. or higher.

[0033] Compound (I) has an SP value of 11.0 (cal / cm 3 ) 1 / 2 Since the colored curable composition is poorly soluble in organic solvents with an SP value of 11.0 (cal / cm 3 ) 1 / 2 When using an organic solvent having a viscosity of less than 100 MPa, it is preferable to prepare a colored dispersion liquid in which the compound (I) is uniformly dispersed in the organic solvent in advance by adding a dispersant and carrying out a dispersion treatment. The colored dispersion liquid may contain a part or all of the organic solvent (E) contained in the colored curable composition. The colored dispersion liquid can be used to prepare a colored curable composition.

[0034] Examples of the dispersant include surfactants, which may be cationic, anionic, nonionic, or amphoteric. Specific examples include polyester, polyamine, and acrylic surfactants. These dispersants may be used alone or in combination of two or more. Examples of the dispersant, in terms of trade name, include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWRENE (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.), and BYK (registered trademark) (manufactured by BYK-Chemie Co., Ltd.). Resin (B) described later may be used as the dispersant.

[0035] When a dispersant is used, the amount of the dispersant (solid content) used is usually 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). When the amount of the dispersant used is within the above range, a colored dispersion liquid in a more uniformly dispersed state tends to be obtained.

[0036] The content of the compound (I) is preferably from 50 to 250 parts by mass, more preferably from 80 to 200 parts by mass, and further preferably from 100 to 180 parts by mass, relative to 100 parts by mass of the resin (B).

[0037] The content of the compound (I) in the total amount of the colorant (A) is preferably from 40 to 100 mass %, more preferably from 60 to 100 mass %, and further preferably from 80 to 100 mass %.

[0038] <<Colorant (A1)>> The colored curable composition of the present invention may contain a dye other than the compound (I) (hereinafter, may be referred to as dye (A1-1)) and / or a pigment (hereinafter, may be referred to as pigment (A1-2)) as the colorant (A) (hereinafter, the dye (A1-1) and the pigment (A1-2) may be collectively referred to as colorant (A1)). These may be used alone or in combination of two or more kinds.

[0039] The dye (A1-1) is not particularly limited as long as it does not include the compound (I), and known dyes can be used, for example, solvent dyes, acid dyes, direct dyes, mordant dyes, etc. Examples of dyes include compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists) and known dyes described in Dyeing Notes (Shikisensha). In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, thiazole dyes, oxazine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and phthalocyanine dyes.

[0040] The pigment (A1-2) is not particularly limited and any known pigment can be used, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists). Examples of pigments classified as pigments include yellow pigments such as CI 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, and 231; Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; Red pigments such as CI Pigment Red 9, 97, 105, 122, 144, 149, 166, 168, 176, 177, 180, 190, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273; Blue pigments such as CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60; Violet pigments such as CI Pigment Violet 1, 19, 23, 32, 36, 38; Green pigments such as CI Pigment Green 7, 36, 58, 59, 62, 63; Brown pigments such as CI Pigment Brown 23, 25; Black pigments such as CI Pigment Black 1 and 7;

[0041] The pigment may be subjected to a rosin treatment, a surface treatment using a derivative having an acidic or basic group introduced therein, a graft treatment to the pigment surface using a polymer compound, a micronization treatment using a sulfuric acid micronization method, a washing treatment using an organic solvent or water to remove impurities, a removal treatment using an ion exchange method for ionic impurities, etc., as necessary. The particle size of the pigment is preferably approximately uniform. The pigment can be made into a pigment dispersion liquid in which the pigment is uniformly dispersed in the dispersant solution by adding a dispersant and performing a dispersion treatment. When a plurality of pigments are used, each of them may be dispersed alone, or a plurality of pigments may be mixed and dispersed. The pigment may also be mixed with the compound (I) and dispersed. Examples of the dispersant include the same as those mentioned above.

[0042] When a dispersant is used, the amount of the dispersant (solid content) used is usually 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. When the amount of the dispersant used is within the above range, a pigment dispersion in a more uniformly dispersed state tends to be obtained.

[0043] When the colorant (A) contains a 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 further preferably 1 to 20 mass%.

[0044] The content of the colorant (A) is preferably 1 to 70 mass%, more preferably 5 to 60 mass%, further preferably 10 to 60 mass%, and even more preferably 15 to 55 mass%, based on the total amount of solids in the colored curable composition. When the content of the colorant (A) is within the above range, the color density when made into a color filter is sufficient, and since the necessary amount of the resin (B) can be contained in the composition, a pattern with sufficient mechanical strength can be formed, which is preferable. Here, the "total amount of solids" in this specification refers to the amount obtained by excluding the content of the organic solvent from the total amount of the colored curable composition. The total amount of solids and the content of each component relative thereto can be measured by a known analytical means such as liquid chromatography or gas chromatography.

[0045] <Resin (B)> The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6]. Resin [K1]: a copolymer having a structural unit derived from at least one member (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond; Resin [K2]: a copolymer having a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter, sometimes referred to as "(c)"); Resin [K3]: a copolymer having structural units derived from (a) and structural units derived from (c); Resin [K4]: a copolymer having a structural unit derived from (a) to which (b) has been added, and a structural unit derived from (c); Resin [K5]: a copolymer having a structural unit derived from (b) to which (a) has been added, and a structural unit derived from (c); Resin [K6]: A copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a polyvalent carboxylic acid and / or a carboxylic acid anhydride.

