KR20220007628A - colored curable resin composition - Google Patents

Abstract

A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the colored curable resin composition further contains a phenolic antioxidant (E), Colored curable resin composition containing resin (B1) in which resin (B) contains the structural unit (b1-1) represented by Formula (1b) [the definition of the symbol in a following formula is as having described in the specification.] .

Description

colored curable resin composition

[0001] The present invention relates to a colored curable resin composition.

[0002] Colored curable resin compositions are used in the manufacture of color filters used in display devices such as liquid crystal displays, electroluminescent displays, and plasma displays, and various resin compositions have been developed. For example, in patent document 1, a solvent, a reactive diluent, a photoinitiator, a coloring agent, and Formula (1):

[0003]

[0004] [The definition of the symbol in formula (1) is as described in Patent Document 1.]

A resin composition for a color filter comprising a copolymer including a structural unit represented by is described.

[0005] 1. WO 2018/110097 A1

[0006] Examples of a method for forming a color filter with the colored curable resin composition include a photolithography method and a method using an inkjet device. In the photolithography method, a colored curable resin composition is usually applied on a substrate, and volatile components such as a solvent are removed by heat drying (pre-bake) and/or drying under reduced pressure to form a composition layer, , the composition layer is irradiated with light (exposed), and a developer is brought into contact with the composition layer after exposure to form (develop) a colored pattern or a colored coating film. After this development, a post-bake for heating the coloring pattern is frequently performed.

[0007] In the conventional colored curable resin composition, the thickness of the colored pattern or colored coating film is greatly reduced due to post-baking in some cases. The present invention has been made in view of such circumstances, and an object thereof is to provide a colored curable resin composition capable of suppressing a decrease in the thickness of the colored pattern or colored coating film due to heating (especially post-baking).

The present invention that can achieve the above object is as follows.

[1] A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D),

The colored curable resin composition further contains a phenol-based antioxidant (E),

Resin (B) is, formula (1b):

[0009]

[0010] In formula (1b), R ^1B represents a hydrogen atom or a methyl group,

R ^2B to R ^4B each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms,

n represents an integer of 1 to 10, and

* represents a binding position,

However, ^{at least one of R 2B} to R ^4B is an alkoxy group having 1 to 6 carbon atoms.]

Colored curable resin composition containing resin (B1) containing the structural unit (b1-1) represented by.

[2] Resin (B1) is a copolymer comprising a structural unit (b1-1), a structural unit derived from a polymerizable unsaturated compound having an acidic group (b1-2), and another structural unit (b1-3); Moreover, the colored curable resin composition as described in said [1] whose quantity of the structural unit (b1-1) when the sum total of all the structural units in a copolymer is 100 mol% is 1-50 mol%.

[3] The colored curable resin composition according to the above [1] or [2], wherein the weight average molecular weight of the resin (B1) is 1,000 to 50,000.

[4] The colored curable resin composition according to any one of [1] to [3], wherein the content of the resin (B1) is 5 to 400 parts by weight with respect to 100 parts by weight of the polymerizable compound (C).

[5] The colored curable resin composition according to any one of [1] to [4], wherein the content of the phenolic antioxidant (E) is 0.1 to 25 parts by weight with respect to 100 parts by weight of the polymerizable compound (C).

[6] The colored curable resin composition according to any one of [1] to [5], wherein the colorant (A) contains a dye (A1) and a pigment (A2).

[7] The colored curable resin composition according to any one of [1] to [6], wherein the polymerizable compound (C) is a radically polymerizable compound, and the polymerization initiator (D) is a photoradical polymerization initiator.

[8] The colorant (A) is a formula (A3-1):

[0011]

[0012] In [Formula (A3-1), R ^41a and R ^42a are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a saturated hydrocarbon group having 6 to 14 carbon atoms which may have a substituent represents an aromatic hydrocarbon group or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41a and R ^42a are bonded to each other, and together with the nitrogen atom to which they are bonded, 3 to 10 membered nitrogen-containing (含)窒素) to form a heterocyclic ring,

R ^43a and R ^44a are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or 7 carbon atoms which may have a substituent ~ 30 represents an aralkyl group, or R ^43a and R ^44a combine to form a 3-10 membered nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded,

R ^47a to R ^54a each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , or optionally a substituent having 1 to 8 carbon atoms represents an alkyl group,

R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms,

Ring T ^1a represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or an aromatic heterocycle having 5 to 10 members which may have a substituent,

The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group,

The substituent which the aromatic hydrocarbon group having 6 to 14 carbon atoms may have is a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and a substituent which may have a substituent. At least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms,

The substituent which the aralkyl group having 7 to 30 carbon atoms may have is a halogen atom, a nitro group, a hydroxy group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and a substituent which may have a substituent. At least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms,

The substituent that the aromatic hydrocarbon ring having 6 to 14 carbon atoms may have is a halogen atom, a nitro group, a hydroxy group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and even if it has a substituent At least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms,

Substituents which the 5- to 10-membered aromatic heterocycle may have include a halogen atom, a nitro group, a hydroxy group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and even if it has a substituent At least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms,

The substituent which the said C1-C8 alkyl group may have is at least one selected from the group which consists of a halogen atom, a hydroxyl group, a formyl group, and an amino group,

When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- or -CO-,

When the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH ₂ - contained in the alkyl group may be substituted with -O- or -CO-,

r represents an integer of 1 or more,

M ^r+ represents a hydrogen ion, an r-valent metal ion, or N ⁺ (R ^55a ) ₄ , four R ^55a may be the same or different;

R ^55a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms,

k is the formula (A3-1a):

[0013]

[In Formula (A3-1a), rings T ^1a , R ^41a to R ^44a and R ^47a to R ^54a each have the same meanings as above.]

_{represents the sum of the number of -SO 3} ^- and -SO ₂ -N ^- -SO ₂ -R ^f that the anion represented by has, and is an integer of 2 or more,

When r is an integer of 2 or more, the plurality of anions represented by the formula (A3-1a) may be the same or different, and

When k-1 is an integer of 2 or more, a plurality of M ^r+ may be the same or different.]

a compound represented by

Formula (A3-2):

[0015]

[0016] In [Formula (A3-2), R ^41b and R ^42b are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a saturated hydrocarbon group having 6 to 14 carbon atoms which may have a substituent represents an aromatic hydrocarbon group or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41b and R ^42b are bonded to form a 3 to 10 membered nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded, ,

R ^43b and R ^44b are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or 7 carbon atoms which may have a substituent ~ 30 represents an aralkyl group, or R ^43b and R ^44b combine to form a 3-10 membered nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded,

R ^47b to R ^54b each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms which may have a substituent;

Ring T ^1b represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or an aromatic heterocycle having 5 to 10 members which may have a substituent,

The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group,

The substituent which the aromatic hydrocarbon group having 6 to 14 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent,

The substituent which the aralkyl group having 7 to 30 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent,

The substituent which the aromatic hydrocarbon ring having 6 to 14 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent,

The substituent which the 5- to 10-membered aromatic heterocyclic ring may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent,

The substituent which the said C1-C8 alkyl group may have is at least one selected from the group which consists of a halogen atom, a hydroxyl group, a formyl group, and an amino group,

When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- or -CO-,

When the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH ₂ - contained in the alkyl group may be substituted with -O- or -CO-,

m represents an integer of 1 or more,

[Y] ^m- represents an m-valent anion, and

When m is an integer greater than or equal to 2, the formula (A3-2c):

[0017]

[In Formula (A3-2c), each of rings T ^1b , R ^41b to R ^44b and R ^47b to R ^54b have the same meanings as above.]

The plurality of cations represented by may be the same or different.]

The colored curable resin composition according to any one of [1] to [7], comprising at least one compound (A3) selected from the group consisting of compounds represented by

[9] The colored curable resin composition according to the above [8], wherein the colorant (A) contains a dye (A1) different from the compound (A3).

[0019] When the colored curable resin composition of the present invention is used, it is possible to suppress a decrease in the thickness of the colored pattern or the colored coating film due to heating (especially post-baking).

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a phenolic antioxidant (E). Moreover, resin (B) contains resin (B1) containing the structural unit (b1-1) represented by said Formula (1b). Below, each component of the colored curable resin composition of this invention is demonstrated in order.

[0021] Unless otherwise specified, each component described in the present specification and a raw material for manufacturing each component may use only one type or may use two or more types together.

[0022] <Colorant (A)>

The colorant (A) is classified into a solvent-soluble dye (A1) and a solvent-insoluble pigment (A2). In one aspect of the present invention, the colorant (A) contains both the dye (A1) and the pigment (A2).

[0023] The dye (A1) preferably includes at least one dye selected from the group consisting of xanthene dyes, triarylmethane dyes and coumarin dyes. When using at least one dye selected from the above group, the total amount is preferably 1 wt% or more and 100 wt% or less, more preferably 2 wt% or more, 100 wt% based on the entire dye (A1) It is weight % or less, More preferably, it is 5 weight% or more and 100 weight% or less.

[0024] The dye (A1) more preferably includes a xanthene dye. When a xanthene dye is used, the content thereof is preferably 1% by weight or more and 100% by weight or less, more preferably 2% by weight or more and 100% by weight or less, with respect to the entire dye (A1), and further Preferably, it is 5 wt% or more and 100 wt% or less, and most preferably 100 wt%. That is, the dye (A1) most preferably consists of a xanthene dye.

[0025] A xanthene dye is a dye containing a compound having a xanthene skeleton in a molecule. As the xanthene dye, for example, C.I. Acid Red 51 (hereinafter, the description of C.I. Acid Red will be omitted and only the number will be described. The same applies to others.), 52, 87, 92, 94, 289, 388, C.I. Acid Violet 9, 30, 102, C.I. Basic Red 1 (rhodamine 6G), 2, 3, 4, 8, C.I. Basic Red 10, 11, C.I. Basic Violet 10 (Rhodamine B), 11, C.I. Solvent Red 218, C.I. Mordant Red 27, C.I. Reactive Red 36 (rose bengal B), sulforodamine G, xanthene dye described in Japanese Patent Application Laid-Open No. 2010-32999 and xanthene dye described in Japanese Patent Publication No. 4492760, etc. can be heard As a xanthene dye, what melt|dissolves in the organic solvent is preferable.

[0026] Preferred examples of the xanthene dye include a compound represented by the formula (1a) (hereinafter sometimes referred to as “compound (1a)”). Compound (1a) may be a tautomer thereof. When the compound (1a) is used, the content thereof is preferably 50% by weight or more, more preferably 70% by weight or more, still more preferably 90% by weight or more with respect to the entire xanthene dye. In particular, it is preferable to use only compound (1a) as the xanthene dye.

[0027]

[0028] In formula (1a), R ¹ to R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and 6 to 10 carbon atoms which may have a substituent represents a monovalent aromatic hydrocarbon group or ^{a group represented by *-R 12} -Si(R ¹³ ) ₃ (wherein * represents a bonding position with a nitrogen atom), —CH ₂ — may be substituted with -O-, -CO- or -NR ^{11 -,}

R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom,

R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ represents;

R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

m represents an integer of 0 to 5, and when m is 2 or more, a plurality of R ⁵ may be the same or different,

a represents an integer of 0 or 1,

X represents a halogen atom,

Z ⁺ represents N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , four R ¹¹ may be the same or different;

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom,

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -CH ₂ - contained in the saturated aliphatic hydrocarbon group is -O-, -CO -, -NH- or -NR ⁸ - may be substituted, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom,

R ¹¹ 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,

R ¹² represents an alkanediyl group having 1 to 10 carbon atoms, -CH ₂ - contained in the alkanediyl group is -O-, -CO-, -NR ⁸ -, -OCO-, -COO-, - OCONH-, -CONH- or -NHCO- may be substituted, and

R ¹³ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and a plurality of R ¹³ may be the same or different, respectively;

_{However, when -SO 3} ^- in the form of an ion exists in formula (1a), the number is one.]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent in R ¹ to R ⁴ include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. can

[0030] The substituent group which may have an aromatic hydrocarbon group, halogen ^{atoms, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, - CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ^{8 ,} or -SO ₂ NR ⁹ R ¹⁰ . Among these, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ are preferable, and -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ are more preferable. Examples of _{^{Z +, -SO 3 - - -SO}} 3 in this case is N ^{+ (R 11)} ₄ are preferred.

[0031] The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in ^{R 1} to R ⁴ and R ⁸ to R ^{11 may be linear, branched or cyclic.} Examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group, isopropyl group, isobutyl group, iso an alkyl group having 1 to 20 carbon atoms, such as a pentyl group, a neopentyl group, and a 2-ethylhexyl group; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group.

Examples of the substituent which the saturated hydrocarbon group in R ¹ to R ⁴ may have include an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom, and a carboxy group.

As the substituent R ^9, and which may have a saturated hydrocarbon group in R ^10, for example, there may be mentioned a hydroxyl group and a halogen atom.

[0033] Examples of the ring formed by ^{R 1} and R ² together and the ring formed by R ³ and R ^{4 together include the following.}

[0034]

[0035] As -OR ⁸ , for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, an icosyloxy group, etc. can be heard

As -CO ₂ R ⁸ , for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group and an icosyloxycarbonyl group, and the like.

[0037] ^{Examples of -SR 8} include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.

Examples of -SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

[0038] _{Examples of -SO 2} NR ⁹ R ¹⁰ include the following:

sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfa Moyl 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)sulfamo group Diyl, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl) N-1 substituted sulfamoyl groups such as sulfamoyl group, N-(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, N such as N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group, N-2 substituted sulfamoyl groups and the like.

[0039] R ⁵ is preferably ^{_{-CO 2 H, -CO 2 - Z}} +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H or SO ₂ NHR ⁹ and is Z ^+, -SO ₃ H or SO ₂ NHR ^{9 -,} more preferably SO ₃ ^-, -SO _3.

m becomes like this. Preferably it is 1-4, More preferably, it is 1 or 2.

[0040] ^{Examples of the alkyl group having 1 to 6 carbon atoms in R 6} and R ⁷ include those having 1 to 6 carbon atoms among the alkyl groups exemplified above.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

[0042] As the ^{alkanediyl group having 1 to 10 carbon atoms in R 12} , for example, a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylene group, isobutylene group, 2-methyltrimethylene group, isopentylene group, isohexylene group, isooctylene group, 2-ethylhexylene group, etc. are mentioned. In these, a C1-C6 alkanediyl group is preferable, and a C1-C4 alkanediyl group is more preferable.

Examples of the alkyl group having 1 to 4 carbon atoms in R ¹³ include a methyl group, an ethyl group, a propyl group, and a butyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms for R ¹³ include a methoxy group, an ethoxy group, a propoxy group, and a t-butoxy group.

As R ¹³ , a methyl group, an ethyl group, a methoxy group or an ethoxy group is preferable, and a methoxy group or an ethoxy group is more preferable.

