TW201741400A - Salt and coloring curable compound for providing material of color filter with an effective resistance to N-methylpyrrolidone (NMP) - Google Patents

Abstract

A salt which consists of (a) a cation represented by the formula (A-I), and (b) a polymer having structural units originating from an anionic compound represented by the formula (A-II). In the formula (A-I), each of R<41> - R<48> independently represents a hydrogen atom, an aliphatic hydrocarbon group with a carbon number of 1-20 which may have substituents, an aryl group with a carbon number of 6-20 which may have substituents, or an aralkyl group with a carbon number of 7-30 which may have substituents; R<41> and R<42>, R<43> and R<44>, and R<45> and R<46> can be bonded with each other to form a ring with the nitrogen atoms to which they are bonded; R<47> and R<48> can be bonded with each other to form a ring with the carbon atoms to which they are bonded. In the formula (A-II), X represents an alkyl group with a carbon number of 2-8 in which one or a plural number of hydrogen atoms may be replaced by fluorine atoms; Y represents a divalent aliphatic hydrocarbon group with a carbon number of 2-8, an arylene group with a carbon number of 6-20, or a group formed by combining thereof; a methylene group that constitutes the aforementioned aliphatic hydrocarbon group may be replaced by an oxygen atom, -CO- or -N(R<52>)-, wherein the adjacent methylene groups are not replaced together and the methylene group at an end is not replaced; R<51> represents a hydrogen atom or a methyl group; R<52> represents a hydrogen atom, an aliphatic hydrocarbon group with a carbon number of 1-20 which may have substituents, an aryl group with a carbon number of 6-20 which may have substituents, or an aralkyl group with a carbon number of 7-30 which may have substituents.

Description

Salt and color hardening composition

This invention relates to a salt and color hardening composition.

A dye represented by the formula (8) is described in, for example, Japanese Patent Publication No. 2012-194466, which is a coloring agent for a color filter or the like which is contained in a liquid crystal display device or the like.

An object of the present invention is to provide a salt which can be used as a coloring agent as a material of a color filter excellent in resistance to N-methylpyrrolidone [NMP].

The invention includes the following invention.

[1] A salt comprising (a) a cation represented by the formula (AI), and (b) a polymer having a structural unit derived from the anionic compound represented by the formula (A-II):

[In the formula (AI), R ⁴¹ to R ⁴⁸ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a aralkyl group having 7 to 30 carbon atoms having a substituent, R ⁴¹ and R ⁴² , R ⁴³ and R ⁴⁴ , and R ⁴⁵ and R ⁴⁶ may be bonded to each other to form a nitrogen atom together with the bonded nitrogen atom. Rings, R ⁴⁷ and R ⁴⁸ may also be bonded to each other to form a ring together with the carbon atoms bonded thereto]

[In the formula (A-II), X represents an alkyl group having 2 or 8 carbon atoms which may be substituted with a fluorine atom; Y represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, carbon a 6 to 20 aryl group, or a combination thereof, wherein the methylene group constituting the above aliphatic hydrocarbon group may be substituted with an oxygen atom, -CO- or -N(R ⁵² )-; The methylene group is not substituted at the same time, and the methylene group at the terminal is not substituted; R ⁵¹ represents a hydrogen atom or a methyl group; and R ⁵² represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, An aryl group having 6 to 20 carbon atoms having a substituent or an aralkyl group having 7 to 30 carbon atoms which may have a substituent.

[2] The salt of [1], wherein X is a perfluoroalkyl group having 2 to 8 carbon atoms.

[3] The salt of [1] or [2], wherein X is perfluorobutyl.

[4] The salt according to any one of [1] to [3] wherein Y is an exoaryl group having 6 to 20 carbon atoms.

[5] The salt according to any one of [1] to [4] wherein Y is a stretching phenyl group.

[6] A coloring agent comprising the salt according to any one of [1] to [5] above.

[7] A colored curable composition comprising the salt according to any one of the above [1] to [6], a resin, a polymerizable compound, and a polymerization initiator.

[8] A coating film formed from the color hardening composition of the above [7].

[9] A color filter formed of the color hardening composition according to [7] above.

[10] A display device comprising the color filter of [9] above.

When a color-curable composition containing the salt of the present invention is used, a color filter excellent in NMP resistance can be provided.