[0046] Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid; Bicyclounsaturated compounds containing a carboxy group, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; Unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids, such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate; Examples include unsaturated acrylates that contain a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid. Among these, acrylic acid, methacrylic acid, etc. are preferred from the standpoint of copolymerization reactivity and solubility of the resulting resin in an aqueous alkaline solution.

[0047] (b) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group. In this specification, the term "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid. The terms "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[0048] Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)").

[0049] Examples of (b1) include a monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and a monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

[0050] 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(glycidyl Examples of such styrene include 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, and 2,4,6-tris(glycidyloxymethyl)styrene.

[0051] Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), compounds represented by formula (BI) and compounds represented by formula (BII).

[0052] [ka] [In formula (BI) and formula (BII), R e and R f represents 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 hydroxy group. X e and X f is a single bond, *-R g -, *-Rg -O-, *-R g -S- or *-R g -NH-. R g represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond to O.]

[0053] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group. R e and R f Preferred examples of the alkyl group include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferred examples include a hydrogen atom and a methyl group.

[0054] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. X e and X f is preferably a single bond, a methylene group, an ethylene group, *-CH 2 -O- and *-CH 2 CH 2 -O- is preferred, and a single bond, *-CH 2 CH 2 -O- (* represents a bond to O).

[0055] The compound represented by formula (BI) includes compounds represented by any one of formulas (BI-1) to (BI-15), etc. Among them, compounds represented by formulas (BI-1), (BI-3), (BII-5), (BI-7), (BI-9) or (BI-11) to (BI-15) are preferred, and compounds represented by formulas (BI-1), (BI-7), (BI-9) or (BI-15) are more preferred.

[0056] [ka]

[0057] The compound represented by formula (BII) includes compounds represented by any of formulas (BII-1) to (BII-15), etc. Among them, compounds represented by formulas (BII-1), (BII-3), (BII-5), (BII-7), (BII-9) or (BII-11) to (BII-15) are preferred, and compounds represented by formulas (BII-1), (BII-7), (BII-9) or (BII-15) are more preferred.

[0058] [ka]

[0059] 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 thereof (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.

[0060] As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, and the like can be mentioned.

[0061] As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.

[0062] As (b), (b1) is preferable in that the reliability of the heat resistance, chemical resistance, etc. of the obtained color filter can be further improved. Furthermore, (b1-2) is more preferable in that the storage stability of the colored curable composition is excellent.

[0063] Examples of (c) include (meth)acrylic acid esters (cf-1) (hereinafter sometimes referred to as "cf-1") that do not have a polycyclic hydrocarbon ring, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate; Tricyclo[5.2.1.0 2,6 ]decan-8-yl(meth)acrylate (commonly known in the art as "dicyclopentanyl(meth)acrylate" and sometimes called "tricyclodecyl(meth)acrylate"), tricyclo[5.2.1.0 2,6 ]decen-8-yl (meth)acrylate (commonly known in the art as "dicyclopentenyl (meth)acrylate"), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and other (meth)acrylic acid esters having a polycyclic hydrocarbon ring (cf-2) (hereinafter sometimes referred to as "(cf-2)"); hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene chloro[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept -2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, bicyclounsaturated compounds such as ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 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-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide; Examples of the copolymer include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. Of these, (meth)acrylic acid esters are preferred.

[0064] In the resin [K1], the ratio of structural units derived from each of them is as follows among all structural units constituting the resin [K1]: Structural units derived from (a): 2 to 60 mol% Structural units derived from (b): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol% Structural units derived from (b): 50 to 90 mol% It is more preferable that: When the ratio of the structural units of the resin [K1] is within the above range, the colored curable composition tends to have excellent storage stability, developability when forming a colored pattern, and solvent resistance of the obtained color filter.

[0065] Resin [K1] can be produced, for example, by referring to the method described in the literature "Experimental Methods of Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published on March 1, 1972) and the cited references described in said literature.

[0066] Specifically, a method is exemplified in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are put into a reaction vessel, and the atmosphere is deoxygenated by, for example, replacing oxygen with nitrogen, and the mixture is heated and kept warm while stirring. The polymerization initiator and solvent used here are not particularly limited, and those usually used in the field can be used. For example, the polymerization initiator includes azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc.), and the solvent may be any one that dissolves each monomer, and examples of the solvent include the organic solvent (E) of the colored curable composition of the present invention, which will be described later.

[0067] The obtained copolymer may be used as it is in the form of a solution after the reaction, or may be used after being concentrated or diluted, or may be used after being extracted as a solid (powder) by a method such as reprecipitation. In particular, by using a solvent contained in the colored curable composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable composition of the present invention, and therefore the manufacturing process of the colored curable composition of the present invention can be simplified.