[0044] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0045] Z ⁺ is N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably N ⁺ (R ¹¹ ) ₄ .

As said N ⁺ (R ¹¹ ) ₄ , it is preferable that at least two of the four R ^{11 are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms.} Moreover, it is preferable that it is 20-80, and, as for total carbon number of four R<^{11>, it is more preferable that it is 20-60. When N +} (R ¹¹ ) ₄ is present in the compound (1a), ^{if R 11} is these groups, a color filter with few foreign substances is formed from the colored curable resin composition of the present invention containing the compound (1a) can do.

As the compound (1a), a compound represented by the formula (2a) (hereinafter sometimes referred to as “compound (2a)”) is preferable. Compound (2a) may be a tautomer thereof.

[0047]

[0048] In formula (2a), R ²¹ to R ²⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a carboxy group, and 6 to 10 carbon atoms which may have a substituent represents a monovalent aromatic hydrocarbon group or ^{a group represented by *-R 12} -Si(R ¹³ ) ₃ (wherein * represents a bonding position with a nitrogen atom), R ²¹ and R ²² together are a nitrogen atom may form a ring containing, R ²³ and R ²⁴ may together form a ring containing a nitrogen atom,

R ^{25 _{is, -SO 3 -, -SO 3 H}} , -SO 3 - represents a Z1 ⁺ or -SO ₂ NHR ^26,

m represents an integer of 0 to 5, and when m is 2 or more, a plurality of R ²⁵ may be the same or different,

a represents an integer of 0 or 1,

X represents a halogen atom,

R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms,

Z1 ⁺ represents N ⁺ (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , four R ²⁷ may be the same or different, and

R ²⁷ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group,

_{However, when -SO 3} ^- in the form of an ion exists in formula (2a), the number is one.]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms for R ²¹ to R ²⁴ include the same groups as those exemplified as the aromatic hydrocarbon group for ^{R 1} to R ^{4 above.} The substituent group which may have an aromatic hydrocarbon, for example, -SO ₃ ^- can be given Z1 ^+, -SO ₃ R ²⁶ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.

The description of the group represented by *-R ¹² -Si(R ¹³ ) ₃ in R ²¹ to R ^{24 is the same as described above.}

[0050] As a combination of ^{R 21} to R ^{24 , R 21} and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the aromatic hydrocarbon group is -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- as Z1 ^+, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ is preferably substituted. A more preferred combination, R ²¹ and R ²³ is a hydrogen atom, R ²² and R ²⁴ has 6 to 10 carbon atoms is 1 the aromatic hydrocarbon group is divalent, the aromatic hydrocarbon group, -SO ₃ ^- Z1 ^+, or -SO ₂ NHR ²⁶ is replaced with When R ²¹ to R ²⁴ are these groups, a color filter excellent in heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).

[0051] Examples of the ring including a nitrogen atom formed together by ^{R 21} and R ²² and a ring including a nitrogen atom formed by R ²³ and R ²⁴ together include, for example, a ring formed by ^{R 1} and R ^{2 together} can be the same as Especially, an aliphatic heterocyclic ring is preferable. Examples of the aliphatic heterocycle include the following.

[0052]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ²¹ to R ²⁴ , R ²⁶ and R ²⁷ include the same groups as those exemplified as the saturated hydrocarbon group for ^{R 8} to R ^{11 .} .

When R ²¹ to R ²⁴ is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a carboxy group, R ²¹ to R ²⁴ are each independently a methyl group which may have a carboxy group, an ethyl group which may have a carboxy group, or a carboxy group It is preferable that it is a propyl group which may have. In addition, as -SO ₃ R ^26, and -SO ₂ NHR ²⁶ R ²⁶ in carbon number 3 to 20 branched chain-like alkyl group is preferred, and a carbon number of 6 to 12 branched alkyl group and more preferably a shape of 2-ethyl A hexyl group is more preferable. If R ²⁶ is these groups, a color filter with little generation|occurrence|production of a foreign material can be formed from the colored curable resin composition of this invention containing a compound (2a).

[0054] Z1 ⁺ is a _{^{N + (R 27) 4,}} Na + or K ^+, preferably N ⁺ (R ²⁷⁾ _4. As said N ⁺ (R ²⁷ ) ₄ , it is preferable that at least two of the four R ^{27 are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms.} Further, the total carbon number of R 4 is ²⁷ 20 to 80 is preferred, more preferably from 20 to 60. When N ⁺ (R ²⁷ ) ₄ is present in the ^{compound (2a), if R 27} is these groups, a color filter with less foreign matter is formed from the colored curable resin composition of the present invention containing the compound (2a). can

m becomes like this. Preferably it is 1-4, More preferably, it is 1 or 2.

[0055] Further, as the compound (1a), a compound represented by the formula (3a) (hereinafter referred to as "compound (3a)" in some cases) is also preferable. Compound (3a) may be a tautomer thereof.

[0056]

[0057] In formula (3a), R ³¹ and R ³² are each independently a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, or a group represented by ^{*-R 12} -Si(R ¹³ ) _{3 (the above} In the formula, * represents a bonding position with a nitrogen atom), and the saturated hydrocarbon group may be substituted with a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom or a carboxy group, and is included in the saturated hydrocarbon group - CH ₂ - may be substituted with -O-, -CO- or -NR ¹¹ -, the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms;

R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms,

R ³¹ and R ³³ may together form a ring containing a nitrogen atom, R ³² and R ³⁴ together may form a ring containing a nitrogen atom, and

p and q each independently represent an integer of 0 to 5, when p is 2 or more, a plurality of R ³³ may be the same or different, and when q is 2 or more, a plurality of R ³⁴ may be the same or different you can, and

R ¹¹ has the same meaning as above.]

[0058] The monovalent saturated hydrocarbon having 1 to 10 carbon atoms in ^{R 31} and R ^{32 may be linear, branched or cyclic.} Examples thereof include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, 2 -C1-C10 alkyl groups, such as an ethylhexyl group; and alicyclic saturated hydrocarbon groups having 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.

The description of the group represented by *-R ¹² -Si(R ¹³ ) ₃ in R ³¹ and R ^{32 is the same as described above.}

R ³¹ and R ³² are Examples 6 to 10 carbon atoms in the monovalent aromatic hydrocarbon group which may have a substituent, for example, there may be mentioned a phenyl group.

As a C1-C3 alkyl group which the aromatic hydrocarbon group may have as a substituent, a methyl group, an ethyl group, and a propyl group are mentioned, for example.

As a C1-C3 alkoxy group which the aromatic hydrocarbon group may have as a substituent, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, for example.

The description of the group represented by *-R ¹² -Si(R ¹³ ) ₃ in R ³¹ and R ^{32 is the same as described above.}

It is preferable that R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms which may have a carboxy group.

[0059] As the ^{alkyl group having 1 to 4 carbon atoms in R 33} and R ³⁴ , for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, etc. can be heard

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group and an isopropylsulfanyl group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.

R ³³ and R ³⁴ are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

[0060] p and q are preferably integers of 0 to 2, and more preferably 0 or 1.

[0061] Examples of the compound (1a) include compounds represented by formulas (1-1) to (1-45). In addition, R ⁴⁰ in the following formula represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. In addition, R ²⁶ in the following formula represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms as described above.

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

As the xanthene dye, C.I. The sulfonamidide of Acid Red 289, C.I. The quaternary ammonium salt of Acid Red 289, C.I. Sulfonamides of Acid Violet 102 or C.I. The quaternary ammonium salt of Acid Violet 102 is preferred. As such a compound, the compound represented by Formula (1-1) - Formula (1-8), Formula (1-11), or Formula (1-12) is mentioned, for example.

Moreover, the compound represented by any one of Formula (1-24) - Formula (1-33), Formula (1-44), and Formula (1-45) is also preferable at the point which is excellent in solubility with respect to an organic solvent.

[0071] As the xanthene dye, a commercially available xanthene dye (eg, “Chugai Aminol Fast Pink RH/C” manufactured by Chugai Kasei Company, Limited, “Rhodamin 6G” manufactured by Taoka Chemical Company, Limited) may be used. can In addition, it is also possible to synthesize a commercially available xanthene dye as a starting material with reference to a known technique (eg, Japanese Patent Application Laid-Open No. 2010-32999).

[0072] The triarylmethane dye is preferably of formula (4a):

[0073]

[0074] In formula (4a), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or a saturated hydrocarbon group having 1 to 20 carbon atoms, and the number of carbon atoms in the saturated hydrocarbon group is In the case of 2 to 20, -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- or -CO-,

R ^9A to R ^12A are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent , wherein the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, -CH ₂ - contained in the saturated hydrocarbon group is -O- or It may be substituted with -CO-, R ^9A and R ^10A may be bonded to form a ring together with the nitrogen atom to which they are bonded, or R ^11A and R ^12A may be bonded to form a ring together with the nitrogen atom to which they are bonded ,

R ^13A represents an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms,

[G] ^g- represents any g-valent counter anion, and

g represents 0 or any natural number, and when g is a natural number of 2 or more, the plurality of cations in the formula (4a) may be the same or different, respectively.]

is a compound represented by

The coumarin dye is a dye including a compound having a coumarin skeleton in a molecule. As the coumarin dye, for example, C.I. Acid Yellow 227, 250; C.I. Disperse Yellow 82, 184; C.I. Solvent Orange 112; C.I. Solvent Yellow 160, 172; The coumarin dye of Unexamined-Japanese-Patent No. 1299948, etc. are mentioned. It is preferable to dissolve in an organic solvent.

[0076] As dyes other than the above, for example, dyes described in the Color Index (published by The Society of Dyers and Colors), dye notes (Dyeing note (SHIKISENSHA CO., LTD. dyes as described. In addition, as a dye, for example, azo dye, cyanine dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styrenic dye reel dyes, quinoline dyes and nitro dyes; and the like. Among these, the dye which melt|dissolves in the organic solvent is preferable.

Specific examples of the dye include the following.

(1) C.I. solvent dye

C.I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;

C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99;

C.I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247;

C.I. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

C.I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

C.I. Solvent Green 1, 3, 5, 28, 29, 32, 33; etc.

(2) C.I. acid dye

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

C.I. Acid Red 73, 80, 91, 97, 138, 151, 211, 274;

C.I. acid green 3, 5, 9, 25, 27, 28, 41;

C.I. Acid Violet 34, 120;

C.I. acid blue 25, 27, 40, 45, 78, 80, 112; etc.

(3) C.I. basic dye

C.I. Basic Green 1; etc.

(4) C.I. reactive dye

C.I. Reactive Yellow 2, 76, 116;

C.I. Reactive Orange 16; etc.

[0081] (5) C.I. direct dye

C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;

C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Blue 40; etc.

[0082] (6) C.I. Disperse Dyes

C.I. Disperse Yellow 51, 54, 76;

C.I. Disperse Violet 26, 27;

C.I. Disperse Blue 1, 14, 56, 60; etc.

[0083] (7) C.I. mordant dye

C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

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

[0084] (8) C.I. vat dye

C.I. Bat Green 1st.

[0085] The pigment (A2) is not particularly limited, and a known pigment can be used, for example, the pigment described in Color Index (published by The Society of Dyers and Colorists) is exemplified.

[0086] The pigment (A2) includes, for example, the following:

C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138 , 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 yellow pigments;

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

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 ;

C.I. Blue pigments, such as pigment blue 15, 15:3, 15:4, 15:6, 60;

C.I. Violet pigments, such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments, such as Pigment Green 7, 36, and 58;

C.I. Brown pigments, such as Pigment Brown 23 and 25;

C.I. Black pigments such as Pigment Black 1 and 7, etc.

The pigment (A2) is preferably a red pigment or a blue pigment.

It is preferable to have absorption in the wavelength range of 580 nm or less, and, as for a red pigment, it is more preferable to have absorption in the wavelength range of 480 nm or more and 560 nm or less. Moreover, it is preferable that the said red pigment transmits the light of the wavelength range of 610 nm or more.

[0088] As the red pigment, known pigments can be used, and for example, those described in Color Index (published by The Society of Dyers and Colorists) are mentioned.

Among the red pigments, anthraquinone pigments, azo pigments, quinacridone pigments, perylene pigments, and diketopyrrolopyrrole pigments are preferable, and anthraquinone pigments and diketopyrrolopyrrole pigments are more preferable.

[0090] As a specific example of a preferred red pigment, C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 202, 208, 209, 215, 216, 224, 242, 254, 255, 264 , 265, 266, 268, 269, 273, and the compound represented by Formula (P) of Unexamined-Japanese-Patent No. 2013-014750, etc. are mentioned. Among these, C.I. Pigment Red 177, 208, 242, 254, 269, and the compound represented by Formula (P) described in Unexamined-Japanese-Patent No. 2013-014750 are more preferable, and C.I. Pigment Red 177, 254, and the compound represented by Formula (P) described in Unexamined-Japanese-Patent No. 2013-014750 are more preferable.

The blue pigment preferably has absorption in a wavelength region of 700 nm or less, and more preferably has absorption in a wavelength region of 580 nm or more and 650 nm or less. Moreover, it is preferable that a blue pigment transmits the light of 400 nm or more wavelength range.

[0092] The blue pigment is preferably a phthalocyanine pigment, more preferably a copper phthalocyanine pigment and/or a zinc phthalocyanine pigment, still more preferably a halogenated copper phthalocyanine pigment and/or a halogenated zinc phthalocyanine pigment, particularly preferably It is a halogenated copper phthalocyanine pigment.

[0093] Specifically, C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60 are preferred, and C.I. Pigment Blue 15, 15:3, 15:4, and 15:6 are more preferable, and C.I. Pigment Blue 15:6 is particularly preferred. By using said blue pigment, optimization of a transmission spectrum is easy and the light resistance and chemical-resistance of a color filter become favorable.

[0094] Pigments, if necessary, rosin treatment, surface treatment using a pigment derivative introduced with acidic or basic groups, graft treatment on the pigment surface with a polymer compound, etc., atomization treatment by sulfuric acid atomization method, etc.; Alternatively, a washing treatment with an organic solvent or water for removing impurities, a removal treatment with an ion exchange method for ionic impurities, or the like may be performed. The pigment preferably has a uniform particle size.

[0095] By performing dispersion treatment using a dispersing agent, a pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained.

[0096] Examples of the dispersant include surfactants. Any of a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant may be sufficient as surfactant. Examples of the surfactant include a polyester-based surfactant, a polyamine-based surfactant, and an acrylic surfactant. As a commercial item of a dispersing agent, For example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by KYOEISHA CHEMICAL Co., LTD.), Solsperse (trademark) (manufactured by Zeneca), EFKA (manufactured by BASF), Ajispa (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Inc.), DISPERBYK (registered trademark) (manufactured by BYK-Chemie), BYKLPN (manufactured by BYK), and the like.