The salt of the present invention (hereinafter referred to as "salt (1)") includes a cation represented by the formula (a) (AI) (hereinafter, sometimes referred to as "(a) cation"), and (b) has a source A polymer of a structural unit of an anionic compound represented by the formula (A-II) (hereinafter, referred to as "(b) polymer").

In the salt (1), the structural unit of the above (b) polymer forms an ionic bond with the (a) cation. However, the structural unit may not all form an ionic bond with the (a) cation.

The salt (1) can be used as a coloring agent and has good NMP resistance. Therefore, the salt (1) is suitable, for example, as a coloring agent in a coloring curable composition.

[In the formula (AI), R ⁴¹ to R ⁴⁸ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a aralkyl group having 7 to 30 carbon atoms having a substituent, R ⁴¹ and R ⁴² , R ⁴³ and R ⁴⁴ , and R ⁴⁵ and R ⁴⁶ may be bonded to each other to form a nitrogen atom together with the bonded nitrogen atom. Rings, R ⁴⁷ and R ⁴⁸ may also be bonded to each other to form a ring together with the carbon atoms bonded thereto]

[In the formula (A-II), X represents an alkyl group in which one or more hydrogen atoms may be substituted with a fluorine atom and has a carbon number of 2 to 8; and Y represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms; a methylene group having 6 to 20 carbon atoms, or a combination thereof, may be substituted with an oxygen atom, -CO- or -N(R ⁵² )-; The adjacent methylene groups are not substituted at the same time, and the methylene group at the terminal is unsubstituted; R ⁵¹ represents a hydrogen atom or a methyl group; and R ⁵² represents a hydrogen atom, and an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent An aryl group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent]

Hereinafter, the (a) cation will be described.

In the formula (AI), the aliphatic hydrocarbon group of R ⁴¹ to R ⁴⁸ may be any of an alkyl group, an alkenyl group and an alkynyl group, and is preferably an alkyl group, a linear chain, a branched chain, and a cyclic group. The carbon number of the aliphatic hydrocarbon group is preferably from 1 to 15, more preferably from 1 to 10, still more preferably from 1 to 6.

Examples of the linear or branched aliphatic hydrocarbon group (preferably an alkyl group) include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, and an n-octyl group. , n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-heptadecyl, n-octadecyl a linear alkyl group such as n-nonadecyl or n-icosyl; isopropyl, t-butyl, isobutyl, tert-butyl, 1-methylbutyl, 1-ethylpropane Base, 2-methylbutyl, isopentyl, neopentyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, third pentyl, 1,3-dimethylbutyl , 3,3-dimethylbutyl, 2-ethylbutyl, 2-ethyl-2-methylpropyl, branched heptyl, 1-methylheptyl, 2-ethylhexyl, 1 , 5-dimethylhexyl, trioctyl, branched fluorenyl, branched fluorenyl, branched undecyl, branched dodecyl, branched tridecyl, branched tetradecyl a branched pentadecyl group, a branched heptadecyl group, a branched octadecyl group, a branched pentadecyl group, and a branched eicosyl group, etc. Group; propenyl group, hexenyl group and the like chain alkenyl group and the like.

Examples of the cyclic aliphatic hydrocarbon group (preferably a cycloalkyl group) include a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cycloheptane. Monocyclic cycloalkyl groups such as cyclo, cyclooctyl, cyclohexylpropyl and cyclododecyl; base, Basis Base, sinosauryl, isobornyl, noranthryl, adamantyl, adamantylmethyl, 1-(1-adamantyl)ethyl, 3,5-dimethyl fund a plurality of cyclic cycloalkyl groups such as an alkyl group and a bicyclooctyl group.

The methylene group of the above aliphatic hydrocarbon group may be substituted with an oxygen atom or the like, and the methine group of the aliphatic hydrocarbon group may be substituted with a nitrogen atom. As such a base, it can be enumerated A heterocyclic group such as a pyridyl group.

Examples of the substituent which the aliphatic hydrocarbon group may have include an aryl group (having a carbon number of, for example, 6 to 10), an alkoxy group (having a carbon number of, for example, 1 to 10), and an aryloxy group (for example, the carbon number is, for example, 6~ 10) an anthraceneoxy group (having a carbon number of, for example, 1 to 10), a halogen atom, a mercaptoamine group, an alkoxycarbonyl group (having a carbon number of, for example, 2 to 11), an aminocarbonyl group, a hydroxyl group, and a cyano group.

