JP2022122265A - Curable composition - Google Patents

Abstract

To provide a curable composition useful for producing a color filter that makes the pattern shape good.SOLUTION: A curable composition according to the present invention contains a resin, a polymerizable compound and a polymerization initiator, and is characterized in that the polymerizable compound contains at least one selected from the group consisting of hexitol poly(meth)acrylate and polyglycerin poly(meth)acrylate.SELECTED DRAWING: Figure 1

Description

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

Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are produced from curable compositions. Dipentaerythritol hexaacrylate modified with ethylene oxide is known as a polymerizable compound used in a curable composition for forming the color filter (Patent Document 1).

JP 2008-164886 A

However, the pattern formed from the curable composition containing dipentaerythritol hexaacrylate modified with ethylene oxide may not necessarily have a satisfactory pattern shape, for example, the top shape is round and the bottom shape has skirting. rice field.

An object of the present invention is to provide a curable composition useful for producing a color filter with good pattern shape.

［式（ＣＡ）中、
Ｙは、水素原子または（メタ）アクリロイル基を表し、式（ＣＡ）が有する（メタ）アクリロイル基の数は１以上６以下である。
ａ～ｆは、それぞれ独立に、－Ｏ－ＣＨ₂－ＣＨ₂－の単位数を表し、ａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆは０以上２４以下である。］
[３] 式（ＣＡ）において、ａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆが３以上２１以下である[２]に記載の硬化性組成物。
[４] 前記ポリグリセリンポリ（メタ）アクリレートが、下記式（ＣＢ）で表される化合物である[１]～[３]のいずれか１項に記載の硬化性組成物。

［式（ＣＢ）中、
Ｚは、水素原子または（メタ）アクリロイル基を表し、式（ＣＢ）が有する（メタ）アクリロイル基の数は１以上（ｎ＋２）以下である。
ｇ～ｉは、それぞれ独立に、－Ｏ－ＣＨ₂－ＣＨ₂－の単位数を表し、０以上５以下の整数である。
ｎは、グリセリンの重合度を表し、２以上２０以下の整数である。］
[５] 式（ＣＢ）において、ｇ～ｉは、それぞれ独立に、１以上３以下である[４]に記載の硬化性組成物。
[６] 前記樹脂が、アルカリ可溶性樹脂である[１]～[５]のいずれか１項に記載の硬化性組成物。
[７] 前記樹脂が、側鎖に（メタ）アクリロイル基を含む構造単位を有する[１]～[６]のいずれか１項に記載の硬化性組成物。
[８] 前記重合開始剤がＯ－アシルオキシム化合物を含む[１]～[７]のいずれか１項に記載の硬化性組成物。
[９] [１]～[８]のいずれか１項に記載の硬化性組成物から形成されるカラーフィルタ。[１０] [９]に記載のカラーフィルタを含む表示装置。
[１１] [９]に記載のカラーフィルタを含む固体撮像素子。 That is, the gist of the present invention is as follows.
[1] containing a resin, a polymerizable compound and a polymerization initiator,
A curable composition in which the polymerizable compound contains at least one selected from the group consisting of hexitol poly(meth)acrylate and polyglycerin poly(meth)acrylate.
[2] The curable composition according to [1], wherein the hexitol poly(meth)acrylate is a compound represented by the following formula (CA).

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

[In the formula (CB),
Z represents a hydrogen atom or a (meth)acryloyl group, and the number of (meth)acryloyl groups in formula (CB) is 1 or more and (n+2) or less.
g to i each independently represent the number of units of --O--CH.sub.2--CH.sub.2-- and _are integers of ₀ or more and 5 or less.
n represents the degree of polymerization of glycerin and is an integer of 2 or more and 20 or less. ]
[5] The curable composition according to [4], wherein g to i in formula (CB) 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 containing a (meth)acryloyl group in its side chain.
[8] The curable composition according to any one of [1] to [7], wherein the polymerization initiator contains an O-acyloxime compound.
[9] A color filter formed from the curable composition according to any one of [1] to [8]. [10] A display device including the color filter according to [9].
[11] A solid-state imaging device including the color filter according to [9].

ADVANTAGE OF THE INVENTION According to this invention, a useful curable composition can be provided for manufacturing a color filter with good pattern shape.

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.

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, polymerization initiator (sometimes referred to as (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 contain a coloring agent (hereinafter sometimes referred to as coloring agent (A)).
The curable composition of the present invention may contain an organic solvent (hereinafter sometimes referred to as organic solvent (E)).
The curable composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as leveling agent (F)).
In this specification, the compounds exemplified as each component can be used singly or in combination unless otherwise specified.

<Colorant (A)>
The coloring agent (A) is not particularly limited, and known dyes and/or pigments can be used. The coloring agent (A) includes compound (I) described later, compound (II) described later, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 231, C.I. I. Pigment Yellow 233, C.I. I. Pigment Blue 16, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62, C.I. I. Pigment Green 63, C.I. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. Pigment Red 269, C.I. I. Pigment Violet 19 and C.I. I. Pigment Violet 23 (hereinafter, these colorants may be collectively referred to as colorant (A2)), and preferably contains one or more selected from compound (I) and compound (II), which will be described later. and more preferably compound (I).

<<Compound (I)>>
The coloring agent (A) may contain a central metal (eg, Cu, Al)-containing phthalocyanine, which may have a substituent, and is a compound represented by formula (I) (hereinafter referred to as compound (I) ) is preferably included.

[In formula (I), X represents a hydrogen atom or a monovalent metal atom.
R ¹ represents a substituted or unsubstituted amino group or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
n represents an integer of 0 to 4;
m represents an integer of 0 to 4;
When formula (I) has a plurality of X, X may be the same or different, and when formula (I) has a plurality of R ¹ , R ¹ may be the same or different. good. ]

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

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

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

Examples of substituted or unsubstituted amino groups represented by R ¹ include amino groups; N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N-pentylamino group, N -hexylamino group, N-heptylamino group, N-octylamino group, N-nonylamino group, N-decylamino group, N-phenylamino group, N,N-dimethylamino group, N,N-diethylamino group, N- (1-methyl)hexylamino group, N-(2-methyl)hexylamino group, N-(3-methyl)hexylamino group, N-(4-methyl)hexylamino group, N-(5-methyl)hexyl An amino group in which one or two hydrocarbon groups such as an amino group are bonded (the hydrocarbon group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms. Included in the hydrocarbon group- CH ₂ — may be replaced with —O—.) and the like.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Aliphatic hydrocarbon groups may be saturated or unsaturated and may be linear or alicyclic.

The saturated or unsaturated chain hydrocarbon group represented by R ¹ includes straight hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. Chain alkyl group, etc.; isopropyl group, (1-ethyl)propyl group, isobutyl group, sec-butyl group, tert-butyl group, (1-ethyl)butyl group, (2-ethyl)butyl group, isopentyl group, neopentyl group, tert-pentyl group, (2-methyl)pentyl group, isohexyl group, (1-methyl)hexyl group, (2-methyl)hexyl group, (3-methyl)hexyl group, (4-methyl)hexyl group, (5-methyl)hexyl group, branched chain alkyl groups such as (3-ethyl)heptyl group, etc.; vinyl group, 1-propenyl group, 2-propenyl group (allyl group), (1-methyl)ethenyl group, alkenyl groups such as 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, (1-(2-propenyl))ethenyl group, (1,2-dimethyl)propenyl group, 2-pentenyl group; mentioned. The number of carbon atoms in the saturated or unsaturated chain hydrocarbon group is preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 8, still more preferably 2 to 8, still more preferably is 3-8.