[0068] In the resin [K2], the ratio of structural units derived from each of them is as follows among all structural units constituting the resin [K2]: Structural units derived from (a): 2 to 45 mol% Structural units derived from (b): 2 to 95 mol% Structural units derived from (c): 1 to 65 mol% It is preferred that Structural units derived from (a): 5 to 40 mol% Structural units derived from (b): 5 to 80 mol% Structural units derived from (c): 5 to 60 mol% It is more preferable that: When the ratio of the structural units of the resin [K2] is within the above range, the colored curable composition tends to have excellent storage stability, developability when forming a colored pattern, and the obtained color filter tends to have excellent solvent resistance, heat resistance, and mechanical strength.

[0069] Resin [K2] can be produced, for example, in the same manner as described above as the method for producing resin [K1].

[0070] In the resin [K3], the ratio of structural units derived from each of them is as follows among all structural units constituting the resin [K3]: Structural units derived from (a): 2 to 60 mol% Structural units derived from (c): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol% Structural units derived from (c): 50 to 90 mol% It is more preferable that: Resin [K3] can be produced, for example, in the same manner as described above as the method for producing resin [K1].

[0071] Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and then adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic acid anhydride contained in (a). First, a copolymer of (a) and (c) is produced in the same manner as described for the production method of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that described for resin [K3].

[0072] Next, a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms contained in (b). Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and (b), a reaction catalyst for the reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (e.g., hydroquinone, etc.), etc. are placed in the flask, and the mixture is reacted, for example, at 60 to 130°C for 1 to 10 hours to produce the 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 adjusting the amount within this range, the storage stability of the colored curable composition, the developability when forming a 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 and unreacted (b) is unlikely to remain, (b1) is preferable as (b) used in the resin [K4], and (b1-1) is more preferable. The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c). The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc. As with the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc.

[0073] Resin [K5] is produced in the first step by the same method as the above-mentioned resin [K1] to obtain a copolymer of (b) and (c). As in the above, the obtained copolymer may be used as it is in the form of a solution after the reaction, or may be a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation. The ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer are, respectively, Structural units derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b): 10 to 90 mol% Structural units derived from (c): 10 to 90 mol% It is more preferable that:

[0074] Furthermore, under the same conditions as in the manufacturing method of resin [K4], resin [K5] can be obtained by reacting the cyclic ether derived from (b) contained in the copolymer of (b) and (c) with the carboxylic acid or carboxylic anhydride contained in (a). The amount of (a) reacted with the copolymer is preferably 5 to 100 moles per 100 moles of (b). Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) used in resin [K5], and (b1-1) is more preferred.

[0075] Resin [K6] is a resin obtained by further reacting resin [K5] with a polycarboxylic acid and / or a carboxylic anhydride. A hydroxyl group generated by the reaction of the cyclic ether derived from (b) with the carboxylic acid or carboxylic anhydride derived from (a) is further reacted with a polycarboxylic acid and / or a carboxylic anhydride. Examples of polycarboxylic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, and tricarbanilic acid. Examples of carboxylic anhydrides include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride. The amount of 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. In other words, it is more preferable that the resin [K6] also has a structural unit in which (a) is added to a structural unit derived from (b), in which a polyvalent carboxylic acid and / or a carboxylic acid anhydride is not added to the hydroxy group generated by the reaction of a cyclic ether derived from (b) with a carboxylic acid or carboxylic acid anhydride derived from (a).

[0076] Resin (B) preferably includes a resin having a structural unit having an ethylenically unsaturated bond in a side chain (resin [K4], resin [K5], or resin [K6]), and more preferably includes a resin having a structural unit including a (meth)acryloyl group in a side chain.

[0077] Examples of resins having a structural unit containing a (meth)acryloyl group in the side chain include resin [K4] using a monomer (ba) (hereinafter sometimes referred to as "(ba)") having a (meth)acryloyl group such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-methyl-3-methacryloyloxymethyloxetane, and tetrahydrofurfuryl acrylate as (b), resin [K5] using a monomer (aa) (hereinafter sometimes referred to as "(aa)") having a (meth)acryloyl group such as acrylic acid, methacrylic acid, and succinic acid mono[2-(meth)acryloyloxyethyl] as (a), and resin [K6] using (aa) as (a). Examples of resins having a structural unit containing a (meth)acryloyl group in the side chain include resin [K6] using (aa) as (a).

[0078] The resin having a structural unit containing a (meth)acryloyl group in the side chain more preferably includes a resin [K6] having a structural unit containing a (meth)acryloyl group in the side chain and 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)acryloyl group in the side chain and not 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 a structural unit derived from (c). It is more preferable that the resin [K6] contains a structural unit having a (meth)acryloyl group in the side chain and no carboxylic acid group derived from a polycarboxylic acid and / or a carboxylic anhydride (structural unit obtained by adding (aa) to a structural unit derived from (b)), and structural units derived from (cf-1) and / or (cf-2). It is particularly preferable that the resin [K6] contains a structural unit having a (meth)acryloyl group in the side chain and no carboxylic acid group derived from a polycarboxylic acid and / or a carboxylic anhydride (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 having a (meth)acryloyl group in the side chain and no carboxylic acid group derived from a polycarboxylic acid and / or a carboxylic anhydride (structural unit obtained by adding (aa) to a structural unit derived from (b)), and structural units derived from (cf-1) and (cf-2).

[0079] In addition, from the viewpoint of increasing the residual film rate, it is preferable that the resin (B) further contains a resin [K1] in addition to a resin having a structural unit having an ethylenically unsaturated bond in a side chain (resin [K4], resin [K5], or resin [K6]).