The carbon number of the aryl group of R ⁴¹ to R ⁴⁸ is preferably 6 to 12.

Specific examples of the aryl group include a phenyl group, a tolylmethyl group, and a xylyl group. Base, ethylphenyl, propylphenyl, isopropylphenyl, butylphenyl, tert-butylphenyl, naphthyl, phenyl, dihydroindenyl, fluorenyl, fluorenyl, fluorene The thiol group, the fluorenyl group and the like may also be a heterocyclic group.

In addition, examples of the substituent which the aryl group may have include an aryloxy group (having a carbon number of, for example, 6 to 10), a halogen atom, and a perfluoroalkyl group (having a carbon number of, for example, 1 to 10, preferably 1 to 5), a perfluoroalkoxy group (having a carbon number of, for example, 1 to 10, preferably 1 to 5), a perfluoroalkylthio group (having a carbon number of, for example, 1 to 10, preferably 1 to 5) , an amine group, a substituted amine group (-N(R ⁵⁴ )(R ⁵⁵ )), a nitro group, a hydroxyl group, a cyano group, an alkoxy group (having a carbon number of, for example, 1 to 10, preferably 1 to 5) , substituted amine indenyl (-CON(R ⁵⁴ )(R ⁵⁵ )), substituted aminoxime (-SO ₂ N(R ⁵⁴ )(R ⁵⁵ )), substituted oxycarbonyl (-CO ₂ R ⁵³ ), substituted oxysulfonyl group (-SO ₃ R ⁵³ ), alkylthio group, arylsulfonyl group, and phenyl group, etc., may have one or more of these . The substitution position of each substituent may be any of or adjacent to, between, and to.

R ⁵³ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ⁵⁴ and R ⁵⁵ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated aliphatic hydrocarbon group may be substituted with -O-, -CO-, -NH- or -N(R ⁵³ )-, and R ⁵⁴ and R ⁵⁵ may be bonded to each other to form a heterocyclic ring containing a 3 to 10 membered ring of a nitrogen atom.

Examples of the saturated hydrocarbon group in R ⁵³ to R ⁵⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a dodecyl group, and a hexadecane group. And a linear alkyl group such as an eicosyl group; a branched alkyl group such as isopropyl, isobutyl, isopentyl, neopentyl or 2-ethylhexyl; cyclopropyl, cyclopentyl or a ring An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a hexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclic fluorenyl group.

The hydrogen atom contained in the saturated hydrocarbon group in R ⁵⁴ and R ⁵⁵ may be substituted, for example, with a hydroxyl group or a halogen atom.

Specific examples of the group represented by R ⁴¹ to R ⁴⁸ include, as the aryl group having a substituent, an aminophenyl group; a (di)alkylamine such as (N,N-dimethylamino)phenyl group; Alkyl substituted aryl; nitrophenyl; hydroxyphenyl; methoxyphenyl, ethoxyphenyl and the like substituted by an alkoxy group; (trifluoromethyl)phenyl; (trifluoromethoxy) An aryl group substituted by a fluoroalkoxy group such as a phenyl group; an aryl group substituted with a fluoroalkylthio group such as a (trifluoromethylthio)phenyl group; a fluorophenyl group, a chlorophenyl group, a bromophenyl group, and an iodine group; An aryl group such as a phenyl group substituted with a halogen; a dimethoxyphenyl group; a fluoromethylphenyl group; a trimethoxyphenyl group; a trimethylphenyl group.

Examples of the aralkyl group of R ⁴¹ to R ⁴⁸ include a benzyl group; an alkyl group-substituted aralkyl group such as a methylbenzyl group and a tert-butylbenzyl group; and a fluoroalkane such as a (trifluoromethyl)benzyl group; Alkyl-substituted aralkyl; methoxyalkyl substituted by alkoxy group such as methoxybenzyl, ethoxybenzyl and methoxyphenylethyl; fluoroalkane such as (trifluoromethoxy)benzyl a substituted aralkyl group; an aralkyl group substituted with a fluoroalkylthio group such as a (trifluoromethylthio)benzyl group; an aralkyl group substituted with a halogen such as a fluorobenzyl group or an iodobenzyl group; and the like.