Saturated or unsaturated alicyclic hydrocarbon groups represented by R ¹ include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups; cyclohexenyl groups (e.g. cycloalkenyl groups such as cycloheptenyl group, cycloheptenyl group and cyclooctenyl group; norbornyl group, adamantyl group, bicyclo[2.2.2]octyl group and the like. The saturated or unsaturated alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 3 to 15 carbon atoms, still more preferably 4 to 15 carbon atoms, still more preferably 4 to 12 carbon atoms, and still more preferably 4 to 12 carbon atoms. Preferably 4-10.

Aromatic hydrocarbon groups represented by R ¹ include phenyl, 1-naphthyl, 2-naphthyl, phenanthryl, anthryl and pyrenyl groups. The number of carbon atoms in 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 is 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 number of carbon atoms is 20 or less. may be a group. Such a group may be, for example, a combination of an aromatic hydrocarbon group and at least one group selected from a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group, In the hydrocarbon group resulting from the combination, a chain hydrocarbon group may be combined as a divalent group (eg, an alkanediyl group). Examples of hydrocarbon groups in combination include aralkyl groups such as benzyl group, phenethyl group and 1-methyl-1-phenylethyl group; arylalkenyl groups such as phenylethenyl group (phenylvinyl group); arylalkynyl group; o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethyl phenyl group, 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, 2,4,6-tri alkylaryl groups such as isopropylphenyl group and 4-butylphenyl group; 2,3-dihydro-4-indenyl group, 1,2,3,5,6,7-hexahydro-4-s-indacenyl group, 5,6 ,7,8-tetrahydro-1-naphthyl group, 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl group or other alkanediyl group-bonded aryl group; biphenylyl an aryl group to which one or more aryl groups such as a terphenylyl group are bonded; a cyclohexylmethylphenyl group, a benzylphenyl group, a (dimethyl(phenyl)methyl)phenyl group, and the like. Further, the above hydrocarbon group may be, for example, a hydrocarbon group obtained by combining a chain hydrocarbon group and an alicyclic hydrocarbon group, examples of which include a 1-methylcyclopropyl group, a 1-methylcyclohexyl group, 2-methylcyclohexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group, 4-pentylcyclohexyl group , a 4-octylcyclohexyl group or other alicyclic hydrocarbon group to which one or more alkyl groups are bonded; cyclopropylmethyl group, cyclopropylethyl group, cyclobutylmethyl group, cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group , a cyclohexylmethyl group, a 2-methylcyclohexylmethyl group, a cyclohexylethyl group, an adamantylmethyl group, and the like to which one or more alicyclic hydrocarbon groups are bonded. The number of carbon atoms in the group obtained by combining two or more chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups is preferably 4 to 20, more preferably 6 to 18, and still more preferably 6. ˜15, even more preferably 6-12.

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, a saturated linear aliphatic hydrocarbon group or a saturated branched A chain aliphatic hydrocarbon group is more preferred.

Substituents which the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ may have include, for example, a halogen atom; a nitrile group; a nitro group; an amino group; a hydroxy group; a methoxy group; an ethoxy group; alkoxy group having 1 to 15 carbon atoms; phenyloxy group, 1-naphthyloxy group, aryloxy group having 6 to 20 carbon atoms such as 2-naphthyloxy group; silyl group; boryl group; monomethylamino group, dimethylamino group Alkylamino groups having 1 to 15 carbon atoms such as , monoethylamino group and diethylamino group; Arylamino groups having 6 to 20 carbon atoms such as monophenylamino group and diphenylamino group; C7 to 20 groups such as benzylamino group aralkylamino group; carboxy group; carbamoyl group; acetyl group, alkylcarbonyl group having 2 to 15 carbon atoms such as propionyl group; Arylcarbonyl group; Alkoxycarbonyl group having 2 to 15 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; Aryl having 7 to 20 carbon atoms such as phenyloxycarbonyl group, 1-naphthyloxycarbonyl group and 2-naphthyloxycarbonyl group An oxycarbonyl group and the like can be mentioned. A halogen atom is preferable as the substituent which the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ may have.

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

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

Examples of compound (I) include compounds represented by formula (I-x1) (hereinafter sometimes referred to as compound (I-x1)).
The numbers n, m1 and m2 are preferably 0 to 4, more preferably 0 to 2, more preferably 0 or 1, even more preferably 0.
r is preferably 0-4, more preferably 0-2, more preferably 0 or 1, even more preferably 0.
Examples of compounds represented by formula (I-x1) include compounds 1 to 81 as shown in Table 1 below. Among compounds 1 to 81, when the sum of the integer represented by n, the integer represented by m1 and the integer represented by m2 is 2 or more, -SO ₃ X, -SO ₂ NH ₂ and/or -SO ₂ ( CH ₂ ) _r Cl are preferably bonded to different benzene rings.

Among them, the compound (I-x1) includes 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 and compound 81 are preferred, compound 11, compound 18, compound 23, compound 30, compound 34, compound 35, compound 39, compound 53, compound 56, compound 60, compound 72 and compound 81 are more preferred, and compound 81 is More preferred.

Specific examples of the compound (I-x1) include C.I. I. Pigment Blue 15:4, C.I. I. Direct Blue 86, C.I. I. Direct Blue 87, C.I. I. Direct Blue 199 and C.I. I. Examples include Reactive Blue 25, and it is particularly preferable to include at least one selected from the group consisting of the above dyes. As the compound (I-x1), C.I. I. Pigment Blue 15:4.

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

As the compound (I-x1), an organic solvent that is soluble in water and has a solubility parameter (SP value) of less than 11.0 (cal/cm ³ ) ^1/2 such as propylene glycol monomethyl ether acetate. is preferably sparingly soluble in In addition, soluble and sparingly soluble can be evaluated by the following methods.
0.1 g of compound (I-x1) is added to a 20 mL sample vial, water or an organic solvent is added using a 10 ml whole pipette, and the tube is capped and treated with ultrasonic waves for 3 minutes. The resulting liquid is stored in a water bath at 23° C. for 60 minutes. 5 ml of this supernatant is filtered through a PTFE 5 μm membrane filter and then through a 0.25 μm membrane filter to remove insolubles. The absorbance spectrum of the resulting filtrate is measured with a UV-visible spectrophotometer (e.g., UV-2500PC manufactured by Shimadzu Corporation) using a 1 cm cell to determine the absorbance (abs) at the maximum absorption wavelength of compound (I-x1). . 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 insoluble, and 40% or more of the upper limit of measurement. If it is, it is evaluated as soluble.

Compound (I-x1) is preferably prepared in advance as a colored dispersion in which compound (I-x1) is uniformly dispersed in an organic solvent by adding a dispersant and performing dispersion treatment. . The 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.

Examples of dispersing agents include surfactants, and cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples include surfactants such as polyester-based, polyamine-based and acrylic-based surfactants. These dispersants may be used alone or in combination of two or more. As the dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), and EFKA (registered trademark). (manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.) and Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), BYK (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and the like. . As a dispersant, a resin (B) (preferably resin [K1]) described later may be used.