[0097] When the pigment dispersion contains a dispersant, its content is preferably 1 part by weight or more and 500 parts by weight or less, and more preferably 5 parts by weight or more and 300 parts by weight based on 100 parts by weight of the pigment (A2). is below. When content of a dispersing agent exists in said range, there exists a tendency for the pigment dispersion liquid of a uniformly dispersed state to be obtained.

The content of the colorant (A) is preferably 1 wt% or more and 60 wt% or less, more preferably 3 wt% or more, 55 wt% or less, with respect to the total amount of solid content, More preferably, it is 5 weight% or more and 50 weight% or less. The "total amount of solid content" in this specification means the quantity which subtracted content of the solvent from the total amount of colored curable resin composition. When content of a coloring agent (A) exists in said range, the color filter with sufficient color density will be obtained. Moreover, since resin and a polymeric compound can be made to contain only a required amount in a composition when content of a coloring agent (A) exists in said range, a color filter with sufficient mechanical strength can be formed. The total amount of solid content and content of each component with respect to this can be measured, for example by well-known analytical means, such as liquid chromatography or gas chromatography.

[0099] When the dye (A1) is used, the content thereof is preferably 0.5% by weight or more, more preferably 1% by weight or more, more preferably 60% by weight or less, and 55% by weight or more with respect to the total amount of solid content. % or less is more preferable. When content of dye (A1) exists in the said range, the coloring curable resin composition with favorable developability with respect to an alkali developing solution can be obtained.

[0100] When the pigment (A2) is used, its content is preferably 1% by weight or more, more preferably 1.5% by weight or more, preferably 60% by weight or less, and 55% by weight based on the total amount of solid content. It is more preferable that it is less than, and it is still more preferable that it is 50 weight% or less. When content of a pigment (A2) exists in the said range, a color filter with favorable chromaticity can be obtained.

[0101] When the dye (A1) and the pigment (A2) are used, the weight ratio of the dye (A1) and the pigment (A2) (dye (A1):pigment (A2)) is preferably 1:99 to 99: 1, more preferably 1:99 to 95:5, particularly preferably 5:95 to 90:10.

[0102] In one aspect of the present invention, the colorant (A) is a formula (A3-1):

[0103]

[0104] A compound represented by (hereinafter sometimes referred to as "compound (A3-1)"), and formula (A3-2):

[0105]

and at least one compound (A3) selected from the group consisting of a compound represented by (hereinafter sometimes referred to as “compound (A3-2)”).

[0107] Compound (A3) (ie, compound (A3-1) and compound (A3-2)) has a structure (eg, counter ion (M ^r+ ) ^k-1 and [Y] ^{m -} depending on the type), it becomes “solvent-soluble dye” or “solvent-insoluble pigment”. That is, both the compound which is a dye and the compound which is a pigment are contained in the range of compound (A3).

[0108] First, definitions of groups and the like in compound (A3) will be described. Unless otherwise specified, the group and the like in the compound (A3) have the following definitions.

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

[0109] The saturated hydrocarbon group may be any of linear, branched, and cyclic. Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group, an icosyl group, an alkyl group having 1 to 20 carbon atoms, such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group.

[0110] The alkyl group may be either linear or branched. As an example of a C1-C10 alkyl group, a C1-C10 thing is mentioned among the examples of the C1-C20 alkyl group mentioned above. Examples of other alkyl groups having different carbon numbers are also the same. In addition, also about groups other than an alkyl group, the illustration of a thing from which carbon number differs is the same. For example, as an example of a C2-C20 saturated hydrocarbon group, a C2-C20 thing is mentioned among the examples of the C1-C20 saturated hydrocarbon group mentioned above.

[0111] The alkanediyl group may be either linear or branched. Examples of the alkanediyl group having 1 to 10 carbon atoms include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylene group, isobutylene group, 2-methyltrimethylene group, iso A pentylene group, an isohexylene group, an isooctylene group, 2-ethylhexylene group, etc. are mentioned.

[0112] The fluoroalkyl group may be either linear or branched. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include monofluoromethyl group, difluoromethyl group, perfluoromethyl group, monofluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, perfluoro Ethyl group, monofluoropropyl group, difluoropropyl group, trifluoropropyl group, tetrafluoropropyl group, pentafluoropropyl group, hexafluoropropyl group, perfluoropropyl group, monofluorobutyl group, Difluorobutyl group, trifluorobutyl group, tetrafluorobutyl group, pentafluorobutyl group, hexafluorobutyl group, heptafluorobutyl group, octafluorobutyl group, and perfluorobutyl group are mentioned. .

[0113] The alkoxy group may be either linear or branched. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an isopropoxy group, an isobutoxy group, an isopentyloxy group, and a neopentyloxy group. can be heard

[0114] Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, and 9-anthryl group.

[0115] Examples of the aralkyl group having 7 to 30 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, and a 3-phenylpropyl group.

[0116] The nitrogen-containing heterocyclic ring may be either a monocyclic ring or a condensed ring. Examples of the 3- to 10-membered nitrogen-containing heterocyclic ring include a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring.

[0117] The aromatic hydrocarbon ring may be either a monocyclic ring or a condensed ring. Any of a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring may be sufficient as a C6-C14 aromatic hydrocarbon ring.

[0118] The aromatic heterocyclic ring may be either a monocyclic ring or a condensed ring. As a 5- to 10-membered aromatic heterocyclic ring, for example, a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, a thiazole ring, a furan ring, a thiophene ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring a ring, an indole ring, a benzimidazole ring, a benzothiazole ring, a quinoline ring, a benzofuran ring, etc. are mentioned.

[0119] Next, the group and the like in the formula (A3-1) will be described.

^{R 41a} and R ^42a in the formula (A3-1) are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or represents an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41a and R ^42a are bonded to form a 3 to 10 membered nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded.

[0120] The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (A3-1) may have is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group.

[0121] When the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (A3-1) is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH ₂ - contained in the saturated hydrocarbon group is substituted with -O- or -CO- there may be Wherein the -CH ₂ - is, -CH ₂ in union with the nitrogen atom - and -CH ₂ in the methyl group terminal of the saturated hydrocarbon group - is not included. _{In addition, -CH 2} -CH ₂ - contained in the saturated hydrocarbon group is not substituted with -OO- or -CO-CO-.

[0122] The substituent which the aromatic hydrocarbon group having 6 to 14 carbon atoms in the formula (A3-1) may have is a halogen atom, a nitro group, a hydroxy group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ - R ^f and at least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms which may have a substituent.

[0123] The substituent which the aralkyl group having 7 to 30 carbon atoms in the formula (A3-1) may have is a halogen atom, a nitro group, a hydroxy group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ - R ^f and at least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms which may have a substituent.

^{R f} in Formula (A3-1) represents a C1-C12 fluoroalkyl group.

[0124] The substituent which the alkyl group having 1 to 8 carbon atoms in the formula (A3-1) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.

[0125] When the alkyl group having 1 to 8 carbon atoms in the formula (A3-1) is an alkyl group having 2 to 8 carbon atoms, -CH ₂ - contained in the alkyl group may be substituted with -O- or -CO-. Wherein the -CH ₂ - is, -CH ₂ of the terminal methyl group of the alkyl group - is not included. _{In addition, -CH 2} -CH ₂ - contained in the alkyl group is not substituted with -OO- or -CO-CO-.

[0126] R ^41a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms.

R ^42a is preferably a phenyl group which may have at least one substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and —SO ₃ ^— , more preferably 1 or 2 carbon atoms as a substituent, 1 to 8 carbon atoms It is a phenyl group which has an alkyl group and _{may have -SO 3} ^- , More preferably, has a 1 or 2 C1-C4 alkyl group as a substituent, and may have _{-SO 3} ^-.

^{[0127] R 43a} and R ^44a in formula (A3-1) are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic hydrocarbon having 6 to 14 carbon atoms which may have a substituent represents a group or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^43a and R ^44a are bonded to form a 3 to 10 membered nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded.

[0128] R ^43a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms.

R ^44a is preferably a phenyl group which may have at least one substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and -SO ₃ ^- , more preferably 1 or 2 carbon atoms as a substituent, 1 to 8 carbon atoms It is a phenyl group which has an alkyl group and _{may have -SO 3} ^- , More preferably, has a 1 or 2 C1-C4 alkyl group as a substituent, and may have _{-SO 3} ^-.

^{[0129] R 47a} to R ^54a in formula (A3-1) are each independently a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , Or the C1-C8 alkyl group which may have a substituent is shown. R ^47a to R ^54a are each independently, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or —SO ₃ ^— , more preferably a hydrogen atom or —SO ₃ ^— .

^{[0130] Ring T 1a} in the formula (A3-1) represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or an aromatic heterocycle having 5 to 10 members which may have a substituent.

[0131] Substituents which the aromatic hydrocarbon ring having 6 to 14 carbon atoms in Formula (A3-1) may have include a halogen atom, a nitro group, a hydroxy group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f and at least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms which may have a substituent.

[0132] Substituents which the 5- to 10-membered aromatic heterocyclic ring in Formula (A3-1) may have include a halogen atom, a nitro group, a hydroxy group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f and at least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms which may have a substituent.

[0133] Ring T ^1a is preferably of formula (1t):

[0134]

It is a ring represented by [0135].

^{R 45a} and R ^46a in the formula (1t) are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or a substituent It represents an aralkyl group having 7 to 30 carbon atoms which it may have, or R ^45a and R ^46a are bonded to form a 3 to 10 membered nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded.

[0136] The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (1t) may have is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group.

[0137] The substituent which the aromatic hydrocarbon group having 6 to 14 carbon atoms in formula (1t) may have is a halogen atom, a nitro group, a hydroxy group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and at least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms which may have a substituent.

[0138] The substituent which the aralkyl group having 7 to 30 carbon atoms in formula (1t) may have is a halogen atom, a nitro group, a hydroxy group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and at least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms which may have a substituent.

[0139] The substituent which the alkyl group having 1 to 8 carbon atoms in formula (1t) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.

[0140] R ^45a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms.

[0141] R ^46a is preferably a phenyl group which may have at least one substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and -SO ₃ ^{-, more preferably 1 or 2 carbon atoms as a substituent} It is a phenyl group which has a -8 alkyl group, and _{may have -SO 3} ^- , More preferably, has a 1 or 2 C1-C4 alkyl group as a substituent, and may have _{-SO 3} ^-.

[0142] R ^56a in formula (1t) is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or a carbon number which may have a substituent It represents an aralkyl group of 7 to 30.

[0143] R ^56a is preferably a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom, an alkyl group having 1 to 8 carbon atoms, and —SO ₃ ^{—, more preferably one or two substituents} It is a phenyl group which has several halogen atoms and _{may have -SO 3} ^- , More preferably, it is a phenyl group which has 1 or 2 fluorine atoms as a substituent, and may have _{-SO 3} ^-.

^{[0144] L 1a} in formula (1t) represents a sulfur atom, an oxygen atom, or -NR ^57a -. R ^57a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L ^1a is preferably a sulfur atom.

[0145] * in formula (1t) represents a bonding position with a carbocation. In other words, -* in formula (1t) represents a bond. -* in other formulas also represents a bond similarly.

[0146] r in the formula (A3-1) represents an integer of 1 or more. r is preferably 2. When r is an integer greater than or equal to 2, the formula (A3-1a):

[0147]

[0148] [In formula (A3-1a), rings T ^1a , R ^41a to R ^44a and R ^47a to R ^54a each have the same meaning as above.]

The plurality of anions represented by may be the same or different. The anion represented by Formula (A3-1a) may be described below as "anion (A3-1a)". The plurality of anions (A3-1a) are preferably the same.

[0149] k in formula (A3-1) represents the sum of the number of _{-SO 3} ^- and -SO ₂ -N ^- -SO ₂ -R ^{f of the anion (A3-1a), and is an integer of 2 or more} . k is preferably 2.

^{[0150] M r+} in the formula (A3-1) represents a hydrogen ion, an r-valent metal ion, or N ⁺ (R ^55a ) ₄ , and four R ^55a may be the same or different. R ^55a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. When k-1 in Formula (A3-1) is an integer of 2 or more, some M ^r+ may be same or different.

[0151] M ^r+ is preferably an r-valent metal ion. Examples of the r-valent metal ion include alkali metal ions such as lithium ions, sodium ions and potassium ions; alkaline earth metal ions such as beryllium ions, magnesium ions, calcium ions, strontium ions, and barium ions; Transition metal ions, such as a titanium ion, a zirconium ion, a chromium ion, a manganese ion, an iron ion, a cobalt ion, a nickel ion, and a copper ion; Typical metal ions, such as a zinc ion, a cadmium ion, an aluminum ion, an indium ion, a tin ion, a lead ion, and a bismuth ion, are mentioned.

[0152] M ^r+ is more preferably a divalent metal ion, still more preferably an alkaline earth metal ion, and particularly preferably a barium ion (Ba ²⁺ ).

[0153] As compound (A3-1),

R ^41a and R ^43a are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

R ^42a and R ^44a are each independently a phenyl group which may have at least one substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and —SO ₃ ^—;

R ^47a to R ^54a are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or —SO ₃ ^— ;

Ring T ^1a is a ring represented by the formula (1t) [wherein R ^45a is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

R ^46a is a phenyl group which may have at least one substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and —SO ₃ ^—;

R ^56a is a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom, an alkyl group having 1 to 8 carbon atoms, and -SO ₃ ^-;

L ^1a is a sulfur atom, and

* indicates a bonding position with a carbocation.],

r is 2,

k represents the sum of the number of _{-SO 3} ^- that the anion (A3-1a) has, and is 2,

two anions (A3-1a) are identical, and

M ^r+ is, Ba ²⁺ phosphorus

A compound (hereinafter sometimes referred to as "compound (A3-1')") is preferable.

[0154] In compound (A3-1'), R ^41a and R ^43a are more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, R ^42a and R ^44a is each independently, More preferably, as a substituent, it has 1 or 2 C1-C8 alkyl group, Furthermore, _{it is a phenyl group which may have -SO 3} ^- , More preferably, it has 1 or 2 carbon atoms as a substituent. It has an alkyl group of 1 to 4 and is a phenyl group which may further have _{-SO 3} ^{- , R 47a} to R ^54a are more preferably a hydrogen atom or -SO ₃ ^- , R ^45a is more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, R ^46a is more preferably a substituent having 1 or 2 alkyl groups having 1 to 8 carbon atoms, and -SO ₃ ^- It is a phenyl group which you may have, More preferably, it has a 1 or 2 C1-C4 alkyl group as a substituent, and it is a phenyl group which may have _{-SO 3} ^{- , and R 56a} is more preferably 1 as a substituent. or a phenyl group having two halogen atoms and _{optionally having -SO 3} ^- , more preferably a phenyl group having one or two fluorine atoms as a substituent and may further have _{-SO 3} ^-.