[0080] The polystyrene-equivalent weight average molecular weight of resin (B) is preferably 3,000 to 100,000, more preferably 4,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.

[0081] The polydispersity of the resin (B) [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1-6, and more preferably 1.2-4.

[0082] 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, calculated as 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 determined, for example, by titration with an aqueous potassium hydroxide solution.

[0083] The content of the resin (B) is preferably 7 to 65 mass%, more preferably 13 to 60 mass%, and further preferably 17 to 55 mass%, based on the total amount of solids in the colored curable composition. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film rate of the colored pattern tend to be improved.

[0084] <Polymerizable compound (C)> The polymerizable compound (C) is a compound that can be polymerized by the active radicals and / or acid generated from the polymerization initiator (D). The polymerizable compound (C) includes a compound (II).

[0085] <<Compound (II)>> Compound (II) is a compound represented by the following formula (II).

[0086] [ka] [In formula (II), R a represents a (q+r)-valent linking group. R b represents an alkanediyl group having 1 to 20 carbon atoms. R c represents an acryloyloxy group or a methacryloyloxy group. p represents an integer of 0 or greater. q represents an integer of 1 or greater. r represents an integer of 0 or greater. Formula (II) is a compound represented by the formula b If R b may be the same or different, and formula (II) may include multiple R c If R c may be the same as or different from each other, and when formula (II) has a plurality of p's, the p's may be the same as or different from each other. However, the sum of the integers represented by p in formula (II) is 2 or more, and the sum of the integers represented by q and r is 3 or more.

[0087] R a Examples of the (q+r)-valent linking group represented by the formula (1) include compounds in which (q+r) hydrogen atoms contained in an aliphatic hydrocarbon having 3 to 30 carbon atoms have been removed to form a linking group, and a methylene group contained in the aliphatic hydrocarbon may be substituted with an oxygen atom to form an ether structure.

[0088] The aliphatic hydrocarbon having 3 to 30 carbon atoms may be saturated or unsaturated, but is preferably saturated. The aliphatic hydrocarbon having 3 to 30 carbon atoms may be a chain aliphatic hydrocarbon, an alicyclic hydrocarbon, or a combination of a chain aliphatic hydrocarbon and an alicyclic hydrocarbon, but is preferably a chain aliphatic hydrocarbon.

[0089] Examples of the chain aliphatic hydrocarbon include linear aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, and pentadecane; and branched aliphatic hydrocarbons such as the hydrocarbons represented by the following formulae (ac-1) to (ac-15).

[0090] [ka]

[0091] The number of carbon atoms in the chain aliphatic hydrocarbon is preferably 3 to 25, more preferably 4 to 20, and even more preferably 6 to 20. In addition, the chain aliphatic hydrocarbon is preferably a branched chain aliphatic hydrocarbon, preferably having a tertiary or higher carbon atom, more preferably having a quaternary carbon atom, and even more preferably having two or more quaternary carbon atoms. Among them, the hydrocarbons represented by formulae (ac-7) to (ac-15) are preferred, and the hydrocarbons represented by formulae (ac-7), (ac-10), (ac-11), and (ac-15) are more preferred.

[0092] Examples of the alicyclic hydrocarbon include cyclohydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, and cyclopentadecane; norbornane, adamantane, and bicyclo[2.2.2]octane. The number of carbon atoms in the alicyclic hydrocarbon is preferably 3 to 28, more preferably 5 to 25, and further more preferably 8 to 23.

[0093] The hydrocarbon obtained by combining a chain aliphatic hydrocarbon and an alicyclic hydrocarbon may be a hydrocarbon obtained by combining two or more of the chain aliphatic hydrocarbons and alicyclic hydrocarbons listed above. In the above-mentioned combined hydrocarbon, the chain aliphatic hydrocarbon may be combined as a monovalent or divalent group (e.g., an alkyl group, an alkanediyl group). Examples of the combined hydrocarbon include methylcyclopropane, 1,3-dimethylcyclobutane, 1,2,4,5-tetramethylcyclohexane, and dicyclohexylmethane. The number of carbon atoms in the combined chain aliphatic hydrocarbon and alicyclic hydrocarbon is preferably 6 to 30, more preferably 6 to 28, and even more preferably 6 to 25.

[0094] The methylene groups contained in the aliphatic hydrocarbon are preferably substituted with oxygen atoms to form an ether structure, more preferably to form one to three ether structures, and even more preferably to form one ether structure.

[0095] In the aliphatic hydrocarbon, the site where a hydrogen atom is removed to form a bonding group is preferably —CH 3 The carbon atoms in the aryl group (including the terminal carbon atoms) are the same as those in the -CH group. 3 It is more preferable that only one hydrogen atom is removed from the moiety to form a linking group.

[0096] R bExamples of the alkanediyl group having 1 to 20 carbon atoms represented by the formula (I) include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, or a decane-1,10-diyl group; and branched alkanediyl groups such as an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a 2-methylpropane-1,2-diyl group, a 2-methylpropane-1,3-diyl group, a butane-1,3-diyl group, a 2-methylbutane-1,4-diyl group, or a pentane-1,4-diyl group.