When a dispersant is used, the amount of the dispersant (solid content) used is usually 1 to 500 parts by mass, preferably 5 to 300 parts by mass, relative to 100 parts by mass of compound (I-x1), It is more preferably 10 to 200 parts by mass, still more preferably 15 to 180 parts by mass. When the amount of the dispersant used is within the above range, there is a tendency to obtain a colored dispersion in a more uniformly dispersed state.

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

Compound (I) also includes a compound represented by formula (I-x2) (hereinafter sometimes referred to as compound (I-x2)).

[In the formula (I-x2), G ¹ represents an alkanediyl group having 2 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. , -CH ₂ - contained in the alkanediyl group may be replaced with -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 to 4; ]

Formula (I-x2) represents that n ^a hydrogen atoms contained in the compound represented by formula (I-0) are replaced with --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 or different.

Examples of the alkanediyl group having 2 to 12 carbon atoms include ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, heptanediyl group, octanediyl group, nonanediyl group, decanediyl group, undecanediyl group and dodecanediyl group. linear alkanediyl group; 2-methylpropanediyl group, 4-methylheptanediyl group, 4-ethylheptanediyl group, 4-propylheptanediyl group, 2-butylheptanediyl group, 3-propyloctanediyl group, branched chain alkanediyl groups such as 2-butylnonanediyl group, 4-methyldecanediyl group, 4-ethyldecanediyl group, and the like;

Examples of the alkanediyl group having 2 to 12 carbon atoms in which —CH ₂ — is replaced with —O— include groups represented by formula (G-1) and groups represented by formula (G-2). .

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

The alkanediyl groups having 1 to 8 carbon atoms represented by G ² to G ⁵ are methylene groups and the alkanediyl groups having 2 to 12 carbon atoms represented by the above G ¹ having 2 to 8 carbon atoms. The same can be mentioned. 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 to 2, more preferably an integer of 0 or 1, still more preferably 0.

Examples of alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group and butyl group. Among them, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.
For example, alkanediyl groups in which a hydrogen atom contained in the group is substituted with a methyl group include (2-methyl)propanediyl group, (1,3-dimethyl)butanediyl group, (1,4-dimethyl)pentanediyl group, (1-methyl) hexanediyl group, (2-methyl) hexanediyl group, (3-methyl) hexanediyl group, (4-methyl) hexanediyl group, (5-methyl) hexanediyl group, (1,5- dimethyl)hexanediyl group, (1,1,3,3-tetradimethyl)butanediyl group, (5,5-dimethyl)hexanediyl group, (7-methyl)octanediyl group, (10-methyl)undecanediyl group, etc. are exemplified.

Examples of alkyl groups having 1 to 8 carbon atoms represented by R ^a and R ^b include straight-chain alkyl groups and branched-chain alkyl groups of saturated or unsaturated chain hydrocarbon groups represented by R ¹ . , and those having 1 to 8 carbon atoms.

—SO ₂ —NH—G ¹ —J ¹ includes, for example, groups represented by the following formulae.

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 formulae.

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 formulae.

When J ¹ is —NR ^a R ^b , —SO ₂ —NH—G ¹ —J ¹ includes, for example, groups represented by the following formulae.

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 formulae.

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. The monovalent organic group includes an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a combination thereof, and the like.
The alkyl group having 1 to 20 carbon atoms includes methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group and the like.
Cycloalkyl groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclodecyl groups.
The aryl group having 6 to 20 carbon atoms includes phenyl group, naphthyl group, anthryl group and the like.
X ^a —CO ₂ ^— is an organic anion containing a CO ₂ ^— group, and Y ^a —SO ₃ ^— is an organic anion including an SO ₃ ^— group. Anions represented by 4) can be mentioned.

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

In --(SO ₂ --NH--G ^{1 --J 1} )na, G ¹ is preferably an alkanediyl group having 3 to 10 carbon atoms, more preferably an alkanediyl group having 4 to 9 carbon atoms, and the alkane A hydrogen atom contained in the diyl group may preferably be substituted with an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms.
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;

The alkanediyl group having 2 to 12 carbon atoms in which -CH ₂ - is replaced 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 formulas (2-1) to (2-92). Among the compounds represented by formulas (2-1) to (2-92), when n ^a is an integer of 2 or more, the plurality of —SO ₂ —NH—G ¹ —J ¹ are each different benzene It is preferably attached to a ring.

As the compound (I-x2), compounds represented by formulas (2-1) to (2-16) are preferable, and compounds represented by formulas (2-9) to (2-12) are more preferable. Preferred are compounds represented by formula (2-11).

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

Colorant (A) preferably contains one or more selected from the group consisting of compound (I-x1) and compound (I-x2), including compound (I-x1) and compound (I-x2) is more preferable.

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

When both the compound (I-x1) and the compound (I-x2) are contained 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, still more preferably 7:93 to 20:80.

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

[in the formula (II),
R ²¹ to R ²⁴ each independently represent a hydrogen atom, an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted carbon number It represents a 6-20 monovalent aromatic hydrocarbon group, and --CH ₂ -- contained in the saturated hydrocarbon group may be replaced with --O--, --CO-- or --NR ³¹ --.
R ²⁵ is —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 carbon atoms.
p represents an integer of 0 to 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 a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ²⁹ and R ³⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the —CH _2- may be substituted with -O-, -CO-, -NH-, or -NR ²⁸ -, and R ²⁹ and R ³⁰ are bonded together with the adjacent nitrogen atom to form a 3- to 10-membered ring It may form a heterocyclic ring.
R ³¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms for R ²¹ to R ²⁴ include methyl group, ethyl group, propyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. , dodecyl group, hexadecyl group, icosyl group, etc.; branched chain alkyl groups, such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group , a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, and other alicyclic saturated hydrocarbon groups having 2 to 20 carbon atoms. The number of carbon atoms in the saturated hydrocarbon group is the number including the carbon atoms of the substituent when the saturated hydrocarbon group has a substituent. Substituents which the saturated hydrocarbon group may have include a halogen atom, -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 the hydrogen atoms contained in the saturated hydrocarbon group are substituted with halogen atoms; good too.

The monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms for R ²¹ to R ²⁴ includes a phenyl group. Examples of monovalent aromatic hydrocarbon groups having substituents include toluyl, xylyl, mesityl, propylphenyl, and butylphenyl groups. When the aromatic hydrocarbon group has a substituent, the number of carbon atoms in the substituent is also included. Examples of substituents which 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 ) is mentioned.

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms for R ²⁸ to R ³¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and nonyl group. , decyl group, dodecyl group, hexadecyl group, icosyl group and other linear alkyl groups; isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and other branched alkyl groups; cyclopropyl group, cyclopentyl group , a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, and other alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁹ and R ³⁰ may have a substituent. The substituent includes a hydroxy 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 group, ethyl group, propyl group and butyl group; Alicyclic saturated hydrocarbon groups having 1 to 4 carbon atoms such as branched alkyl groups are included.

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

—OR ²⁸ includes, for example, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and icosyloxy groups.

—CO ₂ R ²⁸ includes, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group and an icosyloxycarbonyl group.

—SR ²⁸ includes, for example, a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group and an icosylsulfanyl group.
—SO ₂ R ²⁸ includes, for example, a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group and an icosylsulfonyl group.
—SO ₃ R ²⁸ includes, for example, a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and an icosyloxysulfonyl group.

