TW201623263A - Compound - Google Patents

Abstract

The present invention addresses the problem of providing a compound having superior absorbance. The present invention pertains to a compound represented by formula (A-1). [R1a-R8a are a hydrogen atom, an alkyl group, an SO3 - group, or an SO3M group; R9a and R10a are a hydrogen atom, an alkyl group, an aromatic hydrocarbon group, or an aralkyl group; R11a-R20a are a hydrogen atom, an alkyl group, a halogen atom, an SO3 - group, or an SO3M group; R45a and R46a are a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group; and R55a is a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group].

Description

Compound

The present invention relates to a compound useful as a pigment.

A blue dye for a color filter included in a liquid crystal display device or the like, or a solid-state imaging device, and the like, C.I. Acid Blue 90 is disclosed in Patent Document 1. The acid blue 90 has the chemical structure shown below, and is classified as a preferable dye in the above Patent Document 1.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4236559

An object of the present invention is to provide a compound having a high absorbance and a color-curable resin composition containing such a compound.

The invention includes the following invention.

[1] a compound represented by the formula (AI),

[In the formula (AI), R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a and R ^8a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an SO ₃ ^- group. Or SO ₃ M group; R ^9a and R ^10a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted aromatic hydrocarbon group, or a substituted aralkyl group; R ^11a to R ^20a respectively The hydrogen atom, the alkyl group having 1 to 10 carbon atoms, the halogen atom, the SO ₃ ^- group or the SO ₃ M group are independently represented; and in the above R ^1a to R ^20a , the alkyl group constituting the alkyl group may be formed. An oxygen atom is interposed; R ^45a and R ^46a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted; and R ^55a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, Or a substituted aromatic hydrocarbon group; in the above R ^45a , R ^46a , and R ^55a , an oxygen atom may be intercalated between the methylene groups constituting the alkyl group; M represents a hydrogen ion, a metal ion or an ammonium ion. Wherein R ^1a to R ^20a , R ^45a , R ^46a and R ^55a satisfy at least one of (1), (2) and (3), and (4): (1) R ^1a to R ^8a and R ^11a ~ R ^20a is at least one of SO ₃ ^- group or an SO ₃ M group (2) at least one of R ^9a , R ^10a , R ^45a , R ^46a and R ^55a is an aromatic hydrocarbon group having a SO ₃ ^- group or an SO ₃ M group as a substituent; (3) at least R ^9a and R ^10a having a SO ₃ ^- SO ₃ M group or aralkyl group as the substituent on the ring; compound (4) of formula (AI) represented by the sum having SO ₃ ^- is the number of groups 1, SO ₃ M group The number is 0~6].

[2] A colored curable resin composition comprising the compound represented by the formula (A-I) of the above [1].

[3] A color filter which is formed by using the color-curable resin composition of the above [2].

[4] A display device comprising the color filter of [3] above.

The compounds of the invention have a high absorbance. When a color-curable resin composition containing such a compound is used, the amount of the colorant used can be suppressed.

The compound of the present invention is a compound represented by the formula (A-I) (hereinafter sometimes referred to as a compound (A-I)). The compounds of the invention also include the tautomers thereof or salts thereof.

[Chemical 3]

[In the formula (AI), R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a and R ^8a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an SO ₃ ^- group. Or SO ₃ M base.

R ^9a and R ^10a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted aromatic hydrocarbon group, or a substituted aralkyl group.

R ^11a to R ^20a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogen atom, a SO ₃ ^- group or a SO ₃ M group.

In the above R ^1a to R ^20a , an oxygen atom may be intercalated between the methylene groups constituting the alkyl group.

R ^45a and R ^46a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a substituted aromatic hydrocarbon group.

R ^55a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted.

In the above R ^45a , R ^46a , and R ^55a , an oxygen atom may be intercalated between the methylene groups constituting the alkyl group.

M represents a hydrogen ion, a metal ion or an ammonium ion.

Wherein R ^1a to R ^20a , R ^45a , R ^46a and R ^55a satisfy at least one of the requirements of (1), (2) and (3) and the requirements of (4).

(1) At least one of R ^1a to R ^8a and R ^11a to R ^20a is an SO ₃ ^- group or an SO ₃ M group.

(2) At least one of R ^9a , R ^10a , R ^45a , R ^46a and R ^55a is an aromatic hydrocarbon group having a SO ₃ ^- group or an SO ₃ M group as a substituent.

(3) At least one of R ^9a and R ^10a is an aralkyl group having a SO ₃ ^- group or a SO ₃ M group as a substituent on the ring.

(4) The compound represented by the formula (AI) has a number of SO ₃ ^- groups of 1, and the number of SO ₃ M groups is 0 to 6]

The valence of the compound of formula (A-I) is zero.

The alkyl group represented by R ^1a to R ^20a may be any of a straight chain, a branched chain, and a cyclic group. The linear or branched alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group or a fluorenyl group. The alkyl group preferably has a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and more preferably a carbon number of 1 to 6.

The cyclic alkyl group represented by R ^1a to R ^20a may be a single ring or a polycyclic ring. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The cyclic alkyl group is preferably a carbon number of 3 to 10, more preferably a carbon number of 6 to 10.

Specific examples of the alkyl group represented by R ^1a to R ^20a include a linear alkyl group such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group or a n-hexyl group; and an isopropyl group; Branched alkyl such as dibutyl, tert-butyl, isopentyl, 1-methylpentyl, 2-ethylbutyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantane Examples of the cyclic alkyl group and the like include a group represented by the following formula. In the following formula, * represents a bonding key.

In the group represented by R ^1a to R ^20a , examples of the group in which an oxygen atom is interposed between the methylene groups constituting the alkyl group include a group represented by the following formula. In the following formula, * represents a bonding key.

The group having an oxygen atom interposed between the methylene groups constituting the alkyl group is preferably a group having 1 to 10 carbon atoms, more preferably a group having 1 to 6 carbon atoms. The alkyl group to which the oxygen atom is inserted is preferably a linear alkyl group. Further, the carbon number between the oxygen atoms is preferably from 1 to 4, more preferably from 2 to 3.

In the case of R ^9a to R ^10a , examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group.

In R ^9a to R ^10a , examples of the aromatic hydrocarbon group in the aralkyl group include a phenyl group and a naphthyl group. The carbon number of the aralkyl group is preferably from 7 to 20.

In the group represented by R ^9a to R ^10a , examples of the substituent in the aromatic hydrocarbon group and the aralkyl group include a halogen atom such as a fluorine atom, a chlorine atom or iodine; and a carbon number such as a methoxy group or an ethoxy group. Alkoxy group of 1~6; hydroxyl group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; alkoxysulfonyl group; alkanesulfonyl group having 1 to 6 carbon atoms such as methylsulfonyl group; An oxycarbonyl group, an ethoxycarbonyl group; a -SO ₃ H group; a -SO ₃ ^- group; an alkoxycarbonyl group having a carbon number of 1 to 6 or the like.

Specific examples of the aromatic hydrocarbon group which may be substituted include a group represented by the following formula. In the following formula, * represents a bonding key.

Specific examples of the aralkyl group which may be substituted include a group in which a methylene group is bonded to a bond bond of each specific example of the following aromatic hydrocarbon group.

[Chemical 6]

In the group represented by R ^11a to R ^20a , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.

In terms of easiness of synthesis, R ^1a to R ^8a are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group.

In terms of easiness of synthesis, R ^9a to R ^10a are each independently preferably an alkyl group having 1 to 10 carbon atoms, a substituted aromatic hydrocarbon group or a substituted aralkyl group, respectively independently. Preferred is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, a phenyl group having a methyl group, a naphthyl group having a methyl group; unsubstituted or selected from a halogen atom, a methoxy group, an ethoxy group, and an amine group. One or more of a sulfonyl group, a methanesulfonyl group, a methoxycarbonyl group, and an ethoxycarbonyl group, particularly a substituted aralkyl group, each independently and more preferably a linear alkyl group having 1 to 4 carbon atoms base.

In terms of heat resistance, R ^11a to R ^{12a are} preferably at least any one of a halogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably at least one of which is a halogen atom or an alkyl group having 1 to 8 carbon atoms. Further preferably, at least one of them is a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

In terms of heat resistance, R ^13a to R ^{14a are} preferably at least any one of a halogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably at least one of which is a halogen atom or an alkyl group having 1 to 8 carbon atoms. Further preferably, at least one of them is a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

R ^15a to R ^20a are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in terms of easiness of synthesis. Further, it is preferably a hydrogen atom or a methyl group.

Examples of the alkyl group in R ^45a and R ^46a include an alkyl group having 1 to 10 carbon atoms in R ^1a to R ^20a .

In the examples of R ^45a and R ^46a , examples of the alkyl group having 1 to 10 carbon atoms include the groups represented by the following formulas. In the following formula, * represents a bonding key. Among them, an alkyl group having 1 to 8 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred.

[化8]

In R ^45a and R ^46a , a group in which an oxygen atom is interposed between methylene groups constituting the alkyl group is exemplified by the following formula. In the following formula, * represents a bonding key. The alkyl group to which the oxygen atom is inserted is preferably a linear alkyl group. Further, the carbon number between the oxygen atoms is preferably from 1 to 4, more preferably from 2 to 3.

The group having an oxygen atom interposed between the methylene groups constituting the alkyl group is preferably a group having 1 to 10 carbon atoms, more preferably a group having 1 to 6 carbon atoms. The alkyl group to which the oxygen atom is inserted is preferably a linear alkyl group. Further, the carbon number between the oxygen atoms is preferably from 1 to 4, more preferably from 2 to 3.

In R ^45a and R ^46a , examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group.

In the aromatic hydrocarbon group represented by R ^45a and R ^46a , examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom or iodine; a halogen alkyl group having 1 to 6 carbon atoms such as a chloromethyl group or a trifluoromethyl group; Alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; carbon number such as sulfonyl group; An alkanesulfonyl group of 1 to 6; an alkoxycarbonyl group having 1 to 6 carbon atoms such as a methoxycarbonyl group; a -SO ₃ H group; a -SO ₃ ^- group;

Specific examples of the aromatic hydrocarbon group which may be substituted include a group represented by the following formula. In the following formula, * represents a bonding key.