[0097] R b The alkanediyl group represented by the following formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 5 carbon atoms, and even more preferably 2 to 4 carbon atoms.

[0098] R c is preferably an acryloyloxy group.

[0099] p is preferably an integer of 0 to 15, more preferably an integer of 1 to 10, even more preferably an integer of 1 to 8, even more preferably an integer of 1 to 6, still more preferably an integer of 1 to 4, and particularly preferably an integer of 2 to 3. However, the sum 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, even more preferably 4 to 40, even more preferably 5 to 30, and particularly preferably 8 to 20. By including compound (II) in which the sum of the integers represented by p is within the above range as a polymerizable compound, it is possible to provide a colored curable composition in which the pattern does not reflow even when heated at 150° C. or higher.

[0100] As q, an integer of 1 to 12 is preferable, an integer of 2 to 10 is more preferable, and an integer of 4 to 8 is even more preferable.

[0101] As r, an integer of 0 to 6 is preferable, an integer of 0 to 4 is more preferable, an integer of 0 to 2 is even more preferable, an integer of 0 to 1 is even more preferable, and 0 is particularly preferable.

[0102] The sum of the integer represented by q and the integer represented by r is 3 or more, and the sum is preferably 3 to 12, more preferably 4 to 10, even more preferably 5 to 10, and even more preferably 6 to 10.

[0103] As compound (II), compounds II-1 to II-240 represented by formula (II-x) as shown in Tables 2 to 4 are most preferable.

[0104] [ka]

[0105] [Table 2]

[0106] [Table 3]

[0107] [Table 4]

[0108] In Tables 2 to 4, Ax-1 and Ax-2 represent groups represented by the following formulae (Ax-1) and (Ax-2), Bx-1 represents an ethylene group, Bx-2 represents a propane-1,2-diyl group, Cx-1 represents an acryloyloxy group, Cx-2 represents a methacryloyloxy group, and tPx represents the total number of integers represented by px in formula (II-x). In the following formulae (Ax-1) and (Ax-2), * represents a bond.

[0109] [ka]

[0110] Among them, as compound (II), compound II-1 to compound II-120 are preferable, compound II-1 to compound II-96 are more preferable, compound II-1 to compound II-48 are even more preferable, compound II-13 to compound II-36 are even more preferable, compound 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 are even more preferable, and compound II-21, compound II-22, compound II-33, and compound II-34 are particularly preferable.

[0111] As the compound (II), a commercially available product may be used, and examples thereof include A-DPH6E (manufactured by Shin-Nakamura Chemical Co., Ltd., number of ethylene oxide chains: 6), A-DPH12E (manufactured by Shin-Nakamura Chemical Co., Ltd., number of ethylene oxide chains: 12), A-DPH18E (manufactured by Shin-Nakamura Chemical Co., Ltd., number of ethylene oxide chains: 18), A-DPH24E (manufactured by Shin-Nakamura Chemical Co., Ltd., number of ethylene oxide chains: 24), A-DPH48E (manufactured by Shin-Nakamura Chemical Co., Ltd., number of ethylene oxide chains: 48), and A-DPH6PO (manufactured by Shin-Nakamura Chemical Co., Ltd., number of propylene oxide chains: 6). The ethylene oxide chain is the "-OR" in the compound (II). b -"R b corresponds to the group (chain) which is an ethylene group, and the propylene oxide chain corresponds to the "-OR b -"R b corresponds to a group (chain) which is a propylene group, and the number of ethylene oxide chains or propylene oxide chains corresponds to the total number of integers represented by p in compound (II).

[0112] The content of the compound (II) in the total amount of the polymerizable compound (C) is preferably from 50 to 100 mass %, more preferably from 60 to 100 mass %, and further preferably from 80 to 100 mass %.

[0113] <<Polymerizable compound (C1)>> The colored curable composition of the present invention may contain a polymerizable compound (polymerizable compound (C1)) other than the compound (II) as the polymerizable compound (C). The polymerizable compound (C1) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond other than the compound (II), and preferably a (meth)acrylic acid ester compound other than the compound (II).

[0114] Among them, the polymerizable compound (C1) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound (C1) include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0115] The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

[0116] The content of the polymerizable compound (C) is preferably from 5 to 45 mass %, more preferably from 10 to 40 mass %, and further preferably from 15 to 35 mass %, based on the total amount of solids in the colored curable composition.

[0117] <Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization, and known polymerization initiators can be used. Examples of polymerization initiators that generate active radicals include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

[0118] The O-acyloxime compound is a compound having a partial structure represented by the following formula (d1): In the following, * represents a bond.

[0119] [ka]

[0120] Examples of the O-acyloxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethylphenyl)-1,2-diphenyl-2,3-diphenyl-2,4-diphenyl-2,5-diphenyl-2,6-diphenyl-2,7-diphenyl-2,7-diphenyl-2,8-diphenyl-2,9-diphenyl-2,8-diphenyl-2,9-diphenyl-2,7-diphenyl-2,8-diphenyl-2,9 ... Examples of the ethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, etc. Commercially available products such as Irgacure OXE01, OXE02 (both manufactured by BASF), N-1919 (manufactured by ADEKA) may also be used. Among them, the O-acyloxime compound is preferably at least one selected from the group consisting of N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, and more preferably N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine. With these O-acyloxime compounds, a high brightness color filter tends to be obtained.