—SO ₂ NR ²⁹ R ³⁰ is, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-(1,1-dimethylpropyl)sulfamoyl group, N-(1,2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N-(3 -methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethylbutyl)sulfamoyl group, N- heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl)sulfamoyl group, N- N-1 substituted sulfamoyl groups such as (1,5-dimethyl)hexylsulfamoyl group and N-(1,1,2,2-tetramethylbutyl)sulfamoyl group;
N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group moyl group, N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group and N,N-2 substituted sulfamoyl groups such as groups.

—Si(OR ³² )(OR ³³ )(OR ³⁴ ) includes, for example, 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 , SO ₃ ⁻ , —SO ₃ ⁻ (Zd) ⁺ , —SO ₃ H or SO ₂ NHR ²⁹ are more preferred.

p represents an integer of 0 to 5, preferably 1 to 4, more preferably 1 or 2, and even more preferably 1;

The alkyl group having 1 to 6 carbon atoms in R ²⁶ and R ²⁷ includes those having 1 to 6 carbon atoms among the above-mentioned alkyl groups, and the alkyl group having 1 to 2 carbon atoms is preferable. More preferably, R ²⁶ and R ²⁷ are hydrogen atoms.

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

q represents an integer of 0 or 1, with 0 being preferred.

Compound (II) is preferably a compound represented by formula (IIa) (hereinafter sometimes referred to as "compound (IIa)"). The compound represented by formula (IIa) may be used without being combined with a compound (II) other than compound (IIa) (hereinafter sometimes referred to as "compound (IIb)"), or compound (IIa ) and compound (IIb) may be used in combination. Compound (IIa) may be used in combination of two or more.

[In the formula (IIa),
R ^a1 and R ^a4 are each independently a monovalent aromatic hydrocarbon group optionally having 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 above. ]

R ^a1 and R ^a4 are unsubstituted monovalent aromatic hydrocarbon groups or monovalent saturated aliphatic groups having 1 to 4 carbon atoms among the same groups as R ²¹ and R ²⁴ above. Examples include monovalent aromatic hydrocarbon groups having two or less hydrocarbon groups. Among these, monovalent aromatic hydrocarbon groups having two or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms are 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 of 1 to 4 carbon atoms include toluyl group, xylyl group and mesityl group. The aromatic hydrocarbon group preferably has 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, still more preferably 7 to 10 carbon atoms, and most preferably 8 carbon atoms. The number of carbon atoms in the aromatic hydrocarbon group is the number including the carbon atoms in the substituent. The aromatic hydrocarbon group preferably has no substituents other than the saturated aliphatic hydrocarbon group.

The number of saturated aliphatic hydrocarbon groups bonded to the aromatic hydrocarbon group is preferably 1 to 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. Examples of the saturated aliphatic hydrocarbon group include saturated aliphatic hydrocarbon groups having no substituents. The saturated aliphatic hydrocarbon group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, still more preferably 1 to 2 carbon atoms, and most preferably 1 carbon atom.

R ^a2 and R ^a3 include a hydrogen atom, a methyl group and an ethyl group, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

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 are each independently a hydrogen atom, an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituted represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be
at least one saturated hydrocarbon group or aromatic hydrocarbon group contained in R ^b1 to R ^b4 is 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 3 or more C 1-4 monovalent saturated aliphatic hydrocarbon groups as substituents have
R ²⁵ to R ³⁰ , R ³² to R ³⁴ , p, q and Xa have the same meanings as above. ]

As R ^b1 and R ^b4 , among the same groups as R ²¹ and R ²⁴ above, a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a substituent. optionally having a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic having 3 or more monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms as substituents A hydrocarbon group is mentioned. Among these, 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 and having a substituent, or a carbon number An aromatic hydrocarbon group having 3 or more 1 to 4 monovalent saturated aliphatic hydrocarbon groups as substituents is preferred.

The number of carbon atoms in the optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is preferably 1 to 10, more preferably 2 to 8, and even more preferably 2 to 7. The number of carbon atoms in the saturated aliphatic hydrocarbon group is the number including the carbon atoms in the substituent. Substituents include 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 ) are preferred, and -OH, -OR ²⁸ and -CO ₂ are more preferred. 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 ), more preferably —OH, —OR ²⁸ , —CO ₂ H, —CO ₂ R ²⁸ , or —Si(OR ³² ) (OR ³³ ) (OR ³⁴ ); Most preferred is -Si(OR ³² )(OR ³³ )(OR ³⁴ ). The number of substituents per saturated aliphatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, and most preferably 1.

The number of carbon atoms in the optionally substituted monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms is preferably 7 to 20, more preferably 7 to 16, still more preferably 7 to 12, Even more preferably 7-10, particularly preferably 7-8, most preferably 8. The number of carbon atoms in the aromatic hydrocarbon group is the number including the carbon atoms in the substituent. Substituents include monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms, halogen atoms, —OH, —OR ²⁸ and —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 monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon 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 , or -SO ₂ NR ²⁹ R ³⁰ is. More preferably, 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 . The number of substituents per aromatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, and most preferably 2. The substituent is preferably bonded at the ortho-position and/or the meta-position, more preferably at the ortho-position, with respect to the bond of the aromatic hydrocarbon group.

The number of carbon atoms in the aromatic hydrocarbon group having 3 or more substituents of monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms is preferably 9 to 20, more preferably 9 to 13, and further Preferably 9-12, most preferably 9. The number of carbon atoms in the aromatic hydrocarbon group is the number including the carbon atoms in the substituent. The aromatic hydrocarbon group preferably has no substituents other than the saturated aliphatic hydrocarbon group. The number of saturated aliphatic hydrocarbon groups is preferably 3-5, more preferably 3-4, and most preferably 3 per aromatic hydrocarbon group. 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, and is preferably bonded at the ortho-position and para-position. more preferred. The number of carbon atoms in the monovalent saturated aliphatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, most preferably 1. preferable.

R ^b2 and R ^b3 are preferably a hydrogen atom or an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms among the same groups as those of R ²² and R ²³ . be done. Among them, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is more preferable, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which has a substituent is more preferable. preferable.

The number of carbon atoms in the optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4. The number of carbon atoms in the saturated aliphatic hydrocarbon group is the number including the carbon atoms in the substituent. Substituents include 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 ) are preferred, and —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 ), more preferably —OH, —OR ²⁸ , —CO ₂ H, —CO ₂ R ²⁸ , or —Si(OR ³² ) (OR ³³ ) (OR ³⁴ ) and most preferably -CO ₂ H or -CO ₂ R ²⁸ . The number of substituents per saturated aliphatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, and most preferably 1.

As the compound (IIa), compound Nos. specified by the formula (IaX) and Table 2 are used. 1 to 15 are preferred.

The symbols in the formula mean the following groups (* represents a bond below).

As the compound (Ib1), compound Nos. specified by the formula (Ibx) and Table 3 are used. 16 to 35 and compounds represented by formulas A3-1 to A3-8 are preferred.

The symbols in the formula mean the following groups (* represents a bond below).