R ^45a and R ^46a are each independently preferably an alkyl group having 1 to 10 carbon atoms or a substituted aromatic hydrocarbon group, more preferably a halogen atom or a carbon number of 1 to 4, in terms of easiness of synthesis. a haloalkyl group, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group which may be substituted with a methanesulfonyl group, or an alkyl group having 1 to 8 carbon atoms, and further It is preferably an alkyl group having 1 to 8 carbon atoms or an aromatic hydrocarbon group represented by the following formula. In the following formula, * represents a bonding key.

Examples of the alkyl group in R ^55a include an alkyl group in R ^1a to R ^20a .

Specific examples of the alkyl group having 1 to 10 carbon atoms in R ^55a include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, and n-decyl group. a straight-chain alkyl group such as a fluorenyl group; a branched alkyl group such as an isopropyl group, a second butyl group, a third butyl group, an isopentyl group, a 1-methylpentyl group or a 1-propylbutyl group; Examples of the cyclic alkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group include a group represented by the following formula. In the following formula, * represents a bonding key. Among them, an alkyl group having 1 to 8 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred.

In the case of R ^55a , the group in which an oxygen atom is interposed between the methylene groups constituting the alkyl group is, for example, a group represented by the following formula. In the following formula, * represents a bonding key. The alkyl group to which the oxygen atom is inserted is preferably a linear alkyl group. Further, the carbon number between the oxygen atoms is preferably from 1 to 4, more preferably from 2 to 3.

In the case of R ^55a , examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group, and a phenyl group is preferred.

In R ^55a , examples of the substituent in the aromatic hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom or iodine; a halogen alkyl group having 1 to 6 carbon atoms such as a chloromethyl group or a trifluoromethyl group; and a methoxy group; And an alkoxy group having 1 to 6 carbon atoms such as an ethoxy group; a hydroxyl group; an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; an aminesulfonyl group; a methanesulfonyl group having a carbon number of 1 to 6; An alkoxycarbonyl group having a carbon number of 1 to 6 such as a methoxycarbonyl group; a -SO ₃ H group; a -SO ₃ ^- group; Specific examples of the aromatic hydrocarbon group which may be substituted include a group represented by the following formula. In the following formula, * represents a bonding key.

[Chemistry 14]

R ^{55a is} preferably an alkyl group having 1 to 10 carbon atoms or a substituted aromatic hydrocarbon group, more preferably an alkyl group having 1 to 8 carbon atoms or a halogen atom, and having a carbon number of 1 in terms of easiness of synthesis. a haloalkyl group of 4, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group which may be substituted with a methanesulfonyl group, and more preferably represented by the following formula Aromatic hydrocarbon group. In the following formula, * represents a bonding key.

[化15]

In M, examples of the metal ion include alkali metal ions such as lithium ions, sodium ions, and potassium ions.

In M, as the ammonium ion, a quaternary ammonium ion such as a tetraalkylammonium ion or the like is preferable. The quaternary ammonium ion is useful in the case of being contained in the colored curable resin composition.

In terms of absorbance, M is preferably a hydrogen ion or an alkali metal ion, more preferably a hydrogen ion.

The compound represented by the formula (AI) has a number of SO ₃ ^- groups of 1. Further, the SO ₃ M base number can be appropriately set within the range of 0 to 6, more preferably 1 to 3, and still more preferably 1. In the compound (AI), the SO ₃ ^- group and the SO ₃ M group may be used as a substituent represented by R ^1a to R ^8a and R ^11a to R ^20a , and may also be used as the following (1a) and (2a). It has a substituent.

(1a) a substituent in an aromatic hydrocarbon group represented by R ^9a , R ^10a , R ^45a , R ^46a and R ^55a

(2a) a substituent on the ring in the aralkyl group represented by R ^9a and R ^10a

SO ₃ ^- group and SO ₃ M group may also be bonded to the same aromatic ring, but in most cases bonded to the aromatic ring is different.

The compound (A-I) has a valence of 0, which is an electrically neutral compound.

The compound represented by the formula (A-I) includes the compounds 1 to 90 represented by the formula (A-I-1).

[In the formula (AI-1), R ^9a to R ^20a , R ^45a , R ^46a and R ^{55a are} shown in Tables 1 to 6. Wherein the compound of the formula (AI-1) has at least one of a SO ₃ ^- group and a SO ₃ H group as any substituent of R ^1a to R ^8a , R ^11a to R ^20a , (1a) and (2a) ]

[Table 1]

In Tables 1 to 6, Ph1 to Ph5 are as follows. In the following formula, * represents a bonding key.

Among them, the compound represented by the formula (A-I-1) is preferably the compound 31 to the compound 90, more preferably the compound 46 to the compound 60.

The compound (AI) can be produced by sulfonation of a compound of the formula (A-II) (hereinafter sometimes referred to as a compound (A-II)). Examples of the compound (A-II) include a hydrochloride, a phosphate, a perchlorate, a BF ₄ salt, and a PF ₆ salt.

^Wherein R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a and R ^8a each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and R ^9a and R ^10a respectively independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, the aromatic hydrocarbon group may be the substituted or may be substituted with the aralkyl; R ^11a ~ R ^20a each independently represent a hydrogen atom, a carbon number of 1 to 10 An alkyl group or a halogen atom; in the above R ^1a to R ^20a , an oxygen atom may be interposed between the methylene groups constituting the alkyl group; and R ^45a and R ^46a each independently represent a hydrogen atom and a carbon number of 1 to 1; An alkyl group of 10 or an aromatic hydrocarbon group which may be substituted; R ^55a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted; in the above R ^45a , R ^46a , and R ^55a , For the above alkyl group, an oxygen atom may be interposed between the methylene groups constituting the same; M ¹ represents Cl ^- , a phosphate ion, a perchlorate, a BF ₄ salt or a PF ₆ salt]

As a method of sulfonation, various well-known methods are mentioned, for example, the method of Journal of Organic Chemistry, (1994), vol. 59, #11, p. 3232-3236.

The compound (A-II) can be produced, for example, by reacting a compound represented by the formula (B-I) with a compound represented by the formula (C-I). The reaction can be carried out in the presence of an organic solvent or in the absence of a solvent.

[In the formula (BI) and the formula (CI), R ^1a to R ^20a , R ^45a , R ^46a and R ^55a respectively have the same meanings as described above]

Further, the compound (A-II) can also be produced by reacting a compound represented by the formula (B-II) with a compound represented by the formula (C-II) and the formula (C-III). The reaction can be carried out in the presence of an organic solvent or in the absence of a solvent.

[In the formula (B-II), the formula (C-II), and the formula (C-III), R ^1a to R ^20a , R ^45a , R ^46a and R ^55a respectively have the same meanings as described above]

Preferably, the compound represented by the formula (C-II) and the compound represented by the formula (C-III) are the same.

With respect to the compound represented by the formula (BI), the compound represented by the formula (CI) is preferably used in an amount of 0.5 mol or more and 8 mol or less per 1 mol of the compound represented by the formula (BI). The best is 1 mole or more and 3 moles or less.

The total amount of the compound represented by the formula (C-II) and the compound represented by the formula (C-III) relative to the compound represented by the formula (B-II) is relative to the 1 molar formula (B-II). The compound represented is preferably 0.5 mol or more and 8 mol or less, more preferably 1 mol or more and 3 mol or less.

The reaction temperature is preferably from 30 ° C to 180 ° C, more preferably from 80 ° C to 130 ° C. The reaction time is preferably from 1 hour to 12 hours, more preferably from 3 hours to 8 hours.

In terms of yield, any reaction is preferably carried out in an organic solvent. Examples of the organic solvent include a hydrocarbon solvent such as toluene or xylene; a halogenated hydrocarbon solvent such as chlorobenzene, dichlorobenzene or chloroform; an alcohol solvent such as methanol, ethanol, isopropanol or butanol; and a nitro group such as nitrobenzene. A hydrocarbon solvent; a ketone solvent such as methyl isobutyl ketone; a guanamine solvent such as 1-methyl-2-pyrrolidone; The amount of the organic solvent used is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more and 10 parts by mass per part by mass of the compound represented by the formula (BI) or the formula (B-II). the following.

In terms of yield, the above reaction is preferably carried out in the presence of a condensing agent. Examples of the condensing agent include phosphoric acid, polyphosphoric acid, phosphonium chloride, sulfuric acid, and sulfinium chloride.

The amount of the condensing agent used is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.2 parts by mass or more and 5 parts by mass per part by mass of the compound represented by the formula (BI) or the formula (B-II). the following.

The method for obtaining the compound (A-II) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, a method in which a reaction mixture is mixed with a solvent such as an alcohol (for example, methanol), and the precipitated crystals are collected by filtration. It is preferred to add the reaction mixture to a solvent such as the above alcohol. The temperature at the time of adding the reaction mixture is preferably -100 ° C or more and 50 ° C or less, more preferably -80 ° C or more and 0 ° C or less. Further, it is preferred to carry out the stirring at about the same temperature for about 0.5 to 2 hours. The crystals to be filtered are preferably washed with water or the like, followed by drying. Further, it may be further purified by a known method such as recrystallization as needed.

Examples of the method for producing the compound (B-I) and the compound (B-II) include various known methods, for example, the method described in the West German Patent Application No. P3928243.0.

As a method of producing the compound (C-II) and the compound (C-III), various known methods such as the method described in International Publication No. 2012/053211 can be mentioned.

When the compound (CI) is an alkyl group or an aralkyl group, R ^9a and R ^10a may be obtained by reacting a compound represented by the formula (C-IV) (hereinafter referred to as the compound (C-IV)) with an alkylating agent or The aralkylating agent is produced by reacting a compound represented by the formula (CV) (hereinafter referred to as a compound (CV)) with a compound represented by the formula (C-VI) ( Hereinafter, it is produced by reacting the compound (C-VI)). Further, the compound (CI) can be directly produced from the compound (CV) and the compound (C-VI) regardless of the types of R ^9a and R ^10a .