[0155] Among the compound (A3-1), a compound represented by the following formula (A3-1-1) (hereinafter sometimes referred to as “compound (A3-1-1)”) is particularly preferable. In addition, in the following formula (A3-1-1), in _{the description of two "-SO 3} ^- ", each anion has -SO ₃ ^- as a substituent, and the sum of the number _{of -SO 3} ^- in each anion is 2 (that is, the sum of the number _{of -SO 3} ^{- in the two anions is 4).}

[0156]

[0157] Compound (A3-1) is prepared by a known method (eg, the method described in Journal of Organic Chemistry, (1994), vol. 59, #11, pp. 3232-3236, Japanese Patent Application Laid-Open No. 2018-127596) It can be prepared according to the method described in ).

[0158] Next, the group and the like in the formula (A3-2) will be described.

^{R 41b} and R ^42b in the formula (A3-2) are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or represents an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41b and R ^42b are bonded to form a 3 to 10 membered nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded.

[0159] The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (A3-2) may have is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group.

[0160] When the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (A3-2) is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH ₂ - included in the saturated hydrocarbon group is substituted with -O- or -CO- there may be Wherein the -CH ₂ - is, -CH ₂ in union with the nitrogen atom - and -CH ₂ in the methyl group terminal of the saturated hydrocarbon group - is not included. _{In addition, -CH 2} -CH ₂ - contained in the saturated hydrocarbon group is not substituted with -OO- or -CO-CO-.

[0161] The substituent which the aromatic hydrocarbon group having 6 to 14 carbon atoms in the formula (A3-2) may have is a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent. at least one selected from

[0162] The substituent which the aralkyl group having 7 to 30 carbon atoms in the formula (A3-2) may have is a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent. at least one selected from

[0163] The substituent which the C1-C8 alkyl group in formula (A3-2) may have is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group, and an amino group.

[0164] When the alkyl group having 1 to 8 carbon atoms in the formula (A3-2) is an alkyl group having 2 to 8 carbon atoms, -CH ₂ - contained in the alkyl group may be substituted with -O- or -CO-. Wherein the -CH ₂ - is, -CH ₂ of the terminal methyl group of the alkyl group - is not included. _{In addition, -CH 2} -CH ₂ - contained in the alkyl group is not substituted with -OO- or -CO-CO-.

[0165] R ^41b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms.

R ^42b is preferably a phenyl group which may have an alkyl group having 1 to 8 carbon atoms, more preferably a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, still more preferably a phenyl group.

^{[0166] R 43b} and R ^44b in formula (A3-2) are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic hydrocarbon having 6 to 14 carbon atoms which may have a substituent represents a group or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^43b and R ^44b combine to form a 3 to 10 membered nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded.

[0167] R ^43b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms.

R ^44b is preferably a phenyl group which may have an alkyl group having 1 to 8 carbon atoms, more preferably a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, still more preferably a phenyl group.

^{[0168] R 47b} to R ^54b in formula (A3-2) each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms which may have a substituent.

[0169] R ^47b to R ^54b are each independently, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom.

^{[0170] Ring T 1b} in Formula (A3-2) represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or an aromatic heterocycle having 5 to 10 members which may have a substituent.

[0171] The substituent which the aromatic hydrocarbon ring having 6 to 14 carbon atoms in the formula (A3-2) may have is a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent. at least one selected from the group.

[0172] The substituent which the 5- to 10-membered aromatic heterocycle in the formula (A3-2) may have is a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent. at least one selected from the group.

[0173] Ring T ^1b is preferably of formula (2t):

[0174]

It is a ring represented by [0175].

^{R 45b} and R ^46b in the formula (2t) are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or a substituent It represents an aralkyl group having 7 to 30 carbon atoms which it may have, or R ^45b and R ^46b combine to form a 3 to 10 membered nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded.

[0176] The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms in formula (2t) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.

[0177] The substituent which the aromatic hydrocarbon group having 6 to 14 carbon atoms in formula (2t) may have is selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent at least one

[0178] The substituent which the aralkyl group having 7 to 30 carbon atoms in formula (2t) may have is selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent at least one

[0179] The substituent which the C1-C8 alkyl group in formula (2t) may have is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group, and an amino group.

[0180] R ^45b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms.

[0181] R ^46b is preferably a phenyl group which may have an alkyl group having 1 to 8 carbon atoms, more preferably a phenyl group having one or two alkyl groups having 1 to 8 carbon atoms as a substituent, more preferably 1 as a substituent It is a phenyl group having one or two C1-C4 alkyl groups.

[0182] R ^56b in formula (2t) is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or a carbon number which may have a substituent It represents an aralkyl group of 7 to 30.

[0183] R ^56b is preferably a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 8 carbon atoms, more preferably having one or two halogen atoms as a substituent It is a phenyl group, More preferably, it is a phenyl group which has 1 or 2 fluorine atoms as a substituent.

^{[0184] L 1b} in Formula (2t) represents a sulfur atom, an oxygen atom, or -NR ^57b -. R ^57b represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L ^1b is preferably a sulfur atom.

* in Formula (2t) represents a bonding position with a carbocation.

[0185] m in formula (A3-2) represents an integer of 1 or more. m becomes like this. Preferably it is an integer of 1-20, More preferably, it is an integer of 2-14, More preferably, it is an integer of 2-8, Especially preferably, it is 3. When m is an integer greater than or equal to 2, the formula (A3-2c):

[0186]

[0187] [In Formula (A3-2c), each of the rings T ^1b , R ^41b to R ^44b and R ^47b to R ^54b has the same meaning as above.]

The plurality of cations represented by may be the same or different. The cation represented by Formula (A3-2c) may be described below as "cation (A3-2c)". The plurality of cations (A3-2c) is preferably the same.

[0188] [Y] ^m- in formula (A3-2) represents an m-valent anion. [Y] ^m- is preferably a polyacid anion containing a tungsten atom, more preferably [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [SiW ₁₂ O ₄₀ ] ^4- , [SiW ₁₂ O ₄₀ ] ^4- , [SiW ₁₂ O ₄₀ ] ^4- , [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , [SiW ₉ O ₃₄ ] ^10- , [SiW ₁₀ O ₃₆ ] ^8- , [SiW ₁₁ O ₃₉ ] ^8- , [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- or [WO ₄ ] ^2- , more preferably [PW ₁₂ O ₄₀ ] ^3- is.

[0189] As compound (A3-2),

R ^41b , R ^43b and R ^47b to R ^54b are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

R ^42b and R ^44b are each independently a phenyl group which may have an alkyl group having 1 to 8 carbon atoms,

Ring T ^1b is a ring represented by formula (2t) [in formula (2t), R ^45b is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

R ^46b is a phenyl group which may have an alkyl group having 1 to 8 carbon atoms,

R ^56b is a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 8 carbon atoms,

L ^1b is a sulfur atom, and

* indicates a bonding position with a carbocation.],

m is 3,

three cations (A3-2c) are identical, and

[Y] ^m- , [PW ₁₂ O ₄₀ ] ^3-

A compound (hereinafter sometimes referred to as "compound (A3-2')") is preferable.

[0190] In compound (A3-2'), R ^41b and R ^43b are each independently, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms , more preferably an alkyl group having 1 to 4 carbon atoms, R ^42b and R ^44b are each independently, more preferably a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, still more preferably a phenyl group, R ^47b to R ^54b is each independently, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom, R ^45b is more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably Preferably, it is an alkyl group having 1 to 4 carbon atoms, R ^46b is more preferably a phenyl group having 1 or 2 alkyl groups having 1 to 8 carbon atoms as a substituent, more preferably 1 or 2 carbon atoms 1 to 4 as a substituent a phenyl group having an alkyl group, and R ^56b is more preferably a phenyl group having 1 or 2 halogen atoms as a substituent, and still more preferably a phenyl group having 1 or 2 fluorine atoms as a substituent.

[0191] Among the compound (A3-2), a compound represented by the following formula (A3-2-1) (hereinafter sometimes referred to as “compound (A3-2-1)”) is particularly preferable.

[0192]

[0193] Compound (A3-2) can be prepared according to a known method (eg, the method described in Japanese Patent Application Laid-Open No. 2015-28121).

[0194] The compound (A3) is preferably mixed with a solvent that does not dissolve it and used as a dispersion of the compound (A3). When preparing the dispersion liquid of compound (A3), it is preferable to use a dispersing agent. Examples of the dispersant include those described above for the pigment dispersion.

[0195] When the dispersion of compound (A3) contains a dispersant, its content is preferably 1 part by weight or more and 500 parts by weight or less, more preferably 5 parts by weight, based on 100 parts by weight of compound (A3). or more and 300 parts by weight or less. When content of a dispersing agent exists in said range, there exists a tendency for the pigment dispersion liquid of a uniformly dispersed state to be obtained.

[0196] When compound (A3) is used, its content is preferably 1% by weight or more, more preferably 1.5% by weight or more, preferably 60% by weight or less, and 55% by weight based on the total amount of solid content. It is more preferable that it is less than, and it is still more preferable that it is 50 weight% or less.

[0197] When compound (A3) is used, it is preferable to use a dye (A1) different from that of compound (A3). That is, in one preferable aspect of this invention, a coloring agent (A) contains a dye (A1) different from a compound (A3), and a compound (A3). Description of the kind, content, etc. of the dye (A1) in this one aspect is as having mentioned above.

[0198] When using the dye (A1) and the compound (A3), the weight ratio of the dye (A1) to the compound (A3) (dye (A1): compound (A3)) is preferably 0.5:99.5 to 99: 1, More preferably, it is 0.5:99.5-95:5, Especially preferably, it is 0.5:95-90:10.

[0199] <Resin (B)>

The resin (B) used in the present invention has a formula (1b):

[0200]

[0201] In formula (1b), R ^1B represents a hydrogen atom or a methyl group,

R ^2B to R ^4B each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms,

n represents an integer from 1 to 10, and

* represents a binding position,

However, ^{at least one of R 2B} to R ^4B is an alkoxy group having 1 to 6 carbon atoms.]

Resin (B1) containing the structural unit (b1-1) represented by (it may be described hereafter as "structural unit (b1-1)") is included. In resin (B1), only 1 type may be contained and 2 or more types may be contained as structural unit (b1-1). By using resin (B1), the reduction in the thickness of the coloring pattern or colored coating film by heating (particularly post-baking) can be suppressed.

[0202] As ^{an alkyl group having 1 to 6 carbon atoms in R 2B} to R ^4B , for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, an isopentyl group, a neo A pentyl group is mentioned.

[0203] As the ^{alkoxy group having 1 to 6 carbon atoms in R 2B} to R ^4B , for example, a methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, isopropoxy group, isobutoxy group A group, an isopentyloxy group, and a neopentyloxy group are mentioned.

[0204] R ^2B to R ^4B are each independently, preferably a methoxy group, an ethoxy group or a propoxy group, more preferably a methoxy group or an ethoxy group.

n becomes like this. Preferably it is an integer of 1-6, More preferably, it is an integer of 1-3.

[0205] Resin (B1) is preferably a structural unit (b1-1), a structural unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group (hereinafter referred to as “structural unit (b1-2)” ) and another structural unit (b1-3) (hereinafter referred to as “structural unit (b1-3)” in some cases). Here, another structural unit (b1-3) means a structural unit different from a structural unit (b1-1) and a structural unit (b1-2). In the resin (B1) which is a copolymer, the structural unit (b1-1), the structural unit (b1-2), and the structural unit (b1-3) may contain only one type, or two or more types may be included. there may be

[0206] Examples of the acidic group included in the structural unit (b1-2) include a carboxy group, a phosphoric acid group (-OP(=O)(OH) ₂ ), and a sulfo group (-S(=O) ₂ OH). . Among these, a carboxy group is preferable.

[0207] The amount of the structural unit (b1-1) when the total of all structural units in the copolymer is 100 mol%, from the viewpoint of solvent resistance, preferably 1 to 50 mol%, more Preferably it is 5-40 mol%, More preferably, it is 10-30 mol%.

[0208] The amount of the structural unit (b1-2) when the total of all structural units in the copolymer is 100 mol%, from the viewpoint of developability, preferably 10 to 50 mol%, more preferably 15 -45 mol%, more preferably 20-40 mol%.

[0209] The amount of the structural unit (b1-3) when the total of all structural units in the copolymer is 100 mol%, from the viewpoint of developability and solvent resistance, preferably 1 to 89 mol%, more Preferably it is 15-80 mol%, More preferably, it is 30-70 mol%.

[0210] The weight average molecular weight (Mw) of the resin (B1) is 1,000 to 50,000, preferably 2,000 to 40,000, more preferably 3,000 to 30,000 from the viewpoint of developability. The said weight average molecular weight (Mw) is a value computed in polystyrene conversion using gel permeation chromatography (GPC).

[0211] The silyl group equivalent of the resin (B1) is preferably 400 to 4,000, more preferably 500 to 3,000 from the viewpoint of thermal decomposition resistance, thermal yellowing resistance and solvent resistance. . When the silyl group equivalent of resin (B1) is 400 or more, it is effective in improving the thermal decomposition resistance and thermal yellowing resistance of a colored pattern or a colored coating film more. In addition, the silyl group equivalent of resin (B1) is a following formula:

Silyl group equivalent = weight average molecular weight of resin (B1) / average number of silyl groups per molecule

It is a value calculated from A silyl group equivalent is computable from the input amount of the monomer used for manufacture of resin (B1).

[0212] When the resin (B1) is a copolymer including a structural unit (b1-2), the acid value of the resin (B1) is preferably 20 to 300 mgKOH/g, from the viewpoint of developability, More preferably, it is 30-200 mgKOH/g. In addition, the acid value of the resin (B1) is a value measured using a mixture indicator of bromthymol blue and phenol red according to JIS K6901 5.3, and is the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B1). It is a calculated value, and can be calculated|required by titration using potassium hydroxide aqueous solution, for example.

[0213] From the viewpoint of forming a good pattern without defects and peeling after alkali development, the content of the resin (B1) is preferably 5 to 400 parts by weight based on 100 parts by weight of the polymerizable compound (C). , More preferably 7.5 to 375 parts by weight, still more preferably 10 to 350 parts by weight.

[0214] Resin (B1) in the presence of a solvent, the following formula (2b):

[0215]

[0216] [The meaning of the symbol in formula (2b) is the same as above]

A known radical polymerization method using only the compound (m1-1) represented by (hereinafter, sometimes referred to as “compound (m1-1)”) or a monomer mixture containing the compound (m1-1) and another compound It can be prepared by copolymerizing according to

[0217] Resin (B1) which is a copolymer is, for example, by dissolving compound (m1-1) and, if necessary, other compounds in a solvent to prepare a solution, then adding a polymerization initiator to the solution, and heating at 50 to 130 ° C. It can be prepared by reacting for 1 to 20 hours.