<<Colorant (A1)>>
The curable composition of the present invention contains, as the colorant (A), a dye and/or pigment other than the colorant (A2) (hereinafter, the dye and the pigment may be collectively referred to as the colorant (A1)). may contain. These may be used alone or in combination of two or more.

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

When the coloring agent (A1) is a dye, examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes and the like. Dyes include, for example, compounds classified as dyes in the Color Index (published by The Society of Dyers and Colorists) and known dyes described in Dye Note (Shikisensha). According to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes (excluding compound (II)), thiazole dyes, oxazine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, Examples include azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and phthalocyanine dyes (excluding compound (I)).

When the colorant (A1) is a pigment, a known pigment can be used, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colorists).
Pigments classified as pigments include, for example, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 139, yellow pigments such as 147, 148, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. 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, etc. pigment;
C. I. blue pigments such as Pigment Blue 15, 15:1, 15:2;
C. I. Violet color pigments such as Pigment Violet 1, 32, 36, 38;
C. I. Green pigments such as Pigment Green 7 and 36;
C. I. Brown pigments such as Pigment Brown 23 and 25;
C. I. black pigments such as Pigment Black 1 and 7;

If necessary, the pigment may be subjected to rosin treatment, surface treatment using a derivative having an acidic group or basic group, etc., graft treatment to the surface of the pigment using a polymer compound, etc., and atomization treatment such as a sulfuric acid atomization method. , cleaning treatment with an organic solvent or water for removing impurities, treatment for removing ionic impurities by an ion exchange method or the like, and the like may be performed. It is preferable that the particle size of the pigment is substantially uniform. The pigment can be dispersed uniformly in the dispersant solution by adding a dispersant and dispersing the pigment. When a plurality of pigments are used, each pigment may be subjected to dispersion treatment alone, or a plurality of pigments may be mixed and subjected to dispersion treatment. Alternatively, the pigment may be mixed with the compound (I) and subjected to dispersion treatment. Examples of the dispersing agent include those mentioned above.

When a dispersant is used, the amount of the dispersant (solid content) used is usually 10 to 200 parts by mass, preferably 15 to 180 parts by mass, more preferably 20 to 200 parts by mass, based on 100 parts by mass of the pigment. 160 parts by mass. When the amount of the dispersant used is within the above range, there is a tendency to obtain a more uniformly dispersed pigment dispersion.

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

The content of the colorant (A) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, still more preferably 10 to 60% by mass, based on the total solid content of the curable composition. % by mass, and more preferably 15 to 55% by mass. When the content of the coloring agent (A) is within the above range, the color density of the color filter is sufficient, and the necessary amount of the resin (B) can be contained in the composition. It is preferable because a pattern with sufficient strength can be formed.
Here, the term "total amount of solid content" as used herein 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 solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

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

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

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

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

As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as "(b1-1)" ), and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

(b1-1) includes 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-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene , 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene , 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris (glycidyloxymethyl)styrene and the like.

(b1-2) includes vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cychromer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cychromer M100; manufactured by Daicel Corporation), the compound represented by formula (BI) and formula (BII) Compounds represented by 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 is substituted with a hydroxy group. may
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.
* represents a bond with O. ]

Examples of alkyl groups 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.
Alkyl groups in which hydrogen atoms are substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.
R ^e and R ^f are preferably hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group and 2-hydroxyethyl group, more preferably hydrogen atom and methyl group.

The alkanediyl group includes methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane- A 1,6-diyl group and the like can be mentioned.
X ^e and X ^f are preferably a single bond, a methylene group, an ethylene group, *--CH ₂ --O-- and *--CH ₂ CH ₂ --O--, more preferably a single bond and *--CH ₂ CH ₂ --O-- (* represents a bond with O).

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

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

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 in combination, the content ratio of these (the compound represented by the formula (BI): the compound represented by the formula (BII)) is It is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

(b2) is more preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. (b2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane , 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane and the like.

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

(b) is preferably (b1) in that the heat resistance, chemical resistance, and other reliability of the resulting color filter can be further enhanced. Furthermore, (b1-2) is more preferable in that the storage stability of the curable composition is excellent.

(c) includes, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth) Acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate ) Acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) acrylic acid esters having no polycyclic hydrocarbon ring such as benzyl (meth) acrylate (cf-1) (hereinafter “(cf-1) ”);
Tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate (in the technical field, it is commonly called “dicyclopentanyl (meth)acrylate”. cyclodecyl (meth)acrylate”), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate (in the technical field, the common name is “dicyclopentenyl (meth) ) acrylate”), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate and other polycyclic hydrocarbon ring-containing (meth)acrylates (cf- 2) (hereinafter sometimes referred to as "(cf-2)");
Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;
bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5- Hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2′-hydroxyethyl)bicyclo[2.2.1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2 .1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2′-hydroxyethyl)bicyclo[2.2. 1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy -5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2 .2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyl oxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 - dicarbonylimide derivatives such as maleimidopropionate, N-(9-acridinyl)maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , isoprene, 2,3-dimethyl-1,3-butadiene, and the like.
Among these, (meth)acrylates are preferred.

In the resin [K1], the ratio of the structural units derived from each of the total structural units constituting the resin [K1] is
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (b); 40 to 98 mol%
is preferably
Structural unit derived from (a); 10 to 50 mol%
Structural unit derived from (b); 50 to 90 mol%
is more preferable.
When the ratio of the structural units 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. be.

The resin [K1] is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin, 1st edition, 1st edition, published on March 1, 1972) and the literature It can be manufactured with reference to the cited document described in .

Specifically, predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and, for example, by replacing oxygen with nitrogen, a deoxygenated atmosphere is created, and while stirring, A method of heating and keeping warm can be mentioned. The polymerization initiator, solvent, and the like used here are not particularly limited, and those commonly used in the relevant field can be used. For example, polymerization initiators include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, t -Butyl peroxy-2-ethylhexanoate, etc.), and the solvent may be one that dissolves each monomer, such as the solvent described later as the organic solvent (E) of the curable composition of the present invention. is mentioned.

The obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. You can use things. In particular, by using the solvent contained in the curable composition of the present invention as the solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the curable composition of the present invention. The manufacturing process of the curable composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the total structural units constituting the resin [K2] is
Structural unit derived from (a); 2 to 45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
is preferably
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
is more preferable.
When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the curable composition, developability when forming a colored pattern, and the solvent resistance and heat resistance of the obtained color filter are improved. And tend to be excellent in mechanical strength.

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

In the resin [K3], the ratio of the structural units derived from each of the total structural units constituting the resin [K3] is
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (c); 40 to 98 mol%
is preferably
Structural unit derived from (a); 10 to 50 mol%
Structural unit derived from (c); 50 to 90 mol%
is more preferable.
Resin [K3] can be produced, for example, in the same manner as the method for producing resin [K1].

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

Next, part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms of (b).
Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst (e.g., tris ( dimethylaminomethyl)phenol, etc.) and a polymerization inhibitor (e.g., hydroquinone, etc.) are placed in a flask and reacted at, for example, 60 to 130° C. for 1 to 10 hours to produce resin [K4]. can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting it to this range, the storage stability of the curable composition, the developability when forming a pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern tend to be well balanced. be. Since the cyclic ether has high reactivity and unreacted (b) does not easily remain, (b1) is preferable as (b) used in resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect 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 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).
Reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

For resin [K5], as the first step, a copolymer of (b) and (c) is obtained in the same manner as in the method for producing resin [K1] described above. In the same manner as described above, the obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be converted into a solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer is, respectively,
Structural unit derived from (b); 5 to 95 mol%
Structural unit derived from (c); 5 to 95 mol%
is preferably
Structural unit derived from (b); 10 to 90 mol%
Structural unit derived from (c); 10 to 90 mol%
is more preferable.