[0121] The alkylphenone 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.

[0122] [ka]

[0123] Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, etc. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) may also be used.

[0124] Examples of compounds having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal. In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).

[0125] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

[0126] The acylphosphine oxide compound may be 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.

[0127] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913).

[0128] Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 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, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator aid (D1) (especially amines) described below.

[0129] Examples of the polymerization initiator that generates an acid include onium salts such as 4-hydroxyphenyl dimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyl dimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate; nitrobenzyl tosylates; and benzoin tosylates.

[0130] The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound, and more preferably a polymerization initiator containing an O-acyloxime compound.

[0131] The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, thereby improving the productivity of the optical filter.

[0132] <Polymerization initiator aid (D1)> The polymerization initiation aid (D1) is a compound used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator, or a sensitizer. When the polymerization initiation aid (D1) is contained, it is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiator aid (D1) include 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, and N-phenylglycine.

[0133] When these polymerization initiation aids (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to improve.

[0134] <Organic solvent (E)> The organic solvent (E) is not particularly limited, and organic solvents commonly used in the field can be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. can be mentioned.

[0135] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0136] 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, phenetole, and methylanisole.

[0137] The ether ester solvents 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-methyl ... Examples of the alkyl ether acetates include ethyl methoxy-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.

[0138] Examples of ketone solvents 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.

[0139] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0140] Aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0141] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0142] The organic solvent (E) preferably contains one or more selected from the group consisting of ether solvents, ether ester solvents, and ketone solvents, more preferably contains an ether ester solvent and a ketone solvent, and further preferably contains propylene glycol monomethyl ether acetate, and 4-hydroxy-4-methyl-2-pentanone.

[0143] The content of the organic solvent (E) is preferably 70 to 95 mass%, more preferably 75 to 92 mass%, based on the total amount of the colored curable composition of the present invention. In other words, the solid content of the colored curable composition is preferably 5 to 30 mass%, more preferably 8 to 25 mass%. When the content of the organic solvent (E) is within the above range, the flatness during coating is good, and the color density is not insufficient when a color filter is formed, so that the display characteristics tend to be good.

[0144] <Leveling agent (F)> Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms, which may have a polymerizable group in the side chain. Examples of silicone surfactants include surfactants having a siloxane bond in the molecule.Specific examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC).

[0145] The fluorine-based surfactant may include surfactants having a fluorocarbon chain in the molecule.Specific examples include Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by AGC Corporation (formerly Asahi Glass Co., Ltd.)) and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.).

[0146] Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, such as Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0147] When the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.001 to 0.2 mass% and more preferably 0.002 to 0.1 mass% based on the total amount of the colored curable composition. This content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

[0148] <Other ingredients> The colored curable composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, as necessary.

[0149] <Method for producing colored curable composition> The colored curable composition of the present invention can be prepared, for example, by mixing the colorant (A), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the organic solvent (E), as well as the leveling agent (F) and other components that are used as necessary. The colorant (A) may be prepared using the above-mentioned color dispersion or pigment dispersion. The remaining components are mixed with the color dispersion or pigment dispersion to a predetermined concentration to prepare the desired colored curable composition. When the dye (A1-1) is contained, the dye (A1-1) may be dissolved in advance in a part or whole of the organic solvent (E) to prepare a solution. The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm. In addition, the colored curable composition after mixing is preferably filtered through a filter having a pore size of about 0.01 to 10 μm.

[0150] <Manufacturing method for color filters> Examples of methods for producing a colored pattern from the colored curable composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among these, the photolithography method is preferred. The photolithography method is a method in which the colored curable composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film, which is a cured product of the colored composition layer, can be formed by not using a photomask during exposure and / or not developing. The colored pattern or colored coating film thus formed is the color filter of the present invention.

[0151] The substrate may be a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or soda lime glass with a silica-coated surface, a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate, silicon, or a substrate having a thin film of aluminum, silver, or a silver / copper / palladium alloy formed thereon. On these substrates, other color filter layers, resin layers, transistors, circuits, etc. may be formed.

[0152] The formation of each color pixel by photolithography can be carried out using known or conventional devices and conditions. For example, the pixel can be produced as follows. First, the colored curable composition is applied onto a substrate, and then dried by heating and drying (pre-baking) and / or drying under reduced pressure to remove volatile components such as the solvent, thereby obtaining a smooth colored composition layer. Examples of the coating method include spin coating, slit coating, and slit and spin coating. The temperature when drying by heating is preferably 30 to 120° C., more preferably 50 to 110° C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When drying is carried out under reduced pressure, it is preferable to carry out the drying under a pressure of 50 to 150 Pa and at a temperature in the range of 20 to 25°C. The thickness of the colored composition layer is not particularly limited, and may be appropriately selected depending on the intended thickness of the color filter.

[0153] Next, the colored composition layer is exposed through a photomask for forming a desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern depending on the intended use is used. The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, light less than 350 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, around 408 nm, and around 365 nm may be selectively extracted using a bandpass filter that extracts these wavelength ranges. Specifically, the light source may be a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, etc. It is preferable to use an exposure device such as a mask aligner or a stepper, since it is possible to uniformly irradiate the entire exposure surface with parallel light rays and to accurately align the photomask with the substrate on which the colored composition layer is formed.