[0218] Resin (B1), which is a copolymer comprising a structural unit (b1-1), a structural unit (b1-2), and a structural unit (b1-3), in the presence of a solvent, compound (m1-1), acid A polymerizable unsaturated compound having a group (m1-2) (hereinafter sometimes referred to as “compound (m1-2)”), and other polymerizable unsaturated compounds (m1-3) (hereinafter “compound (m1-3)”) It can be prepared by copolymerizing a monomer mixture consisting of ) according to a known radical polymerization method. Here, another polymerizable unsaturated compound (m1-3) means a polymerizable unsaturated compound different from a compound (m1-1) and a compound (m1-2). Further, the structural unit (b1-1) is derived from the compound (m1-1), the structural unit (b1-2) is derived from the compound (m1-2), and the structural unit (b1-3) is derived from the compound (m1-) 3) comes from

[0219] Resin (B1) as a copolymer is, for example, by dissolving compound (m1-1), compound (m1-2) and compound (m1-3) in a solvent to prepare a solution, and then adding a polymerization initiator to the solution It can be prepared by adding and reacting at 50 to 130° C. for 1 to 20 hours.

[0220] As the compound (m1-1), for example, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyldimethoxysilane, 3-(meth)acrylo Iloxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropylethyldiethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltrie Toxysilane etc. are mentioned. Among these, from the viewpoint of availability and reactivity, 3-(meth)acryloyloxypropyltrimethoxysilane and 3-(meth)acryloyloxypropyltriethoxysilane are preferable. Here, "3-(meth)acryloyloxypropylmethyldimethoxysilane" means at least one selected from 3-acryloyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropylmethyldimethoxysilane do. Other identical descriptions have the same meaning.

[0221] Examples of the acidic group of compound (m1-2) include a carboxy group, a phosphoric acid group (-OP(=O)(OH) ₂ ), and a sulfo group (-S(=O) ₂ OH). Among these, a carboxy group is preferable.

[0222] As the compound (m1-2), for example, (meth)acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-acryloyloxyethylphthalic acid, 2 -(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl acid phosphate, etc. are mentioned. Among these, (meth)acrylic acid is preferable from a viewpoint of availability and reactivity.

[0223] The compound (m1-3) includes, for example, the following:

butadiene;

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) Acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclo Hexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, rosin (meth) acrylate, norbornyl (meth) acrylate, 5-methyl novo Nyl (meth) acrylate, 5-ethyl norbornyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate , perfluoroethyl (meth) acrylate, perfluoro-propyl (meth) acrylate, perfluoro-isopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, glycerol mono(meth)acrylate, butanetriol mono(meth)acrylate, pentanetriol mono(meth)acrylate, dicyclopentenyl ( Meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, naphthalene (meth) acrylate, anthracene (meth) acrylate, 2- (2- Vinyloxyethoxy) ethyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) Acrylate, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl ( meth) acrylate, 2-isocyanato-1,1-dimethylethyl (meth) acrylate, 4-isocyana Natocyclohexyl (meth) acrylate, the isocyanato group of the (meth) acrylate having the above isocyanato group (eg, 2-isocyanatoethyl (meth) acrylate) blocking agent (blocking agent) (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N-tert-butyl having a blocked isocyanato group obtained by blocking using aminoethyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, hexamethylpiperidyl (meth)acrylate;

(meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di isopropylamide, (meth)acrylic acid anthracenylamide, N-isopropyl (meth)acrylamide, (meth)acrylmorpholine, diacetone (meth)acrylamide;

Norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetra Cyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-ethyltetra cyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 ^2,6] deca-8-ene, tricyclo [5.2.1.0 ^{2, 6} ]deca-3-ene, tricyclo[4.4.0.1 ^2,5 ]undeca-3-ene, tricyclo[6.2.1.0 ^1,8 ]undeca-9-ene, tricyclo[6.2.1.0 ^{1, 8]} undec-4-ene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6] dodeca-3-ene, 8-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6] dodeca-3-ene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,12] dodeca-3-ene, 8-ethylidene tetracyclo [4.4 .0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]dodeca-3-ene, pentacyclo[6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ]pentadeca-4-ene, Pentacyclo[7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ]pentadeca-3-ene, 5-norbornene-2,3-dicarboxylic acid anhydride, (meth)acrylic acid anilide, (meth) ) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinylpyridine, vinyl acetate, vinyltoluene;

styrene and its derivatives;

diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconic acid;

Maleic anhydride, itaconic anhydride, citraconic anhydride.

[0224] From the viewpoint of ease of availability and reactivity, as compound (m1-3), methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl ( meth) acrylate, glycidyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, N,N-diethylaminoethyl (meth) acrylate, (meth) acrylic acid N,N-dimethylamide, (meth)acrylmorpholine, styrene, vinyltoluene and norbornene are preferable, and methyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, glycy More preferred are dil(meth)acrylate, (3-ethyloxetan-3-yl)methyl(meth)acrylate, styrene and vinyltoluene.

[0225] From the viewpoint of thermal decomposition resistance and thermal yellowing resistance, as compound (m1-3), alkyl (meth) acrylate is preferable, methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl ( meth)acrylate is more preferable.

[0226] From the viewpoint of solvent resistance, as compound (m1-3), a polymerizable group having a functional group that reacts with an acidic group (eg, glycidyl group, oxetanyl group, isocyanato group, blocked isocyanato group) A compound is preferable, and glycidyl (meth)acrylate and (3-ethyloxetan-3-yl)methyl methacrylate are more preferable.

[0227] Examples of the blocking agent used for the block of the isocyanato group described above include the following:

lactam-based blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propiolactam;

alcohol-based blocking agents such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol;

Butylphenol such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, oxybenzoate ester; phenolic blocking agents such as thymol, p-naphthol, p-nitrophenol, and p-chlorophenol;

active methylene-based blocking agents such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone;

mercaptan-based blocking agents such as butyl mercaptan, thiophenol, and tert-dodecyl mercaptan;

amine-based blocking agents such as diphenylamine, phenylnaphthylamine, aniline and carbazole;

acid amide-based blocking agents such as acetanilide, acetanisidide, acetate amide, and benzamide;

acid imide-based blocking agents such as succinimide and maleic imide;

imidazole-based blocking agents such as imidazole, 2-methylimidazole and 2-ethylimidazole;

urea-based blocking agents such as urea, thiourea, and ethyleneurea;

Carbamidate type blocking agents, such as N-phenylcarbamate phenyl and 2-oxazolidone;

imine-based blocking agents such as ethyleneimine and polyethyleneimine;

oxime-based blocking agents such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime;

Bisulfite-based blocking agents such as sodium bisulfite and potassium bisulfite.

[0228] In order to control the weight molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the resin (B1) within preferred ranges, and to suppress gelation during polymerization, the solvent used for the polymerization has 3 to It is preferable to include the hydroxyl group containing solvent of 10. Examples of the hydroxyl group-containing solvent having 3 to 10 carbon atoms include monoalcohols such as propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol and benzyl alcohol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether (poly)alkylene glycol monoalkyl ethers, such as these are mentioned.

[0229] The solvent used for the polymerization may contain a solvent other than the solvent containing a hydroxyl group having 3 to 10 carbon atoms. Examples of the solvent include (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxypropionate ethyl, ethoxyethyl acetate, ethyl hydroxyacetate, 3-methyl-3-methoxybutylacetate, 3 -Methyl-3-methoxybutyl propionate, ethyl acetate, butyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butyl propionate, ethyl butyrate, propyl butyrate, butyric acid esters such as isopropyl, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; Carboxylic acid amides, such as N-methylpyrrolidone, N,N- dimethylformamide, and N,N- dimethylacetamide, etc. are mentioned. Among these, from a reactive viewpoint, (poly) alkylene glycol monoalkyl ether acetates are preferable.

[0230] The content of the hydroxyl group-containing solvent having 3 to 10 carbon atoms with respect to the total solvent used for the polymerization is 10 to 100 from the viewpoint of controlling the weight molecular weight and molecular weight distribution (Mw/Mn) of the resin (B1). It is preferable that it is weight %, and it is more preferable that it is 20 to 100 weight%.

[0231] The amount of the solvent used in the polymerization is not particularly limited, but it is preferably based on 100 parts by weight of the total amount of the compound (m1-1), the compound (m1-2) and the compound (m1-3) used. is 30 to 1,000 parts by weight, more preferably 50 to 800 parts by weight.

[0232] The polymerization initiator that can be used for the polymerization is not particularly limited, but for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) ), 2,2'-azobis(isobutyric acid)dimethyl, benzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, and the like. Although the usage-amount of a polymerization initiator is not specifically limited, Preferably it is 0.5-20 weight part with respect to a total of 100 weight part of the usage-amounts of compound (m1-1), compound (m1-2), and compound (m1-3); More preferably, it is 1.0-10 weight part.

[0233] Resin (B1) is preferably a copolymer of (meth)acrylic acid, 3-(meth)acryloyloxypropyltrimethoxysilane and methyl (meth)acrylate. In the case of using compound (A3), resin (B1) is preferably a copolymer of (meth)acrylic acid, 3-(meth)acryloyloxypropyltriethoxysilane and dicyclopentanyl (meth)acrylate. to be.

[0234] The resin (B) may contain a different resin (B2) from the resin (B1). The resin (B2) is preferably an alkali-soluble resin, and at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as “monomer (m2-1)” in some cases) It is preferable that it is a polymer containing the structural unit derived from ). In the said polymer, only 1 type may be contained and 2 or more types may be contained as for the said structural unit.

[0235] Resin (B2) is a monomer (hereinafter referred to as "monomer (m2-2)" having a structural unit derived from the monomer (m2-1) and a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond. It is more preferable that it is a copolymer containing the structural unit derived from ). The copolymer may contain other structural units. As other structural units, for example, a structural unit derived from a monomer (hereinafter sometimes referred to as "monomer (m2-3)") different from the monomer (m2-1) and the monomer (m2-2), ethylenically unsaturated and structural units having a bond. In the copolymer, any of the structural units may contain only one type, or two or more types may be included.

[0236] Examples of the monomer (m2-1) include the following:

unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and o-, m-, p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-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 , a bicyclo unsaturated compound containing a carboxyl group, such as 5-carboxymethylbicyclo[2.2.1]hept-2-ene and 5-carboxyethylbicyclo[2.2.1]hept-2-ene;

Carboxylic anhydrides, such as an anhydride of the said unsaturated dicarboxylic acid except fumaric acid and mesaconic acid;

Unsaturated mono[(meth)acryl] of a polyvalent carboxylic acid having a divalent or higher value, such as monosuccinic acid [2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] royloxyalkyl]esters;

Unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

[0237] As the monomer (m2-1), acrylic acid, methacrylic acid and maleic anhydride are preferable from the viewpoint of reactivity and solubility of the resin obtained in aqueous alkali solution.

[0238] The monomer (m2-2) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond. It is preferable that a monomer (m2-2) is a monomer which has a C2-C4 cyclic ether structure and a (meth)acryloyloxy group. Examples of the cyclic ether structure having 2 to 4 carbon atoms include an oxirane ring, an oxetane ring and a tetrahydrofuran ring.

[0239] As the monomer (m2-2), for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “monomer (m2-2-1)”), an oxetanyl group and an ethylenically unsaturated bond A monomer having a bond (hereinafter sometimes referred to as “monomer (m2-2-2)”) and a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as “monomer (m2-2-3)” in some cases) and the like.

[0240] As the monomer (m2-2-1), for example, a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “monomer (m2-2-1a)” may be ) and a monomer having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "monomer (m2-2-1b)").

[0241] The monomer (m2-2-1a) is preferably a monomer having a glycidyl group and an ethylenically unsaturated bond. As the monomer (m2-2-1a), for example, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether , Vinyl benzyl glycidyl ether, α-methylvinyl benzyl 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(glycy diloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene and 2,4,6-tris(glycidyloxymethyl)styrene methyl) styrene and the like.

[0242] As the monomer (m2-2-1b), for example, vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Seroxide (registered trademark) 2000; manufactured by Daicel Corporation), 3, 4-epoxycyclohexylmethyl (meth)acrylate (eg, Cyclomer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cyclomer (registered trademark) M100) ; Daicel Corporation), the compound represented by the formula (BI), the compound represented by the formula (BII), etc. are mentioned.

[0243]

[0244] In formulas (BI) and (BII), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxy group,

X ^a and X ^b each independently represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S- or *-R ^c -NH-,

R ^c represents an alkanediyl group having 1 to 6 carbon atoms, and

* indicates a bonding position with O.]

[0245] Examples of the compound represented by the formula (BI) include a compound represented by any one of formulas (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) and formula (I-11) to formula (I-15) ) is preferable, and the compound represented by any one of formulas (I-1), (I-7), (I-9) and (I-15) is more preferable.

[0246]

[0247] Examples of the compound represented by the formula (BII) include a compound represented by any one of formulas (II-1) to (II-15). Among them, formulas (II-1), (II-3), (II-5), (II-7), (II-9), and (II-11) to (II-15) ) is preferable, and the compound represented by any one of formulas (II-1), (II-7), (II-9) and (II-15) is more preferable.

[0248]

[0249] In addition, the compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone, respectively, or the compound represented by the formula (BI) and the compound represented by the formula (BII) are used in combination You can do it. When these are used together, the molar ratio of the compound represented by the formula (BI) and the compound represented by the formula (BII) (the compound represented by the formula (BI): the compound represented by the formula (BII)) is preferably 5: It is 95-95:5, More preferably, it is 10:90-90:10, More preferably, it is 20:80-80:20.

[0250] Examples of the monomer (m2-3) include the following:

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, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth ) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate, tricyclo [5.2 .1.0 ^2,6 ]decen-9-yl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylic (meth)acrylates such as late, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

hydroxy group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;

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

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl- dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N-(9-acridinyl)maleimide;

Vinyl group-containing aromatic compounds, such as styrene, (alpha)-methylstyrene, vinyltoluene, and p-methoxystyrene;

vinyl group-containing nitriles such as (meth)acrylonitrile;

halogenated hydrocarbons such as vinyl chloride and vinylidene chloride;

vinyl group-containing amides such as (meth)acrylamide;

esters such as vinyl acetate;

dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.

[0251] From the viewpoint of reactivity and heat resistance, as the monomer (m2-3), styrene, vinyltoluene, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate, tricyclo[5.2 .1.0 ^2,6 ]decan-9-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decene- 9-yl(meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene and benzyl(meth)acrylate are preferred. .

[0252] The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acryloyl group. The resin (B2) having such a structural unit is a polymer containing a structural unit derived from a monomer (m2-1) and a structural unit derived from a monomer (m2-2), a group capable of reacting with the group of the structural unit; It can obtain by adding the monomer which has an ethylenically unsaturated bond.