The carbon number of the aralkyl group of R ⁴¹ to R ⁴⁸ is preferably 7 to 22, more preferably 7 to 15.

In the formula (AI), R ⁴¹ and R ⁴² , R ⁴³ and R ⁴⁴ , and R ⁴⁵ and R ⁴⁶ may be bonded to each other to form a ring together with the nitrogen atoms bonded thereto. As the ring, piperidine, Porphyrin, pyrrolidine, piperazine , hexamethyleneimine, etc. Examples of the group represented by (R ⁴¹ )(R ⁴² )N-, (R ⁴³ )(R ⁴⁴ )N-, and (R ⁴⁵ )(R ⁴⁶ )N- include pyrrolidinyl and piperidin. base, Lolinyl, N-ethylpipe Base, dimethylamino, dipropylamino, dibutylamino, N-ethyl-N-isobutylamino, N-ethyl-benzylamino, dipentylamino, two Hexylamino group, dioctylamino group, N-ethyl-N-tetradecylamino group, dibenzylamino group and the like.

In the formula (AI), R ⁴⁷ and R ⁴⁸ may be bonded to each other to form a ring together with the carbon atoms to be bonded thereto, and examples of the ring include benzene and the like. In the case where R ⁴⁷ and R ⁴⁸ are bonded to each other, examples of the group represented by -C ₆ H ₂ (R ⁴⁷ )(R ⁴⁸ )- include an anthranyl group and the like.

As the (a) cation, in terms of easy production of the salt (1), an R ⁴⁵ hydrogen atom in the formula (AI) is preferred, and R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁶ are independent of each other. In the above aliphatic hydrocarbon group, R ⁴⁷ and R ⁴⁸ are bonded to each other to form a ring together with the bonded carbon atoms. When R ⁴¹ to R ⁴⁴ are the above aliphatic hydrocarbon group, it is more preferably a chain aliphatic hydrocarbon group, more preferably an alkyl group, particularly preferably an ethyl group or a methyl group.

R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁶ may be different from each other or may be the same, but from the viewpoint of easily synthesizing the (a) cation, they are preferably all the same.

Specific examples of the (a) cation include cations represented by the formulae (A-I-1) to (A-I-14). Among these, cations represented by the formulae (A-I-1), (A-I-8) and (A-I-12) are preferred.

(a) The cation can be synthesized by a known method. As a method of synthesizing the cation, for example, the method described in "General Synthetic Dyes" (Sakaguchi, Sankyo Publishing, 1968) is referred to.

In addition to the (a) cation, the salt (1) also contains (b) a structural unit derived from an anionic compound represented by the formula (A-II) (hereinafter, sometimes referred to as "(b-1) compound"). Polymer.

[In the formula (A-II), X may be substituted with one or a plurality of fluorine atoms having an alkyl group having 2 to 8 carbon atoms.

Y represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an extended aryl group having 6 to 20 carbon atoms, or a combination thereof, and the methylene group constituting the above aliphatic hydrocarbon group and aryl group can be Substituted as an oxygen atom, -CO- or -N(R ⁵² )-. Wherein, the adjacent methylene groups are not substituted at the same time, and the methylene group at the end is not substituted.

R ⁵¹ represents a hydrogen atom or a methyl group.

R ⁵² represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent ]

In the formula (A-II), as for X, from the viewpoint of increasing the acidity of the quinone acid, it is preferred that the hydrogen atom is substituted with a linear or branched carbon number of 2 to 8 of a fluorine atom. Fluoroalkyl.

Examples of the perfluoroalkyl group include perfluoropropyl groups such as -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ and -CF(CF ₃ ) ₂ ; -CF ₂ CF ₂ CF ₂ CF ₃ and -CF ₂ CF. Examples of the perfluorobutyl group such as (CF ₃ ) ₂ and -C(CF ₃ ) ₃ include a perfluoropropyl group such as -CF ₂ CF ₂ CF ₃ and -CF(CF ₃ ) ₂ ; -CF ₂ CF ₂ CF. ₂ perfluorobutyl such as CF ₃ , -CF ₂ CF(CF ₃ ) ₂ and -C(CF ₃ ) ₃ , more preferably -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ And a perfluorobutyl group such as -C(CF ₃ ) ₃ , particularly preferably -CF ₂ CF ₂ CF ₂ CF ₃ .

