TW202235526A - Curable composition - Google Patents

Abstract

The purpose of the present invention is to provide a curable composition useful for manufacturing a color filter having favorable pattern shape. A curable composition according to the present invention is characterized by containing a resin, a polymerizable compound, and a polymerization initiator, the polymerizable compound including at least one substance selected from the group consisting of hexitol poly(meth)acrylate and polyglycerin poly(meth)acrylate.

Description

hardening composition

The present invention relates to a curable composition, a color filter, a display device and a solid-state imaging element.

Display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays, or charge coupled device (Charge Coupled Device, CCD) or complementary metal-oxide semiconductor (Complementary Metal-Oxide-Semiconductor Transistor, CMOS) sensors Color filters used in solid-state imaging devices such as chromatograms are made of curable compositions. Dipentaerythritol hexaacrylate modified with ethylene oxide is known as a polymerizable compound used in the curable composition for forming the color filter (Patent Document 1). [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-164886

[Problem to be Solved by the Invention] However, the pattern formed from the curable composition containing dipentaerythritol hexaacrylate modified with ethylene oxide may not necessarily satisfy the pattern shape such that the top shape is round and the bottom shape is dragged.

An object of the present invention is to provide a curable composition useful for producing a color filter having a good pattern shape. [Means to solve the problem]

[式（CA）中， Y表示氫原子或(甲基)丙烯醯基，式（CA）所具有的(甲基)丙烯醯基的數量為1以上且6以下， a～f分別獨立地表示-O-CH ₂-CH ₂-的單元數，a+b+c+d+e+f為0以上且24以下]。 [3] 如[2]所述的硬化性組成物，其中式（CA）中，a+b+c+d+e+f為3以上且21以下。 [4] 如[1]至[3]中任一項所述的硬化性組成物，其中所述聚甘油聚(甲基)丙烯酸酯為下述式（CB）所表示的化合物。

[式（CB）中， Z表示氫原子或(甲基)丙烯醯基，式（CB）所具有的(甲基)丙烯醯基的數量為1以上且（n+2）以下， g～i分別獨立地表示-O-CH ₂-CH ₂-的單元數，為0以上且5以下的整數， n表示甘油的聚合度，為2以上且20以下的整數]。 [5] 如[4]所述的硬化性組成物，其中式（CB）中，g～i分別獨立地為1以上且3以下。 [6] 如[1]至[5]中任一項所述的硬化性組成物，其中所述樹脂為鹼可溶性樹脂。 [7] 如[1]至[6]中任一項所述的硬化性組成物，其中所述樹脂具有在側鏈包含(甲基)丙烯醯基的結構單元。 [8] 如[1]至[7]中任一項所述的硬化性組成物，其中所述聚合起始劑包含O-醯基肟化合物。 [9] 一種彩色濾光片，由如[1]至[8]中任一項所述的硬化性組成物形成。 [10] 一種顯示裝置，包括如[9]所述的彩色濾光片。 [11] 一種固體攝像元件，包括如[9]所述的彩色濾光片。 [發明的效果] That is, the gist of the present invention is as follows. [1] A curable composition comprising: a resin, a polymerizable compound, and a polymerization initiator, the polymerizable compound comprising poly(meth)acrylate selected from hexitol poly(meth)acrylate and polyglycerol poly(meth)acrylate At least one of the groups formed. [2] The curable composition according to [1], wherein the hexitol poly(meth)acrylate is a compound represented by the following formula (CA).

[In formula (CA), Y represents a hydrogen atom or a (meth)acryl group, and the number of (meth)acryl groups contained in formula (CA) is 1 to 6, and a to f independently represent The number of units of -O-CH ₂ -CH ₂ -, a+b+c+d+e+f is 0 to 24]. [3] The curable composition according to [2], wherein in the formula (CA), a+b+c+d+e+f is 3 or more and 21 or less. [4] The curable composition according to any one of [1] to [3], wherein the polyglycerol poly(meth)acrylate is a compound represented by the following formula (CB).

[In formula (CB), Z represents a hydrogen atom or a (meth)acryl group, and the number of (meth)acryl groups contained in formula (CB) is 1 or more and (n+2) or less, and g to i Each independently represents the number of units of -O-CH ₂ -CH ₂ -, and is an integer of 0 to 5, and n represents the degree of polymerization of glycerin, and is an integer of 2 to 20]. [5] The curable composition according to [4], wherein in the formula (CB), g to i are each independently 1 or more and 3 or less. [6] The curable composition according to any one of [1] to [5], wherein the resin is an alkali-soluble resin. [7] The curable composition according to any one of [1] to [6], wherein the resin has a structural unit including a (meth)acryl group in a side chain. [8] The curable composition according to any one of [1] to [7], wherein the polymerization initiator contains an O-acyl oxime compound. [9] A color filter formed of the curable composition according to any one of [1] to [8]. [10] A display device including the color filter described in [9]. [11] A solid-state imaging device including the color filter described in [9]. [Effect of the invention]

According to the present invention, it is possible to provide a curable composition useful for producing a color filter having a good pattern shape.

The curable composition of the present invention includes: a resin (hereinafter, sometimes referred to as resin (B)), a polymerizable compound (hereinafter, sometimes referred to as polymerizable compound (C)), and a polymerization initiator (hereinafter, When called polymerization initiator (D)). The polymerizable compound (C) contains at least one selected from the group consisting of hexitol poly(meth)acrylate and polyglycerin poly(meth)acrylate. The curable composition of the present invention may also contain a colorant (hereinafter, may be referred to as a colorant (A)). The curable composition of the present invention may also contain an organic solvent (hereinafter, may be referred to as an organic solvent (E)). The curable composition of the present invention may also contain a leveling agent (hereinafter, may be referred to as a leveling agent (F)). In addition, in this specification, unless otherwise specified, the compound illustrated as each component can be used individually or in combination of multiple types.

＜Coloring agent (A)＞ The coloring agent (A) is not particularly limited, and known dyes and/or pigments can be used. The colorant (A) preferably contains compounds selected from the following compound (I), the following compound (II), C.I. Pigment Yellow 138, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Yellow 231, C.I. C.I. Pigment Blue 16, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Green 62, C.I. Pigment Green 63, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 269, C.I. Hereinafter, these colorants may be collectively referred to as one or more of the colorants (A2)), more preferably include compound (I) and compound (II) described later, and more preferably include compound (I).

＜＜Compound (I)＞＞ The colorant (A) may contain a phthalocyanine containing a central metal (such as Cu, Al) which may have a substituent, preferably a compound represented by formula (I) (hereinafter, sometimes referred to as compound (I)) .

[In the 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 0-4. m represents an integer of 0-4. When the formula (I) has a plurality of Xs, the Xs may be the same or different, and when the formula (I) has a plurality of R ^1s , the R ^1s may be the same or different. ]

Compound (I) represents a compound in which (n+m) hydrogen atoms contained in a compound represented by the following formula (I-0) are substituted with n pieces of -SO ₃ X and m pieces of -SO ₂ R ¹ .

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

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, more preferably a hydrogen atom or Na.

The substituted or unsubstituted amino group represented by R ¹ includes: amino group; N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N-pentylamino, N-hexylamino, N-heptylamino, N-octylamino, N-nonylamino, N-decylamino, N-phenylamino, N, N-dimethylamino, N,N-diethylamino, N-(1-methyl)hexylamino, N-(2-methyl)hexylamino, N-(3-methyl) Hexylamine, N-(4-methyl)hexylamine, N-(5-methyl)hexylamine, etc. are bonded with 1 or 2 hydrocarbon groups (as the hydrocarbon group, preferably the carbon number 1 to 15, more preferably 1 to 10 carbons. The -CH ₂ - contained in the hydrocarbon group may be substituted by -O-.) and the like.

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

As the saturated or unsaturated chain hydrocarbon group represented by R, there may be mentioned straight ^- chain alkanes such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. Base, etc.; isopropyl, (1-ethyl) propyl, isobutyl, second butyl, third butyl, (1-ethyl) butyl, (2-ethyl) butyl, isopentyl Base, neopentyl, third pentyl, (2-methyl)pentyl, isohexyl, (1-methyl)hexyl, (2-methyl)hexyl, (3-methyl)hexyl, (4- Methyl) hexyl, (5-methyl) hexyl, (3-ethyl) heptyl and other branched chain alkyl groups; vinyl, 1-propenyl, 2-propenyl (allyl), (1- Methyl) vinyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, (1-(2-propenyl)) vinyl, (1,2-dimethyl) propene Alkenyl groups such as 2-pentenyl groups, etc. The carbon number of the saturated or unsaturated chain hydrocarbon group is preferably 1-15, more preferably 1-10, still more preferably 1-8, still more preferably 2-8, still more preferably 3-8.

^The saturated or unsaturated alicyclic hydrocarbon groups represented by R include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; cyclohexenyl ( For example, cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl, cyclooctenyl and other cycloalkenyl groups; norbornyl, adamantyl, bicyclo[2.2.2]octyl, etc. The number of carbon atoms in the saturated or unsaturated alicyclic hydrocarbon group is preferably 3-18, more preferably 3-15, still more preferably 4-15, still more preferably 4-12, still more preferably 4-10.

Examples of the aromatic hydrocarbon group represented by R1 include phenyl, ¹ -naphthyl, 2-naphthyl, phenanthrenyl, anthracenyl, and pyrenyl. The carbon number of the aromatic hydrocarbon group is preferably 6-20, more preferably 6-18, still more preferably 6-15, still more preferably 6-12.

The hydrocarbon group represented by R ¹ may be a combination of two or more of the chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups listed above as long as the upper limit of the carbon number is 20 or less. Such a group may be, for example, a group formed by combining an aromatic hydrocarbon group with at least one selected from a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. In the hydrocarbon group formed by this combination, the chain Hydrocarbon groups can be combined as divalent groups (such as alkanediyl groups). As the example of the hydrocarbon group formed by combination, can enumerate: aralkyl groups such as benzyl, phenethyl, 1-methyl-1-phenethyl; phenyl vinyl (phenyl ethyl) (phenyl vinyl (phenyl vinyl) )) and other aryl alkenyl groups; phenylethynyl and other aryl alkynyl groups; 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, 2,4,6-triisopropylphenyl, 4-butylphenyl and other alkylaryl groups; 2,3- Dihydro-4-indenyl, 1,2,3,5,6,7-hexahydro-4-symmetric dicyclopentadienyl, 5,6,7,8-tetrahydro-1-naphthyl , 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl and other aryl groups bonded with alkanediyl; biphenyl, terphenyl, etc. An aryl group having one or more aryl groups bonded thereto; cyclohexylmethylphenyl, benzylphenyl, (dimethyl(phenyl)methyl)phenyl, and the like. In addition, the hydrocarbon group may be, for example, a hydrocarbon group obtained by combining a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples thereof include: 1-methylcyclopropyl, 1-methylcyclohexyl, 2- Methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl , 4-pentylcyclohexyl, 4-octylcyclohexyl and other alicyclic hydrocarbon groups bonded with more than one alkyl group; cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, Cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, 2-methylcyclohexylmethyl, cyclohexylethyl, adamantylmethyl, etc. Alkyl groups bonded with more than one alicyclic hydrocarbon group, etc. . The carbon number of the group obtained by combining two or more of a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group is preferably from 4 to 20, more preferably from 6 to 18, still more preferably from 6 to 15, still more preferably 6 to 12.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ is preferably an aliphatic hydrocarbon group, more preferably a saturated chain aliphatic hydrocarbon group, further preferably a saturated straight chain aliphatic hydrocarbon group or a saturated branched chain aliphatic hydrocarbon group.

Examples of substituents that the hydrocarbon group having ¹ to 20 carbon atoms represented by R1 include: a halogen atom; a nitrile group; a nitro group; an amino group; a hydroxyl group; alkoxy; aryloxy with 6 to 20 carbons such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy; silyl; boron; monomethylamino, dimethyl Alkylamine groups with 1 to 15 carbons such as amine, monoethylamine, and diethylamine; arylamines with 6 to 20 carbons such as monophenylamine and diphenylamine; benzyl Aralkylamine groups with 7 to 20 carbons such as aminoamino group; carboxyl group; aminoformyl group; acetyl, propionyl and other alkylcarbonyl groups with 2 to 15 carbons; benzoyl, 1-naphthyl Arylcarbonyl with 7 to 20 carbons such as carbonyl and 2-naphthylcarbonyl; alkoxycarbonyl with 2 to 15 carbons such as methoxycarbonyl and ethoxycarbonyl; phenoxycarbonyl and 1-naphthyloxycarbonyl , 2-naphthyloxycarbonyl and other aryloxycarbonyl groups having 7 to 20 carbon atoms. The substituent that the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ may have is preferably a halogen atom.