(wherein R ^1a to R ^20a are the same as above; R ^{1B is} the same as R ^9a and R ^10a , R ^{2B is the} same as R ^11a and R ^13a , R ^{3B is the} same as R ^12a and R ^14a , and R ^4B and R ^15a , R identical ^18a, R ^5B and R ^16a, R ^19a identical, R ^6B and R ^17a, R ^20a identical; R ^7B, R ^8B is a halogen atom).

As the alkylating agent, a known alkylating agent such as an alkyl halogen or a sulfate can be used, and in particular, in view of easiness of obtaining, an alkyl halogen is preferable, and in terms of easiness of synthesis, it is preferably a first stage. Alkyl iodide. As the aralkylating agent, a benzyl halide or the like can be used.

Specific examples of the alkylating agent include methyl iodide, ethyl iodide, iodobutane, ethyl bromide, n-butane bromide, dimethyl sulfate, and diethyl sulfate. Specific examples of the aralkylating agent include benzyl iodide, benzyl bromide and the like.

The alkylating agent or the aralkylating agent is preferably used in an amount of 2 mol or more, 6 mol or less, more preferably 2 mol or more, per 1 mol of the compound represented by the formula (C-IV). , 4 moles below.

The reaction temperature is preferably from 20 ° C to 180 ° C, more preferably from 30 ° C to 50 ° C. The reaction time is preferably from 10 minutes to 10 hours, more preferably from 30 minutes to 2 hours.

In terms of yield, any reaction is preferably carried out in an organic solvent. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; and nitro hydrocarbon solvents such as nitrobenzene. a ketone solvent such as methyl isobutyl ketone; a guanamine solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or 1-methyl-2-pyrrolidone. The amount of the organic solvent used is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more and 10 parts by mass or less based on 1 part by mass of the compound represented by the formula (C-IV).

In terms of yield, the above reaction is preferably carried out in the presence of a basic substance. Examples of the basic substance include sodium hydride, LDA (Lithium diisopropylamide), DIBAL (Diisobutyl Aluminium), and potassium t-butoxide.

The amount of the basic substance used is preferably 2 mol or more and 6 mol or less, more preferably 2 mol or more and 4 mol or less, per 1 mol of the compound represented by the formula (C-IV).

The method for obtaining the compound (C-I) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, a method in which a reaction mixture is mixed with a solvent such as an alcohol (for example, methanol), and the precipitated crystals are collected by filtration. The reaction mixture is preferably added to a solvent such as the above alcohol. The temperature at the time of adding the reaction mixture is preferably -100 ° C or more and 50 ° C or less, more preferably -80 ° C or more and 0 ° C or less. Further, it is preferred to carry out the stirring at about the same temperature for about 0.5 to 2 hours. The crystals to be filtered are preferably washed with water or the like and then dried. Further, it may be further purified by a known method such as recrystallization as needed.

The above compound (C-IV) can be produced by reacting the compound (C-V) with the compound (C-VI) as described above. Further, the above compound (C-I) can also be produced by reacting the compound (C-V) with the compound (C-VI) as described above.

In the formula (C-VI), examples of the halogen atom represented by R ^7B and R ^8B include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and from the viewpoint of easiness of obtaining a raw material, it is preferred. Fluorine atom, chlorine atom.

The amount of the compound (C-V) to be used is preferably 2 mol or more and 5 mol or less, more preferably 2 mol or more and 3 mol or less, relative to 1 mol of the compound (C-VI).

The reaction temperature is preferably from 20 ° C to 180 ° C, more preferably from 30 ° C to 50 ° C. The reaction time is preferably from 10 minutes to 10 hours, more preferably from 30 minutes to 2 hours.

In terms of yield, any reaction is preferably carried out in an organic solvent. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; and nitro hydrocarbon solvents such as nitrobenzene. Ketone solvent such as methyl isobutyl ketone; N,N-dimethylformamide, N,N-dimethyl A decylamine solvent such as acetamide or 1-methyl-2-pyrrolidone. The amount of the organic solvent used is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more and 10 parts by mass or less based on 1 part by mass of the compound represented by the formula (C-VI).

In terms of productivity, the above reaction is preferably carried out in the presence of a palladium compound, a phosphine compound and a basic substance.

Examples of the palladium compound include palladium (II) acetate, palladium (II) chloride, palladium (II) bromide, bis(2,4-pentanedioic acid)palladium (II), and bis(dibenzylideneacetone). Palladium (0), tris(dibenzylideneacetone) dipalladium (0), and the like.

The amount of the palladium compound used is preferably 0.0001 mol or more and 0.5 mol or less, more preferably 0.001 mol or more and 0.1 mol or less, per 1 mol of the compound (C-VI).

As the phosphine compound, dppf (Bis(diphenylphosphino)ferrocene, bis(diphenylphosphino)ferrocene), Xantphos (4,5-bis(diphenylphosphino)-9,9-dimethyloxa) can be cited. BIN), BINAP((±)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthalene,(±)-2,2'-bis-(diphenylphosphino)-1,1'-linked Naphthalene), Xphos (2-dicyclohexylphosphine-2', 4',6'-triisopropylbiphenyl), Sphos (2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl ), MePhos (2-dicyclohexylphosphine-2'-methylbiphenyl), and the like.

The amount of the phosphine compound used is preferably 0.001 mol or more and 0.5 mol or less, more preferably 0.003 mol or more and 0.1 mol or less per 1 mol of the compound (C-VI).

Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium butoxide, and potassium t-butoxide.

The amount of the basic compound used is preferably 1 mol or more and 5 mol or less, more preferably 1 mol or more and 3 mol or less, per 1 mol of the compound (C-VI).

The method for obtaining the compound (C-IV) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, a method in which a reaction mixture is mixed with a solvent such as an alcohol (for example, methanol), and the precipitated crystals are collected by filtration. The reaction mixture is preferably added to the above In a solvent such as an alcohol. The temperature at the time of adding the reaction mixture is preferably -100 ° C or more and 50 ° C or less, more preferably -80 ° C or more and 0 ° C or less. Further, it is preferred to carry out the stirring at about the same temperature for about 0.5 to 2 hours. The crystals to be filtered are preferably washed with water or the like, followed by drying. Further, it may be further purified by a known method such as recrystallization as needed.

The compound (A-I) of the present invention can be applied to a fibrous product, for example, by kneading into a fibrous material, impregnating, adhering, etc., to color the fibrous material. Further, the compound (A-I) of the present invention can be contained in the colored curable resin composition as a dye of a coloring agent (hereinafter sometimes referred to as "colorant (A)"). The colored curable resin composition preferably further contains a resin (B), and more preferably contains a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). Further, it is also preferred to further include a polymerization initiation aid (D1), a leveling agent (F), and the like.

In the present specification, the compounds exemplified as the respective components may be used singly or in combination of plural kinds unless otherwise specified.

<Colorant (A)>

The coloring agent (A) may be used alone as a dye having the compound (AI) of the present invention as an active ingredient, but may further contain other dyes (A1), pigments (P), or the like for color adjustment, that is, to adjust the spectral characteristics. a mixture of such.

Examples of the dye (A1) include dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes, for example, according to colorimetric index (The The Society of Dyers and Colourists publishes a compound classified as a dye or a dye known as a dyeing note (color dyeing company). Further, according to the chemical structure, an azo dye, a cyanine dye, a triphenylmethane dye, Dyes, phthalocyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, methine azo dyes, strontium succinate dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and Nitro dyes, etc. Among these, it is preferred to use an organic solvent-soluble dye.

Specific examples include CI Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, only the number is described), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; CI solvent red 24, 45, 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, 218, 222, 227, 230, 245, 247; CI solvent orange 2, 7, 11, 15, 26, 41, 54, 56, 99; CI solvent blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97 , 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. CI solvent dye, CI 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; CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216 , 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346 , 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75 , 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 9, 17, 19, 30, 102; CI Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59 , 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151 , 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335 CI acid green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109 and other CI acid dyes, CI direct yellow 2, 33, 34, 35, 38, 39 , 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232 233, 234, 241, 243, 246, 250; CI 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; CI acid red 73, 80, 91, 92, 97, 138, 151, 211, 274, 289; CI acid green 3, 5, 9, 25, 27, 28, 41 CI Acid Violet 34, 120; CI Acid Blue 25, 27, 40, 45, 78, 80, 112 and other CI acid dyes, CI 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; CI direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI direct blue 1, 2, 6, 8 , 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108 , 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170 , 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225 ,226,228,229,236,237,238,242,243,244,245,246,247,248,249,250,251,252,256,257,259, CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other CI direct dyes, CI disperse yellow 51, 54, 76 and other CI Disperse dye, CI basic red 1, 10; CI basic blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65 , 66, 67, 68; CI alkaline green 1 and other CI basic dyes, CI reactive yellow 2, 76, 116; CI reactive orange 16; CI reactive red 36 and other CI reactive dyes, CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43 , 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32 , 37, 40, 41, 44, 45, 47, 48, 53, 58; CI mordant blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61, 74, 77, 83, 84; CI mord green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34 CI mordant dyes such as 35, 41, 43, and 53, CI vat dyes such as CI reduction green 1, and the like.

Among them, a blue dye, a violet dye, and a red dye are preferred.

These dyes may be used alone or in combination of two or more.

Further, regarding the classification according to the chemical structure, it is preferably dye. As As the dye, a known one can be used. For example, a compound represented by the formula (1) is preferred.