Furthermore, under the same conditions as in the method for producing resin [K4], the cyclic ether derived from (b) in the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic anhydride of (a). Resin [K5] can be obtained by reacting substances.
The amount of (a) to be reacted with the copolymer is preferably 5 to 100 mol per 100 mol of (b). Since the cyclic ether has high reactivity and unreacted (b) does not easily remain, (b1) is preferable as (b) used in resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by reacting resin [K5] with a polyvalent carboxylic acid and/or a carboxylic acid anhydride. The hydroxy group generated by the reaction of the cyclic ether derived from (b) and the carboxylic acid or carboxylic anhydride derived from (a) is further reacted with a polyvalent carboxylic acid and/or a carboxylic anhydride.
Polyvalent carboxylic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, tricarbanilic acid and the like. Carboxylic anhydrides include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, and 3,4,5,6-tetrahydrophthalic acid. anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and the like. The amount of polyvalent carboxylic acid and/or carboxylic acid anhydride used is preferably 0.05 to 1 mol, more preferably 0.1 to 0.5 mol, per 1 mol of (a) used. That is, the resin [K6] has a polyhydric carboxylic acid and/or carboxylic anhydride attached to the hydroxy group generated by the reaction between the cyclic ether derived from (b) and the carboxylic acid or carboxylic anhydride derived from (a). It is more preferable to have a structural unit obtained by adding (a) to a structural unit derived from (b) to which no substance is added.

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

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

As the resin having a structural unit containing a (meth)acryloyl group in the side chain, a structural unit containing a (meth)acryloyl group in the side chain and containing a carboxylic acid group derived from a polyvalent carboxylic acid and/or a carboxylic acid anhydride (A structural unit obtained by adding (aa) to a structural unit derived from (b) and further adding a polyvalent carboxylic acid and/or a carboxylic acid anhydride) and a (meth)acryloyl group in a side chain, A structural unit not containing a carboxylic acid group derived from a carboxylic acid and/or a carboxylic acid anhydride (a structural unit obtained by adding (aa) to a structural unit derived from (b)), and a structure derived from (c) A structural unit ((b (aa) is added to a structural unit derived from ), and a structural unit obtained by further adding a polyvalent carboxylic acid and / or a carboxylic acid anhydride), and a (meth) acryloyl group in a side chain, a polyvalent carboxylic acid and / or a structural unit not containing a carboxylic acid group derived from a carboxylic anhydride (a structural unit obtained by adding (aa) to a structural unit derived from (b)), (cf-1) and / or (cf -2) more preferably contains a resin [K6] having a structural unit derived from, containing a (meth) acryloyl group in the side chain, a carboxylic acid group derived from a polyvalent carboxylic acid and / or a carboxylic acid anhydride A structural unit (a structural unit obtained by adding (aa) to a structural unit derived from (b) and further adding a polyvalent carboxylic acid and / or carboxylic acid anhydride) and a (meth) acryloyl group in the side chain and a structural unit (a structural unit obtained by adding (aa) to a structural unit derived from (b)) that does not contain a carboxylic acid group derived from a polyvalent carboxylic acid and/or a carboxylic acid anhydride), and (cf- It is particularly preferable to contain a resin [K6] having structural units derived from 1) and (cf-2).

As the resin (B), from the viewpoint of increasing the film retention rate, resins other than resins (resin [K4], resin [K5], or resin [K6]) having a structural unit having an ethylenically unsaturated bond in the side chain In addition, it is preferable that resin [K1] is further included.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 4,000 to 90,000, still more preferably 5,000 to 80,000, and More preferably 8,000 to 70,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the colored pattern tends to be improved.

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

The acid value of the resin (B) is preferably 20 to 170 mg-KOH/g, more preferably 25 to 150 mg-KOH/g, still more preferably 30 to 130 mg-KOH/g, in terms of solid content. 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 7 to 65% by mass, more preferably 13 to 60% by mass, still more preferably 17 to 55% by mass, based on the total solid content of the curable composition. %, still more preferably 20 to 50 mass %. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film rate tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and/or acid generated from the polymerization initiator (D). The polymerizable compound contains at least one selected from the group consisting of hexitol poly(meth)acrylate and polyglycerin poly(meth)acrylate, preferably hexitol poly(meth)acrylate or polyglycerin poly(meth)acrylate. More preferably, it contains xitol polyacrylate or polyglycerin polyacrylate.

<<hexitol poly(meth)acrylate>>
Hexitol poly(meth)acrylate contained as the polymerizable compound (C) has a structure in which one or more (meth)acryloyl groups are introduced to six hydroxyl groups present in hexitol. Six hydroxyl groups present in hexitol may be modified with ethylene oxide, that is, hexitol poly(meth)acrylate has an ethylene oxide chain represented by —O—CH ₂ —CH ₂ — at the hydroxyl group end of hexitol. and a (meth)acryloyl group may be bonded to the oxygen atom of the ethylene oxide chain.

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

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

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 0 or more and 6 or less, more preferably 1 or more and 5 or less, and still more preferably 4 or less.

Each (meth)acryloyl group represented by Y may be the same or different, ie, a methacryloyl group, an acryloyl group, or both a methacryloyl group and an acryloyl group. Among them, the (meth)acryloyl group represented by Y is preferably an acryloyl group.

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

As the hexitol poly(meth)acrylate, compounds represented by formulas (CA-1) to (CA-36) shown in Table 4 are preferable.
Compounds represented by formulas (CA-1) to (CA-18) are more preferred,
Compounds represented by formulas (CA-1) to (CA-6) and formulas (CA-13) to (CA-18) are more preferred, and formulas (CA-2) to (CA-5), Compounds represented by formulas (CA-14) to (CA-17) are even more preferred, and compounds represented by formulas (CA-3) and (CA-17) are particularly preferred.

As the hexitol poly(meth)acrylate, sorbitol poly(meth)acrylate represented by formula (CA-I) is more preferable.

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

As the hexitol poly ₍ meth)acrylate, a commercially available product may be used. 1), MT2518 (manufactured by Toagosei Co., Ltd., a+b+c+d+e+f=6, H ₂ C═CH—CO—* group in Y is 3; H—* group is 3) and other sorbitol poly(meth)acrylates.

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

<<Polyglycerin Poly(meth)acrylate>>
The polyglycerin poly(meth)acrylate contained as the polymerizable compound (C) has a structure in which one or more (meth)acryloyl groups are introduced into the hydroxyl groups of polyglycerin formed by polymerizing two or more glycerins. The hydroxyl groups of polyglycerin may be modified with ethylene oxide, that is, polyglycerol poly(meth)acrylate has an ethylene oxide chain represented by —O—CH ₂ —CH ₂ — at the hydroxyl group end of polyglycerin. A (meth)acryloyl group may be bonded to the oxygen atom of the ethylene oxide chain.