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

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

Examples of the compound (I) include compounds represented by formula (I-x1) (hereinafter, may be referred to as compound (I-x1)). The number of n, m1 and m2 is preferably 0-4, more preferably 0-2, still more preferably 0 or 1, still more preferably 0. r is preferably 0-4, more preferably 0-2, still more preferably 0 or 1, still more preferably 0. Examples of the compound represented by the formula (I-x1) include Compound 1 to Compound 81 as shown in Table 1 below. Among compounds 1 to 81, when the total 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 Or -SO ₂ (CH ₂ ) _r Cl is bonded to different benzene rings respectively.

[Table 1] compound x no ml m2 r compound x no ml m2 r 1 Na 1 0 0 - 41 h 1 0 0 - 2 Na 1 0 1 1 42 h 1 0 1 1 3 Na 1 0 1 2 43 h 1 0 1 2 4 Na 1 0 1 3 44 h 1 0 1 3 5 Na 1 0 2 1 45 h 1 0 2 1 6 Na 1 0 2 2 46 h 1 0 2 2 7 Na 1 0 2 3 47 h 1 0 2 3 8 Na 1 0 3 1 48 h 1 0 3 1 9 Na 1 0 3 2 49 h 1 0 3 2 10 Na 1 0 3 3 50 h 1 0 3 3 11 Na 1 1 0 - 51 h 1 1 0 - 12 Na 1 1 1 1 52 h 1 1 1 1 13 Na 1 1 1 2 53 h 1 1 1 2 14 Na 1 1 1 3 54 h 1 1 1 3 15 Na 1 1 2 1 55 h 1 1 2 1 16 Na 1 1 2 2 56 h 1 1 2 2 17 Na 1 1 2 3 57 h 1 1 2 3 18 Na 1 2 0 - 58 h 1 2 0 - 19 Na 1 2 1 1 59 h 1 2 1 1 20 Na 1 2 1 2 60 h 1 2 1 2 twenty one Na 1 2 1 3 61 h 1 2 1 3 twenty two Na 1 3 0 - 62 h 1 3 0 - twenty three Na 2 0 0 - 63 h 2 0 0 - twenty four Na 2 0 1 1 64 h 2 0 1 1 25 Na 2 0 1 2 65 h 2 0 1 2 26 Na 2 0 1 3 66 h 2 0 1 3 27 Na 2 0 2 1 67 h 2 0 2 1 28 Na 2 0 2 2 68 h 2 0 2 2 29 Na 2 0 2 3 69 h 2 0 2 3 30 Na 2 1 0 - 70 h 2 1 0 - 31 Na 2 1 1 1 71 h 2 1 1 1 32 Na 2 1 1 2 72 h 2 1 1 2 33 Na 2 1 1 3 73 h 2 1 1 3 34 Na 2 2 0 - 74 h 2 2 0 - 35 Na 3 0 0 - 75 h 3 0 0 - 36 Na 3 0 1 1 76 h 3 0 1 1 37 Na 3 0 1 2 77 h 3 0 1 2 38 Na 3 0 1 3 78 h 3 0 1 3 39 Na 3 1 0 - 79 h 3 1 0 - 40 Na 4 0 0 - 80 h 4 0 0 - 81 - 0 0 0 -

Among them, compound (I-x1) is preferably compound 1, compound 11, compound 18, compound 22, compound 23, compound 30, compound 34, compound 35, compound 39, compound 40, compound 53, compound 56, compound 60, compound 72, compound 81, more preferably compound 11, compound 18, compound 23, compound 30, compound 34, compound 35, compound 39, compound 53, compound 56, compound 60, compound 72, compound 81, and more preferably Compound 81.

As the compound (I-x1), specifically, C.I. Pigment Blue 15:4, C.I. Direct Blue 86, C.I. Direct Blue 87, C.I. Direct Blue 199, and C.I. Reactive Blue 25 are particularly preferred. At least one of the groups formed. The compound (I-x1) is more preferably C.I. Pigment Blue 15:4.

The method for producing compound (I-x1) is not particularly limited, and can be produced with reference to the synthesis example described in JP-A-2011-28236.

The compound (I-x1) is preferably a compound that is soluble in water and poorly soluble in organic solvents such as propylene glycol monomethyl ether acetate with a solubility parameter (SP value) of less than 11.0 (cal/cm ³ ) ^1/2 . In addition, solubility and poor solubility can be evaluated by the following method. Put 0.1 g of the compound (I-x1) into a 20 mL sample vial, then use a 10 ml whole pipette (whole pipet) to put in water or an organic solvent, close the cap, and treat with ultrasonic waves for 3 minutes. The obtained liquid was left still and stored in a 23 degreeC water bath for 60 minutes. 5 ml of the supernatant was filtered through a polytetrafluoroethylene (PTFE) 5 μm membrane filter, and further filtered through a 0.25 μm membrane filter to remove insoluble matter. The absorbance spectrum of the obtained filtrate was measured with a UV-visible spectrophotometer (for example, UV-2500PC manufactured by Shimadzu Corporation) using a 1 cm cell, and the absorbance (abs ). At this time, if the absorbance (abs) is less than 40% of the upper limit of measurement (in the case of UV-2500PC manufactured by Shimadzu Corporation, the absorbance (abs) is less than 2), it is evaluated as poorly soluble, and if the absorbance ( abs) is more than 40% of the upper limit of the measurement, then it is evaluated as soluble.

Preferably, the compound (I-x1) is dispersed by containing a dispersant, and a colored dispersion liquid in which the compound (I-x1) is uniformly dispersed in an organic solvent is prepared in advance. This colored dispersion may contain part or all of the organic solvent (E) contained in the curable composition. A curable composition can be prepared using the colored dispersion.

As a dispersant, a surfactant etc. are mentioned, for example, Any of cationic, anionic, nonionic, and amphoteric surfactants may be used. Specifically, surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants, and the like are exemplified. These dispersants can be used alone or in combination of two or more. As a dispersant, when expressed by a trade name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (manufactured by BASF Corporation), Ajisper (registered trademark) (Ajinomoto Fine- Techno (stock) manufacturing) and Disperbyk (Disperbyk) (registered trademark) (BYK-Chemie (BYK-Chemie) (stock) manufacturing), BYK (BYK) (registered trademark) (BYK-Chemie (BYK) -Chemie) (Share) Manufacturing) etc. As a dispersant, resin (B) (preferably resin [K1]) described later can be used.

When using a dispersant, the amount of the dispersant (solid content) used is usually 1 to 500 parts by mass, preferably 5 to 300 parts by mass, based on 100 parts by mass of the compound (I-x1), More preferably, it is 10 mass parts - 200 mass parts, More preferably, it is 15 mass parts - 180 mass parts. When the usage-amount of this dispersant exists in the said range, it exists in the tendency to obtain the colored dispersion liquid of a more uniform dispersion state.

The content of the compound (I-x1) is preferably from 1% by mass to 100% by mass, more preferably from 3% by mass to 60% by mass, and still more preferably from 4% by mass to 30% by mass, in the total amount of the colorant (A). %, and more preferably 5% by mass to 20% by mass.

Moreover, as a compound (I), the compound represented by formula (I-x2) (it may be called a compound (I-x2) hereafter) is mentioned.

[In formula (I-x2), G ¹ represents an alkanediyl group with 2 to 12 carbons, and the hydrogen atoms contained in the alkanediyl group can be substituted by an alkyl group with 1 to 4 carbon numbers, and the alkanediyl group contained -CH ₂ - contained may be substituted by -O-. J ¹ represents a hydrogen atom, -NR ^a R ^b or -NR ^a R ^b H ⁺ Q ^- . R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Q ^- represents a halide ion, BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , X ^a -CO ₂ ^- or Y ^a -SO ₃ ^- . X ^a and Y ^a each independently represent a monovalent organic group. n ^a represents an integer of 1-4. ]

Formula (I-x2) represents that n ^a hydrogen atoms contained in the compound represented by formula (I-0) are substituted by -SO ₂ -NH-G ¹ -J ¹ . When n ^a is an integer of 2 or more, a plurality of -SO ₂ -NH-G ¹ -J ¹ may be the same as or different from each other.

Examples of the alkanediyl group having 2 to 12 carbon atoms include ethylidene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, and nonanediyl. 2-methylpropanediyl, 4-methylheptanediyl, 4-ethylheptanediyl, etc. Base, 4-propylheptanediyl, 2-butylheptanediyl, 3-propyloctanediyl, 2-butylnonanediyl, 4-methyldecanediyl, 4-ethyldecanediyl Branched chain alkanediyl, etc.

Examples of the C 2-C12 alkanediyl group substituted by -CH ₂ - with -O- include groups represented by formula (G-1) and groups represented by formula (G-2).

[In formula (G-1) and formula (G-2), G ² to G ⁵ independently represent an alkanediyl group with 1 to 8 carbon atoms; n ¹ represents an integer of 1 to 3; n ² represents 0 to 3 where the total number of carbon atoms and oxygen atoms contained in the group represented by formula (G-1) is 3 to 12, and the total number of carbon atoms and oxygen atoms contained in the group represented by formula (G-2) The total number of atoms is 2 to 12; * indicates a bond with -NH-. ]

Examples of the alkanediyl groups having 1 to 8 carbons represented by G ² to G ⁵ include methylene and the alkane groups having 2 to 8 carbons in the alkanediyl groups having 2 to 12 carbons represented by G ¹ . Those with the same two bases. The alkanediyl groups having 1 to 8 carbon atoms represented by G ² to G ⁵ may be the same or different. n ¹ is preferably an integer of 1-2, more preferably an integer of 1. n ² is preferably an integer of 0-2, more preferably an integer of 0 or 1, and still more preferably 0.

As a C1-C4 alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned. Among them, methyl and ethyl are preferred, and methyl is more preferred. For example, as a group in which the hydrogen atom contained in the alkanediyl group is substituted with a methyl group, (2-methyl)propanediyl group, (1,3-dimethyl)butanediyl group, (1,4-dimethyl)butanediyl group, (1,4 -Dimethyl)pentanediyl, (1-methyl)hexanediyl, (2-methyl)hexanediyl, (3-methyl)hexanediyl, (4-methyl)hexanediyl Alkanediyl, (5-methyl)hexanediyl, (1,5-dimethyl)hexanediyl, (1,1,3,3-tetra-dimethyl)butanediyl, ( 5,5-Dimethyl)hexanediyl, (7-methyl)octanediyl, (10-methyl)undecanediyl, etc.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^a and R ^b include linear alkyl groups and branched chain alkyl groups having 1 to 8 carbon atoms in the saturated or unsaturated chain hydrocarbon group represented by R ¹ . 8 is the same alkyl group.

As _-SO2 -NH- ^{G1 -} J1, the group represented by the following formula is mentioned, for example.

When G ¹ is a group represented by formula (G-1), -SO ₂ -NH-G ¹ -J ¹ includes, for example, groups represented by the following formulas.

When G ¹ is a group represented by formula (G-2), -SO ₂ -NH-G ¹ -J ¹ includes, for example, groups represented by the following formulas.

When J ¹ is -NR ^a R ^b , as -SO ₂ -NH-G ¹ -J ¹ , groups represented by the following formulas are exemplified.

When J ¹ is -NR ^a R ^b H ⁺ Q ^- , examples of -SO ₂ -NH-G ¹ -NR ^a R ^b H ⁺ include groups represented by the following formulas.

Q ^- represents a halide ion, BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , X ^a -CO ₂ ^- or Y ^a -SO ₃ ^- . X ^a and Y ^a represent monovalent organic groups. Examples of the monovalent organic group include an alkyl group having 1 to 20 carbons, a cycloalkyl group having 3 to 20 carbons, an aryl group having 6 to 20 carbons, and a combination thereof. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group. Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclodecyl group. Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, anthracenyl and the like. X ^a -CO ₂ ^- is an anion of an organic compound containing a CO ₂ ^- group, and Y ^a -SO ₃ ^- is an anion of an organic compound containing a group of SO ₃ ^- , for example, represented by formula (Q-1) ~ formula (Q-4) of anions.