[In the formula (1), R ¹ and R ² each independently represent a phenyl group which may have a substituent; and R ³ and R ⁴ each independently represent a monovalent saturated radical having a carbon number of 1 to 10, and the saturated hydrocarbon group The hydrogen atom may be substituted with a halogen atom, and -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ¹¹ -; R ¹ and R ³ may also be bonded to each other. a ring, which forms a ring containing a nitrogen atom together with the nitrogen atom to which the bond is bonded, and R ² and R ⁴ may be bonded to each other to form a ring containing a nitrogen atom together with the nitrogen atom to be bonded; ⁵ represents -OH, -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 ; ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer of 0 to 4; and when m is an integer of 2 or more, plural R ^{5 's} may be the same or different; ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom; Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ ; R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a C 1-20 monovalent saturated hydrocarbon group of 1, R ⁹ and R ¹⁰ may be bonded to each other with the nitrogen atom Together form a 3 to 10 membered nitrogen-containing heterocyclic ring; R ¹¹ each independently represent a hydrogen atom, a C 1-20 monovalent saturated hydrocarbon group or the carbon atoms of the aralkyl group having 7 to 10]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and a octyl group. a linear alkyl group having 1 to 20 carbon atoms such as a thiol group, a decyl group, a decyl group, a dodecyl group, a hexadecyl group or an eicosyl group; an isopropyl group, an isobutyl group, a second butyl group, and a third group a branched alkyl group having 3 to 20 carbon atoms such as butyl, isopentyl, neopentyl and 2-ethylhexyl; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and tricyclic An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a mercapto group.

Examples of the -CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a third butoxycarbonyl group, a hexyloxycarbonyl group, and an eicosyloxycarbonyl group.

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a third butoxysulfonyl group, a hexyloxysulfonyl group, and Alkoxysulfonyl and the like.

Examples of -SO ₂ NR ⁹ R ¹⁰ include an aminesulfonyl group; N-methylaminesulfonyl group, N-ethylaminesulfonyl group, N-propylaminesulfonyl group, and N-isopropyl group; Aminesulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-tert-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentyl Aminesulfonyl, N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl Aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)amine Sulfonyl, N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl) Aminesulfonyl, N-(3,3-dimethylbutyl)aminesulfonyl, N-heptylaminesulfonyl, N-(1-methylhexyl)aminesulfonyl, N-(1 ,4-dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethylhexyl)amine N-monosubstituted amine sulfonyl group such as sulfonyl, N-(1,1,2,2-tetramethylbutyl)amine sulfonyl; N,N-dimethylamine sulfonyl, N,N -ethylmethylamine sulfonyl, N,N-diethylamine sulfonyl, N,N -propylmethylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-t-butylmethylamine sulfonyl, N,N-butylethylamine sulfonyl, An N,N-disubstituted amine sulfonyl group such as N,N-bis(1-methylpropyl)amine sulfonyl group or N,N-heptylmethylamine sulfonyl group.

R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 member nitrogen-containing heterocyclic ring together with a nitrogen atom. Examples of the hetero ring include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms of R ³ and R ⁴ include those having 1 to 10 carbon atoms. The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms of R ³ and R ⁴ may be substituted with a halogen atom, and -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- , -CO- or -NR ¹¹ -.

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

Examples of the saturated hydrocarbon group substituted by a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, and a chlorobutyl group.

Examples of the alkyl group having 1 to 6 carbon atoms of R ⁶ and R ⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, and a second butyl group. , tert-butyl, isopentyl and neopentyl.

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

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

The above ⁺ N(R ¹¹ ) _{4 is} preferably at least two of the four R ¹¹ groups being a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ¹¹ is preferably from 20 to 80, more preferably from 20 to 60.

The phenyl group representing R ¹ and R ² may have a substituent. Examples of the substituent include a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , - SO ₂ R ⁸ , -SO ₃ R ⁸ and -SO ₂ NR ⁹ R ¹⁰ . Among these substituents, -R ^{8 is} preferred, and a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is more preferred. As this case, -SO ₃ ^- Z ^{+ is} preferably -SO ₃ ^- N ⁺ (R ¹¹ ) ₄ .

Examples of -OR ⁸ include 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, and two. Decaconyloxy and the like.

Examples of -SR ⁸ include a methylthio group, an ethylthio group, a butylthio group, a hexylthio group, a sulfoniumthio group, and an eicosylthio group.

Examples of the -SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butasulfonyl group, a hexylsulfonyl group, a sulfonyl group, and an eicosylsulfonyl group.

R ³ and R ^{4 are} preferably an unsubstituted monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, still more preferably a methyl group and an ethyl group.

R ¹ and R ³ may also be bonded to each other to form a ring containing a nitrogen atom together with the nitrogen atoms bonded thereto, and R ² and R ⁴ may be bonded to each other, together with the nitrogen atom to which the bond is bonded. And forming a ring containing nitrogen atoms. Examples of the ring containing the nitrogen atom include the following.

R ^{5 is} preferably -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ .

R ⁶ and R ^{7 are} preferably a hydrogen atom, a methyl group and an ethyl group, and more preferably a hydrogen atom.

m is preferably an integer of 0 to 2, more preferably 0 or 1.

The compound (1) is preferably a compound represented by the formula (2).

In the formula (2), R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 4 carbon atoms; p and q each independently represent an integer of 0 to 5; and p is 2 or more. In the case, the plurality of R ²³ may be the same or different. When q is 2 or more, the plurality of R ²⁴ may be the same or different.

Examples of the alkyl group having 1 to 4 carbon atoms of R ²¹ , R ²² , R ²³ and R ²⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group and a second butyl group. , third butyl, and the like.

Preferably, R ²¹ and R ²² are each independently a methyl group and an ethyl group. R ²³ and R ^{24 are} preferably a methyl group.

p and q are preferably an integer of 0 to 2, more preferably 0 or 1.

The compound (1) is preferably a compound represented by the formula (3).

[化28]

[In the formula (3), R ³¹ and R ³² each independently represent an alkyl group having 1 to 4 carbon atoms; and R ³³ and R ³⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]

The alkyl group having 1 to 4 carbon atoms which represents R ³¹ , R ³² , R ³³ and R ³⁴ may be the same as described above. Preferably, R ³¹ and R ³² are each independently a methyl group or an ethyl group. Preferably, R ³³ and R ³⁴ are each independently a hydrogen atom or a methyl group.

The compound (1) is, for example, a compound represented by each of the formulae (1-1) to (1-7). Among them, the compound represented by the formula (1-1) is preferred from the viewpoint of excellent solubility in an organic solvent.

The pigment (P) is not particularly limited, and a known pigment can be used, and for example, A pigment classified as a pigment according to a colorimetric index (published by The Society of Dyers and Colourists).

As the pigment, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, Yellow pigments such as 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, Orange pigments such as 55, 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, Red pigments such as 216, 224, 242, 254, 255, 264, 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; CI Pigment Violet 1, 19, 23, 29 , purple pigments such as 32, 36, 38; CI pigment green 7, 36, 58 and other green pigments; CI pigment brown 23, 25 and other brown pigments; CI pigment black 1, 7 and other black pigments.

The pigment (P) is preferably a phthalocyanine pigment and two The pigment is more preferably at least one selected from the group consisting of CI Pigment Blue 15:6 and Pigment Violet 23. By containing the above pigment, it is easy to optimize the transmission spectrum, and the color filter has good light resistance and chemical resistance.

The pigment may be subjected to a rosin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment on the surface of the pigment by a polymer compound or the like, or a method using a sulfuric acid micronization method. The micronization treatment, the cleaning treatment by an organic solvent or water for removing impurities, the removal treatment of ionic impurities by an ion exchange method, or the like. The pigment preferably has a uniform particle size.

The pigment can be dispersed by a pigment dispersant to form a pigment A pigment dispersion in a state of being uniformly dispersed in a solution. The pigments may be separately subjected to dispersion treatment, or a plurality of types may be mixed and dispersed.

Examples of the pigment dispersant include a surfactant, and any of a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. Specific examples thereof include a pigment dispersant such as a polyester-based compound, a polyamine-based compound, and an acrylic resin. These pigment dispersants may be used singly or in combination of two or more. As a pigment dispersing agent, the brand name KP (made by Shin-Etsu Chemical Co., Ltd.), FLOWLEN (made by Kyoei Chemical Co., Ltd.), Solsperse (registered trademark) (made by Zeneca Co., Ltd.), EFKA (registered trademark) (manufactured by BASF Corporation), Ajisper (registered trademark) (manufactured by Ajinomoto Fine Chemical Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and the like.

In the case of using a pigment dispersant, the amount thereof is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency to obtain a pigment dispersion liquid in a uniformly dispersed state.

The content of the compound (A-I) is preferably 1% by mass or more and 100% by mass or less, more preferably 10% by mass or more and 100% by mass or less based on the total amount of the coloring agent (A).

When the dye (A1) is contained, the content of the dye (A) is preferably 0.5% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 90% by mass or less based on the total amount of the coloring agent (A). When the pigment (P) is contained, the content of the coloring agent (A) is preferably 35 mass% or more and 99 mass% or less, more preferably 1 mass% or more and 70 mass% or less. Further, it is preferably 1% by mass or more and 50% by mass or less.

The content of the colorant (A) is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and further preferably 5% by mass based on the total amount of the solid content component. Above 50% by mass. When the content of the colorant (A) is within the above range, the desired degree of spectroscopicity can be obtained.

In the present specification, the "total amount of the solid content component" means the total amount of the components from which the solvent (E) is removed from the colored curable resin composition. The total amount of the solid content component and the content of each component with respect to the total amount can be measured, for example, by a known analytical method such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is preferably an alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter sometimes referred to as "resin (B)")) contains a structural unit derived from at least one monomer (Ba) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. Copolymer.

Examples of such a resin (B) include the following resins [K1] to [K6].