[0154] The colored composition layer after exposure is developed by contacting it with a developer, thereby forming a colored pattern on the substrate. By development, the unexposed areas of the colored composition layer are dissolved in the developer and removed. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds 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 contain a surfactant. The developing method may be any of a puddle method, a dipping method, a spray method, etc. Furthermore, the substrate may be inclined at an arbitrary angle during the developing. After development, it is preferable to wash with water.

[0155] Furthermore, it is preferable to perform post-baking on the obtained colored pattern. The post-baking temperature is preferably 150 to 250° C., more preferably 170 to 245° C., and further preferably 180 to 240° C. The post-baking time is preferably 1 to 120 minutes, and more preferably 5 to 60 minutes.

[0156] The thickness of the coating film after post-baking is, for example, preferably 3 μm or less, more preferably 2.0 μm or less. The lower limit of the thickness of the coating film is not particularly limited, but is usually 0.3 μm or more, and may be 0.5 μm or more.

[0157] According to the colored curable composition of the present invention, it is possible to provide a colored curable composition having high reflow resistance of a pattern during post-baking, which is useful for producing a color filter having a good pattern shape. The color filter is useful as a filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state imaging device. EXAMPLES

[0158] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the examples, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

[0159] (Synthesis Example 1) A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to create a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80° C. with stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6] A solution of 289 parts of a mixture of decan-9-yl acrylate (content ratio 1:1) dissolved in 125 parts of propylene glycol monomethyl ether acetate was dropped using a dropping pump over about 5 hours. Meanwhile, a solution of 33 parts of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was dropped into the flask using another dropping pump over about 6 hours. After the dropping was completed, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a polymer (resin (B-1)) solution with a polymer solid content of 35.1%. The weight average molecular weight Mw of the produced copolymer (polymer; resin (B-1)) was 9200, the degree of dispersion was 2.08, and the acid value converted to solid content was 77 mg-KOH / g. The produced copolymer has the following structural units.

[0160] [ka]

[0161] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC under the following conditions. Equipment: K2479 (Shimadzu Corporation) Column: SHIMADZU Shim-pack GPC-80M Column temperature: 40°C Solvent: THF (tetrahydrofuran) Flow rate; 1.0mL / min Detector: RI Calibration standard material: 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) calculated in terms of polystyrene obtained above was taken as the dispersity.

[0162] (Synthesis Example 2) 276.8 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while replacing with nitrogen and heated to 120°C. Next, a monomer mixture consisting of 92.4 g of 2-ethylhexyl acrylate, 184.9 g of glycidyl methacrylate, and 12.3 g of dicyclopentanyl methacrylate, to which 35.3 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator) had been added, was dropped into the flask from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was stirred for another 30 minutes at 120°C to carry out a copolymerization reaction, producing an addition copolymer. After that, the flask was replaced with air, and 93.7 g of acrylic acid, 1.5 g of triphenylphosphine (catalyst), and 0.8 g of methoquinone (polymerization inhibitor) were added to the above addition copolymer solution, and the reaction was continued at 110°C for 10 hours, and the epoxy group derived from glycidyl methacrylate was reacted with acrylic acid to cleave the epoxy group, and at the same time, a polymerizable unsaturated bond was introduced into the side chain 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, and the hydroxyl group generated by the cleavage of the epoxy group was reacted with succinic anhydride to introduce a carboxyl group into the side chain, thereby obtaining a polymer. Finally, 383.3 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and a polymer (resin (B-2)) solution with a polymer solid content of 40% was obtained. The weight average molecular weight Mw of the produced copolymer (polymer; resin (B-2)) was 6.3 x 10 3 The acid value calculated as solid content was 34 mg-KOH / g.

[0163] (Preparation of Dispersion 1) 14 parts of CI Direct Blue 86, 4.1 parts of dispersant (BYK BYKLPN-6919), 2.8 parts of resin (B-1) (solid content equivalent), 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 (LAU). The zirconia beads were then removed by filtration to obtain Dispersion 1.

[0164] (Preparation of Dispersion 2) 14 parts of CI Direct Blue 199, 4.1 parts of dispersant (BYKLPN-6919 manufactured by BYK), 2.8 parts of resin (B-1) (solid content equivalent), 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). The zirconia beads were then removed by filtration to obtain dispersion 2.

[0165] [Examples 1 to 4, Comparative Examples 1 to 2] (Preparation of Colored Curable Composition) The components shown in Table 5 were mixed to obtain each colored curable composition.