[R ^y represents an alkyl group having 1 to 20 carbon atoms. m ^a represents an integer of 0-5. ] Q ^- is preferably X ^a -CO ₂ ^- and ^Ya -SO ₃ ^- , more preferably an anion represented by the formula (Q-4). Such anions tend to increase the solubility of the compound represented by the formula (I-x2) in solvents.

In -(SO ₂ -NH-G ¹ -J ¹ )n ^a , G ¹ is preferably an alkanediyl group with 3 to 10 carbons, more preferably an alkanediyl group with 4 to 9 carbons, and the alkanediyl group The hydrogen atoms contained in may be substituted by preferably an alkyl group having 1 to 3 carbons, more preferably an alkyl group having 1 to 2 carbons. J ¹ is preferably a hydrogen atom. n ^a is preferably an integer of 2-4, more preferably an integer of 2-3, and still more preferably an integer of 3.

-CH ₂ -Alkanediyl having 2 to 12 carbon atoms substituted with -O- is preferably a group represented by formula (G-1). G ² is preferably an alkanediyl group having 1 to 5 carbon atoms, more preferably an alkanediyl group having 1 to 3 carbon atoms. G ³ is preferably an alkanediyl group having 1 to 3 carbon atoms, more preferably an alkanediyl group having 1 to 2 carbon atoms.

Examples of the compound represented by formula (I-x2) include compounds represented by formula (2-1) to formula (2-92). Among the compounds represented by formula (2-1) to formula (2-92), when n ^a is an integer of 2 or more, it is preferable that a plurality of -SO ₂ -NH-G ¹ -J ¹ are respectively bonded on different benzene rings.

Compound (I-x2) is preferably a compound represented by formula (2-1) to formula (2-16), more preferably a compound represented by formula (2-9) to formula (2-12), More preferably, it is a compound represented by formula (2-11).

The content of the compound (I-x2) is preferably from 1 mass % to 100 mass % in the total amount of the colorant (A), more preferably from 10 mass % to 98 mass %, still more preferably from 40 mass % to 97 mass % %, more preferably 60% by mass to 96% by mass, particularly preferably 80% by mass to 95% by mass.

The coloring agent (A) preferably contains at least one selected from the group consisting of compound (I-x1) and compound (I-x2), more preferably contains compound (I-x1) and compound (I-x2 ).

The content of compound (I-x1) and compound (I-x2) is preferably from 70% by mass to 100% by mass in the total amount of the colorant (A), more preferably from 80% by mass to 100% by mass, still more preferably It is 90 mass % - 100 mass %.

When both the compound (I-x1) and the compound (I-x2) are included as the colorant (A), the mass ratio of the compound (I-x1): compound (I-x2) is preferably 2:98 to 98 :2, more preferably 5:95 to 45:55, more preferably 7:93 to 20:80.

＜＜Compound (II)＞＞ The coloring agent (A) preferably contains a compound represented by formula (II) (hereinafter, may be referred to as compound (II)). Compound (II) is a dye containing a compound having a xanthene skeleton in its molecule. Compound (II) may also be its tautomer.

[In formula (II), R ²¹ to R ²⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have a substituent, or a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms that may have a substituent -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ³¹ -. R ²⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- (Zd) ⁺ , -CO ₂ H, -CO ₂ ^- (Zd) ⁺ , -CO ₂ R ²⁸ , -SO ₃ R ²⁸ , or -SO ₂ NR ²⁹ R ³⁰ . R ²⁶ and R ²⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbons. p represents an integer of 0-5. When p is 2 or more, multiple R ²⁵ may be the same or different. q represents an integer of 0 or 1. Xa represents a halogen atom. (Zd) ⁺ represents ⁺ N(R ³¹ ) ₄ , Na ⁺ , or K ⁺ , and the four R ³¹ may be the same or different. R ²⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be replaced by halogen atoms. R ²⁹ and R ³⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents, and the -CH ₂ - contained in the saturated hydrocarbon group can be modified by -O-, -CO-, - NH-, or -NR ²⁸ -substitution, R ²⁹ and R ³⁰ may be bonded to form a 3- to 10-membered heterocyclic ring together with adjacent nitrogen atoms. R ³¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. ]

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms in R ²¹ to R ²⁴ include methyl, ethyl, propyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, deca Straight-chain alkyl groups such as dialkyl, hexadecyl, and eicosyl; branched-chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; cyclopropyl C2-20 alicyclic saturated hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and tricyclodecanyl. When having a substituent, the carbon number of the saturated hydrocarbon group includes the carbon number of the substituent. Examples of substituents that a saturated hydrocarbon group may have include halogen atoms, -OH, -OR ²⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- (Zd) ⁺ , -CO ₂ H, -CO ₂ R ²⁸ , -SR ²⁸ , -SO ₂ R ²⁸ , -SO ₃ R ²⁸ , -SO ₂ NR ²⁹ R ³⁰ , or -Si(OR ³² )(OR ³³ )(OR ³⁴ ). R ³² , R ³³ and R ³⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and hydrogen atoms contained in the saturated hydrocarbon group may be substituted by halogen atoms.

Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms in R ²¹ to R ²⁴ include a phenyl group. Examples of the monovalent aromatic hydrocarbon group having a substituent include a toluyl group, xylyl group, mesityl group, propylphenyl group, and butylphenyl group. When having a substituent, the carbon number of the aromatic hydrocarbon group is the number including the carbon number of the substituent. Examples of substituents that the aromatic hydrocarbon group may have include halogen atoms, -R ²⁸ , -OH, -OR ²⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- (Zd) ⁺ , -CO ₂ H , -CO ₂ R ²⁸ , -SR ²⁸ , -SO ₂ R ²⁸ , -SO ₃ R ²⁸ , -SO ₂ NR ²⁹ R ³⁰ , or -Si(OR ³² )(OR ³³ )(OR ³⁴ ).

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms in R ²⁸ to R ³¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Straight-chain alkyl groups such as dodecyl, hexadecyl, and eicosyl; branched-chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl ; C3-20 alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and tricyclodecanyl.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁹ and R ³⁰ may have a substituent. Examples of the substituent include a hydroxyl group and a halogen atom.

Examples of monovalent saturated hydrocarbon groups having 1 to 4 carbon atoms in R ³² to R ³⁴ include linear alkyl groups such as methyl, ethyl, propyl, and butyl; branched groups such as isopropyl and isobutyl; An alicyclic saturated hydrocarbon group having 1 to 4 carbon atoms such as a chain alkyl group.

(Zd) ⁺ is ⁺ N(R ³¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ³¹ ) ₄ . Preferably, at least two of the four R ³¹ in ⁺ N(R ³¹ ) ₄ are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, the total carbon number of four ^R31s is preferably from 20 to 80, more preferably from 20 to 60. When ⁺ N(R ³¹ ) ₄ is present in the compound (II), when R ³¹ is these groups, a color filter with less foreign matter can be formed from a negative resist composition containing the compound (II).

Examples of -OR ²⁸ include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, di Decyloxy.

Examples of -CO ₂ R ²⁸ include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl and eicosyloxycarbonyl.

Examples of -SR ²⁸ include methylmercapto, ethylmercapto, butylmercapto, hexylmercapto, decylmercapto, eicosylmercapto and the like. Examples of -SO ₂ R ²⁸ include methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and eicosylsulfonyl. Examples of -SO ₃ R ²⁸ include: methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl, ethanol Alkoxysulfonyl.

Examples of -SO ₂ NR ²⁹ R ³⁰ include: sulfamoyl group; N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropyl group Aminosulfonyl group, N-butylaminosulfonyl group, N-isobutylsulfamoyl group, N-second butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group Aminosulfonyl, N-(1-ethylpropyl)sulfamoyl, N-(1,1-dimethylpropyl)sulfamoyl, N-(1,2-dimethylpropyl) base) sulfamoyl group, N-(2,2-dimethylpropyl) sulfamoyl group, N-(1-methylbutyl) sulfamoyl group, N-(2-methylbutyl) Aminosulfonyl, N-(3-methylbutyl)sulfamoyl, N-cyclopentylsulfamoyl, N-hexylsulfamoyl, N-(1,3-dimethylbutyl ) sulfamoyl group, N-(3,3-dimethylbutyl) sulfamoyl group, N-heptyl sulfamoyl group, N-(1-methylhexyl) sulfamoyl group, N-( 1,4-Dimethylpentyl)sulfamoyl, N-octylsulfamoyl, N-(2-ethylhexyl)sulfamoyl, N-(1,5-dimethyl)hexyl N-1 substituted sulfamoyl group such as sulfamoyl group, N-(1,1,2,2-tetramethylbutyl)sulfamoyl group; N,N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl, N,N-diethylsulfamoyl, N,N-propylmethylsulfamoyl, N,N-isopropylmethylsulfamoyl, N,N-tert-butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-bis(1-methylpropyl)sulfamoyl, N,N-heptyl N, N-2 substituted sulfamoyl, such as methylsulfamoyl, etc.

Examples of -Si(OR ³² )(OR ³³ )(OR ³⁴ ) include a trimethoxysilyl group, a triethoxysilyl group, and the like.

R ²⁵ is preferably -CO ₂ H, -CO ₂ ^- (Zd) ⁺ , -CO ₂ R ²⁸ , -SO ₃ ^- , -SO ₃ ^- (Zd) ⁺ , -SO ₃ H, or SO ₂ NHR ²⁹ , More preferably, it is SO ₃ ^- , -SO ₃ ^- (Zd) ⁺ , -SO ₃ H or SO ₂ NHR ²⁹ .

p represents the integer of 0-5, Preferably it is 1-4, More preferably, it is 1 or 2, More preferably, it is 1.

The alkyl group having 1 to 6 carbons in R ²⁶ and R ²⁷ may include an alkyl group having 1 to 6 carbons among the alkyl groups listed above, preferably an alkyl group having 1 to 2 carbons. R ²⁶ and R ²⁷ are more preferably hydrogen atoms.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ³¹ include benzyl, phenylethyl, phenylbutyl and the like.

q represents an integer of 0 or 1, preferably 0.

As the compound (II), preferably, a compound represented by the formula (IIa) (hereinafter may be referred to as "compound (IIa)") is exemplified. The compound represented by formula (IIa) may not be used in combination with compounds other than compound (IIa) in compound (II) (hereinafter sometimes referred to as "compound (IIb)"), and compound (IIa) may be used in combination with compound ( IIb) Used in combination. In addition, compound (IIa) can also be used in combination of 2 or more types.

[In formula (IIa), R ^a1 and R ^a4 are each independently a monovalent aromatic hydrocarbon group which may have two or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms. R ^a2 and R ^a3 are each independently a hydrogen atom, a methyl group, or an ethyl group. R ²⁵ to R ²⁷ , p, q, and Xa have the same meanings as described above. ]

Examples of R ^a1 and R ^a4 include a monovalent aromatic hydrocarbon group having no substituent in the same groups as R ²¹ and R ²⁴ above, or a monovalent saturated aliphatic hydrocarbon group having two or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms. Monovalent aromatic hydrocarbon group. Among them, a monovalent aromatic hydrocarbon group having two or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms is preferred.

A phenyl group is mentioned as a monovalent aromatic hydrocarbon group which does not have a substituent. Examples of the monovalent aromatic hydrocarbon group having two or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms include toluyl group, xylyl group, mesityl group and the like. The carbon number of the aromatic hydrocarbon group is preferably 7-20, more preferably 7-16, still more preferably 7-10, most preferably 8. The carbon number of the aromatic hydrocarbon group includes the carbon number of the substituent. The aromatic hydrocarbon group preferably does not have a substituent other than the saturated aliphatic hydrocarbon group.

The number of the saturated aliphatic hydrocarbon groups bonded to the aromatic hydrocarbon groups is preferably 1-2, more preferably 2. The saturated aliphatic hydrocarbon group is preferably bonded at the ortho or meta position, more preferably at the ortho position, with respect to the bond of the aromatic hydrocarbon group. As this saturated aliphatic hydrocarbon group, the saturated aliphatic hydrocarbon group which does not have a substituent is mentioned. The carbon number of the saturated aliphatic hydrocarbon group is preferably 1-4, more preferably 1-3, still more preferably 1-2, most preferably 1.

Examples of R ^a2 and R ^a3 include a hydrogen atom, a methyl group, and an ethyl group. Among these, a hydrogen atom or a methyl group is preferred, and a hydrogen atom is more preferred.