The resin [K1] is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (Ba) (hereinafter sometimes referred to as "(Ba)") and a ring having a carbon number of 2 to 4 a copolymer of an ether structure and an ethylenically unsaturated bond monomer (Bb) (hereinafter sometimes referred to as "(Bb)"); a resin [K2] (Ba), (Bb), and a copolymerizable with (Ba) a copolymer of a monomer (Bc) (which is different from (Ba) and (Bb)) (hereinafter sometimes referred to as "(Bc)"); a copolymer of a resin [K3] (Ba) and (Bc); Resin [K4] a resin obtained by reacting a copolymer of (Ba) and (Bc) with (Bb); resin [K5] is carried out by copolymerizing (Bb) and (Bc) with (Ba) Resin obtained by the reaction; resin [K6] A resin obtained by reacting a copolymer of (Bb) and (Bc) with (Ba) and further reacting with a carboxylic acid anhydride.

Specific examples of (Ba) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; and Acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydroortylene Unsaturated dicarboxylic acids such as dicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5- drop Alkene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-A Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2 - alkene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other carboxyl-containing bicyclic unsaturated compounds; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl Phthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl An anhydride of an unsaturated dicarboxylic acid such as tetrahydrophthalic anhydride or bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride; succinic acid mono [2-(methyl) propylene oxime Unsaturated mono[(methyl)acryloxyalkylene group of a polyvalent carboxylic acid having two or more kinds, such as a ethyl ethyl ester] or a mono [2-(methyl) propylene oxyethyl ester] phthalic acid An ester; an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl)acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable in terms of the aspect of the copolymerization reactivity or the solubility of the obtained resin in an aqueous alkaline solution.

(Bb), for example, means a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and ethylenic unsaturation A polymerizable compound of a bond.

(Bb) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

In the present specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

As (Bb), for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond can be cited. (Bb1) (hereinafter sometimes referred to as "(Bb1)"), a monomer (Bb2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(Bb2)")), having a tetrahydrofuranyl group A monomer (Bb3) having an ethylenically unsaturated bond (hereinafter sometimes referred to as "(Bb3)") or the like.

(Bb1), for example, a monomer (Bb1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(Bb1-1)")), A monomer (Bb1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(Bb1-2)").

Examples of (Bb1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidylvinyl Ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-甲Base-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-double (shrinkage) Glyceryloxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris (shrinkage) Glyceryloxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5 - Tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, and the like.

(Bb1-2), vinyl cyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Daicel Co., Ltd.), ( 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; A compound represented by the formula (BI), a compound represented by the formula (BII), and the like.

[化30]

[In the formula (BI) and the formula (BII), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group; X ^a and X ^b represent a single bond, * -R ^c -, * -R ^c -O-, * -R ^c -S- or * -R ^c -NH-; R ^c represents a carbon number of 1 to 6 alkane Base; * indicates the bond with O]

Examples of the alkyl group having 1 to 4 carbon atoms of R ^a and R ^b include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group.

Examples of the alkyl group in which the hydrogen atom of R ^a and R ^b is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, and 3- Hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc. .

R ^a and R ^{b are} preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group is preferable, and a hydrogen atom and a methyl group are more preferable.

Examples of the alkanediyl group of R ^c include a linear or branched alkanediyl group, and specific examples thereof include a methylene group, an ethylidene group, a propane-1,3-diyl group, and a butane-1. a linear alkanediyl group such as a 4-diyl group, a pentane-1,5-diyl group or a hexane-1,6-diyl group; or a branched alkanediyl group such as a propane-1,2-diyl group.

As X ^a and X ^b , a single bond, * -R ^c -, or * -R ^c -O-, more preferably a single bond, or * -R ^c -O-, particularly preferably a single bond, may be mentioned. , methylene, ethyl, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, more preferably a single bond, * -CH ₂ CH ₂ -O- (* represents and O Key button).

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

The compound represented by the formula (BII) may, for example, be a compound represented by any one of the formulae (BII-1) to (BII-15). Among them, preferred are formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) or formula (BII-11) to formula (BII). The compound represented by -15) is more preferably a compound represented by the formula (BII-1), the formula (BII-7), the formula (BII-9) or the formula (BII-15).

[化33]

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used singly or in combination with the compound represented by the formula (BII). In the case where the compounds are used in combination, the content ratio of the compound represented by the formula (BI) and the compound represented by the formula (BII) is preferably from 5:95 to 95:5, more preferably 10:90 on a molar basis. ~90:10, and further preferably 20:80~80:20.

As (Bb2), a monomer having an oxetanyl group and a (meth)acryloxy group is more preferable. Examples of (Bb2) include 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, and 3- Ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropene oxime Ethyloxyoxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3 -ethyl-3-propene oxime Oxyethyl oxetane and the like.

As (Bb3), a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group is more preferable. Specific examples of (Bb3) include tetrahydrofurfuryl acrylate (for example, Viscoat V #150, manufactured by Osaka Organic Chemical Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(Bb) is preferably (Bb1) in terms of further improving the reliability of heat resistance and chemical resistance of the obtained color filter. Further, it is more preferably (Bb1-2) from the viewpoint of excellent storage stability of the colored curable resin composition.

Examples of (Bc) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Tributyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid ring Amyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate In the technical field, the customary name is "dicyclopentyl (meth) acrylate"; also, sometimes referred to as "tricyclodecyl (meth) acrylate), trimethyl (meth) acrylate [5.2.1.0 ^2,6 ]decene-8-yl ester (in the technical field, the conventional name is "dicyclopentenyl (meth) acrylate)", dicyclopentyloxyethyl (meth) acrylate, ( Methyl) acrylate Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (methyl) (meth) acrylates such as benzyl acrylate; hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; maleic acid a dicarboxylic acid diester such as diethyl ester, diethyl fumarate or diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]heptane- 2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2- Alkene, 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-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxy Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2 -ene, 5-hydroxymethyl-5- Bicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2- Alkene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-double a bicyclic unsaturated compound such as (cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide, N-cyclohexylmethyleneimine, N -Benzyl succinimide, N-succinimide-3-butyleneimine benzoate, N-succinimide-4-butyleneimine Butyrate, N-succinimide-6-m-butylimide hexanoate, N-succinimide-3-oxenimide propionate, N-(9 -Acridine-based dicarbonyl ruthenium derivatives such as maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and para Vinyl-containing aromatic compounds such as oxystyrene; vinyl-containing nitriles such as acrylonitrile and methacrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; and ethylene-containing acrylamide and methacrylamide Base ; Vinyl acetate ester; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-hexadiene and the like.

Among these, (Bc) is preferably a vinyl group-containing aromatic compound, a dicarbonyl quinone imine derivative or a bicyclic unsaturated compound in terms of copolymerization reactivity and heat resistance. Specifically, it is preferably styrene, vinyl toluene, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, double ring [2.2.1] Hept-2-ene and the like.

In the resin [K1], the ratio of the structural unit derived from each monomer is preferably from 2 to 60 mol% of the structural unit derived from (Ba) among all the structural units constituting the resin [K1]. The structural unit derived from (Bb) is 40 to 98% by mole, more preferably 10 to 50% by mole of the structural unit derived from (Ba), and 50 to 90% by mole of the structural unit derived from (Bb) .

When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the developability in forming a colored pattern, and the tendency of the color filter obtained by the color filter are excellent. .

Resin [K1] can be found, for example, in the literature "Experimental Method for Polymer Synthesis" (Dazu Takashi, Publisher, Chemical Co., Ltd., 1st Edition, 1st Printing, March 1, 1972) Methods and fabrications are disclosed in the literature.

Specifically, a specific amount of (Ba) and (Bb), a polymerization initiator, a solvent, and the like are placed in a reaction container, and for example, by replacing oxygen with nitrogen to form a deoxidizing atmosphere, heating is performed while stirring. And the method of insulation. In addition, the polymerization initiator, the solvent, and the like used herein are not particularly limited, and a general user in the field can be used. Examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxidation. The solvent (such as benzamidine peroxide) may be a solvent (E) which is a solvent (E) of the color-curable resin composition of the present invention, and a solvent or the like described below, as long as it dissolves each monomer.

Further, the obtained copolymer may be directly used as a solution after the reaction, or a solution which is concentrated or diluted, or may be used as a solid (powder) by reprecipitation or the like. In particular, in the polymerization, the solvent contained in the colored curable resin composition of the present invention can be used as a solvent, and the solution after the reaction can be directly used for the preparation of the colored curable resin composition of the present invention. The manufacturing steps of the colored curable resin composition of the present invention are simplified.

In the resin [K2], the ratio of the structural unit derived from each monomer is preferably from 2 to 45 mol% of the structural unit derived from (Ba) among all the structural units constituting the resin [K2]. The structural unit derived from (Bb) is 2 to 95 mol%, the structural unit derived from (Bc) is 1 to 65 mol%, and more preferably the structural unit derived from (Ba) is 5 to 40 mol%. The structural unit derived from (Bb) is 5 to 80 mol%, and the structural unit derived from (Bc) is 5 to 60 mol%.

When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability in forming a colored pattern, and the solvent resistance and heat resistance of the obtained color filter are obtained. And the tendency to have excellent mechanical strength.

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

In the resin [K3], the ratio of the structural unit derived from each monomer is preferably from 2 to 60 mol% of the structural unit derived from (Ba) in all the structural units constituting the resin [K3]. The structural unit derived from (Bc) is 40 to 98 mol%, more preferably 10 to 50 mol% of the structural unit derived from (Ba), and 50 to 90 mol% of the structural unit derived from (Bc).

The resin [K3] can be produced, for example, in the same manner as the method described in the production method of the resin [K1].

The resin [K4] can be produced by obtaining a copolymer of (Ba) and (Bc), and adding a cyclic ether having 2 to 4 carbon atoms of (Bb) to a carboxylic acid having (Ba) And / or carboxylic anhydride.

First, a copolymer of (Ba) and (Bc) is produced in the same manner as the method described in the method for producing the resin [K1]. In this case, the ratio of the structural units derived from the respective monomers is preferably The same ratio as those listed in the resin [K3].

Next, a cyclic ether having 2 to 4 carbon atoms which is contained in (Bb) is reacted with a part of the carboxylic acid and/or carboxylic anhydride derived from (Ba) in the above copolymer.