[0166] [Table 5]

[0167] In Table 5, the components are as follows: Compound (z): A compound represented by the following formula (z):

[0168] [ka] Resin (B): Resin (B-2) (solid content conversion) Polymerizable compound (C-1): Dipentaerythritol polyacrylate ("A9550" manufactured by Shin-Nakamura Chemical Co., Ltd., solid content equivalent) Polymerizable compound (C-2): Ethylene oxide modified dipentaerythritol hexaacrylate ("A-DPH6E" manufactured by Shin-Nakamura Chemical Co., Ltd., number of ethylene oxide chains: 6, solid content equivalent) Polymerizable compound (C-3): Ethylene oxide modified dipentaerythritol hexaacrylate ("A-DPH12E" manufactured by Shin-Nakamura Chemical Co., Ltd., number of ethylene oxide chains: 12, solid content equivalent) Polymerizable compound (C-4): Ethylene oxide modified dipentaerythritol hexaacrylate ("A-DPH48E" manufactured by Shin-Nakamura Chemical Co., Ltd., number of ethylene oxide chains: 48, solid content equivalent) Polymerization initiator (D): N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine Organic solvent (E-1): 4-hydroxy-4-methyl-2-pentanone Organic solvent (E-2): Propylene glycol monomethyl ether acetate

[0169] (Preparation of colored patterns) A colored curable composition was applied by spin coating onto a 4-inch silicon substrate so that the film thickness after post-baking would be 0.8 μm, and then pre-baked at 80° C. for 2 minutes to obtain a colored composition layer. After cooling, the substrate on which the colored composition layer was formed was exposed to 300 mJ / cm 2 using an exposure machine (NSR-1755i7A; manufactured by Nikon Corporation). 2 The sample was irradiated with light at an exposure dose of (365 nm standard). A photomask with a dot pattern of 1.0 μm square was used. The colored composition layer after light irradiation was developed by immersion in an aqueous developer containing tetramethylammonium hydroxide at 23° C. for 30 seconds, and then washed with water to obtain a colored pattern I after development (before post-baking). Furthermore, the substrate on which the colored pattern I was formed was post-baked at 230° C. for 10 minutes to obtain a colored pattern II after post-baking.

[0170] (Evaluation of reflow resistance of colored patterns) The silicon wafer substrate having the colored pattern I or colored pattern II obtained above was observed at a magnification of 30,000 times using an electron microscope (S-4100, Hitachi High-Tech Corporation). In a side view of the colored pattern (see FIG. 1), the colored pattern width lc (width length indicated by lc in FIG. 1) at a height hb (height indicated by hb in FIG. 1) of 90% of the film thickness la (length indicated by la in FIG. 1) was measured, and the change rate of lc before and after post-baking (lc of colored pattern II / lc of colored pattern I×100(%)) was calculated and evaluated according to the following criteria. The results are shown in Table 6. ○: Change in lc before and after post-bake is 90% or more △: The change rate of lc before and after post-bake is 70% or more and less than 90% ×: The change in lc before and after post-bake is less than 70%

[0171] [Table 6]

Claims

1. The composition includes a colorant, an organic solvent, a resin, a polymerizable compound, and a polymerization initiator. The colorant comprises a compound represented by formula (I), The colored curable composition contains the polymerizable compound represented by formula (II). 【Chemistry 1】 In formula (I), X represents a hydrogen atom or a monovalent metal atom. R 1 represents a substituted or unsubstituted amino group or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. n represents an integer of 1 to 4. m represents an integer of 0 to 4. When formula (I) has a plurality of X, X may be the same or different from each other, and when formula (I) has a plurality of R 1 If R 1 may be the same or different. 【Chemistry 2】 [In formula (II), R a represents a (q+r)-valent linking group. R b represents an alkanediyl group having 1 to 20 carbon atoms. R c represents an acryloyloxy group or a methacryloyloxy group. p represents an integer of 0 or more. q represents an integer of 1 or more. and r represents an integer of 0 or more. Formula (II) b If R b may be the same or different, and formula (II) may include a plurality of R c If R c may be the same as or different from each other, and when formula (II) has a plurality of p's, the p's may be the same as or different from each other. However, the sum of the integers represented by p in formula (II) is 2 or more, and the sum of the integers represented by q and r is 3 or more.

2. The colored curable composition according to claim 1, further comprising a dispersant, the amount of the dispersant (solid content) used being 300 parts by mass or less per 100 parts by mass of the compound represented by formula (I).

3. The colored curable composition according to claim 1 or 2, comprising at least one 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 formula (I).

4. In the compound represented by formula (II), R a represents a group obtained by removing (q+r) hydrogen atoms from an aliphatic hydrocarbon having 3 to 30 carbon atoms (a methylene group contained in the aliphatic hydrocarbon may be substituted with an oxygen atom to form an ether structure).

5. In the compound represented by formula (II), R b The colored curable composition according to any one of claims 1 to 4, wherein represents an alkanediyl group having 1 to 10 carbon atoms.

6. The colored curable composition according to any one of claims 1 to 5, wherein in the compound represented by formula (II), r represents an integer of 0 to 6.

7. The colored curable composition according to any one of claims 1 to 6, wherein in the compound represented by formula (II), q represents an integer of 2 to 12.

8. The colored curable composition according to any one of claims 1 to 7, wherein in the compound represented by formula (II), the sum of integers represented by p in formula (II) is 2 to 60.

9. The colored curable composition according to any one of claims 1 to 8, wherein the resin has a structural unit containing a (meth)acryloyl group in a side chain.

10. The colored curable composition according to any one of claims 1 to 9, wherein the polymerization initiator comprises an O-acyloxime compound.

11. A color filter formed from the colored curable composition according to any one of claims 1 to 10.

12. A display device comprising the color filter according to claim 11.

13. A solid-state imaging device comprising the color filter according to claim 11.

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