As Y, a linear or branched alkyl group, an extended aryl group and an extended aryl group alkyl group are preferable. The carbon number of Y is preferably from 1 to 10. In detail, the carbon number of the linear or branched alkyl group is preferably from 1 to 10, the carbon number of the extended aryl group is preferably from 6 to 20, and the carbon number of the extended arylalkyl group is preferably 7 ~20.

The alkylene group may be any of a linear chain and a branched chain, and examples thereof include a methylene group, an exoethyl group, a n-propyl group, an exo-propyl group, and a butyl group.

Examples of the aryl group include a phenyl group and a naphthyl group.

The alkylene group may, for example, be an exoarylmethylene group, an exoaryl extended ethyl group, an extended aryl extended propyl group, an extended aryl extended butyl group, an extended aryl extended pentyl group, and an extended aryl group. The aryl group side of the extended alkyl group is bonded to a sulfur atom.

The methylene group constituting the alkylene group, the aryl group or the arylalkyl group may be substituted with an oxygen atom, -CO- or -N(R ⁵² )-. Wherein, the adjacent methylene groups are not substituted at the same time, and the methylene group at the end is not substituted.

R ⁵² represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent Specific examples of R ⁵² include aliphatic hydrocarbon groups, aryl groups and aralkyl groups similar to those of R ⁴¹ .

Y is preferably an exoaryl group having 6 to 20 carbon atoms and an exoarylalkyl group having 7 to 10 carbon atoms, more preferably an aryl group, an aryl methylene group, an exoaryl group, an ethyl group or a stretching group. The aryl propyl group, the aryl group butyl group, the aryl group pentyl group and the aryl group hexyl group are further preferably an aryl group, particularly preferably a phenyl group.

Examples of the (b-1) compound include an anion represented by the formula (A-II-1), the formula (A-II-2), and the formula (A-II-3).

(b-1) The compounds may be used singly or in combination of two or more.

In the (b) polymer, the higher the proportion of the structural unit derived from the (b-1) compound, the higher the proportion of the (a) cation in the salt (1), and it is preferable in this respect. From the above viewpoints, in the (b) polymer, the structural unit derived from the (b-1) compound and the structural unit other than the structural unit are preferably from 1/1 to 1/10, more preferably 1 /1~1/8, and further preferably 1/1~1/7. In the polymer (b), the proportion of the structural unit derived from the compound (b-1) is preferably 3 mol% or more and 50 mol% or less, more preferably 5 mol% or more and 50 mol% or less.

(b-1) The compound can be represented, for example, by a compound represented by the formula (D-II) (hereinafter sometimes referred to as "compound (D-II)") and a compound represented by the formula (E-II) (below It is sometimes called "compound (E-II)") and is produced by reaction. The reaction can be carried out in the presence of an organic solvent or in the absence of a solvent.

[In the formulae (D-II) and (E-II), X, Y, and R ⁵¹ respectively have the same meanings as described above]

In the above reaction, the amount of the compound (E-II) is 1 mol relative to the compound (D-II). It is preferably 0.5 mol or more and 8 mol or less, more preferably 1 mol or more and 4 mol or less.

The reaction temperature is preferably 0 to 50 ° C, more preferably 5 to 30 ° C. The reaction time is preferably from 1 to 12 hours, more preferably from 3 to 6 hours.

As for the reaction of the compound (D-II) with the compound (E-II), it is preferably carried out in an organic solvent from the viewpoint of productivity.

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 nitration such as nitrobenzene. A hydrocarbon solvent; a ketone solvent such as methyl isobutyl ketone; a guanamine solvent such as 1-methyl-2-pyrrolidone;

In the above reaction, the amount of the organic solvent is 1 part by mass, preferably 1 part by mass or more, 20 parts by mass or less, more preferably 2 parts by mass, based on the total of the compound (D-II) and the compound (E-II). Above 10 parts by mass or less.

As for the above reaction, from the viewpoint of productivity, it is preferably carried out in the presence of an amine. Examples of the amine include a trialkylamine such as triethylamine or diisopropylethylamine.

In the above reaction, when an amine is used, it is used in an amount of 1 mol based on the compound (D-II), preferably 0.1 mol or more, 20 mol or less, more preferably 0.2 mol or more, and 5 mol. the following.