[0253] As a structural unit having an ethylenically unsaturated bond, for example, a structural unit obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid unit, and 2-hydroxyethyl (meth)acryl to a maleic anhydride unit A structural unit obtained by adding a rate, a structural unit obtained by adding (meth)acrylic acid to a glycidyl (meth)acrylate unit, a structural unit obtained by adding a carboxylic acid anhydride to a structural unit having a hydroxyl group, etc. are mentioned. have.

[0254] The polymer including the structural unit derived from the monomer (m2-1) can be produced by, for example, polymerizing the monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. A polymerization initiator, a solvent, etc. are not specifically limited, What is normally used in the said field|area can be used. As the polymerization initiator, for example, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide, etc.) can be heard There will be no limitation in particular as long as each monomer is melt|dissolved as a solvent, For example, the solvent (H) mentioned later is mentioned. In addition, the obtained polymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was extracted as solid (powder) by methods, such as re-precipitation.

[0255] In the production of a polymer containing a structural unit derived from a monomer (m2-1), a carboxylic acid anhydride having an ethylenically unsaturated bond may be used as the monomer. Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3 ,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, and the like.

[0256] As the resin (B2), for example, 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth) ) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid Copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^{2 ,6} ]decyl (meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/2-hydroxyethyl(meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] Decyl (meth)acrylate/(meth)acrylic acid/vinyltoluene copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/(meth)acrylic acid/2-ethylhexyl (meth) ) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / tricyclo [5.2.1.0 ^2,6 ] decenyl (meth) acrylate / (meth) acrylic acid /N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer, benzyl (meth)acrylate/(meth)acrylic acid copolymer; A styrene/(meth)acrylic acid copolymer and the resin of Unexamined-Japanese-Patent No. H09-106071, Unexamined-Japanese-Patent No. 2004-29518, and Unexamined-Japanese-Patent No. 2004-361455, etc. are mentioned.

[0257] When using a combination of two or more resins (B2), the combination is 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/2-hydroxyethyl(meth)acrylate copolymer, 3,4 -epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/vinyltoluene copolymer, and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acryl It is preferable to include at least one selected from the group consisting of rate/(meth)acrylic acid/2-ethylhexyl(meth)acrylate copolymer.

[0258] The weight average molecular weight (Mw) of the resin (B2) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. The molecular weight distribution (Mw/Mn) (that is, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) of the resin (B2) is preferably 1.1 to 6, more preferably 1.2 to 4 is Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin (B2) are values calculated in terms of polystyrene using gel permeation chromatography (GPC).

[0259] The acid value (in terms of solid content) of the resin (B2) is preferably 10 to 300 mgKOH/g, more preferably 20 to 250 mgKOH/g, still more preferably 20 to 200 mgKOH/g, still more preferably 20 to 170 mgKOH/g, still more preferably 30 to 170 mgKOH/g, particularly preferably 50 to 150 mgKOH/g, still more preferably 60 to 140 mgKOH/g, and most preferably 60 to 135 mgKOH/g. The acid value of the resin (B2) is a value calculated as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B2), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

[0260] When the resin (B2) is used, the content of the colorant (A) relative to 100 parts by weight is preferably 1 to 1,200 parts by weight, more preferably 5 to 1,000 parts by weight, still more preferably 10 to 800 parts by weight.

[0261] When the resin (B2) is used, its content with respect to the total amount of solid content is preferably 1 to 50% by weight, more preferably 1 to 45% by weight, still more preferably 1 to 40% by weight, Most preferably, it is 1 to 30% by weight.

[0262] <Polymerizable compound (C)>

The polymerizable compound (C) is a compound capable of polymerization with active radicals and/or acids generated from the polymerization initiator (D). The polymerizable compound (C) is preferably a radically polymerizable compound. As a radically polymerizable compound, the compound etc. which have a polymerizable ethylenically unsaturated bond are mentioned, for example. The radically polymerizable compound is preferably (meth)acrylates.

[0263] Examples of the polymerizable compound (C) include the following:

1 ethylenically unsaturated, such as nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone compounds having a bond;

1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyl of bisphenol A) compounds having two ethylenically unsaturated bonds, such as oxyethyl) ether and 3-methylpentanediol di(meth)acrylate;

compounds having three ethylenically unsaturated bonds, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris(2-(meth)acryloyloxyethyl)isocyanurate;

Pentaerythritol tetra (meth) acrylate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, etc. compounds having four ethylenically unsaturated bonds;

compounds having five ethylenically unsaturated bonds such as dipentaerythritol penta (meth) acrylate;

Dipentaerythritol hexa(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth) compounds having six ethylenically unsaturated bonds such as acrylates;

Seven or more ethylenic properties, such as tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, and tetrapentaerythritol deca (meth) acrylate A compound having an unsaturated bond.

[0264] The polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 or 6 ethylenically unsaturated bonds. Specifically, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable. As a commercial item of a polymeric compound (C), For example, KAYARAD (trademark) DPHA (Nippon Kayaku Co., Ltd.), A-TMM-3LM-N (SHIN-NAKAMURA CHEMICAL CO., LTD.) and A9550 (SHIN) -NAKAMURA CHEMICAL CO., LTD.) etc. are mentioned.

[0265] The molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less. In addition, the molecular weight of 1,000 or more polymeric compound (C) is a weight average molecular weight (Mw) computed in polystyrene conversion using gel permeation chromatography (GPC).

[0266] The content of the polymerizable compound (C) is preferably 7 to 65% by weight, more preferably 13 to 60% by weight, and still more preferably 17 to 55% by weight with respect to the total amount of solid content. When content of a polymeric compound (C) exists in said range, there exists a tendency for the residual-film rate at the time of coloring pattern formation and the chemical-resistance of a color filter to improve.

[0267] The weight ratio of the resin (B) to the polymerizable compound (C) (resin (B): polymerizable compound (C)) is preferably 20:80 to 80:20, more preferably 35 :65~80:20.

[0268] <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 a known polymerization initiator can be used. The polymerization initiator (D) is preferably a photoradical polymerization initiator. It is more preferable that the polymerizable compound (C) is a radically polymerizable compound, and the polymerization initiator (D) is a photoradical polymerization initiator (that is, the colored curable resin composition of the present invention is a photocurable resin composition). do.

[0269] The photoradical polymerization initiator is preferably at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds, more preferably O-acyloxime compounds.

[0270] The O-acyloxime compound is a compound having a partial structure represented by formula (d1) (wherein * indicates a bonding position).

[0271]

[0272] As the O-acyloxime compound, for example, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanyl) Phenyl)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]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-a2-methyl-4-( 3,3-Dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl｝-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-( 2-Methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carr Bazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-[4-(2-hydroxyethyloxy)phenylsulfanylphenyl]propan-1-one- 2-immigration and the like. TR-PBG327 (manufactured by Changzhou Tronly New Electronic Materials), Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) OXE03, Irgacure (registered trademark) OXE04 (or higher) , BASF Corporation), you may use commercial items, such as N-1919 (made by ADEKA CORPORATION). Among them, the O-acyloxime compound is TR-PBG327 (manufactured by Changzhou Tronly New Electronic Materials), Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) OXE03, Irgacure (trademark) OXE04 (above, manufactured by BASF), N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4 -phenylsulfanylphenyl)octan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine TR-PBG327 (manufactured by Changzhou Tronly New Electronic Materials), Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) OXE03, Irgacure At least one selected from the group consisting of (registered trademark) OXE04 (above, manufactured by BASF) and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine is more preferable. When these O-acyl oxime compounds are used, there exists a tendency for the color filter with high brightness to be obtained.

[0273] The alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3) (in the formulas below, * indicates a bonding position). In these partial structures, the benzene ring may have a substituent.

[0274]

[0275] Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino- 1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) phenyl] butan-1-one; and the like. You may use commercial items, such as Irgacure (trademark) 369, Irgacure (trademark) 907, and Irgacure (trademark) 379 (above, BASF Corporation make).

As the compound having a partial structure represented by formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2) -Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, an oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one; α,α-diethoxyacetophenone, benzyldimethyl ketal, and the like.

From a viewpoint of a sensitivity, as an alkylphenone compound, the compound which has a partial structure represented by Formula (d2) is preferable.

[0276] As the triazine compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 -Bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-) 2-yl)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(trichloro and romethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0277] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. You may use commercial items, such as Irgacure (trademark) 819 (made by BASF).

[0278] As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3) -dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-Open Nos. H06-75372 and H06-75373), 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(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication Nos. S48-38403 and S62-174204), 4,4'5,5' and a biimidazole compound in which the phenyl group at the -position is substituted with a carboalkoxy group (see, for example, Japanese Patent Application Laid-Open No. H07-10913) and the like.

[0279] Other polymerization initiators (D) include, for example, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, benzophenone compounds such as 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization initiation adjuvant (F) (especially amines) mentioned later.

[0280] As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluene Sulfonate, 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluene Onium salts, such as sulfonate and diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

[0281] The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight in total of the resin (B) and the polymerizable compound (C). to be. When content of a polymerization initiator (D) exists in said range, since there exists a tendency for the sensitivity of the colored curable resin composition of this invention to improve and exposure time to shorten, productivity of a color filter improves.

[0282] <Phenolic antioxidant (E)>

The colored curable resin composition of this invention is characterized by including a phenol-type antioxidant (E) as one of the characteristics. By using a phenolic antioxidant (E), the decrease in the thickness of the coloring pattern or colored coating film by heating (particularly post-baking) can be suppressed. Moreover, the heat resistance of a colored pattern or a colored coating film can be improved by using a phenolic antioxidant (E).

[0283] In the present specification, "phenolic antioxidant" means an antioxidant having a phenolic hydroxyl group. For this reason, for example, the antioxidant containing both a phenolic hydroxyl group and a phosphorus atom is classified not as a phosphorus antioxidant but as a phenolic antioxidant in this specification. In addition, the phenolic antioxidant in this specification also contains the antioxidant (it may describe as "protected phenolic antioxidant" hereafter) which has the protected phenolic hydroxyl group.

[0284] Examples of the phenolic antioxidant include the following:

(1) Alkylthiomethylphenol

2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecyl Thiomethyl-4-nonylphenol.

[0285] (2) tocopherols

α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol.

[0286] (3) O-benzyl derivatives, N-benzyl derivatives and S-benzyl derivatives

3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris(3, 5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert -Butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

[0287] (4) hydroxybenzylated malonate derivatives

Dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methyl Benzyl)malonate, didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetra) Methylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

[0288] (5) Aromatic hydroxybenzyl derivatives

1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,4-bis(3,5-di-tert-butyl- 4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-tert-butyl-4-hydroxybenzyl)phenol.

[0289] (6) triazine derivatives

2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2-n-octylthio-4 ,6-bis(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy- 3,5-di-tert-butylphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-phenoxy)-1,3, 5-triazine, tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocy Anurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 2,4,6-tris(3,5- Di-tert-Butyl-4-hydroxyphenylpropyl)-1,3,5-triazine, tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, tris[2-(3) ',5'-di-tert-butyl-4'-hydroxycinnamoyloxy)ethyl]isocyanurate.

[0290] (7) benzylphosphonate derivatives

Dimethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5 -di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5-di-tert-butyl-4 -Calcium salt of hydroxybenzylphosphonic acid monoester.

[0291] (8) acylaminophenol derivatives

4-hydroxylaurylate anilide, 4-hydroxystearate anilide, octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbanate.

[0292] (9) ester of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid and the following monohydric or polyhydric alcohols

Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thio Ethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecane ol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.

[0293] (10) ester of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid and the following monohydric or polyhydric alcohols

Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thio Ethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecane ol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.

[0294] (11) ester of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid and the following monohydric or polyhydric alcohols

Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thio Ethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecane ol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.

[0295] (12) Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and the following monohydric or polyhydric alcohols

Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thio Ethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecane ol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.

[0296] (13) Amide of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid

N,N'-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]hydrazine, N,N'-bis[3-(3',5'- Di-tert-butyl-4'-hydroxyphenyl)propionyl]hexamethylenediamine, N,N'-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propy onyl]trimethylenediamine.

[0297] Those in which the phenolic hydroxyl group of the phenolic antioxidants exemplified above are protected with a protecting group can also be used as the phenolic antioxidant in the present invention. Examples of the protecting group include an ether protecting group, an acetal protecting group, an acyl protecting group, and a silyl ether protecting group. Examples of the ether-based protecting group include a methyl group, a benzyl group, a p-methoxybenzyl group, and a tert-butyl group. Examples of the acetal protecting group include a methoxymethyl group, a 2-tetrahydropyranyl group, and an ethoxyethyl group. As an acyl-type protecting group, an acetyl group, a pivaloyl group, and a benzoyl group are mentioned. Examples of the silyl ether protecting group include a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a triisopropylsilyl group, and a tert-butyldiphenylsilyl group. Further, as the protecting group, a tert-butoxycarbonyl (Boc) group may be used. As the protecting group of the phenolic hydroxyl group, a Boc group is preferable.

[0298] As the phenol-based antioxidant, a commercially available product may be used. As a commercial item of a phenolic antioxidant, Sumilizer (trademark) GP (made by Sumitomo Chemical Company, Limited) and Adekastave (trademark) AO series (made by ADEKA CORPORATION) are mentioned, for example. As a commercial item of the protected phenolic antioxidant, ADEKA ARCLS (trademark) GPA-5001 (made by ADEKA CORPORATION) is mentioned, for example.

[0299] From the viewpoint of suppressing the reduction in the thickness of the colored pattern or colored coating film by heating and obtaining a good colored pattern after alkali development, the content of the phenolic antioxidant (E) is 100 parts by weight of the polymerizable compound (C) , Preferably it is 0.1-25 weight part, More preferably, it is 0.2-20 weight part, More preferably, it is 0.5-20 weight part, Especially preferably, it is 3-10 weight part.

[0300] <Polymerization initiation aid (F)>

The colored curable resin composition of this invention may contain the polymerization initiation adjuvant (F) further. A polymerization initiation adjuvant (F) is a compound used in order to accelerate|stimulate superposition|polymerization of the polymeric compound which superposition|polymerization was started by a polymerization initiator, or a sensitizer. Examples of the polymerization initiation auxiliary (F) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

[0301] As the amine compound, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminomethylbenzoate, 4-dimethylaminoethylbenzoate, 4-dimethylaminobenzoate isoamyl, benzoate 2-dimethylaminoethyl , 4-dimethylaminobenzoate 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone), 4,4'-bis(diethylamino) Benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. are mentioned. Among these, 4,4'-bis(diethylamino)benzophenone is preferable. As an amine compound, you may use commercial items, such as EAB-F (made by HODOGAYA CHEMICAL CO., LTD.).