After the manufacture of the copolymer of (Ba) and (Bc), the reaction environment of the flask (Bb), carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris(dimethyl) is replaced by nitrogen in the atmosphere of the flask. Amine [K4] can be produced by putting a polymerization inhibitor (for example, hydroquinone or the like) into a flask, for example, at 60 to 130 ° C for 1 to 10 hours.

The amount of (Bb) used is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, relative to (Ba) 100 moles. By adjusting the amount of use of (Bb) to the above range, the storage stability of the colored curable resin composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern are obtained. The balance has become a good trend. Since the reactivity of the cyclic ether is high and it is difficult to remain unreacted (Bb), (Bb) used as the resin [K4] is preferably (Bb1), and further preferably (Bb1-1).

The amount of the above reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (Ba), (Bb) and (Bc). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (Ba), (Bb) and (Bc).

The reaction conditions such as the method of charging each reagent, the reaction temperature, and the reaction time can be appropriately adjusted in consideration of the heat generation amount of the production equipment or the polymerization. Further, the charging method or the heat generation amount of the polymerization can be considered in the same manner as the polymerization conditions, and the charging method or the reaction temperature can be appropriately adjusted.

When the resin [K5] was produced, the copolymer of (Bb) and (Bc) was obtained in the same manner as in the above-described production method of the resin [K1]. Similarly to the above, the obtained copolymer may be directly used as a solution after the reaction, or a solution which is concentrated or diluted, or may be used as a solid (powder) by reprecipitation or the like.

The respective ratios of the structural units derived from (Bb) and (Bc) with respect to the total number of moles of all the structural units constituting the copolymer of the above (Bb) and (Bc)

Preferably, the structural unit derived from (Bb) is 5 to 95 mol %, The structural unit derived from (Bc) is 5 to 95 mol%, more preferably 10 to 90 mol% from the structural unit derived from (Bb), and 10 to 90 mol% from the structural unit derived from (Bc) .

Further, in the second step, the carboxylic acid or carboxylic anhydride having (Ba) and the copolymer of (Bb) and (Bc) are derived from the same conditions as in the method for producing the resin [K4]. The cyclic ether of (Bb) is reacted, whereby the resin [K5] can be obtained.

In the second stage, the amount of (Ba) to be reacted with the copolymer of (Bb) and (Bc) described above is preferably from 5 to 80 moles per 100 moles (Bb). Since the reactivity of the cyclic ether is high and it is difficult to remain unreacted (Bb), (Bb) used for the resin [K5] is preferably (Bb1), and further preferably (Bb1-1).

The resin [K6] is a resin obtained by further reacting a carboxylic anhydride with a resin [K5]. The carboxylic acid anhydride is reacted with a hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.

The resin [K6] is a resin obtained by further reacting a carboxylic anhydride with a resin [K5], and specifically, can be produced by, for example, carboxylic anhydride and a cyclic ether derived from (Bb) The hydroxyl group produced by the reaction of the carboxylic acid or carboxylic anhydride of Ba) is reacted.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetra. Hydrogen phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, bicyclo[2.2.1]hept-2-ene-5,6- Dicarboxylic anhydride and the like. The amount of the carboxylic anhydride to be used is preferably from 0.5 to 1 mol per mol of the (Ba).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and (meth)acrylic acid 3,4-epoxytricyclo[ 5.2.1.0 ^2,6 ]Phenyl ester / (meth)acrylic copolymer and other resins [K1]; glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, (A Glycidyl acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.4.1.0 ^2,6 ]decyl methacrylate/(meth)acrylic acid/N- Cyclohexylm-butyleneimine copolymer, 3,4-epoxytricyclo[5.4.1.0 ^2,6 ]decyl methacrylate / (meth) acrylate / vinyl toluene copolymer, 3- Resin such as methyl-3-(methyl)propenyloxymethyloxetane/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid Resin, copolymer of styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/(meth)acrylic acid copolymer [K3]; Addition of a resin of glycidyl (meth)acrylate to a benzyl acrylate/(meth)acrylic acid copolymer, in (methyl) Addition of a resin of glycidyl (meth)acrylate to tricyclodecyl enoate/styrene/(meth)acrylic acid copolymer, tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer to which a resin such as a resin of glycidyl (meth)acrylate is added [K4]; (meth)acrylic acid and tricyclodecyl (meth)acrylate / (meth)acrylic acid a resin obtained by reacting a copolymer of glycidyl ester, a resin obtained by reacting a copolymer of (meth)acrylic acid with tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate Resin [K5]; reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate to further obtain the obtained resin and tetrahydrophthalic acid A resin such as a resin obtained by reacting an acid anhydride [K6] or the like.

The resin (B) is preferably one selected from the group consisting of a resin [K1], a resin [K2], and a resin [K3], and more preferably selected from the group consisting of a resin [K2] and a resin [K3]. One of them. When it is such a resin, the colored curable resin composition is excellent in developability. From the viewpoint of the adhesion between the colored pattern and the substrate, the resin [K2] is further preferable.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 5,000 to 30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is also high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.

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

The acid value of the resin (B) is preferably from 50 to 170 mg-KOH/g, more preferably from 60 to 150 mg- KOH/g is further preferably 70 to 135 mg-KOH/g. Here, the acid value is a value measured by neutralizing the amount (mg) of potassium hydroxide required for 1 g of the resin (B), and can be obtained, for example, by titration with an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55% by mass, based on the total amount of the solid content component. When the content of the resin (B) is in the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film ratio tend to be improved.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include a polymerizable compound having an ethylenically unsaturated bond, and the like. It is a (meth) acrylate compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include mercaptophenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylate. And 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like, and the above (Ba), (Bb) and (Bc).

Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di( Methyl) acrylate, triethylene glycol di(meth) acrylate, bisphenol A bis(acryloxyethyl) ether, 3-methyl pentanediol di(meth) acrylate, and the like.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylic acid. Ester, dipentaerythritol hexa(meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol nin (meth) acrylate Ester, tris(2-(methyl)propenyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra(methyl) propyl Ethyl ester, ethylene glycol modified dipentaerythritol hexa(meth) acrylate, propylene glycol modified pentaerythritol tetra(meth) acrylate, propylene glycol modified dipentaerythritol hexa(meth) acrylate, caprolactone modified pentaerythritol Tetrakis (meth) acrylate, caprolactone-modified dipentaerythritol hexa(meth) acrylate, etc., among which dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55% by mass, based on the total amount of the solid content component. When the content of the polymerizable compound (C) is in the above range, the residual film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

Further, the content 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: by mass: 65~80:20.

When the content of the polymerizable compound (C) is in the above range, the residual film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating a living radical, an acid or the like by the action of light or heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include an O-indenyl hydrazine compound, a phenylalkyl ketone compound, a biimidazole compound, and three. a compound, a fluorenylphosphine oxide compound, and the like.

The above O-indenyl ruthenium compound is a compound having a partial structure represented by the formula (Dd1). Hereinafter, * indicates a keying key.

[化35]

Examples of the above O-indenyl ruthenium compound include N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imide and N-benzylformamide. 1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentyl Propane-1-keto-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzomethyl)-9H-indazol-3-yl]ethane -1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolyl) Methoxy)benzylidene}-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzene Mercapto)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylidene-1-(9-ethyl-6-(2-methyl) Benzhydryl)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (made by ADEKA Co., Ltd.) can also be used. Wherein, the O-indenyl hydrazine compound is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyl hydrazine 1-(4-phenylthiophenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentyl At least one of the group consisting of propan-1-one-2-imine, more preferably N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2- Imine.

The phenylalkyl ketone compound is, for example, a compound having a partial structure represented by the formula (Dd2) or a partial structure represented by the formula (Dd3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (Dd2) include 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propane-1-one and 2-dimethyl group. Amino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl ]-1- [4-(4-morpholino)phenyl]butan-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used.

Examples of the compound having a partial structure represented by the formula (Dd3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4] -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 a ketone oligomer, α,α-diethoxyacetophenone, benzoin dimethyl ketal or the like.

The phenylalkyl ketone compound is preferably a compound having a partial structure represented by the formula (Dd2) in terms of sensitivity.

The biimidazole compound may, for example, be a compound represented by the formula (Dd4).

[In the formula (Dd4), R ^d1 to R ^d6 represent an aryl group having 6 to 10 carbon atoms which may have a substituent]

Examples of the aryl group having 6 to 10 carbon atoms of R ^d1 to R ^d6 include a phenyl group, a tolylmethyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferable.

Examples of the substituent which may be substituted on the aryl group of the above R ^d1 to R ^d6 include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferred.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, Japanese Patent Laid-Open No. Hei 6-75372, Japanese Patent Laid-Open No. Hei 6-75373, etc.) 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5 , 5'-tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, see Japanese Patent Publication No. Sho 48-38403, Japan) Japanese Patent Publication No. Sho 62-174204, etc., an imidazole compound in which a phenyl group at the 4,4', 5, 5'-position is substituted with an alkoxycarbonyl group (for example, see Japanese Patent Laid-Open Publication No. Hei 7-10913, etc.). Among them, preferred are compounds represented by the following formulas and mixtures thereof.

As the above three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-sunflower-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

The above fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone and methyl phthalate; 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl Ketone, 2,4,6-trimethyl a benzophenone compound such as benzophenone; an anthraquinone compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone; 10-butyl-2-chloroacridone, benzoin, phenylacetaldehyde Methyl ester, titanocene compound, and the like.

These are preferably used in combination with the polymerization starting assistant (D1) (especially an amine) described below.

Examples of the polymerization initiator which generates an acid include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethenyloxybenzene. Dimethyl hydrazine p-toluene sulfonate, 4-ethoxy phenyl phenyl benzyl hexafluoroantimonate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate, An anthracene salt such as diphenylphosphonium p-toluenesulfonate or diphenylphosphonium hexafluoroantimonate, or a nitrobenzyl tosylate or a benzoin tosylate.