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

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

n is preferably 3 or more, more preferably 4 or more, 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, still more preferably 4 or more, still more preferably 5 or more, preferably 20 or less, more preferably 18 or less, and further It is preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less.
The number of hydrogen atoms represented by Z is preferably 0 or more and 5 or less, more preferably 1 or more and 4 or less, and still more preferably 1 or more and 3 or less.

Each (meth)acryloyl group represented by Z may be the same or different, ie, it may be a methacryloyl group, an acryloyl group, or both a methacryloyl group and an acryloyl group. Among them, the (meth)acryloyl group represented by Z is preferably an acryloyl group.

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

As polyglycerin poly(meth)acrylate, compounds represented by formulas (CB-1) to (CB-56) shown in Table 5 are preferable,
Compounds represented by formulas (CB-1) to (CB-28) are more preferred,
Compounds represented by formulas (CB-1) to (CB-4) and formulas (CB-25) to (CB-28) are more preferred, and formulas (CB-1) and (CB-25) The indicated compounds are even more preferred.

Commercially available products may be used as polyglycerin poly(meth)acrylate, for example, SA-TE6 represented by formula (CB-1), SA-ZE12 represented by formula (CB-25) (both of which are Sakamoto manufactured by Yakuhin Kogyo Co., Ltd.) and the like.

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

<<polymerizable compound (C1)>>
The curable composition of the present invention may contain a polymerizable compound (polymerizable compound (C1)) other than hexitol poly(meth)acrylate and polyglycerin poly(meth)acrylate as the polymerizable compound (C). The polymerizable compound (C1) is a compound that can be polymerized by an active radical and/or an acid generated from the polymerization initiator (D). (Meth)acrylic acid ester compounds are preferred (except for hexitol poly(meth)acrylate and polyglycerin poly(meth)acrylate).

Among them, the polymerizable compound (C1) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl ) isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like.

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

The content of at least one selected from the group consisting of hexitol poly(meth)acrylate and polyglycerin poly(meth)acrylate is preferably 80 to 100 mass in the total amount of the polymerizable compound (C) from the viewpoint of pixel trailing. %, more preferably 90 to 100% by mass, still more preferably 100% by mass.

The content of the polymerizable compound (C) is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, more preferably 15 to 40% by mass, based on the total 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 initiating polymerization by generating active radicals, acids, etc. by the action of light or heat, and known polymerization initiators can be used. Examples of polymerization initiators that generate active radicals include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds.

The O-acyloxime compound is a compound having a partial structure represented by the following formula (d1). Below, * represents a bond.

Examples of the O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane, -1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2, 4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -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-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine and the like. Commercially available products such as Irgacure OXE01 and OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may also be used. Among them, O-acyloxime compounds include N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl ) butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)- At least one selected from the group consisting of 3-cyclopentylpropan-1-one-2-imine is preferred, and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2- More preferred is the imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine. These O-acyl oxime compounds tend to give high-brightness color filters.

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

Examples of compounds having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4 -morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one etc. Commercial products such as Irgacure 369, 907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), 379 (manufactured by BASF) may be used.

Examples of compounds having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2 -hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxy Acetophenone, benzyl dimethyl ketal and the like can be mentioned.
From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4- methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxy styryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4 -bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. is mentioned.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products 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 (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4, 4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetra(alkoxyphenyl)biimidazole, 2,2′-bis( 2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxy phenyl)biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), a biimidazole in which the phenyl group at the 4,4'5,5'-position is substituted with a carboalkoxy group; Examples thereof include imidazole compounds (see, for example, JP-A-7-10913).

Furthermore, the polymerization initiator (D) includes 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- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with a polymerization initiation aid (D1) (especially amines) described later.

Polymerization initiators that generate acids include, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxy Onium salts such as phenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate and benzoin tosylate.

As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds is preferred, and O-acyloxy Polymerization initiators containing at least one selected from the group consisting of amine compounds and alkylphenone compounds are more preferred, and polymerization initiators containing O-acyloxime compounds are even more preferred.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 0.5 parts by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is from 1 to 25 parts by mass, more preferably from 1 to 20 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, thereby improving the productivity of the optical filter.

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

When using these polymerization initiation aids (D1), the content 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). It is preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of color filters tends to improve.

<Organic solvent (E)>
The organic solvent (E) is not particularly limited, and organic solvents commonly used in this field can be used. For example, ester solvent (solvent containing -COO- in the molecule but not containing -O-), ether solvent (solvent containing -O- in the molecule but not containing -COO-), ether ester solvent (solvent containing -COO- in the molecule solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-, - solvents containing no CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

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

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

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

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 non, cyclohexanone, isophorone, and the like.

Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.

Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

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

The content of the organic solvent (E) is preferably 70-95% by mass, more preferably 75-92% by mass, relative to the total amount of the curable composition of the present invention. In other words, the solids content of the curable composition is preferably 5-30% by weight, more preferably 8-25% by weight. When the content of the organic solvent (E) is within the above range, the flatness at the time of coating is improved, and when a color filter is formed, the color density is not insufficient, so the display characteristics tend to be improved. be.

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

Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, Florard FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Florado F171, Flora F172, Flora F173, Flora F177, Flora F183, Flora F554 R30, RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Examples include S382, SC101, SC105 (manufactured by AGC Co., Ltd. (former Asahi Glass Co., Ltd.)) and E5844 (manufactured by Daikin Fine Chemicals Laboratory Co., Ltd.).

Examples of the fluorine atom-containing silicone-based surfactants include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, F477 and F443 (manufactured by DIC Corporation) and the like can be mentioned.

When the leveling agent (F) is included, the content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.002 to It is 0.1% by mass. This content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The curable composition of the present invention optionally contains additives known in the art such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers and chain transfer agents. It's okay.

<Method for producing curable composition>
The curable composition of the present invention includes, for example, a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and optionally a colorant (A), an organic solvent (E), leveling It can be prepared by mixing the agent (F) and other ingredients.
The colorant (A) may be prepared using the above-described color dispersion or pigment dispersion. A desired curable composition can be prepared by mixing the remaining components with the coloring dispersion or the pigment dispersion so as to have a predetermined concentration.
When the dye (A1-1) is included, the dye (A1-1) may be dissolved in advance in part or all of the organic solvent (E) to prepare a solution. It is preferable to filter the solution through a filter having a pore size of about 0.01 to 1 μm.
The curable composition after mixing is preferably filtered through a filter having a pore size of about 0.01 to 10 μm.

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

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass whose surface is coated with silica; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; A thin film of aluminum, silver, silver/copper/palladium alloy, etc., is formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by the photolithographic method can be carried out using a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a curable composition is applied onto a substrate, dried by heating (pre-baking) and/or dried under reduced pressure to remove volatile components such as solvents, and dried to obtain a smooth colored composition layer.
Examples of coating methods include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
The temperature for heat drying is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
When drying under reduced pressure, it is preferably carried out at a pressure of 50 to 150 Pa and a temperature of 20 to 25°C.
The film thickness of the colored composition layer is not particularly limited, and may be appropriately selected according to the desired film thickness of the color filter.

The colored composition layer is then exposed through a photomask to form the desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern suitable for the intended use is used.
The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You can Specifically, light sources include mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, and the like.
It is possible to uniformly irradiate the entire exposure surface with parallel light rays and to perform accurate alignment between the photomask and the substrate on which the colored composition layer is formed. is preferred.