As compound (IIb), a compound represented by formula (Ib1) (hereinafter sometimes referred to as "compound (Ib1)") is preferably used.

[In the formula (Ib1), R ^b1 to R ^b4 independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with a carbon number of 1 to 20 that may have a substituent, or a monovalent aromatic hydrocarbon group with a carbon number of 6 to 20 that may have a substituent. At least one saturated hydrocarbon group or aromatic hydrocarbon group contained in R ^b1 to R ^b4 has a halogen atom, -OH, -OR ²⁸ , -CO ₂ H, -CO ₂ R ²⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- (Zd) ⁺ , -SR ²⁸ , -SO ₂ R ²⁸ , -SO ₃ R ²⁸ , -SO ₂ NR ²⁹ R ³⁰ , or -Si(OR ³² )(OR ³³ )(OR ³⁴ ) As a substituent, or at least one aromatic hydrocarbon group contained in R ^b1 to R ^b4 has three or more monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbons as a substituent, R ²⁵ to R ³⁰ , R ³² to R ³⁴ , p, q and Xa have the same meanings as above. ]

Examples of R ^b1 and R ^b4 include hydrogen atoms in the same groups as R ²¹ and R ²⁴ above, monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms that may have substituents, and C 6 to C 20 saturated hydrocarbon groups that may have substituents. A monovalent aromatic hydrocarbon group of 20, or an aromatic hydrocarbon group having three or more monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms as substituents. Among them, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms having a substituent, or a monovalent saturated hydrocarbon group having three or more carbon atoms having 1 to 4 carbon atoms is preferred. An aromatic hydrocarbon group with a saturated aliphatic hydrocarbon group as a substituent.

The carbon number of the monovalent saturated hydrocarbon group having 1-20 carbon atoms which may have a substituent is preferably 1-10, more preferably 2-8, still more preferably 2-7. The number of carbons in the saturated aliphatic hydrocarbon group includes the number of carbons in the substituent. Preferred substituents are halogen atoms, -OH, -OR ²⁸ , -CO ₂ H, -CO ₂ R ²⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- (Zd) ⁺ , -SR ²⁸ , -SO ₂ R ²⁸ , -SO ₃ R ²⁸ , -SO ₂ NR ²⁹ R ³⁰ , or -Si(OR ³² )(OR ³³ )(OR ³⁴ ), more preferably -OH, -OR ²⁸ , -CO ₂ H, -CO ₂ R ²⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- (Zd) ⁺ , -SR ²⁸ , -SO ₂ R ²⁸ , -SO ₃ R ²⁸ , or -Si(OR ³² ) (OR ³³ )(OR ³⁴ ), further preferably -OH, -OR ²⁸ , -CO ₂ H, -CO ₂ R ²⁸ , or -Si(OR ³² )(OR ³³ )(OR ³⁴ ), most preferably - Si(OR ³² )(OR ³³ )(OR ³⁴ ). In each saturated aliphatic hydrocarbon group, the number of substituents is preferably 1-5, more preferably 1-3, still more preferably 1-2, most preferably 1.

The carbon number of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent is preferably 7 to 20, more preferably 7 to 16, still more preferably 7 to 12, still more preferably 7 to 10, particularly preferably 7 to 8, with 8 being the best. The carbon number of the aromatic hydrocarbon group includes the carbon number of the substituent. The substituent is preferably a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, -OH, -OR ²⁸ , -CO ₂ H, -CO ₂ R ²⁸ , -SO ₃ ^- , -SO ₃ H , -SO ₃ ^- (Zd) ⁺ , -SR ²⁸ , -SO ₂ R ²⁸ , -SO ₃ R ²⁸ , -SO ₂ NR ²⁹ R ³⁰ , or -Si(OR ³² )(OR ³³ )(OR ³⁴ ), More preferably, a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbons, -OH, -OR ²⁸ , -CO ₂ H, -CO ₂ R ²⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- (Zd ) ⁺ , -SR ²⁸ , -SO ₂ R ²⁸ , -SO ₃ R ²⁸ , or -SO ₂ NR ²⁹ R ³⁰ . Further preferred are monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms, -OR ²⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- (Zd) ⁺ , -SR ²⁸ , -SO ₂ R ²⁸ , -SO ₃ R ²⁸ , or -SO ₂ NR ²⁹ R ³⁰ . In each aromatic hydrocarbon group, the number of substituents is preferably 1-5, more preferably 1-3, still more preferably 1-2, most preferably 2. The substituent is preferably bonded at the ortho-position and/or meta-position, more preferably at the ortho-position, with respect to the bonding bond of the aromatic hydrocarbon group.

The carbon number of the aromatic hydrocarbon group having three or more monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbons as substituents is preferably 9 to 20, more preferably 9 to 13, further preferably 9 to 12, most preferably 9. The carbon number of the aromatic hydrocarbon group includes the carbon number of the substituent. The aromatic hydrocarbon group preferably does not have a substituent other than the saturated aliphatic hydrocarbon group. In each aromatic hydrocarbon group, the number of the saturated aliphatic hydrocarbon groups is preferably 3-5, more preferably 3-4, most preferably 3. The saturated aliphatic hydrocarbon group is preferably bonded at the ortho-position and/or para-position with respect to the bond of the aromatic hydrocarbon group, more preferably at the ortho-position and para-position. The carbon number of the monovalent saturated aliphatic hydrocarbon group is preferably 1-5, more preferably 1-3, still more preferably 1-2, most preferably 1.

R ^b2 and R ^b3 preferably include a hydrogen atom in the same group as R ²² and R ²³ above, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Among them, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is more preferred, and a monovalent saturated hydrocarbon group having a substituent having 1 to 20 carbon atoms is still more preferred.

The carbon number of the monovalent saturated hydrocarbon group having 1-20 carbon atoms which may have a substituent is preferably 1-10, more preferably 1-6, still more preferably 1-4. The carbon number of the saturated aliphatic hydrocarbon group is the number of carbons also including the substituent. As the substituent, preferably, a halogen atom, -OH, -OR ²⁸ , -CO ₂ H, -CO ₂ R ²⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- (Zd) ⁺ , -SR ²⁸ , -SO ₂ R ²⁸ , -SO ₃ R ²⁸ , -SO ₂ NR ²⁹ R ³⁰ , or -Si(OR ³² )(OR ³³ )(OR ³⁴ ), more preferably -OH, -OR ²⁸ , -CO ₂ H, -CO ₂ R ²⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- (Zd) ⁺ , -SR ²⁸ , -SO ₂ R ²⁸ , -SO ₃ R ²⁸ , or -Si( OR ³² )(OR ³³ )(OR ³⁴ ), further preferably -OH, -OR ²⁸ , -CO ₂ H, -CO ₂ R ²⁸ or -Si(OR ³² )(OR ³³ )(OR ³⁴ ), most preferably is -CO ₂ H or -CO ₂ R ²⁸ . In each saturated aliphatic hydrocarbon group, the number of substituents is preferably 1-5, more preferably 1-3, still more preferably 1-2, most preferably 1.

Compound (IIa) is preferably compound No.1 to No.15 identified in Formula (IaX) and Table 2.

[Table 2] No. R ^ax1 R ^ax2 R ^ax3 R ^ax4 1 Ph h h Ph 2 Ph _{CH3 CH3} Ph 3 Ph CH ₃ CH ₂ CH ₃ CH ₂ Ph 4 o-tolyl h h o-tolyl 5 o-tolyl _{CH3 CH3} o-tolyl 6 o-tolyl CH ₃ CH ₂ CH ₃ CH ₂ o-tolyl 7 m-tolyl h h m-tolyl 8 m-tolyl _{CH3 CH3} m-tolyl 9 m-tolyl CH ₃ CH ₂ CH ₃ CH ₂ m-tolyl 10 p-tolyl h h p-tolyl 11 p-tolyl _{CH3 CH3} p-tolyl 12 p-tolyl CH ₃ CH ₂ CH ₃ CH ₂ p-tolyl 13 2,6-Xylyl h h 2,6-Xylyl 14 2,6-Xylyl _{CH3 CH3} 2,6-Xylyl 15 2,6-Xylyl CH ₃ CH ₂ CH ₃ CH ₂ 2,6-Xylyl

The symbols in the formula mean the following groups (hereinafter, * represents a bonding bond).

As compound (Ib1), compounds represented by formula (Ibx) and compounds No. 16 to No. 35 identified in Table 3, and formulas A3-1 to A3-8 are preferable.

[table 3] No. ^{Rbx1 Rx2 Rx3 wxya} 16 _{CH3 CH3 CH3} PrTMS 17 CH ₃ CH ₂ CH ₃ CH _{2 CH3} PrTMS 18 CH ₃ CH ₂ CH ₃ CH ₂ CH ₃ CH ₂ PrTMS 19 Ph PrCOOH PrCOOH Ph 20 o-tolyl PrCOOH PrCOOH o-tolyl twenty one m-tolyl PrCOOH PrCOOH m-tolyl twenty two p-tolyl PrCOOH PrCOOH p-tolyl twenty three 2,6-Xylyl PrCOOH PrCOOH 2,6-Xylyl twenty four MT1 h h MT1 25 MT1 _{CH3 CH3} MT1 26 MT1 CH ₃ CH ₂ CH ₃ CH ₂ MT1 27 MT2 h h MT2 28 MT2 _{CH3 CH3} MT2 29 MT2 CH ₃ CH ₂ CH ₃ CH ₂ MT2 30 MT3 h h MT3 31 MT3 _{CH3 CH3} MT3 32 MT3 CH ₃ CH ₂ CH ₃ CH ₂ MT3 33 2,4,6-Mesitylyl h h 2,4,6-Mesitylyl 34 2,4,6-Mesitylyl _{CH3 CH3} 2,4,6-Mesitylyl 35 2,4,6-Mesitylyl CH ₃ CH ₂ CH ₃ CH ₂ 2,4,6-Mesitylyl

The symbols in the formula refer to the following groups (the following * represents a bonding bond).

＜＜Coloring agent (A1)＞＞ In the curable composition of the present invention, as the colorant (A), dyes and/or pigments other than the colorant (A2) may be contained (hereinafter, the dye and the pigment may be collectively referred to as the colorant (A1)) . These may be used alone or in combination of two or more.

The coloring agent (A1) is not particularly limited as long as it does not include the coloring agent (A2), and known dyes and/or pigments can be used.

When the coloring agent (A1) is a dye, for example, a solvent dye, an acid dye, a direct dye, a mordant dye, etc. are mentioned. Examples of dyes include compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists), or those described in dyeing notes (Shikisensha Co., Ltd.). known dyes. In addition, depending on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes (except Compound (II)), 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 (among them, other than compound (I)) and the like.

When the colorant (A1) is a pigment, known pigments can be used, for example, pigments classified in the Color Index (published by The Society of Dyers and Colourists) can be listed. of pigments. Pigments classified as pigments include, for example, C.I. pigment yellow (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, 139, 147, 148, 153, 154, 166, 173, 194, 214 and other yellow pigments; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. Pigment red (pigment red) 9, 97, 105, 122, 144, 149, 166, 168, 176, 177, 180, 190, 192, 209, 215, 216, 224, 255, 264, 265, 266, 268 , 273 and other red pigments; C.I. Pigment Blue 15, 15:1, 15:2 and other blue pigments; C.I. Pigment violet (pigment violet) 1, 32, 36, 38 and other purple pigments; C.I. Pigment green (pigment green) 7, 36 and other green pigments; C.I. Pigment brown (pigment brown) 23, 25 and other brown pigments; C.I. Pigment black (pigment black) 1, 7 and other black pigments, etc.

Pigments may be subjected to rosin treatment, surface treatment using derivatives introduced with acidic groups or basic groups, etc., grafting treatment on the surface of pigments using polymer compounds, etc., micronization treatment by sulfuric acid micronization method, etc. Cleaning treatment with an organic solvent or water to remove impurities, removal treatment of ionic impurities with an ion exchange method, and the like. The particle size of the pigment is preferably substantially uniform. The pigment can be prepared as a pigment dispersion liquid in a state of being uniformly dispersed in a dispersant solution by containing a dispersant and performing a dispersion treatment. In the case of using a plurality of pigments, the dispersion treatment may be performed individually or in combination of multiple pigments. In addition, a pigment may be mixed with the compound (I) for dispersion treatment. Examples of the dispersant include the same dispersants as described above.