As the polymerization initiator (D), a polymerization initiator which produces a living radical is preferred, and specifically comprises a compound selected from the group consisting of a phenylalkyl ketone compound, The polymerization initiator of at least one of the group consisting of the compound, the fluorenylphosphine oxide compound, the O-mercapto fluorene compound, and the biimidazole compound is more preferably a polymerization initiator containing an O-fluorenyl hydrazine compound.

The content of the polymerization initiator (D) is preferably from 0.1 to 40 parts by mass, more preferably from 1 to 30 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C).

<Polymerization starter (D1)>

The polymerization initiation aid (D1) is a compound or a sensitizer for promoting polymerization of a polymerization-polymerizable compound by polymerization initiator. In the case where the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiation assistant (D1) include an amine compound, an alkoxy fluorene compound, and 9-oxosulfuric acid. Compounds, carboxylic acid compounds, and the like.

Examples of the amine compound include an alkanolamine such as triethanolamine, methyldiethanolamine or triisopropanolamine; methyl 4-dimethylaminobenzoate and ethyl 4-dimethylaminobenzoate; 4-Ethylaminobenzoic acid isoamyl ester, 2-dimethylaminoethyl benzoate, 4-dimethyl Aminobenzoic acid esters such as 2-ethylhexyl benzoate; N,N-dimethyl-p-toluidine; 4,4'-bis(dimethylamino)benzophenone (commonly known as rice Alkyl benzophenones such as ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone And preferably, an alkylaminobenzophenone is preferred, and 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

The above alkoxy fluorene compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

As the above 9-oxygen sulfur Compounds can be exemplified by 2-isopropyl-9-oxosulfur 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxybenzenesulfide. Acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine , naphthoxyacetic acid, and the like.

When the polymerization initiator (D1) is used, the content is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). 1 to 20 parts by mass. When the amount of the polymerization starting aid (D1) is in this range, a colored pattern can be formed with higher sensitivity, and the productivity of the colored filter tends to be improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent which is usually used in the field can be used. Examples thereof include an ester solvent (a solvent containing -COO- or a solvent containing no -O-), an ether solvent (a solvent containing -O- in the molecule, and a solvent containing no -COO-), and an ether ester solvent (including -COO in the molecule). - a solvent with -O-), a ketone solvent (a solvent containing -CO-, a solvent containing no -COO-), an alcohol solvent (containing OH in the molecule, and containing no -O-, -CO-, and -COO-) Solvent), aromatic hydrocarbon solvent, guanamine Agent, dimethyl alum, and the like.

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and two. Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl b Ethyl ether, methyl anisole, and the like.

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

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.

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

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

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

These solvents may be used singly or in combination of two or more.

Among them, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol A are preferred. Ether acetate, 3-methoxy-1-butanol, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, N-methylpyrrolidone, 4-hydroxyl -4-methyl-2-pentanone, N,N-dimethylformamide, etc., more preferably ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether Acetate, 3-methoxy-1-butanol, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, N-methylpyrrolidone.

The content of the solvent (E) is preferably from 70 to 95% by mass, more preferably from 75 to 92% by mass, based on the total amount of the colored curable resin composition. In other words, the total amount of the solid content of the colored curable resin composition is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating becomes good, and when the color filter is formed, the absorbance is insufficient, so that the display characteristics tend to be good.

<Leveling agent (F)>

Examples of the leveling agent (F) include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. These may also have a polymerizable group on the side chain.

Examples of the polyoxymethylene-based surfactant include a surfactant having a decane bond in the molecule. Specifically, 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 Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401 , TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC Corporation), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Precision Chemical Research Co., Ltd.).

Examples of the polyfluorene-based surfactant having a fluorine atom include a surfactant having a decane bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Corporation).

When the leveling agent (F) is contained, the content thereof is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass based on the total amount of the colored curable resin composition. Hereinafter, it is more preferably 0.005 mass% or more and 0.07 mass% or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be made good.

<Other ingredients>

The colored curable resin composition may optionally contain additives such as a filler, other polymer compound, adhesion promoter, antioxidant, light stabilizer, chain transfer agent, and the like as known in the art.

<Method for Producing Colored Curable Resin Composition>

The coloring curable resin composition can be, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), if necessary, a leveling agent. (F), a polymerization starting aid (D1) and other components are prepared by mixing.

When the pigment (P) is contained, the pigment is preferably partially or completely mixed with one of the solvents (E), and dispersed by using a bead mill or the like so that the average particle diameter of the pigment is about 0.2 μm or less. At this time, part or all of the above pigment dispersant and resin (B) may be blended as needed. In the pigment dispersion liquid thus obtained, the target coloring curable resin composition can be prepared by mixing the remaining components so as to have a specific concentration.

Further, it is preferred to prepare a solution by dissolving the compound (A-I) in part or all of the solvent (E) in advance. Further preferably, the solution is filtered using a filter having a pore diameter of about 0.01 to 1 μm.

Preferably, the mixed color-curable resin composition is filtered using a filter having a pore diameter of about 0.01 to 10 μm.

<Method of Manufacturing Color Filter>

The method of producing a colored pattern by the colored curable resin composition of the present invention includes a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred. In the photolithography method, the colored curable resin composition is applied onto a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask to develop the film. In the photolithography method, a colored coating film which is a cured product of the coloring composition layer can be formed by using no mask and/or no development at the time of exposure. The colored pattern or colored coating film thus formed is the color filter of the present invention.

The film thickness of the produced color filter is not particularly limited and may be depending on the purpose or use. It is suitably adjusted, for example, to 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or soda lime glass coated with cerium oxide, or polycarbonate, polymethyl methacrylate or polyparaphenylene is used. A plate of a resin such as ethylene formate or a substrate obtained by forming an aluminum, silver, silver/copper/palladium alloy film or the like on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may also be formed on the substrates.

The formation of pixels of various colors by the photolithography method can be carried out using known or conventional devices or conditions. For example, it can be produced by the following method.

First, the colored curable resin composition is applied onto a substrate, and dried by heating (pre-baked) and/or dried under reduced pressure to dry and remove volatile components such as a solvent to obtain a smooth colored composition layer.

Examples of the coating method include a spin coating method, a slit coating method, a slit and a spin coating method, and the like.

The temperature at the time of heat drying is preferably from 30 to 120 ° C, more preferably from 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

In the case of drying under reduced pressure, it is preferably carried out at a temperature of from 50 to 150 Pa at a temperature ranging from 20 to 25 °C.

The film thickness of the colored composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.

Next, the colored composition layer is exposed through a photomask used to form the target colored pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use can be used.

As the light source used for the exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, using a filter that cuts off the wavelength region to cut off light that is less than 350 nm, or using a band pass filter that extracts the wavelength regions to selectively extract near 436 nm, Light near 408 nm and around 365 nm. Specifically, examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

In order to uniformly illuminate the entire surface of the exposure surface, or to precisely align the reticle with the substrate on which the colored composition layer is formed, it is preferable to use an exposure apparatus such as a reticle alignment machine and a stepper.

The coloring pattern is formed on the substrate by developing the exposed coloring composition layer in contact with the developing solution. By development, the unexposed portion of the colored composition layer is dissolved in the developer to be removed. As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration of the basic compound in the aqueous solution is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass. Further, the developer may also contain a surfactant.

The development method may be any of a liquid coating method, a dipping method, and a spray method. Further, the substrate can be tilted at an arbitrary angle during development.

It is preferred to carry out water washing after development.

Further, it is preferred to post-bake the obtained color pattern. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 160 to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

Since the compound of the present invention has a high absorbance, it is possible to produce a high-intensity color filter by using the color-curable resin composition using the same. The color filter can be used as a color filter for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

The present application claims the benefit of priority to Japanese Patent Application No. 2014-223768, filed on Jan. 31, 2014. The entire contents of the specification of Japanese Patent Application No. 2014-223768, filed on Jan. 31,,,,,,,,,

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. In the examples, the % and the parts indicating the content or the amount used are based on mass unless otherwise specified.

Hereinafter, the structure of the compound was confirmed by mass analysis (LC: Model 1200 manufactured by Agilent, MASS: LC/MSD model manufactured by Agilent), and UV-VIS (V-650 manufactured by JASCO Corporation).

[Example 1]

The following reaction was carried out under a nitrogen atmosphere. After adding 32.2 parts of potassium thiocyanate and 160.0 parts of acetone to a flask equipped with a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. Then, 50.0 parts of 2-fluorobenzhydryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Then, after cooling the reaction mixture in an ice bath, 40.5 parts of N-ethyl o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Then, after cooling the reaction mixture in an ice bath, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Then, 31.3 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, stirring was carried out for 7 hours under heating under reflux. Then, after the reaction mixture was allowed to stand to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene was added thereto, followed by stirring for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes, and as a result, it was separated into an organic layer and an aqueous layer. After the water layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1 equivalent of hydrochloric acid, and then washed with 200 parts of tap water, and finally washed with 200 parts of saturated brine. After adding an appropriate amount of Glauber's salt to the organic layer and stirring for 30 minutes, it was filtered to obtain a dried organic layer. The obtained organic layer was distilled off in an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C to obtain 49.9 parts of the compound of formula (B-I-2). The yield was 51%.

The following reaction was carried out under a nitrogen atmosphere. After adding 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide to a flask equipped with a cooling tube and a stirring device, the mixed solution was cooled in an ice bath. Under ice cooling, 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in small portions over 30 minutes, and the mixture was stirred for 1 hour while being warmed to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added to the reaction liquid in small portions, and stirred at room temperature for 24 hours. The reaction liquid was added in small portions to 200 parts of ice water, and then allowed to stand at room temperature for 15 hours, and water was removed by decantation to obtain a viscous solid in the form of a residue. After 60 parts of methanol was added to the viscous solid, stirring was carried out for 15 hours at room temperature. The precipitated solid was separated by filtration and purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60 ° C to obtain 9.8 parts of the compound of formula (C-I-2). The yield was 53%.