The method for obtaining the compound (A-II) from the reaction mixture obtained by the above reaction is not particularly limited, and various known methods can be employed. As the above-mentioned method, for example, a method in which the reaction mixture is mixed with water, the organic layer is separated, and concentrated, thereby being extracted. The extracted compound is preferably purified by column chromatography and then dried.

Examples of the method for producing the compound (D-II) include various known methods, for example, those described in J. Fluorine Chem. 128 (2007) 1353-1358.

As a method for producing the compound (E-II), various known methods can be cited, for example, as recorded in Journal of Molecular Catalysis A: Chemical 311 (2009) 46-53. The method of loading.

(b) The polymer may contain a compound derived from the formula (A-III) in addition to the structural unit derived from the compound (b-1) (hereinafter, sometimes referred to as "(b-2)-containing epoxy) The structural unit of the compound ").

[In the formula (A-III), R ⁶¹ represents a hydrogen atom or a methyl group. A represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a methylene group constituting the aliphatic hydrocarbon group may be substituted with an oxygen atom or -CO-]

The divalent aliphatic hydrocarbon group represented by A is not particularly limited, and is preferably a linear or branched alkylene group.

Examples of the alkylene group include a linear alkyl group such as a methylene group, an exoethyl group, a n-propyl group and a butyl group; and a branched alkyl group such as an exo-propyl group and a branched butyl group. The carbon number of the aliphatic hydrocarbon group is preferably from 1 to 5.

The group in which the methylene group of the aliphatic hydrocarbon group is substituted with an oxygen atom may, for example, be a linear or branched oxyalkylene group, and the methylene group as the aliphatic hydrocarbon group may be substituted with an oxygen atom and a -CO- group. Examples thereof include a linear or branched carbonyloxyalkylene group.

Preferably, the methylene group bonded to the epoxy group is not substituted with an oxygen atom or -CO-, and preferably the carbonyloxyalkyl group is bonded to the -C(CH ₂ )R ⁶¹ on the carbonyl side. Examples of the oxyalkylene group include an oxyethyl group, an oxypropyl group, and an oxybutyl group. Examples of the carbonyloxyalkyl group include a carbonyloxymethylene group. Among these, from the viewpoint of availability of raw materials and ease of production, a carbonyloxyalkylene group is preferred, and a carbonyloxymethylene group is more preferred.

Examples of the (b-2) epoxy group-containing compound include glycidyl (meth)acrylate and the like. These compounds may be used singly or in combination of two or more.

Adding a salt (1) having a higher ratio of (b-2) an epoxy group-containing compound to coloring In the curable composition, a color filter having a high NMP resistance can be obtained.

From the viewpoint of the above, in the (b) polymer, the ratio of the structural unit derived from the (b-2) epoxy group-containing compound is preferably 50 mol% or more and 97 mol% or less, more preferably 50% or more, 95% or less.

The ratio of the structural unit derived from the compound (b-1) to the structural unit derived from the (b-2) epoxy group-containing compound is preferably from 1/1 to 1/7.

In the polymer (b), the total ratio of the structural unit derived from the (b-1) compound and (b-2) the epoxy group-containing compound is preferably 50 mol% or more, more preferably 70 mol%. The above is further preferably 90 mol% or more.

(b) The polymer may contain structural units derived from other compounds in addition to the structural unit derived from the (b-1) compound and (b-2) the epoxy group-containing compound, and the other compounds contain ethylenicity. A compound having a functional group of an unsaturated bond (hereinafter, referred to as "(b-3) a compound containing an ethylenically unsaturated bond").

The (b-3) functional group having an ethylenically unsaturated bond is preferably a functional group having an ethylenic double bond, and specific examples thereof include a vinyl group, an allyl group, and a (meth)acrylic group. Base) acryl fluorenyl and vinyl cycloalkyl. Among these, a vinyl group, an allyl group, a (meth)acrylic group, and a (meth)acryl fluorenyl group are preferable from the viewpoint of reactivity and ease of synthesis.

(b-3) The compound containing an ethylenically unsaturated bond is preferably a compound containing a functional group having an ethylenically unsaturated bond in the molecule from the viewpoint of easiness of production.