When using a dispersant, the amount of the dispersant (solid content) used is usually 10 to 200 parts by mass, preferably 15 to 180 parts by mass, more preferably 20 parts by mass, based on 100 parts by mass of the pigment Parts to 160 parts by mass. When the usage-amount of this dispersant exists in the said range, there exists a tendency for the pigment dispersion liquid of a more uniform dispersion state to be obtained.

When the colorant (A) contains the colorant (A1), the content of the colorant (A1) is preferably 1% by mass to 60% by mass, more preferably 1% by mass, of the total amount of the colorant (A). % to 40% by mass, more preferably 1% to 20% by mass.

The content of the colorant (A) is preferably from 1% by mass to 70% by mass, more preferably from 5% by mass to 60% by mass, and still more preferably from 10% by mass to the total amount of solid content of the curable composition. 60% by mass, more preferably 15% by mass to 55% by mass. When the content of the coloring agent (A) is within the above range, the color density when used as a color filter is sufficient, and the required amount of resin (B) can be contained in the composition, so a pattern with sufficient mechanical strength can be formed. , so it is better. Here, the "total amount of solid content" in this specification refers to the amount obtained by subtracting the content of the organic solvent from the total amount of the curable composition. The total amount of solid content and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

＜Resin (B)＞ The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. As resin (B), the following resin [K1] - resin [K6] etc. are mentioned. Resin [K1]: having monomer (a) derived from at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter, sometimes referred to as "(a)") Structural unit, copolymer with 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]: has a structural unit derived from (a) and a structural unit derived from (b), and a monomer derived from (c) that can be copolymerized with (a) (wherein, with (a) and (b) ) different) (hereinafter, there are cases referred to as "(c)") copolymers of structural units; Resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c); Resin [K4]: a copolymer having a structural unit derived from (b) added to a structural unit derived from (a) and a structural unit derived from (c); Resin [K5]: a copolymer having a structural unit derived from (a) added to a structural unit derived from (b) 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 carboxylic anhydride.

Examples of (a) specifically include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6- Tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids; 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, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other carboxyl-containing bicyclic unsaturated compounds; 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, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and other unsaturated dicarboxylic Acid anhydrides; Mono-[2-(meth)acryloxyethyl] succinate, mono-[2-(meth)acryloxyethyl] phthalate and other dibasic or higher polycarboxylic acids unsaturated mono[(meth)acryloxyalkyl]esters; Unsaturated acrylic esters, such as α-(hydroxymethyl)acrylates, which contain hydroxyl and carboxyl groups in the same molecule. Among these, acrylic acid, methacrylic acid, and the like are preferable from the viewpoint of copolymerization reactivity or the solubility of the obtained resin in an alkaline aqueous solution.

(b) means, for example, 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 ethylenic A polymeric compound with an unsaturated bond. (b) Preferably, it is a single monomer of a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group. In addition, in this specification, "(meth)acrylic acid" means at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Expressions such as "(meth)acryl" and "(meth)acrylate" also have the same meaning.

Examples of (b) include a monomer (b1) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(b1)"), a monomer having an oxetanyl group and an ethylene Monomer (b2) having a sexually unsaturated bond (hereinafter, sometimes referred to as "(b2)"), and monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "( b3)", etc.

Examples of (b1) include monomers (b1-1) having a structure obtained by epoxidizing a straight-chain or branched aliphatic unsaturated hydrocarbon (hereinafter referred to as "(b1-1) "), a monomer (b1-2) having a structure obtained by epoxidizing an alicyclic unsaturated hydrocarbon (hereinafter, sometimes referred to as "(b1-2)").

Examples of (b1-1) include: glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (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-methylene Benzyl benzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl) base) styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyl oxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4, 5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene and the like.

Examples of (b1-2) include: vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; Daicel (manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cyclomer A400; manufactured by Daicel), (meth)acrylic acid 3,4 - Epoxycyclohexyl methyl ester (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), a compound represented by the formula (BI), a compound represented by the formula (BII), and the like.

[In formula (BI) and formula (BII), R ^e and R ^f represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group. X ^e and X ^f represent a single bond, *-R ^g -, *-R ^g -O-, *-R ^g -S- or *-R ^g -NH-. R ^g represents an alkanediyl group having 1 to 6 carbon atoms. * indicates a bonding bond with O].

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

Examples of the alkanediyl group include methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5 -diyl, hexane-1,6-diyl, etc. As X ^e and X ^f , preferably a single bond, methylene, ethylidene, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, more preferably a single bond, * -CH ₂ CH ₂ -O- (* indicates a bonding bond with O).

Examples of the compound represented by formula (BI) include compounds represented by any one of formula (BI-1) to formula (BI-15), and the like. Among them, formula (BI-1), formula (BI-3), formula (BII-5), formula (BI-7), formula (BI-9) or formula (BI-11) ~ formula (BI The compound represented by -15) is more preferably a compound represented by formula (BI-1), formula (BI-7), formula (BI-9) or formula (BI-15).

Examples of the compound represented by formula (BII) include compounds represented by any one of formula (BII-1) to formula (BII-15), and the like. Among them, formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) or formula (BII-11) ~ formula (BII The compound represented by -15) is more preferably a compound represented by formula (BII-1), formula (BII-7), formula (BII-9) or formula (BII-15).

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

(b2) is more preferably a monomer having an oxetanyl group and a (meth)acryloxy group. Examples of (b2) include: 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-methyl-3-methyl Acryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl Oxetane, 3-ethyl-3-acryloyloxyethyl oxetane and the like.

(b3) is more preferably a monomer having a tetrahydrofuryl group and a (meth)acryloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), (b1) is preferable from the viewpoint of further improving reliability such as heat resistance and chemical resistance of the obtained color filter. Furthermore, (b1-2) is more preferable at the point which is excellent in the storage stability of a curable composition.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second-butyl (meth)acrylate, second-butyl (meth)acrylate, Tributyl, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, (Meth)acrylates (cf-1) that do not have a polycyclic hydrocarbon ring, such as naphthyl (meth)acrylate and benzyl (meth)acrylate (hereinafter sometimes referred to as "(cf-1)") ; Tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in this technical field, it is called "dicyclopentyl (meth)acrylate" as a common name. In addition, there are "Tricyclodecyl (meth)acrylate"), Tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate (known as a common name in this technical field "Dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, etc. Polycyclic hydrocarbon ring (meth)acrylates (cf-2) (hereinafter sometimes referred to as "(cf-2)"); 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 2 - Hydroxyl-containing (meth)acrylates such as hydroxypropyl esters; 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-methoxy Bicyclo[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 -Bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethyl Oxybicyclo[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-tertiary Butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2 -ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1] Hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N- Cyclohexylmaleimide, N-Benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl -4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-succinimidyl-3-maleimide Dicarbonyl imide derivatives such as imide propionate, N-(9-acridyl)maleimide, etc.; styrene, α-methylstyrene, m-methylstyrene, p- Methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3- Butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. Among these, (meth)acrylates are preferable.

The ratio of the structural units derived from each in the resin [K1] is preferably Structural unit derived from (a): 2 mol% to 60 mol% Structural unit derived from (b): 40 mol% to 98 mol%, better to Structural unit derived from (a): 10 mol% to 50 mol% Structural unit derived from (b): 50 mol% to 90 mol%. When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the curable composition, the developability when forming a colored pattern, and the solvent resistance of the obtained color filter tend to be excellent. .

For the resin [K1], for example, the method and Manufactured by citing references recorded in this document.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, and oxygen is replaced with nitrogen gas to create a deoxygenated environment, while stirring The method of heating and keeping warm at the same time. In addition, the polymerization initiator, solvent, etc. used here are not specifically limited, Those commonly used in this field can be used. For example, examples of polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides. Oxides (benzoyl peroxide, tertiary butyl peroxy-2-ethylhexanoate, etc.), as solvents, as long as they dissolve each monomer, examples include organic compounds as the curable composition of the present invention. The solvent (E) and the solvent etc. mentioned later.

In addition, the obtained copolymer may be used as it is after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by reprecipitation or the like. In particular, by using the solvent contained in the curable composition of the present invention as a solvent during the polymerization, the solution after the reaction can be directly used in the preparation of the curable composition of the present invention, so that the curable composition of the present invention can be used The manufacturing steps of the curable composition are simplified.

The ratio of the structural units derived from each in the resin [K2] is preferably Structural unit derived from (a): 2 mol% to 45 mol% Structural unit derived from (b): 2 mol% to 95 mol% Structural unit derived from (c): 1 mol% to 65 mol%, better to Structural unit derived from (a): 5 mol% to 40 mol% Structural unit derived from (b): 5 mol% to 80 mol% Structural unit derived from (c): 5 mol% to 60 mol% When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the curable composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance and Tendency to be excellent in mechanical strength.

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

The ratio of the structural units derived from each in the resin [K3] is preferably Structural unit derived from (a): 2 mol% to 60 mol% Structural unit derived from (c): 40 mol% to 98 mol% better to Structural unit derived from (a): 10 mol% to 50 mol% Structural unit derived from (c): 50 mol% to 90 mol% Resin [K3] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

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

Next, the cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer. Following the production of the copolymer of (a) and (c), the atmosphere in the flask was replaced from nitrogen to air, and (b), a reaction catalyst of carboxylic acid or carboxylic acid anhydride and cyclic ether (for example, tris(dimethyl Aminomethyl) phenol, etc.) and polymerization inhibitors (such as hydroquinone, etc.) are put into a flask, and reacted at 60°C to 130°C for 1 hour to 10 hours, thereby producing a resin [ K4]. The usage-amount of (b) is preferably 5 mol to 80 mol, more preferably 10 mol to 75 mol, based on 100 mol of (a). By setting it as this range, there exists a tendency for the balance of the storage stability of a curable composition, the developability at the time of pattern formation, and the solvent resistance of the obtained pattern, heat resistance, mechanical strength, and sensitivity to become favorable. (b1) is preferable as (b1) used for resin [K4], and (b1-1) is more preferable at the point that the reactivity of a cyclic ether is high and unreacted (b) is hard to remain|survive. The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 parts by mass to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). Reaction conditions, such as an addition method, reaction temperature, and time, can be adjusted suitably in consideration of the manufacturing facility, the calorific value by superposition|polymerization, etc. In addition, like the polymerization conditions, the addition method and the reaction temperature can be appropriately adjusted in consideration of production facilities, heat generation due to polymerization, and the like.

Regarding the resin [K5], as a first stage, a copolymer of (b) and (c) was obtained in the same manner as the method for producing the resin [K1]. In the same manner as above, the obtained copolymer may be used as a solution after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by reprecipitation or the like. The ratios of the structural units derived from (b) and (c) to the total molar number of all structural units constituting the copolymer are preferably Structural unit derived from (b): 5 mol% to 95 mol% Structural unit derived from (c): 5 mol% to 95 mol%, better to Structural unit derived from (b): 10 mol% to 90 mol% Structural unit derived from (c): 10 mol% to 90 mol%.

Furthermore, the carboxylic acid or carboxylic acid anhydride contained in (a) and the cyclic ether derived from (b) contained in the copolymer of (b) and (c) are prepared under the same conditions as the production method of resin [K4]. Reaction, whereby the resin [K5] can be obtained. The amount of (a) used to react with the copolymer is preferably 5 mol to 100 mol relative to 100 mol of (b). (b1) is preferable as (b1) used for resin [K5], and (b1-1) is more preferable at the point that the reactivity of a cyclic ether is high and unreacted (b) is hard to remain|survive.

Resin [K6] is resin obtained by further reacting polyhydric carboxylic acid and/or carboxylic anhydride with resin [K5]. Furthermore, polyhydric carboxylic acid and/or carboxylic acid anhydride and the hydroxyl group produced by reaction of the cyclic ether originating in (b) and the carboxylic acid or carboxylic anhydride originating in (a) are made to react. Examples of the polyvalent carboxylic acid include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, tricarballylic acid, and the like. 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, 5,6-dicarboxybicyclo[2.2.1] Hept-2-ene anhydride, etc. The usage-amount of polyhydric carboxylic acid and/or carboxylic acid anhydride is preferably 0.05-1 mole with respect to 1 mole of usage-amount of (a), More preferably, it is 0.1-0.5 mole. That is, it is more preferable that the resin [K6] also has a structural unit in which no addition is made to the hydroxyl group generated by the reaction of the cyclic ether derived from (b) and the carboxylic acid or carboxylic anhydride derived from (a). The structural unit of (a) is added to the structural unit derived from polyhydric carboxylic acid and/or carboxylic acid anhydride, (b).