The following reaction was carried out under a nitrogen atmosphere. 8.2 parts of the compound represented by the formula (BI-2), 10.0 parts of the compound represented by the formula (CI-2), and 20.0 parts of toluene were placed in a flask equipped with a cooling tube and a stirring device, and then 12.2 parts of phosphonium chloride was added. It was stirred at 95 to 100 ° C for 3 hours. Then, after cooling the reaction mixture to room temperature, it was diluted with 170.0 parts of isopropyl alcohol. Then, the diluted reaction solution is injected into 300.0 parts of saturated brine. Then, 100 parts of toluene was added and stirred for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes, and as a result, it was separated into an organic layer and an aqueous layer. After the water layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. After adding an appropriate amount of Glauber's salt to the organic layer and stirring for 30 minutes, it was filtered to obtain an organic layer. The obtained organic layer was distilled off in an evaporator to remove a solvent, whereby a blue-purpur solid was obtained. Further, the blue-violet solid was dried under reduced pressure at 60 ° C to obtain 18.4 parts of the compound represented by the formula (A-II-2). The yield was 100%.

Identification of compounds represented by formula (A-II-2)

(mass analysis) ionization mode = ESI+: m/z = 687.3 [M-Cl] ⁺

Exact quality: 722.3

The following reaction was carried out under a nitrogen atmosphere. After 2.0 parts of the compound represented by the formula (A-II-2) and 7.3 parts of dichloromethane were placed in a flask equipped with a cooling tube and a stirring device, the reaction solution was cooled in an ice bath. Then, 1.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred overnight while warming to room temperature. Then, while the reaction solution was cooled in an ice bath, it was diluted with 34.0 parts of N,N-dimethylformamide. Then, the diluted reaction solution was poured into 140.0 parts of toluene, followed by stirring for 30 minutes. Then, the stirring was stopped, and decantation was carried out to obtain a blue-violet viscous solid. Further, the blue-violet viscous solid was dried under reduced pressure at 60 ° C to obtain 2.3 parts of the compound represented by the formula (A-I-2). The yield was 100%.

In the formula (AI-2), "-SO ₃ ^- " and "-SO ₃ H" each represent a carbon atom bonded to at least one of the six phenyl rings.

Identification of compounds represented by formula (A-I-2)

(mass analysis) ionization mode = ESI +: m / z = 847.3 [M + H] ⁺

ESI-:m/z=845.5[MH] ^-

Exact quality: 846.2

0.35g compound of formula (AI-2) represented dissolved in ethyl lactate to become the volume of 250cm ^3, in which the use of ethyl lactate 2cm ³ was diluted to become the volume of 100cm ³ (at a concentration of 0.028g / L The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length of 1 cm). The compound showed an absorbance of 2.5 (arbitrary units) at λ max = 627 nm.

[Comparative Example 1]

The CI Acid Blue 90 (trade name of Daiwa BLUE 300, Daiwa Kasei) was dissolved in 0.35 g of ethyl lactate became the volume of 250cm ^3, in which the use of ethyl lactate 2cm ³ was diluted to become the volume of 100cm ³ (concentration: 0.028 g/L), and an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). The compound showed an absorbance of 2.2 (arbitrary units) at λ max = 615 nm.

The absorbance of the compound (A-I-2) of Example 1 and the absorption of C.I. Acid Blue 90 of Comparative Example 1. The luminosity is 0.3 (concentration is 0.028 g/L).

[Embodiment 2]

The following reaction was carried out under a nitrogen atmosphere. After introducing 24.2 parts of N-ethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 240 parts of N,N-dimethylformamide into a flask equipped with a cooling tube and a stirring device, the mixed solution was cooled in an ice bath. After 8.0 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in small portions over 30 minutes under ice cooling, the mixture was stirred for 1 hour while warming to room temperature. 14.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added to the reaction liquid in small portions, and stirred at room temperature for 72 hours. Water was added to the reaction mixture, and the mixture was extracted with dichloromethane, and washed three times with saturated brine. It was dried over magnesium sulfate, and concentrated after filtration. The obtained crude material was purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60 ° C to obtain 7.4 parts of the compound of formula (C-I-3). The yield was 27%.

The following reaction was carried out under a nitrogen atmosphere. 7.6 parts of the compound represented by the formula (BI-2), 10.0 parts of the compound represented by the formula (CI-3), and 20.0 parts of toluene were placed in a flask equipped with a cooling tube and a stirring device, and then 11.4 parts of phosphonium chloride was added. It was stirred at 95 to 100 ° C for 3 hours. Then, after cooling the reaction mixture to room temperature, it was diluted with 170.0 parts of isopropyl alcohol. Then, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added, and stirred for 30 minutes. Stirring was then stopped and allowed to stand for 30 minutes, and the result was separated into an organic layer and an aqueous layer. After the water layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. Add an appropriate amount of awning to the organic layer The nitrate was stirred for 30 minutes and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off in an evaporator to remove a solvent, whereby a blue-purpur solid was obtained. The obtained blue-violet solid was purified by column chromatography. The purified blue-purple solid was dried under reduced pressure at 60 ° C to obtain 17.8 parts of the compound of formula (A-II-3). The yield was 100%.

Identification of compounds represented by formula (A-II-3)

(mass analysis) ionization mode = ESI +: m / z = 715.3 [M-Cl] ⁺

Exact mass: 750.3

When the compound represented by the formula (A-II-3) is sulfonated in the same manner as in the example 1, the compound represented by the formula (A-I-3) can be obtained.

In the formula (AI-3), "-SO ₃ ^- " and "-SO ₃ H" each represent a carbon atom bonded to at least one of the six phenyl rings.

[Example 3]

The following reaction was carried out under a nitrogen atmosphere. After adding 28.9 parts of potassium thiocyanate and 160.0 parts of acetone to a flask equipped with a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. Then, 50.0 parts of 2,6-difluorobenzhydryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Then, after cooling the reaction mixture in an ice bath, 36.4 parts of N-ethyl o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Then, after cooling the reaction mixture in an ice bath, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Then, 28.1 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred under heating and reflux for 7 hours. Then, after the reaction mixture was allowed to stand to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene was added thereto, followed by stirring for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes, and as a result, it was separated into an organic layer and an aqueous layer. After the water layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1 equivalent of hydrochloric acid, and then washed with 200 parts of tap water, and finally washed with 200 parts of saturated brine. An appropriate amount of Glauber's salt was added to the organic layer, and after stirring for 30 minutes, filtration was carried out to obtain a dried organic layer. The obtained organic layer was distilled off in an evaporator to remove a solvent to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C to obtain 25.2 parts of the compound of formula (B-I-3). The yield was 27%.

The following reaction was carried out under a nitrogen atmosphere. 8.1 parts of the compound represented by the formula (BI-3), 10.0 parts of the compound represented by the formula (CI-3), and 20.0 parts of toluene were placed in a flask equipped with a cooling tube and a stirring device, and then 11.4 parts of phosphonium chloride was added. It was stirred at 95 to 100 ° C for 3 hours. Then, after cooling the reaction mixture to room temperature, it was diluted with 170.0 parts of isopropyl alcohol. Then, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added, and stirred for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes, and as a result, it was separated into an organic layer and an aqueous layer. After the water layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of Glauber's salt was added to the organic layer, and after stirring for 30 minutes, filtration was carried out to obtain a dried organic layer. The obtained organic layer was distilled off in an evaporator to remove a solvent, whereby a blue-purpur solid was obtained. The obtained blue-violet solid was purified by column chromatography. The purified blue-purple solid was dried under reduced pressure at 60 ° C to obtain 18.3 parts of the compound of formula (A-II-4). The yield was 100%.

Identification of compounds represented by formula (A-II-4)

(mass analysis) ionization mode = ESI+: m/z = 733.3 [M-Cl] ⁺

Exact quality: 768.3

When the compound represented by the formula (A-II-4) is sulfonated in the same manner as in the example 1, the compound represented by the formula (A-I-4) can be obtained.

In the formula (AI-4), "-SO ₃ ^- " and "-SO ₃ H" each represent a carbon atom bonded to at least one of the six phenyl rings.

[Industrial availability]

The compounds of the invention have a high absorbance. When the color-curable resin composition for producing a liquid crystal display part contains the compound of the present invention, the amount used may be small.

Claims (4)

a compound represented by the formula (AI): [In the formula (AI), R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a and R ^8a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an SO ₃ ^- group. Or SO ₃ M group; R ^9a and R ^10a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted aromatic hydrocarbon group, or a substituted aralkyl group; R ^11a to R ^20a respectively The hydrogen atom, the alkyl group having 1 to 10 carbon atoms, the halogen atom, the SO ₃ ^- group or the SO ₃ M group are independently represented; and in the above R ^1a to R ^20a , the alkyl group constituting the alkyl group may be formed. An oxygen atom is interposed; R ^45a and R ^46a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted; and R ^55a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, Or a substituted aromatic hydrocarbon group; in the above R ^45a , R ^46a , and R ^55a , for the above alkyl group, an oxygen atom may be interposed between the methylene groups constituting the same; M represents a hydrogen ion, a metal ion or an ammonium ion. Wherein R ^1a to R ^20a , R ^45a , R ^46a and R ^55a satisfy at least one of (1), (2) and (3), and (4): (1) R ^1a to R ^8a and R ^11a ~ R ^20a is at least one of SO ₃ ^- group or an SO ₃ M ^{; (2) R 9a, R} 10a, R 45a, R 46a and R ^55a having at least one of SO ₃ ^- SO ₃ M group or an aromatic hydrocarbon group as a substituent group; at least (3) R ^9a, and R ^10a of One is an aralkyl group having a SO ₃ ^- group or a SO ₃ M group as a substituent on the ring; (4) the compound represented by the formula (AI) has a number of SO ₃ ^- groups of 1, SO ₃ M group The number is 0~6]. A colored curable resin composition comprising the compound represented by the formula (A-I) of claim 1. A color filter which is formed by using the colored curable resin composition of claim 2. A display device comprising the color filter of claim 3.