[0302] As the alkoxyanthracene compound, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

[0303] As the thioxanthone compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxythioxanthone etc. are mentioned.

[0304] As the carboxylic acid compound, for example, phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenyl Sulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

[0305] The polymerization initiation auxiliary (F) is preferably a thioxanthone compound, and more preferably 2,4-diethylthioxanthone.

[0306] When the polymerization initiation auxiliary (F) is used, the content of the resin (B) and the polymerizable compound (C) relative to 100 parts by weight in total is preferably 0.1 to 30 parts by weight, more preferably 1 ~ 20 parts by weight. Moreover, when using a polymerization initiation adjuvant (F), its content with respect to 100 weight part of polymerization initiator (D) becomes like this. Preferably it is 5-80 weight part, More preferably, it is 10-60 weight part, More preferably, 15 to 55 parts by weight. When the amount of the polymerization initiation auxiliary (F) is within the above range, a coloring pattern can be formed with high sensitivity and the productivity of the color filter tends to be improved.

[0307] <thiol compound (G)>

The colored curable resin composition of this invention may contain the thiol compound (G) further. The thiol compound (G) is a compound having a sulfanyl group (-SH).

[0308] As the compound having one sulfanyl group, for example, 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxa Sol, 2-sulfanylnicotinic acid, 2-sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-Amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6- Hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanyl Pyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propylpyrimidine, 2- Sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2- Thiol, 2-sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5 -sulfanyl-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol , 3-sulfanyl 1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1,3,4-thiadiazole, 5-amino-1,3,4-thia Diazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl)methanethiol, 2-sulfanyl-5-thiazolidone, 2-sulfanyl Thiazoline, 2-sulfanyl-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2-sulfa Nyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro- 2-sulfanylbenzothiazole, 2-sulfanylnaphthoimidazole, 2-sulfanylnaphthooxazole, 3-sulfanyl-1,2,4-triazole, 4-amino-6-sulfanylpyrazolo[ 2,4-d]pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo[2,4 -d] pyrimidine etc. are mentioned.

[0309] Examples of the compound having two or more sulfanyl groups include hexanedithiol, decanedithiol, 1,4-bis(methylsulfanyl)benzene, butanediolbis(3-sulfanylpropionate), butanediolbis( 3-sulfanyl acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylol propane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylol propane tris (3-sulfa) nylpropionate) (alias "trimethylolpropanetris(3-mercaptopropionate)"), trimethylolpropanetris(3-sulfanylacetate), pentaerythritoltetrakis(3-sulfanylpropionate) , pentaerythritol tetrakis (3-sulfanyl acetate), tris hydroxyethyl tris (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3- Sulfanylbutyloxy)butane and the like.

[0310] The thiol compound (G) is preferably a compound having two or more sulfanyl groups, and more preferably trimethylolpropane tris(3-sulfanylpropionate).

[0311] When using the thiol compound (G), its content is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the polymerizable compound (C). When content of a thiol compound (G) exists in this range, there exists a tendency for a sensitivity to become high and developability to become favorable.

[0312] <Solvent (H)>

The colored curable resin composition of this invention may contain the solvent (H) further. The solvent (H) is not specifically limited, The solvent normally used in this field|area can be used. As the solvent (H), for example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and not containing -COO-) ), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing -COO- and -O- in the molecule) solvents containing but not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like. In addition, the concept of "-O-" does not include "-O-" in "-COO-", and the concept of "-CO-" includes "-CO-" in "-COO-" doesn't happen

[0313] As the ester solvent, for example, methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isobutyrate and propyl, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0314] As the ether solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran , tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenol netol and methylanisole; and the like.

[0315] As the ether ester solvent, for example, methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3 -Methyl ethoxypropionate, 3-ethoxyethyl propionate, 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2-methoxypropylpropionate, 2-ethoxymethylpropionate, 2-ethoxypropionateethyl, 2- Methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl, 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 dipropylene glycol methyl ether acetate are mentioned. .

[0316] As the ketone solvent, for example, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 -pentanone, diacetone alcohol, cyclopentanone, cyclohexanone, isophorone, etc. are mentioned.

[0317] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

[0318] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.

[0319] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

[0320] The solvent (H) is preferably an organic solvent having a boiling point of 120° C. or more and 180° C. or less at 1 atm from the viewpoint of coating properties and drying properties. Examples of the solvent (H) include 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, and diethylene glycol monomethyl ether. , diethylene glycol monoethyl ether, diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide are preferable, 3-methoxy-1-butanol, propylene glycol monomethyl Ether acetate, propylene glycol monomethyl ether, ethyl lactate, diacetone alcohol, and ethyl 3-ethoxypropionate are more preferable.

[0321] When the solvent (H) is used, its content is preferably 35 to 95% by weight, more preferably 40 to 92% by weight, based on the entire colored curable resin composition of the present invention. In other words, the total amount of solid content of colored curable resin composition becomes like this. Preferably it is 5-65 weight%, More preferably, it is 8-60 weight%. When the content of the solvent (H) is within the above range, flatness at the time of application becomes favorable, and since color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

[0322] <Leveling agent (I)>

The colored curable resin composition of this invention may contain the leveling agent (I). As a leveling agent (I), silicone type surfactant, a fluorine type surfactant, etc. are mentioned, for example. These may have a polymeric group in a side chain.

[0323] The silicone-based surfactant includes, for example, a surfactant having a siloxane bond in the molecule. Commercially available products include, for example, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by 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, TSF-4446, TSF4452 and TSF4460 (Momentive Performance Materials Japan LLC) manufacture) and the like.

[0324] The silicone-based surfactant may have a fluorine atom. Examples of the silicone-based surfactant having a fluorine atom include Megapac (registered trademark) R08, Megapac BL20, Megapac F475, Megapac F477, and Megapac F443 (manufactured by DIC CORPORATION).

[0325] The fluorine-based surfactant includes, for example, a surfactant having a fluorocarbon chain in the molecule. Commercially available products include, for example, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Limited), Megapac (registered trademark) F142D, Megapac F171, Megapac F172, Megapac F173, Megapac F177, Megapac F183, Megapac F554, Megapac R30, Megapac RS-718-K (manufactured by DIC CORPORATION), eftop (registered trademark) EF301, eftop EF303, eftop EF351, eftop EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd.), Sufflon (registered trademark) S381, Sufflon S382, Sufflon SC101, Sufflon SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Genkyusho), and the like. .

[0326] When the leveling agent (I) is used, its content is preferably 0.001% by weight or more and 0.2% by weight or less, and more preferably 0.002% by weight or more and 0.1% by weight or less with respect to the entire colored curable resin composition. , more preferably 0.01% by weight or more and 0.05% by weight or less. In addition, content of the dispersing agent used for manufacture of a pigment dispersion liquid is not contained in this content. When content of a leveling agent (I) exists in said range, the flatness of a color filter can be made favorable.

[0327] <Other ingredients>

The colored curable resin composition of this invention may contain well-known additives in the said technical field, such as a filler, another high molecular compound, an adhesion promoter, an optical stabilizer, and a chain transfer agent, as needed.

[0328] <Method for producing colored curable resin composition>

The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B) (resin (B1) and optionally, a resin (B2)), a polymerizable compound (C), a polymerization initiator (D), and a phenol type. It can prepare by mixing antioxidant (E), and a solvent (H), a leveling agent (I), a polymerization initiation adjuvant (F), a thiol compound (G), and other components as needed.

[0329] In the case of using the pigment (A2), the pigment (A2) is mixed with a part or all of the solvent (H) in advance, and the average particle diameter of the pigment (A2) is about 0.2 μm or less, and the bead mill is performed. It is preferable to disperse the pigment (A2) using a (bead mill) or the like to prepare a pigment dispersion. At this time, you may mix|blend part or all of a dispersing agent and resin (B) (especially resin (B2)) as needed. The pigment dispersion liquid obtained in this way is mixed with the remaining component so that it may become a predetermined|prescribed density|concentration, and the target colored curable resin composition can be prepared.

[0330] When using the dye (A1), the dye (A1) may be dissolved in a part or all of the solvent (H) in advance to prepare a dye solution. It is preferable to filter the said solution with the filter whose pore diameter is about 0.01-1 micrometer. Moreover, it is preferable to filter the colored curable resin composition obtained by mixing the said component with the filter whose pore diameter is about 0.01-10 micrometers.

[0331] <Method for manufacturing color filter and liquid crystal display device>

As a method of forming a color filter with the colored curable resin composition of this invention, the method of using a photolithographic method and an inkjet apparatus is mentioned, for example. In the photolithography method, a colored curable resin composition is usually applied on a substrate, and volatile components such as a solvent are removed by heat drying (pre-baking) and/or drying under reduced pressure to form a composition layer, and through a photomask The composition layer is irradiated with light (exposed), and a developer is brought into contact with the composition layer after exposure to form a colored pattern (developed). After this development, the post-baking which heats a coloring pattern is performed frequently. In the said photolithographic method, the colored coating film which is the hardened|cured material of the said composition layer can be formed by not using and/or not developing a photomask at the time of exposure. Thus, the obtained colored pattern and colored coating film can be used as a color filter.

[0332] Examples of the substrate include a glass plate, a resin plate, and a silicon plate. On the said board|substrate, aluminum, silver, a silver/copper/palladium alloy thin film etc. may be formed. Moreover, on the said board|substrate, another color filter layer, a resin layer, a transistor, a circuit, etc. may be formed.

[0333] The thickness of the color filter to be produced is not particularly limited, and may be appropriately adjusted according to the intended use, for example, 0.1 to 30 μm, preferably 1 to 20 μm, more preferably 1 to 6 μm.

[0334] Formation of the coloring pattern (pixel) by the photolithography method can be performed under known or customary apparatus and conditions. For example, a coloring pattern can be formed as follows.

[0335] First, a colored curable resin composition is applied on a substrate, and volatile components such as a solvent are removed by heat drying (pre-baking) and/or drying under reduced pressure to obtain a smooth composition layer. As a coating method, the spin coating method, the slit coating method, the slit-and-spin coating method, etc. are mentioned, for example.

[0336] Next, the composition layer is irradiated with light (exposure) through a photomask for forming a desired colored pattern. It is preferable to use an exposure apparatus such as a mask aligner and a stepper, since it is possible to uniformly irradiate parallel rays to the entire exposure surface and to perform accurate alignment between the photomask and the substrate on which the composition layer is formed.

[0337] By bringing the composition layer after exposure into contact with a developer, a colored pattern is formed on the substrate (development). By development, the unexposed portion of the composition layer is dissolved in the developer and removed. As a developing solution, the aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, and tetramethylammonium hydroxide, is preferable. Any of a puddle method, a dipping method, a spray method, etc. may be sufficient as the image development method. Moreover, you may incline a board|substrate at arbitrary angles at the time of development. It is preferable to wash with water after image development.

[0338] The color filter produced from the colored curable resin composition of the present invention is useful as a color filter used in a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

[Example]

[0339] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, of course, and is carried out with appropriate changes within a range suitable for the purpose of the above and below. It is also possible, and all of these are included in the technical scope of the present invention. In addition, in the following, unless otherwise indicated, "part" means "weight part", and "%" other than thickness retention means "weight%".

[0340] In the following, the structure of the compound was confirmed by mass spectrometry (LC; 1200 manufactured by Agilent Technologies, Inc., MASS; LC/MSD manufactured by Agilent Technologies, Inc.).

[0341] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin obtained in Production Example were measured using GPC under the following conditions.

Device; K2479 (manufactured by Shimadzu Corporation)

column; SHIMADZU Shim-pack GPC-80M

column temperature; 40℃

menstruum; THF (tetrahydrofuran)

flow rate; 1.0mL/min

detector; RI

calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-228, A-2500, A-500 (manufactured by TOSOH CORPORATION)

Ratio (Mw/Mn) of the polystyrene conversion weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution.

[0342] <Preparation Example 1: Preparation of resin (B1-1)>

750.0 g of 3-methoxybutanol was put into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the mixture was stirred while replacing with nitrogen, and the temperature was raised to 80°C.

Next, in a monomer mixture consisting of 25.6 g (0.30 mol) of methacrylic acid, 146.4 g (0.50 mol) of 3-methacryloyloxypropyltrimethoxysilane and 49.2 g (0.49 mol) of methyl methacrylate, 2, 28.8 g of 2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) was added dropwise through a dropping funnel into the flask.

After completion of the dropwise addition, the mixture was stirred at 80° C. for 5 hours to carry out a copolymerization reaction to obtain a resin (B1-1) (weight average molecular weight (Mw): 5,500, acid value: 82 mgKOH/g, silyl group equivalent: 500). .

[0343] <Preparation Example 2: Preparation of resin (B1-2)>

750.0 g of propylene glycol monomethyl ether was put into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the mixture was stirred while replacing with nitrogen, and the temperature was raised to 80°C.

Next, in a monomer mixture consisting of 39.2 g (0.46 mol) of methacrylic acid, 132.0 g (0.46 mol) of 3-methacryloyloxypropyltriethoxysilane, and 50.1 g (0.23 mol) of dicyclopentanyl methacrylate, 28.8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) was added dropwise through a dropping funnel into the flask.

After completion of the dropwise addition, the mixture was stirred at 80° C. for 5 hours to carry out a copolymerization reaction to obtain a resin (B1-2) (weight average molecular weight (Mw): 4,000, acid value: 135 mgKOH/g, silyl group equivalent: 550). .

[0344] <Preparation Example 3: Preparation of resin (B2-1)>

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen atmosphere was substituted, 280 parts of propylene glycol monomethyl ether acetate was put, and it heated to 80 degreeC, stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-ylacrylic A mixed solution of 289 parts of a mixture (content ratio of 1:1) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution obtained by dissolving 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was maintained at 80° C. for 4 hours, then cooled to room temperature, and a solution of a copolymer (resin (B2-1)) having a solid content of 35.1% and a viscosity of 125 mPas measured by a type B viscometer (23° C.) got it The obtained copolymer had a weight average molecular weight (Mw) of 9.2×10 ³ , a molecular weight distribution (Mw/Mn) of 2.08, and an acid value (in terms of solid content) of 77 mgKOH/g. Resin (B2-1) has the following structural units (in the following formula, * represents a bonding position.).

[0345]

[0346] <Preparation Example 4: Preparation of red pigment dispersion>

50.6 parts of red pigment synthesized as described below, 10.1 parts of dispersant (BYKLPN-6919 manufactured by BYK; 60% solution of propylene glycol monomethyl ether acetate), 20.3 parts of resin (B2-1) (in terms of solid content), propylene glycol mono 64.5 parts of methyl ether and 216.0 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 µm zirconia beads were added, and the resulting mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain a red pigment dispersion.

[0347] The red pigment used to prepare the dispersion of the red pigment was synthesized as follows.