Examples of the (b-3) compound containing an ethylenically unsaturated bond include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and second (meth)acrylate. Ester, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearic acid (meth)acrylate ester, (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate, 2-methyl-cyclohexyl ester, (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decane -8-yl ester (sometimes referred to as "dicyclopentyl (meth) acrylate) in the technical field as a conventional name. Also, sometimes referred to as "trimethyl decyl (meth) acrylate) "), trimethyl [meth) acrylate [5.2.1.0 ^2,6 ] decene-8-yl ester (in the technical field, sometimes referred to as "dicyclopentenyl (meth) acrylate)" As a customary name), dicyclopentyloxyethyl (meth)acrylate, (meth)acrylic acid Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate and (meth)acrylic acid (meth) acrylate such as benzyl ester; (hydroxy) (meth) acrylate such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; diethyl maleate a dicarboxylic acid diester such as diethyl fumarate or diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene , 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5 -(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]g 2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di (2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[ 2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methyl double Ring [2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis ( a bicyclic unsaturated compound such as cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide, N-cyclohexylmethyleneimine, N-benzyl Isobutyleneimine, N-butylenediamine-3-butylimide imide benzoate, N-butylenediamine-4-butyleneimine Butyrate, N-butanediamine-6-butylenediamine hexanoate, N-butylenediamine-3-oxenimide propionate and N- (9-acridinyl) dicarbonyl ruthenium imide such as maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, pair Vinyl-containing aromatic compounds such as methoxystyrene; vinyl nitriles such as acrylonitrile and methacrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; acrylamide and methacrylamide Vinylamine Vinyl acetate ester; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like hexadiene.

Among these, from the viewpoint of copolymerization reactivity and ease of availability, a vinyl-containing aromatic compound such as styrene or an alkyl (meth)acrylate such as methyl (meth)acrylate is preferable.

The molecular weight of the polymer (b) is preferably 2,000 or more and 30,000 or less in terms of the weight average molecular weight (Mw) from the viewpoint of ensuring the content of the (a) cation contained in the salt (1). The weight average molecular weight (Mw) is more preferably 7,000 or more, still more preferably 10,000 or more, still more preferably more than 10,000, particularly preferably 11,000 or more, more preferably 25,000 or less, still more preferably 20,000 or less.

(b) The more the weight average molecular weight (Mw) of the polymer becomes larger, the more the color-curable composition having a lower content of the resin (B) to be described later can be obtained. The molecular weight distribution (Mw/Mn) is preferably from 1.0 to 4.0, more preferably from 1.0 to 2.0.

(b) The molecular weight of the polymer can be estimated by a size exclusion chromatography (SEC) method, which is a molecular weight converted from styrene as a standard substance.

(b) The polymer can be produced, for example, by polymerizing (preferably, radically polymerizing) an alkylamine salt of the compound (b-1), preferably an alkylamine salt of the compound (b-1) and (b) -2) A compound containing an epoxy group is produced by radical polymerization.

The radical polymerization is preferably carried out in the presence of a reaction solvent, and examples of the reaction solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

In the above polymerization, a phenylamine salt, a pyrrole salt, a pyridinium salt or the like of the compound (b-1) may be used instead of the alkylamine salt of the compound (b-1).

In the salt (I), the ratio of the (a) cation to the structural unit derived from the (b-1) compound (cation/anion) is preferably 0.8 or more, or 1 or less, more preferably 0.85 or more, on the molar basis. Preferably, it is less than 1, and further preferably 0.95 or less. The salt having the above ratio (cation/anion) of less than 1 becomes derived from the structural unit of the (b-1) compound more than the (a) cation, and the impurity derived from the (a) cation raw material is less.

The salt (1) can be synthesized by adding a salt having an (a) cation to the (b) polymer to carry out a salt exchange reaction.

Examples of the inorganic salt having the (a) cation include (a) a hydrochloride hydrochloride, a phosphate, a sulfate, a perchlorate, a BF ₄ salt, and a PF ₆ salt. The above salt exchange reaction can also be carried out by using (a) a benzenesulfonate or a naphthalenesulfonate of a cation instead of the inorganic salt having the (a) cation.

Specifically, the salt exchange reaction can be carried out by dissolving the polymer (b) in a reaction solvent as needed, adding an inorganic salt containing the (a) cation, stirring, and extracting and purifying by filtration. The precipitate.