The resin (B) is preferably a resin containing a structural unit having an ethylenically unsaturated bond in the side chain (resin [K4], resin [K5], or resin [K6]), more preferably a resin containing a structural unit having an ethylenically unsaturated bond in the side chain. A resin whose chain contains structural units of (meth)acryl groups.

As a resin having a structural unit including a (meth)acryl group in a side chain, for example, use of glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3 -Methyl-3-methacryloxymethyloxetane, tetrahydrofurfuryl acrylate, and other monomers (ba) having (meth)acrylyl groups (hereinafter sometimes referred to as "( ba)") As the resin [K4] of (b), use acrylic acid, methacrylic acid, succinic acid mono[2-(meth)acryloxyethyl] ester, etc., which have a (meth)acryl group. Monomer (aa) (hereinafter sometimes referred to as "(aa)") is used as the resin [K5] of (a), or (aa) is used as the resin of (a) [K6]. As a resin having a structural unit including a (meth)acryloyl group in a side chain, it is preferable to include a resin [K6] using (aa) as (a).

As a resin having a structural unit containing a (meth)acryl group in the side chain, it is more preferable to include a resin [K6] containing a (meth)acryl group in the side chain, containing Structural unit of carboxylic acid group of acid and/or carboxylic acid anhydride (a structural unit obtained by adding (aa) to the structural unit derived from (b) and further adding polycarboxylic acid and/or carboxylic anhydride); Structural unit including (meth)acryl group in chain but not carboxylic acid group derived from polycarboxylic acid and/or carboxylic acid anhydride (structural unit obtained by adding (aa) to structural unit derived from (b)) and a resin [K6] derived from the structural unit of (c), and preferably a resin [K6] comprising: a side chain comprising a (meth)acryloyl group, comprising a polycarboxylic acid derived from and/or a resin [K6] Or the structural unit of the carboxylic acid group of the carboxylic acid anhydride (the structural unit obtained by adding (aa) to the structural unit derived from (b), and then adding polycarboxylic acid and/or carboxylic anhydride); the side chain contains (form group) acryl group, a structural unit not containing a carboxylic acid group derived from polycarboxylic acid and/or carboxylic acid anhydride (a structural unit obtained by adding (aa) to a structural unit derived from (b); and derived from The resin [K6] having structural units of (cf-1) and/or (cf-2) is preferably a resin [K6] comprising: a (meth)acryloyl group in a side chain, a source Structural unit derived from carboxylic acid group of polycarboxylic acid and/or carboxylic anhydride (a structural unit obtained by adding (aa) to the structural unit derived from (b) and further adding polycarboxylic acid and/or carboxylic anhydride) ; A structural unit that contains a (meth)acryloyl group in the side chain and does not contain a carboxylic acid group derived from a polycarboxylic acid and/or carboxylic acid anhydride (obtained by adding (aa) to the structural unit derived from (b) structural units); resins derived from structural units of (cf-1) and (cf-2) [K6].

In addition, as the resin (B), from the viewpoint of increasing the remaining film rate, it is preferable to include a resin containing a structural unit having an ethylenically unsaturated bond in a side chain (resin [K4], resin [K5], or In addition to resin [K6]), it also includes resin [K1].

The polystyrene conversion weight average molecular weight of resin (B) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 4,000-90,000, More preferably, it is 5,000-80,000, More preferably, it is 8,000-70,000. When the molecular weight is within the above range, the hardness of the color filter increases, the remaining film rate increases, the solubility of the unexposed portion to the developing solution becomes favorable, and the resolution of the colored pattern tends to improve.

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

In terms of solid content, the acid value of the resin (B) is preferably 20 mg-KOH/g to 170 mg-KOH/g, more preferably 25 mg-KOH/g to 150 mg-KOH/g, and more preferably 30 mg-KOH/g～130 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably from 7% by mass to 65% by mass, more preferably from 13% by mass to 60% by mass, and still more preferably from 17% by mass to 55% by mass, based on the total amount of solids in the curable composition. % by mass, and more preferably 20% by mass to 50% by mass. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and remaining film ratio of the colored pattern tend to increase.

＜Polymerizable compound (C)＞ The polymerizable compound (C) is a compound that can be polymerized by active radicals and/or acids generated from the polymerization initiator (D). The polymerizable compound includes at least one selected from the group consisting of hexitol poly(meth)acrylate and polyglycerol poly(meth)acrylate, preferably hexitol poly(meth)acrylate Or polyglycerol poly(meth)acrylate, more preferably hexitol polyacrylate or polyglycerol polyacrylate.

<<Hexitol poly(meth)acrylate>> Hexitol poly(meth)acrylate contained as a polymerizable compound (C) has one or more ( The structure of the meth)acryl group. The 6 hydroxyl groups present in the hexitol can be modified by ethylene oxide, that is, the hexitol poly(meth)acrylate can have -O-CH ₂ -CH ₂ - at the hydroxyl end of the hexitol (meth)acryloyl group may also be bonded to the oxygen atom of the oxirane chain.

Hexitol poly(meth)acrylate is preferably a compound represented by the following formula (CA).

[In formula (CA), Y represents a hydrogen atom or a (meth)acryl group, and the number of (meth)acryl groups contained in formula (CA) is 1 to 6, and a to f independently represent The number of units of -O-CH ₂ -CH ₂ -, a+b+c+d+e+f is 0 to 24].

The number of (meth)acryloyl groups represented by Y is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and may be 5 or less. The number of hydrogen atoms represented by Y is preferably from 0 to 6, more preferably from 1 to 5, still more preferably from 4.

The (meth)acryl groups represented by Y may be the same or different, that is, methacryl, acryl, or both methacryl and acryl. Among them, the (meth)acryl group represented by Y is preferably an acryl group.

In the formula (CA), a+b+c+d+e+f (number of ethylene oxide) is preferably 3 or more, more preferably 4 or more, further preferably 5 or more, still more preferably 6 or more, And it is preferably 21 or less, more preferably 20 or less, still more preferably 19 or less, still more preferably 18 or less.

The hexitol poly(meth)acrylate is preferably a compound represented by formula (CA-1) to formula (CA-36) shown in Table 4, More preferably, it is a compound represented by formula (CA-1) to formula (CA-18), Further preferred are compounds represented by formula (CA-1) to formula (CA-6), formula (CA-13) to formula (CA-18), and more preferably formula (CA-2) to formula (CA- 5) Compounds represented by formulas (CA-14) to (CA-17), particularly preferably compounds represented by formulas (CA-3) and (CA-17).

[Table 4] Y(A) Y(M) Y(H) a+b+c+d+e+f Y(A) Y(M) Y(H) a+b+c+d+e+f CA-1 1 0 5 6 CA-19 0 1 5 6 CA-2 2 0 4 6 CA-20 0 2 4 6 CA-3 3 0 3 6 CA-21 0 3 3 6 CA-4 4 0 2 6 CA-22 0 4 2 6 CA-5 5 0 1 6 CA-23 0 5 1 6 CA-6 6 0 0 6 CA-24 0 6 0 6 CA-7 1 0 5 12 CA-25 0 1 5 12 CA-8 2 0 4 12 CA-26 0 2 4 12 CA-9 3 0 3 12 CA-27 0 3 3 12 CA-10 4 0 2 12 CA-28 0 4 2 12 CA-11 5 0 1 12 CA-29 0 5 1 12 CA-12 6 0 0 12 CA-30 0 6 0 12 CA-13 1 0 5 18 CA-31 0 1 5 18 CA-14 2 0 4 18 CA-32 0 2 4 18 CA-15 3 0 3 18 CA-33 0 3 3 18 CA-16 4 0 2 18 CA-34 0 4 2 18 CA-17 5 0 1 18 CA-35 0 5 1 18 CA-18 6 0 0 18 CA-36 0 6 0 18 Y(A): Number of acryl groups in Y Y(M): Number of methacryl groups in Y Y(H): Number of hydrogen atoms in Y

The hexitol poly(meth)acrylate is more preferably a sorbitol poly(meth)acrylate represented by the formula (CA-I).

[In the formula (CA-I), Y and a to f are the same as described above. ] Preferably, compounds represented by formulas (CA-1) to (CA-36) shown in Table 4 also have the same structure.

As the hexitol poly(meth)acrylate, a commercially available product can be used, for example: MT2519 (manufactured by Toagosei Co., Ltd., a+b+c+d+e+f=18, _H2 in Y C=CH-CO-* group is 5; H-* group is 1), MT2518 (manufactured by Toagosei Co., Ltd., a+b+c+d+e+f=6, H ₂ C=CH in Y -CO-* group is 3; H-* group is 3) and other sorbitol poly(meth)acrylates.

The content of hexitol poly(meth)acrylate is preferably from 50% by mass to 100% by mass in the total amount of the polymerizable compound (C), more preferably from 60% by mass to 100% by mass, still more preferably 80% by mass. Mass % to 100 mass %.

<<Polyglycerol poly(meth)acrylate>> Polyglycerol poly(meth)acrylate contained as a polymerizable compound (C) has one or more hydroxyl groups introduced into polyglycerol formed by polymerizing two or more glycerols. (Meth)acryloyl structure. The hydroxyl group of polyglycerol can be modified by ethylene oxide, that is, polyglycerol poly(meth)acrylate can have an oxirane chain represented by -O-CH ₂ -CH ₂ - at the hydroxyl end of polyglycerol, A (meth)acryloyl group may also be bonded to the oxygen atom of the oxirane chain.

Polyglycerol poly(meth)acrylate is preferably a compound represented by the following formula (CB).

[In formula (CB), Z represents a hydrogen atom or a (meth)acryl group, and the number of (meth)acryl groups contained in formula (CB) is 1 or more and (n+2) or less, and g to i Each independently represents the number of units of -O-CH ₂ -CH ₂ -, and is an integer of 0 to 5, and n represents the degree of polymerization of glycerin, and is an integer of 2 to 20].

n is preferably 3 or more, more preferably 4 or more, and is preferably 18 or less, more preferably 15 or less, still more preferably 12 or less.

The number of (meth)acryloyl groups represented by Z is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, still more preferably 5 or more, and is preferably 20 or less, more preferably 18 or less , more preferably 16 or less, still more preferably 14 or less, particularly preferably 12 or less. The number of hydrogen atoms represented by Z is preferably from 0 to 5, more preferably from 1 to 4, still more preferably from 1 to 3.

The (meth)acryl groups represented by Z may be the same or different, that is, methacryl, acryl, or both methacryl and acryl. Among them, the (meth)acryl group represented by Z is preferably an acryl group.

In the formula (CB), g to i (the number of ethylene oxides) are each independently preferably from 1 to 3, more preferably from 2 to 3, particularly preferably from 1.

As the polyglycerin poly(meth)acrylate, it is preferably a compound represented by formula (CB-1) to formula (CB-56) shown in Table 5, More preferably, it is a compound represented by formula (CB-1) to formula (CB-28), Further preferred are compounds represented by formula (CB-1) to formula (CB-4), formula (CB-25) to formula (CB-28), and more preferably formula (CB-1), formula (CB- 25) The indicated compound.