174 g of tert-amyl alcohol and 22.2 g of metallic sodium were reacted at 130° C. under a nitrogen atmosphere to synthesize sodium tert-amyl alcohol. This was heated to 60° C., and 91.0 g of 4-bromobenzonitrile, 71.05 g of di-tert-amyl succinate, and 108.9 g of tert-amyl alcohol were added, and the resulting suspension was heated to 85° C. or lower. Stirred for 2 hours. After stirring this suspension as it is at 85 degreeC for 18 hours or more, it added to the mixed solution of 200 g of methanol, 1000 g of water, and sulfuric acid 49.21g cooled to -10 degreeC. After the addition of the suspension was completed, the obtained mixture was stirred for 5 hours while maintaining at 0° C. to complete the reaction, and then the solid was collected by filtration. The recovered solid was alternately washed with methanol and water. This washing was repeatedly performed until the discoloration of methanol and water used for washing disappeared and salt precipitation disappeared. The solid material after washing was dried in a vacuum dryer at 80°C for 18 hours to obtain a red pigment.

[0348] <Preparation Example 5: Preparation of blue pigment dispersion>

C.I. Pigment Blue 15:6 19.2 parts, dispersant (BYKLPN-6919 manufactured by BYK; propylene glycol monomethyl ether acetate 60% solution) 6.7 parts, Resin (B2-1) 7.7 parts (in terms of solid content), ethyl lactate 14.6 parts and propylene 143.8 parts of glycol monomethyl ether acetate were mixed, 600 parts of 0.4 µm zirconia beads were added, and the resulting mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion of blue pigment.

[0349] <Preparation Example 6: Preparation of compound (A3-1-1)>

According to the method described in Example 7 of Japanese Patent Application Laid-Open No. 2018-127596, a compound represented by the following formula (A3-1-1) was prepared.

[0350]

[0351] <Preparation Example 7: Preparation of compound (A3-2-1)>

According to the method described in Synthesis Example 19 of Japanese Patent Application Laid-Open No. 2015-38201, a compound represented by the following formula (A3-2-1) was prepared.

[0352]

[0353] <Preparation Example 8: Preparation of dispersion of compound (A3-1-1)>

7 parts of compound (A3-1-1), 3 parts of a dispersant (DISPERBYK (registered trademark)-2050 manufactured by BYK-Chemie; 52% solution of propylene glycol monomethyl ether acetate), 3 parts of resin (B2-1) (in terms of solid content) part, 81 parts of propylene glycol monomethyl ether acetate, 6 parts of diacetone alcohol, and 300 parts of 0.2 mm zirconia beads were mixed, and the resulting mixture was shaken for 3 hours using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to prepare a dispersion of compound (A3-1-1). In addition, although compound (A3-1-1) is a dye soluble in diacetone alcohol, in order to improve the reliability of compound (A3-1-1) with respect to heat resistance and light resistance, propylene glycol monomethyl ether acetate is used, A dispersion of compound (A3-1-1) was prepared and used.

[0354] <Preparation Example 9: Preparation of dispersion of compound (A3-2-1)>

14 parts of compound (A3-2-1), 2 parts of a dispersant (BYKLPN-6919 manufactured by BYK; 60% solution of propylene glycol monomethyl ether acetate), 6 parts of resin (B2-1) (in terms of solid content), propylene glycol monomethyl 74 parts of ether acetate, 4 parts of diacetone alcohol, and 300 parts of 0.2 mm zirconia beads were mixed, and the resulting mixture was shaken for 3 hours using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to prepare a dispersion of compound (A3-2-1). In addition, although compound (A3-2-1) is a dye soluble in diacetone alcohol, in order to improve the reliability of compound (A3-2-1) with respect to heat resistance and light resistance, propylene glycol monomethyl ether acetate is used, A dispersion of compound (A3-2-1) was prepared and used.

[0355] Examples 1 to 16 and Comparative Examples 1 to 5

(1) Preparation of colored curable resin composition

Each component was mixed so that it might become a composition shown to following Tables 1-3, and the colored curable resin composition was obtained.

[0356] Each component used in the preparation of the colored curable resin composition is as follows.

<Dye (A1)>

(A1-1): a dye represented by the following formula (A1-1) obtained by the method described in Example 1 of Japanese Patent Application Laid-Open No. 2016-27075

(A1-2): A dye represented by the following formula (A1-2) obtained by the method described in Example 2 of Japanese Patent Application Laid-Open No. 2017-226814

(A1-3): a dye represented by the following formula (A1-3) obtained by the method described in Synthesis Example 2 of Japanese Patent Laid-Open No. 2016-176075

[0357]

[0358] <Dispersion of Pigment (A2)>

Dispersion of red pigment: the dispersion obtained in Preparation Example 4

Dispersion of blue pigment: the dispersion obtained in Preparation Example 5

[0359] <Dispersion of Compound (A3)>

Dispersion of compound (A3-1-1): the dispersion obtained in Preparation Example 8

Dispersion of compound (A3-2-1): the dispersion obtained in Preparation Example 9

[0360] <Resin (B)>

(B1-1): Resin (B1-1) obtained in Production Example 1

(B1-2): the resin obtained in Production Example 2 (B1-2)

(B2-1): Resin (B2-1) obtained in Production Example 3 (preparation of dispersion of pigment (A2), preparation of dispersion of compound (A3), and use in Comparative Example 4)

[0361] <Polymerizable compound (C)>

(C-1): dipentaerythritol hexaacrylate (“KAYARAD (registered trademark) DPHA” manufactured by Nippon Kayaku Co., Ltd.)

[0362] <Polymerization initiator (D)>

(D-1): a compound represented by the following formula (D-1) ("TR-PBG327" manufactured by Changzhou Tronly New Electronic Materials)

(D-2): "Irgacure (registered trademark) 907" manufactured by BASF

[0363]

[0364] <Phenolic antioxidant (E)>

(E-1): 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f ][1.3.2]dioxaphospepine (“Smilizer (registered trademark) GP” manufactured by Sumitomo Chemical Company, Limited)

(E-2): Manufactured by ADEKA CORPORATION 「Adeka Arcles (registered trademark) GPA-5001」

(E-3): manufactured by ADEKA CORPORATION “Adekastave (registered trademark) AO-60”

[0365] <phosphorus antioxidant>

TPP: triphenylphosphite (manufactured by ADEKA CORPORATION "ADEKA STAB (registered trademark) TPP")

[0366] <Polymerization initiation aid (F)>

(F-1): 2,4-diethyl thioxanthone (“KAYACURE (registered trademark) DETX-S” manufactured by Nippon Kayaku Co., Ltd.)

[0367] <thiol compound (G)>

(G-1): trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.)

[0368] <Solvent (H)>

(H-1): 3-methoxy-1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 158° C.)

(H-2): diacetone alcohol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 168° C.)

(H-3): propylene glycol monomethyl ether acetate (manufactured by KH Neochem Co., Ltd., 146° C.)

(H-4): propylene glycol monomethyl ether (manufactured by KH Neochem Co., Ltd., boiling point 121°C)

[0369] <Leveling agent (I)>

(I-1): Silicone-based surfactant (“Toray Silicone SH8400” manufactured by Dow Corning Toray Co., Ltd.)

[0370] (2) Formation of a color filter (colored coating film)

On a 2-inch square glass substrate (Eagle 2000; manufactured by Corning Incorporated), a colored curable resin composition was applied by spin coating and then pre-baked at 100° C. for 3 minutes to form a composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by TOPCON CORPORATION), in an atmospheric atmosphere, the composition layer was irradiated with light at an exposure amount of ^{60 mJ/cm 2 (based on 365 nm).} The colored coating film was obtained by performing post-baking at 230 degreeC for 20 minutes in oven after light irradiation. It was 3.0 micrometers when the thickness of the obtained colored coating film was measured after standing to cool using the film thickness measuring apparatus (DEKTAK3; Japan Vacuum Engineering Co., Ltd. make).

[0371] (3) Evaluation of thickness retention rate

The thickness of the formed colored coating film before and after post-baking was measured using a film thickness measuring apparatus (DEKTAK3; manufactured by Japan Vacuum Engineering Co., Ltd.), and the following formula:

Thickness retention rate (%) = (thickness after post-baking / thickness before post-baking) x 100

According to the thickness retention rate was calculated. A result is shown to Tables 1-3.

[0372] [Table 1]

[0373] [Table 2]

[0374] [Table 3]

[0375] As is clear from the results shown in Tables 1 to 3, coloring of Examples 1 to 16 using a phenolic antioxidant and resin (B1) (ie, resin (B1-1) or resin (B1-2)) The curable resin composition is a colored curable resin of Comparative Examples 1, 3 and 5 in which an antioxidant is not used, or Comparative Example 2 in which a phosphorus antioxidant is used instead of a phenolic antioxidant, and Comparative Example 4 in which the resin (B1) is not used. Compared with a composition, the thickness reduction of the colored coating film by a post-baking can be suppressed.

Industrial Applicability

[0376] When the colored curable resin composition of the present invention is used, it is possible to suppress a decrease in the thickness of the colored pattern or the colored coating film due to heating (especially post-baking). The color filter manufactured from the colored curable resin composition of this invention is useful as a color filter used for a display apparatus (For example, a liquid crystal display device, organic electroluminescent apparatus, electronic paper, etc.) and a solid-state image sensor.

Claims (9)

A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), comprising:
The colored curable resin composition further contains a phenol-based antioxidant (E),
Resin (B) is, formula (1b):

[In formula (1b), R ^1B represents a hydrogen atom or a methyl group,
R ^2B to R ^4B each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms,
n represents an integer of 1 to 10, and
* represents a binding position,
However, ^{at least one of R 2B} to R ^4B is an alkoxy group having 1 to 6 carbon atoms.]
Colored curable resin composition containing resin (B1) containing the structural unit (b1-1) represented by. According to claim 1,
Resin (B1) is a copolymer containing a structural unit (b1-1), a structural unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group, and another structural unit (b1-3), and is a copolymer Colored curable resin composition whose quantity of structural unit (b1-1) when the sum total of all the structural units in it is 100 mol% is 1-50 mol%. 3. The method of claim 1 or 2,
Colored curable resin composition whose weight average molecular weights of resin (B1) are 1,000-50,000. 4. The method according to any one of claims 1 to 3,
Colored curable resin composition whose content of resin (B1) is 5-400 weight part with respect to 100 weight part of polymeric compound (C). 5. The method according to any one of claims 1 to 4,
Colored curable resin composition whose content of a phenolic antioxidant (E) is 0.1-25 weight part with respect to 100 weight part of polymeric compound (C). 6. The method according to any one of claims 1 to 5,
Coloring curable resin composition in which a coloring agent (A) contains a dye (A1) and a pigment (A2). 7. The method according to any one of claims 1 to 6,
The colored curable resin composition in which a polymeric compound (C) is a radically polymerizable compound, and a polymerization initiator (D) is a photoradical polymerization initiator. 8. The method according to any one of claims 1 to 7,
The colorant (A) has the formula (A3-1):

[In formula (A3-1), R ^41a and R ^42a are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent , or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41a and R ^42a are bonded to each other and together with the nitrogen atom to which they are bonded, a 3 to 10 membered nitrogen-containing hetero form a ring,
R ^43a and R ^44a are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or 7 carbon atoms which may have a substituent ~ 30 represents an aralkyl group, or R ^43a and R ^44a combine to form a 3-10 membered nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded,
R ^47a to R ^54a each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , or optionally a substituent having 1 to 8 carbon atoms represents an alkyl group,
R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms,
Ring T ^1a represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or an aromatic heterocycle having 5 to 10 members which may have a substituent,
The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group,
The substituent which the aromatic hydrocarbon group having 6 to 14 carbon atoms may have is a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and a substituent which may have a substituent. At least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms,
The substituent which the aralkyl group having 7 to 30 carbon atoms may have is a halogen atom, a nitro group, a hydroxy group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and a substituent which may have a substituent. At least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms,
The substituent that the aromatic hydrocarbon ring having 6 to 14 carbon atoms may have is a halogen atom, a nitro group, a hydroxy group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and even if it has a substituent At least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms,
Substituents which the 5- to 10-membered aromatic heterocycle may have include a halogen atom, a nitro group, a hydroxy group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and even if it has a substituent At least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms,
The substituent which the said C1-C8 alkyl group may have is at least one selected from the group which consists of a halogen atom, a hydroxyl group, a formyl group, and an amino group,
When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- or -CO-,
When the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH ₂ - contained in the alkyl group may be substituted with -O- or -CO-,
r represents an integer of 1 or more,
M ^r+ represents a hydrogen ion, an r-valent metal ion, or N ⁺ (R ^55a ) ₄ , four R ^55a may be the same or different;
R ^55a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms,
k is the formula (A3-1a):

[In formula (A3-1a), rings T ^1a , R ^41a to R ^44a and R ^47a to R ^54a each have the same meanings as above.]
_{represents the sum of the number of -SO 3} ^- and -SO ₂ -N ^- -SO ₂ -R ^f that the anion represented by has, and is an integer of 2 or more,
When r is an integer of 2 or more, the plurality of anions represented by the formula (A3-1a) may be the same or different, and
When k-1 is an integer of 2 or more, a plurality of M ^r+ may be the same or different.]
a compound represented by
Formula (A3-2):

[In formula (A3-2), R ^41b and R ^42b are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent , or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41b and R ^42b are bonded to form a 3-10 membered nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded,
R ^43b and R ^44b are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or 7 carbon atoms which may have a substituent ~ 30 represents an aralkyl group, or R ^43b and R ^44b combine to form a 3-10 membered nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded,
R ^47b to R ^54b each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms which may have a substituent;
Ring T ^1b represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or an aromatic heterocycle having 5 to 10 members which may have a substituent,
The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group,
The substituent which the aromatic hydrocarbon group having 6 to 14 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent,
The substituent which the aralkyl group having 7 to 30 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent,
The substituent which the aromatic hydrocarbon ring having 6 to 14 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent,
The substituent which the 5- to 10-membered aromatic heterocyclic ring may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent,
The substituent which the said C1-C8 alkyl group may have is at least one selected from the group which consists of a halogen atom, a hydroxyl group, a formyl group, and an amino group,
When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- or -CO-,
When the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH ₂ - contained in the alkyl group may be substituted with -O- or -CO-,
m represents an integer of 1 or more,
[Y] ^m- represents an m-valent anion, and
When m is an integer greater than or equal to 2, the formula (A3-2c):

[In formula (A3-2c), rings T ^1b , R ^41b to R ^44b and R ^47b to R ^54b each have the same meaning as above.]
The plurality of cations represented by may be the same or different.]
A colored curable resin composition comprising at least one compound (A3) selected from the group consisting of compounds represented by 9. The method of claim 8,
Coloring curable resin composition in which a coloring agent (A) contains the dye (A1) different from a compound (A3).