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

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

The film thickness of the coating film after post-baking is, for example, preferably 3 μm or less, more preferably 2.0 μm or less. Although the lower limit of the film thickness of the coating film is not particularly limited, 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, it is possible to provide a curable composition useful for producing a color filter having a good pattern shape. The color filter is useful as a filter for use in display devices (eg, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

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

(Resin synthesis example 1)
A suitable amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the flask was heated to 80°C while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2. A solution of 289 parts of a mixture of 1.0 ^2,6 ]decane-9-yl acrylate (content ratio is 1:1) dissolved in 125 parts of propylene glycol monomethyl ether acetate was added dropwise over about 5 hours using a dropping pump. . On the other hand, a solution obtained by dissolving 33 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator in 235 parts of propylene glycol monomethyl ether acetate was added to the flask over about 6 hours using another dropping pump. Dripped. After completion of dropping, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a polymer (resin (B-1)) solution having a polymer solid content of 35.1%. The resulting copolymer (polymer; resin (B-1)) had a weight average molecular weight Mw of 9200, a dispersity of 2.08, and an acid value of 77 mg-KOH/g in terms of solid content. The resulting copolymer has the following structural units.

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

(Resin synthesis example 2)
277 parts of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and the mixture was stirred while being replaced with nitrogen and heated to 120°C. Then, to a monomer mixture consisting of 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate and 12.3 parts of dicyclopentanyl methacrylate, 35.3 parts of t-butyl peroxy-2-ethylhexanoate (Polymerization initiator) was added dropwise into the flask from the dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 120° C. for 30 minutes to carry out 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 methoquinone (polymerization inhibitor) were introduced into the above addition copolymer solution. The reaction was continued at 110° C. for 10 hours to cleave the epoxy group and introduce a polymerizable unsaturated bond into the side chain of the polymer at the same time as the reaction between the epoxy group derived from glycidyl methacrylate and acrylic acid. Next, 24.2 parts of succinic anhydride was added to the reaction system, and the reaction was continued at 110°C for 1 hour to react the hydroxy groups generated by the cleavage of the epoxy groups with succinic anhydride to introduce carboxyl groups into the side chains. , to obtain the polymer. Finally, 383 parts of propylene glycol monomethyl ether acetate was added to the reaction solution to obtain a polymer (resin (B-2)) solution with a polymer solid content of 40%. The resulting copolymer (polymer; resin (B-2)) had a weight average molecular weight Mw of 6.3×10 ³ and an acid value converted to solid content of 34 mg-KOH/g.

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

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

Resin (B): Resin (B-2) (solid content conversion)
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)

Polymerizable compound (C-2): ethylene oxide-modified sorbitol acrylate (manufactured by the same method as in Production Example 5 of WO 2020/218365, a + b + c + d + e + f = 18, H ₂ C=CH-CO-* group in Y is 5 ; H-* group is 1, converted to solid content)

Polymerizable compound (C-3): ethylene oxide-modified sorbitol acrylate (manufactured by the same method as in Production Example 4 of WO 2020/218365, a + b + c + d + e + f = 6, H ₂ C=CH-CO-* group in Y is 3 ; H-* group is 3, converted to solid content)

Polymerizable compound (C-4): ethylene oxide-modified polyglycerin acrylate A compound obtained by adding 264 parts of ethylene oxide to 314 parts of tetraglycerin was reacted with 649 parts of acrylic acid at 85°C for 18 hours, and then toluene and a large amount of Water and an amount of sodium hydroxide to neutralize unreacted acrylic acid are added, the organic layer is taken out with a separating funnel, toluene is distilled off with an evaporator, and an acrylate reaction product of tetraglycerin ethylene oxide (6 mol) adduct is obtained. got The viscosity of the product was 440 mPa·s (25° C.), and the reaction ratio of acrylic acid determined from the saponification value was 95% with respect to hydroxyl groups. (Converted to solid content)

Polymerizable compound (C-5): ethylene oxide-modified polyglycerin acrylate A compound obtained by adding 528 parts of ethylene oxide to 758 parts of decaglycerin was reacted with 1297 parts of acrylic acid at 85°C for 18 hours, and then toluene and a large amount of Water and an amount of sodium hydroxide to neutralize unreacted acrylic acid are added, the organic layer is taken out with a separating funnel, toluene is distilled off with an evaporator, and an acrylate reaction product of decaglycerin ethylene oxide (24 mol) adduct is obtained. got The viscosity of the product was 890 mPa·s (25° C.), and the reaction ratio of acrylic acid determined from the saponification value was 93% with respect to hydroxyl groups. (Converted to solid content)

Polymerization initiator (D-1): N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine (manufactured by Changzhou Strong Electronic New Materials Co., Ltd. "PBG-327 (O-acyl oxime compound)”)
Polymerization initiator (D-2): (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one) (manufactured by BASF Irgacure-907 (alkylphenone 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 Dow Corning Toray Co., Ltd.)

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

[Evaluation of footing property of colored pattern]
The colored pattern formed on the silicon wafer substrate having colored pattern I or colored pattern II obtained above was observed with an electron microscope (S-4100, manufactured by Hitachi High-Tech Co., Ltd.) at a magnification of 30,000. In the side view of the colored pattern shown in FIG. 1, the colored pattern width (CD-half) at a height hb of 50% of the film thickness la, and the colored pattern width (CD-half) at a height h0 of 0% of the film thickness la -bottom) was measured, the (CD-half)/(CD-bottom) ratio was determined, and evaluated based on the following criteria. Results are shown in Tables 6 and 7.
○: (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%

la Film thickness hb 50% height of film thickness la h0 0% height of film thickness la CD-half Colored pattern width at height hb CD-bottom Colored pattern width at height h0

Claims (11)

including a resin, a polymerizable compound and a polymerization initiator,
A curable composition in which the polymerizable compound contains at least one selected from the group consisting of hexitol poly(meth)acrylate and polyglycerin 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 the formula (CA),
Y represents a hydrogen atom or a (meth)acryloyl group, and formula (CA) has 1 or more and 6 or less (meth)acryloyl groups.
a to f each independently represents the number of units of --O--CH ₂ --CH ₂ --, and a+b+c+d+e+f is 0 or more and 24 or less. ] 3. The curable composition according to claim 2, wherein a+b+c+d+e+f in formula (CA) is 3 or more and 21 or less. The curable composition according to any one of claims 1 to 3, wherein the polyglycerin poly(meth)acrylate is a compound represented by the following formula (CB).

[In the formula (CB),
Z represents a hydrogen atom or a (meth)acryloyl group, and the number of (meth)acryloyl groups in formula (CB) is 1 or more and (n+2) or less.
g to i each independently represent the number of units of --O--CH.sub.2--CH.sub.2-- and _are integers of ₀ or more and 5 or less.
n represents the degree of polymerization of glycerin and is an integer of 2 or more and 20 or less. ] 5. The curable composition according to claim 4, wherein g to i in formula (CB) 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 containing a (meth)acryloyl group in a side chain. The curable composition according to any one of claims 1 to 7, wherein the polymerization initiator comprises an O-acyloxime compound. A color filter formed from the curable composition according to any one of claims 1 to 8. A display device comprising the color filter according to claim 9 . A solid-state imaging device comprising the color filter according to claim 9 .

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