[table 5] no g h i Z(A) Z(M) Z(H) no g h i Z(A) Z(M) Z(H) CB-1 4 1 1 1 6 0 0 CB-29 4 1 1 1 0 6 0 CB-2 4 1 1 1 5 0 1 CB-30 4 1 1 1 0 5 1 CB-3 4 1 1 1 4 0 2 CB-31 4 1 1 1 0 4 2 CB-4 4 1 1 1 3 0 3 CB-32 4 1 1 1 0 3 3 CB-5 5 1 1 1 7 0 0 CB-33 5 1 1 1 0 7 0 CB-6 5 1 1 1 6 0 1 CB-34 5 1 1 1 0 6 1 CB-7 5 1 1 1 5 0 2 CB-35 5 1 1 1 0 5 2 CB-8 5 1 1 1 4 0 3 CB-36 5 1 1 1 0 4 3 CB-9 6 1 1 1 8 0 0 CB-37 6 1 1 1 0 8 0 CB-10 6 1 1 1 7 0 1 CB-38 6 1 1 1 0 7 1 CB-11 6 1 1 1 6 0 2 CB-39 6 1 1 1 0 6 2 CB-12 6 1 1 1 5 0 3 CB-40 6 1 1 1 0 5 3 CB-13 7 1 1 1 9 0 0 CB-41 7 1 1 1 0 9 0 CB-14 7 1 1 1 8 0 1 CB-42 7 1 1 1 0 8 1 CB-15 7 1 1 1 7 0 2 CB-43 7 1 1 1 0 7 2 CB-16 7 1 1 1 6 0 3 CB-44 7 1 1 1 0 6 3 CB-17 8 1 1 1 10 0 0 CB-45 8 1 1 1 0 10 0 CB-18 8 1 1 1 9 0 1 CB-46 8 1 1 1 0 9 1 CB-19 8 1 1 1 8 0 2 CB-47 8 1 1 1 0 8 2 CB-20 8 1 1 1 7 0 3 CB-48 8 1 1 1 0 7 3 CB-21 9 1 1 1 11 0 0 CB-49 9 1 1 1 0 11 0 CB-22 9 1 1 1 10 0 1 CB-50 9 1 1 1 0 10 1 CB-23 9 1 1 1 9 0 2 CB-51 9 1 1 1 0 9 2 CB-24 9 1 1 1 8 0 3 CB-52 9 1 1 1 0 8 3 CB-25 10 1 1 1 12 0 0 CB-53 10 1 1 1 0 12 0 CB-26 10 1 1 1 11 0 1 CB-54 10 1 1 1 0 11 1 CB-27 10 1 1 1 10 0 2 CB-55 10 1 1 1 0 10 2 CB-28 10 1 1 1 9 0 3 CB-56 10 1 1 1 0 9 3 Z(A): Number of acryl groups in Z Z(M): Number of methacryl groups in Z Z(H): Number of hydrogen atoms in Z

As the polyglycerin poly(meth)acrylate, commercially available products can be used, for example, SA-TE6 represented by the formula (CB-1) and SA-ZE12 represented by the formula (CB-25) (both Sakamoto Pharmaceutical Co., Ltd. Industry (shares) manufacturing), etc.

The content of polyglycerin poly(meth)acrylate is preferably from 50% by mass to 100% by mass, more preferably from 60% by mass to 100% by mass, and still more preferably 80% by mass, in the total amount of the polymerizable compound (C). %~100% by mass.

＜＜Polymerizable compound (C1)＞＞ In the curable composition of the present invention, as the polymerizable compound (C), polymerizable compounds other than hexitol poly(meth)acrylate and polyglycerol poly(meth)acrylate (polymerizable compound (C1 )). The polymerizable compound (C1) is a compound that can be polymerized by active radicals and/or acids generated from the polymerization initiator (D), examples of which include: hexitol poly(meth)acrylate and polyglycerol Compounds having polymerizable ethylenically unsaturated bonds other than poly(meth)acrylates are preferably (meth)acrylate compounds (excluding hexitol poly(meth)acrylate and polyglycerol poly (meth)acrylates).

Among them, the polymerizable compound (C1) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate Esters, Tris(2-(Meth)acryloxyethyl)isocyanurate, Ethylene glycol modified pentaerythritol tetra(meth)acrylate, Ethylene glycol modified dipentaerythritol hexa(methyl) Acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate (meth)acrylate, etc.

The weight average molecular weight of the polymerizable compound (C1) is preferably from 150 to 2,900, more preferably from 250 to 1,500.

From the viewpoint of pixel smearing, the content of at least one selected from the group consisting of hexitol poly(meth)acrylate and polyglycerol poly(meth)acrylate is within the range of the polymeric compound (C ) in the total amount is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and still more preferably 100% by mass.

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

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

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

As the O-acyl oxime compound, for example, N-benzoyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyl Acyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3 -Cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- Base] ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxo Heterocyclopentylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl- 6-(2-Methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-( 4-phenylthiophenyl)-3-cyclohexylpropan-1-one-2-imine, etc. Commercially available products such as Irgacure OXE01 and OXE02 (the above, manufactured by BASF), and N-1919 (manufactured by ADEKA) can also be used. Among them, the O-acyl oxime compound is preferably selected from N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, N- Benzoyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl) Composed of octane-1-one-2-imine and N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine At least one of the groups, more preferably N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, N-benzyl Acyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine. These O-acyl oxime compounds tend to provide a high-brightness color filter.

The phenylalkyl ketone 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.

As a compound having a partial structure represented by the formula (d2), for example, 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethyl Amino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl ]-1-[4-(4-morpholinyl)phenyl]butan-1-one, etc. You can also use Irgacure 369, 907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one), 379 (above, BASF ( BASF) and other commercially available products.

As a compound having a partial structure represented by formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4 -(2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 - Ketone oligomers, α,α-diethoxyacetophenone, benzoyl dimethyl ketal, etc. From the viewpoint of sensitivity, as the phenylalkyl ketone compound, a compound having a partial structure represented by the formula (d2) is preferable.

As the triazine compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis( Trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5- Triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2- Base) vinyl]-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 etc.

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

Examples of the biimidazole compound include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2, 3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2 ,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5, 5'-tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japan Japanese Patent Laid-Open No. 62-174204, etc.), imidazole compounds in which the 4,4', 5,5'-position phenyl is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Laid-Open No. 7-10913, etc.), etc. .

Furthermore, 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, methyl o-benzoylbenzoate , 4-phenylbenzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra(tert-butyl carbonyl peroxide) diphenyl Benzophenone compounds such as ketone and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2- Chloracridone, benzoyl, methyl phenylglyoxylate, titanocene compound, etc. These are preferably used in combination with a polymerization initiation aid (D1) (especially amines) described later.

As a polymerization initiator that generates an acid, for example, 4-hydroxyphenyldimethylcolumbitium p-toluenesulfonate, 4-hydroxyphenyldimethylcolumbite hexafluoroantimonate, 4-acetyloxybenzene Dimethylpercited toluenesulfonate, 4-acetyloxyphenyl-methyl-benzylpercite hexafluoroantimonate, triphenylpercited toluenesulfonate, triphenylpercite hexafluoroantimonate salt, onium salts such as diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, or nitrobenzyl toluenesulfonate, benzoin toluenesulfonate, etc.

As the polymerization initiator (D), it is preferable to contain at least one selected from the group consisting of phenalkone compounds, triazine compounds, acyl phosphine oxide compounds, O-acyl oxime compounds and biimidazole compounds. A polymerization initiator, more preferably a polymerization initiator comprising at least one selected from the group consisting of O-acyl oxime compounds and phenylkone compounds, and further preferably comprising O-acyl oxime compounds Polymerization initiator.

The content of the polymerization initiator (D) is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 25 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). , and more preferably 1 to 20 parts by mass. When content of a polymerization initiator (D) exists in the said range, since there exists a tendency for a sensitivity to become high and exposure time to shorten, the productivity of an optical filter will improve.

＜Polymerization Initiation Auxiliary (D1)＞ The polymerization initiation aid (D1) is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound whose polymerization is started by a polymerization initiator. In the case of containing the polymerization initiation aid (D1), it is usually used in combination with the polymerization initiator (D). Examples of polymerization initiation aids (D1) include: 4,4'-bis(dimethylamino)benzophenone (commonly known as Michelerone), 4,4'-bis(diethylamine) base) benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, N-phenylglycine, etc.

When these polymerization initiation aids (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C), and more preferably Preferably, it is 1 mass part - 20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with high sensitivity, and the productivity of the color filter tends to improve.

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

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Butyl propionate, Isopropyl butyrate, Ethyl butyrate, Butyl butyrate, Methyl pyruvate, Ethyl pyruvate, Propyl pyruvate, Methyl acetylacetate, Ethyl acetylacetate, Cyclo Hexanol acetate and γ-butyrolactone, etc.

Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Ethylene 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 ether, diethylene glycol dipropyl ether, diethylene glycol Dibutyl ether, anisole, phenetole and methyl anisole, etc.

Examples of ether ester solvents include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Diethyl 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 Etc.

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, etc.

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

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

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

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

The content of the organic solvent (E) is preferably from 70% by mass to 95% by mass, more preferably from 75% by mass to 92% by mass, based on the total amount of the curable composition of the present invention. In other words, the solid content of the curable composition is preferably 5% by mass to 30% by mass, more preferably 8% by mass to 25% by mass. When the content of the organic solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density does not become insufficient when forming a color filter, so the display characteristics tend to be good.

＜Leveling agent (F)＞ Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, silicone-based surfactants having fluorine atoms, and the like. These may have a polymeric group in a side chain. Examples of the silicone-based surfactant include those having a siloxane bond in the molecule, and the like. Specifically, Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone Ketone (Toray silicone) SH28PA, Toray silicone (Toray silicone) SH29PA, Toray silicone (Toray silicone) SH30PA, Toray silicone (Toray silicone) SH8400 (trade name, Toray Dow Corning (Toray Dow Corning) (share ) manufacturing), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Industry Co., Ltd. (Momentive Performance Materials Japan) Co., Ltd.) etc.

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

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule, and the like. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477 and Megafac F443 (DIC) (Share) manufacturing), etc.

When the leveler (F) is included, the content of the leveler (F) is preferably from 0.001% by mass to 0.2% by mass, more preferably from 0.002% by mass to 0.1% by mass, based on the total amount of the curable composition %. In addition, this content rate does not include the content rate of the said pigment dispersant. When the content rate of a leveling agent (F) exists in the said range, the flatness of a color filter can be made favorable.

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

<Manufacturing method of curable composition> The curable composition of the present invention can be prepared, for example, by mixing resin (B), polymerizable compound (C), and polymerization initiator (D), and if necessary, colorant (A) and organic solvent (E), leveling agent (F) and other ingredients. The colorant (A) can be prepared using the above colored dispersion liquid or pigment dispersion liquid. The intended curable composition can be prepared by mixing the remaining components in the colored dispersion liquid or pigment dispersion liquid so as to have a predetermined concentration. When the dye (A1-1) is included, the dye (A1-1) may be dissolved in part or all of the organic solvent (E) in advance to prepare a solution. Preferably, the solution is filtered with a filter having a pore diameter of about 0.01 μm to 1 μm. In addition, the curable composition after mixing is preferably filtered through a filter having a pore diameter of about 0.01 μm to 10 μm.

＜Manufacturing method of color filter＞ Examples of methods for producing colored patterns from the curable composition of the present invention include photolithography, inkjet methods, and printing methods. Among them, photolithography is preferred. Photolithography is a method in which the curable composition is coated on a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, by not using a photomask and/or not performing development at the time of exposure, it is possible to form a colored coating film that is a cured product of the coloring composition layer. The colored pattern or colored coating film thus formed is the color filter of the present invention.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass whose surface is coated with silica; or polycarbonate, polymethyl methacrylate, polyparaffin Resin plates such as ethylene phthalate; silicon; aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the above-mentioned substrates. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates.

The formation of pixels of each color by photolithography can be carried out under known or commonly used devices or conditions. For example, it can be produced as follows. First, a curable composition is applied on a substrate, and then dried by removing volatile components such as solvents by heating (pre-baking) and/or drying under reduced pressure to obtain a smooth colored composition layer. As a coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. are mentioned. The temperature at the time of heating and drying is preferably from 30°C to 120°C, more preferably from 50°C to 110°C. In addition, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes. When performing reduced-pressure drying, it is preferable to carry out at the temperature range of 20-25 degreeC under the pressure of 50 Pa-150 Pa. The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the intended color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on this photomask is not specifically limited, The pattern corresponding to the intended use is used. As a light source used for exposure, the light source which emits the light of the wavelength of 250 nm - 450 nm is preferable. For example, for light less than 350 nm, use a filter that cuts off this wavelength range, or for light around 436 nm, around 408 nm, or around 365 nm, use a bandpass filter that extracts these wavelength ranges for selection Sexual take out. Specifically, as a light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned. It is preferable to use a mask aligner and a stepper in order to uniformly irradiate the entire exposure surface with parallel light rays or to perform accurate alignment between the mask and the substrate on which the colored composition layer is formed. ) and other exposure devices.

A colored pattern is formed on the substrate by making the exposed colored composition layer contact a developing solution for development. By image development, the unexposed part of a coloring composition layer dissolves in a developing solution, and is removed. As a developing solution, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, or the like is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01% by mass to 10% by mass, more preferably 0.03% by mass to 5% by mass. Furthermore, the developer may also contain a surfactant. The developing method may be any one of a liquid covering method, a dipping method, a spraying method, and the like. Furthermore, the board|substrate can also be inclined at arbitrary angles at the time of image development. After image development, it is preferable to perform water washing.

Furthermore, it is preferable to post-bak the obtained colored pattern. The post-baking temperature is preferably from 150°C to 250°C, more preferably from 170°C to 245°C, and still more preferably from 180°C to 240°C. The post-baking time is preferably from 1 minute to 120 minutes, more preferably from 5 minutes to 60 minutes.

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

According to the curable composition of the present invention, a curable composition useful for producing a color filter with a good pattern shape can be provided. The color filter is useful as a filter used in a display device (for example, a liquid crystal display device, an organic electroluminescence (EL) device, electronic paper, etc.) and a solid-state imaging device. [Example]

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

(Resin Synthesis Example 1) An appropriate amount of nitrogen gas was passed through a flask including a reflux cooler, a dropping funnel, and a stirrer to form a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was put in, and heated to 80° C. while stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2 .1.0 ^2,6 ]decane-9-yl ester mixture (content ratio 1:1) 289 parts dissolved in 125 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over about 5 hours Inside. On the other hand, using another dropping pump, 33 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate and The resulting solution was added dropwise to the flask over about 6 hours. After completion of the dropwise addition, the same temperature was maintained for 4 hours, and then cooled to room temperature to obtain a polymer (resin (B-1)) solution having a polymer solid content of 35.1%. The produced copolymer (polymer; resin (B-1)) had a weight average molecular weight Mw of 9200, a degree of dispersion of 2.08, and an acid value in terms of solid content of 77 mg-KOH/g. The resulting copolymer has the following structural units.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of resin was performed under the following conditions using gel permeation chromatography (Gel Permeation Chromatography, GPC). Device: K2479 (manufactured by Shimadzu Corporation) Column: Shimadzu (SHIMADZU) Shim-pack GPC-80M Column temperature: 40°C Solvent: THF (tetrahydrofuran) Flow rate: 1.0 mL/min Detector: RI Standard material for calibration: TSK standard polystyrene (STANDARD POLYSTYRENE) F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.) The ratio (Mw/Mn) of the obtained polystyrene-equivalent weight average molecular weight to the number average molecular weight was defined as the degree of dispersion.

(Resin Synthesis Example 2) 277 parts of propylene glycol monomethyl ether acetate were put into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and stirred while replacing nitrogen, and the temperature was raised to 120°C. Next, add 35.3 parts of peroxy-2-ethylhexyl to a monomer mixture containing 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate and 12.3 parts of dicyclopentanyl methacrylate. Acetate tert-butyl ester (polymerization initiator) was added dropwise into the flask from the dropping funnel over 2 hours. After completion of the dropwise addition, stirring was further carried out at 120° C. for 30 minutes to perform a copolymerization reaction to produce an addition copolymer. Thereafter, the inside of the flask was replaced with air, and 93.7 parts of acrylic acid, 1.5 parts of triphenylphosphine (catalyst) and 0.8 parts of p-methoxyphenol (polymerization inhibitor) were dropped into the addition copolymer solution, The reaction was continued at 110° C. for 10 hours, and the epoxy group was cleaved by the reaction of the epoxy group derived from glycidyl methacrylate with acrylic acid, and at the same time, a polymerizable unsaturated bond was introduced into the side chain of the polymer. Next, add 24.2 parts of succinic anhydride to the reaction system, and continue the reaction at 110°C for 1 hour to react the hydroxyl group generated by the cleavage of the epoxy group with succinic anhydride, introduce carboxyl groups in the side chain, and obtain a polymer . Finally, 383 parts of propylene glycol monomethyl ether acetate were added to the reaction solution to obtain a polymer (resin (B-2)) solution having a polymer solid content of 40%. The produced copolymer (polymer; resin (B-2)) had a weight average molecular weight Mw of 6.3×10 ³ and an acid value in terms of solid content of 34 mg-KOH/g.

[Preparation of dispersion liquid 1] 12.1 parts of C.I. Pigment Blue 15:4 (compound represented by the following formula (A-1)), 3.6 parts of dispersant (BYKLPN-6919 manufactured by BYK Corporation), 5.4 parts of resin (B-1) (solid content conversion ), 11.9 parts of diacetone alcohol, and 67 parts of propylene glycol monomethyl ether acetate were mixed, 300 parts of 0.4 mm zirconia beads were added, and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion liquid 1 .

[Example 1 to Example 8, Comparative Example 1 to Comparative Example 2] The components shown in Table 6 and Table 7 were mixed to obtain each colored curable resin composition. In addition, in Table 6 and Table 7, each component is as follows. Compound (A-2): a compound represented by the following formula (A-2)

Resin (B): Resin (B-2) (converted to solid content) Polymerizable compound (C-1): Ethylene oxide modified dipentaerythritol hexaacrylate ("A-DPH6E" manufactured by Shin-Nakamura Chemical Co., Ltd., a+b+c+d+e+f=6, Converted to solid content)

Polymeric compound (C-2): Ethylene oxide modified sorbitol acrylate (manufactured by the same method as Production Example 5 of International Publication No. 2020/218365, a+b+c+d+e+f =18, the H ₂ C=CH-CO-* group in Y is 5; the H-* group is 1, converted into solid components)

Polymerizable compound (C-3): Ethylene oxide modified sorbitol acrylate (manufactured by the same method as Production Example 4 of International Publication No. 2020/218365, a+b+c+d+e+f =6, the H ₂ C=CH-CO-* group in Y is 3; the H-* group is 3, converted into solid components)

Polymerizable compound (C-4): Ethylene oxide modified polyglycerin acrylate With respect to the compound obtained by adding 264 parts of ethylene oxide to 314 parts of tetraglycerin, 649 parts of acrylic acid were reacted at 85° C. for 18 hours, followed by adding toluene, a large amount of water, and neutralizing unreacted acrylic acid. Sodium hydroxide was used to extract the organic layer with a separatory funnel, and the toluene was distilled off with an evaporator to obtain an acrylate reaction product of a tetraglycerol ethylene oxide (6 mol) adduct. The viscosity of the product was 440 mPa·s (25°C), and the reaction ratio of acrylic acid to the hydroxyl group was 95% calculated from the saponification value. (Converted to solid content)

Polymerizable compound (C-5): Ethylene oxide modified polyglycerin acrylate 1297 parts of acrylic acid were reacted at 85° C. for 18 hours with respect to a compound obtained by adding 528 parts of ethylene oxide to 758 parts of decaglycerin, followed by adding toluene, a large amount of water, and neutralizing unreacted acrylic acid. Sodium hydroxide was used to extract the organic layer with a separatory funnel, and toluene was distilled off with an evaporator to obtain an acrylate reactant of decaglycerol ethylene oxide (24 mol) adduct. The viscosity of the product was 890 mPa·s (25°C), and the reaction ratio of acrylic acid to the hydroxyl group was 93% calculated from the saponification value. (Converted to solid content)

Polymerization initiator (D-1): N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine (Changzhou Qiangli Electronic New Material (Co., Ltd.) "PBG-327 (O-acyl oxime compound)") Polymerization initiator (D-2): (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one) (BASF Co., Ltd. Irgacure-907 (Phenyl Ketone Compound) Solvent (E-1): diacetone alcohol Solvent (E-2): Propylene glycol monomethyl ether acetate Leveling agent (F-1): Polyether-modified silicone oil ("Toray Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.)

[Preparation of colored pattern] On a 4-inch silicon substrate, a colored curable resin composition was coated by spin coating 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 irradiated with light at an exposure dose of 300 mJ/cm ² (based on 365 nm) using an exposure machine (NSR-1755i7A; manufactured by Nikon Co., Ltd.). As the photomask, a photomask in which a 1.0 μm square dot pattern was formed was used. The colored composition layer after light irradiation was dipped and developed in an aqueous developer solution containing tetramethylammonium hydroxide at 23° C. for 30 seconds, washed with water, and the colored pattern I after development (before post-baking) was obtained. Furthermore, the substrate on which the colored pattern I was formed was post-baked at 230° C. for 10 minutes to obtain the colored pattern II after post-baking.

[Evaluation of dragging properties of colored patterns] With respect to the silicon wafer substrate having the obtained colored pattern I or colored pattern II, the formed colored pattern was observed at a magnification of 30,000 times using an electron microscope (S-4100, manufactured by Hitachi High-Tech Co., Ltd.). Under the side view of the colored pattern shown in Figure 1, measure the colored pattern width (CD-half) at the height hb of 50% of the film thickness la and the colored pattern width (CD-half) at the height h0 of 0% of the film thickness la -bottom), the (CD-half)/(CD-bottom) ratio was obtained and evaluated based on the following criteria. The results are shown in Table 6 and Table 7. 〇: (CD-half)/(CD-bottom) ratio is 100% to 90% or more △: (CD-half)/(CD-bottom) ratio is 70% or more and less than 90% ×: (CD-half)/(CD-bottom) ratio is less than 70%

[Table 6] Unit is part Comparative example 1 Example 1 Example 2 Example 3 Example 4 Dispersion 1 A-1 53.4 53.4 53.4 53.4 53.4 dye A-2 52.2 52.2 52.2 52.2 52.2 Resin (B) B-2 57.1 57.1 57.1 57.1 57.1 Polymeric compound (C) C-1 40 C-2 40 C-3 40 C-4 40 C-5 40 Polymerization initiator (D) D-1 7 7 7 7 7 Solvent (E) E-1 393 393 393 393 393 E-2 364 364 364 364 364 leveling agent (F) F-1 0.1 0.1 0.1 0.1 0.1 pixel dragging x 〇 △ 〇 〇

[Table 7] Unit is part Example 5 Example 6 Example 7 Comparative example 2 Example 8 Dispersion 1 A-1 53.4 53.4 53.4 dye A-2 52.2 52.2 52.2 Resin (B) B-2 57.1 67.1 47.1 60 60 Coincident compound (C) C-1 40 C-2 C-3 C-4 40 30 50 40 C-5 Polymerization initiator (D) D-1 6 7 7 2 2 D-2 1 Solvent (E) E-1 393 393 393 243 243 E-2 364 364 364 243 243 leveling agent (F) F-1 0.1 0.1 0.1 0.1 0.1 pixel dragging 〇 〇 〇 x △

1a: film thickness hb: height of 50% of film thickness 1a h0: height of 0% of film thickness 1a CD-half: Coloring pattern width at height hb CD-bottom: The width of the coloring pattern at height h0

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

Claims (11)

A curable composition comprising: resin, polymerizable compound and polymerization initiator, The polymerizable compound includes at least one selected from the group consisting of hexitol poly(meth)acrylate and polyglycerol poly(meth)acrylate. The curable composition according to claim 1, wherein the hexitol poly(meth)acrylate is a compound represented by the following formula (CA),

In formula (CA), Y represents a hydrogen atom or a (meth)acryl group, the number of (meth)acryl groups contained in formula (CA) is 1 to 6, and a to f each independently represent - The number of units of O-CH ₂ -CH ₂ -, a+b+c+d+e+f is 0 or more and 24 or less. The curable composition according to claim 2, wherein in formula (CA), a+b+c+d+e+f is 3 or more and 21 or less. The curable composition according to any one of claims 1 to 3, wherein the polyglycerol poly(meth)acrylate is a compound represented by the following formula (CB),

In formula (CB), Z represents a hydrogen atom or a (meth)acryl group, and the number of (meth)acryl groups contained in formula (CB) is not less than 1 and not more than (n+2), and g to i are respectively independently represents the number of units of -O-CH ₂ -CH ₂ -, and is an integer of 0 to 5, and n represents the degree of polymerization of glycerin, and is an integer of 2 to 20. The curable composition according to claim 4, wherein in the formula (CB), g to i are each independently 1 or more and 3 or less. The curable composition according to any one of claims 1 to 5, wherein the resin is an alkali-soluble resin. The curable composition according to any one of claims 1 to 6, wherein the resin has a structural unit including a (meth)acryl group in a side chain. The curable composition according to any one of claims 1 to 7, wherein the polymerization initiator comprises an O-acyl oxime compound. A color filter formed of the curable composition according to any one of Claims 1 to 8. A display device, comprising the color filter as claimed in Claim 9. A solid-state imaging device, comprising the color filter described in claim 9.

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