The (a) cation is preferably 80 mol% to 100 mol% (preferably 85 mol% or more, based on the structural unit derived from the (b-1) compound in the (b) polymer. It is added in such a manner that it is less than 100% by mole, more preferably 85% by mole or more, and less than 95% by mole.

Examples of the reaction solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, or methanol, ethanol, isopropanol, n-butanol, and 2-ethoxyethanol. Alcohols such as 1-methoxy-2-propanol, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylhydrazine and acetonitrile Wait. The reaction temperature is suitably 0 to 40 °C.

★ Salt (1) can be used as a coloring agent. The salt (1) can generally be used as a blue dye. The salt (1) is excellent in solubility in an organic solvent such as ethyl lactate. A coloring agent containing the salt (1) is also included in the scope of the invention of the present application. The coloring agent of the invention of the present application may be a coloring agent containing only the salt (1), or may be a coloring agent further including other coloring agents described later.

The color hardening composition of the present invention comprises a salt (1), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). In the above coloring curable composition, the salt (1) is usually contained as the coloring agent (A).

The color hardening composition of the present invention preferably further contains a solvent (E), and more preferably further contains a leveling agent (F).

In the present specification, the resin (B) is different from the (b) polymer or the salt (1) in that it does not have a structural unit derived from the (b-1) compound.

It is preferred that the color hardening composition of the present invention further comprises a polymerization initiation aid (D1).

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)>

As the coloring agent (A), the salt (1) may be used alone, and further, other coloring agents may be contained. By adding other colorants, the color grading, that is, the spectral characteristics can be adjusted.

As other coloring agents, a dye (A1), a pigment (P), or a mixture of these may be mentioned.

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, which can be exemplified by the color index (The Society). A dye classified as a dye in the Dyers and Colourists, or a known dye as described in the dyeing notes (color dyeing). Examples of the dye (A1) include azo dyes, cyanine dyes, other triarylmethane dyes, dibenzopyran dyes, phthalocyanine dyes, naphthoquinone dyes, quinone imine dyes, and methine dyes. , methine azo dye, strontium succinate dye, acridine dye, styryl dye, coumarin dye, quinoline dye and nitro dye. Among these, an organic solvent-soluble dye can be preferably used.

More specifically, C.I. Solvent Yellow 4 (hereinafter, the description of C.I. Solvent Yellow is omitted, only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; CI solvent red 45, 49, 125, 130, 218; CI solvent orange 2, 7, 11, 15, 26, 56; CI solvent blue 4, 5, 37, 67, 70, 90; CI solvent green 1,4,5,7,34,35, 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, 15, 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 direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Violet 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, 1 71, 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, 260, 268, 274, 275, 293; 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 dispersion yellow 54, 76 and other CI disperse dyes, CI alkaline 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 basic green 1st CI basic dye, 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 mord 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, 35, 41, 43, 53 and other CI mord Materials, C. I.. C.I. Vat Green 1 vat dyes and the like, 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.

As the pigment (P), a known pigment can be used without particular limitation, and for example, it can be exemplified by a color index (published as a pigment in The Society of Dyers and Colourists). material.

As the pigment (P), CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125 can be cited. Yellow pigments such as 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55 , 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216 , red pigments such as 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 including the above pigment, the transmission spectrum is optimized, and the light resistance and chemical resistance of the color filter are improved.

The pigment (P) 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 a pigment surface by a polymer compound or the like, or a sulfuric acid micronization method. The micronization treatment, the cleaning treatment using an organic solvent or water for removing impurities, the removal treatment of an ionic impurity by an ion exchange method, or the like. Preferably, the particle size of the pigment (P) is uniform.

The pigment (P) can be subjected to dispersion treatment by containing a pigment dispersant to prepare a pigment dispersion in a state in which the pigment dispersant is uniformly dispersed in a solution. The pigment (P) may be separately subjected to dispersion treatment, or a plurality of kinds may be mixed and dispersed.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used alone or in combination of two or more. As a pigment dispersing agent, the product name is KP (made by Shin-Etsu Chemical Co., Ltd.), FLOWLEN (made by Kyoeisha Chemical Co., Ltd.), Solsperse (made by Zeneca Co., Ltd.), EFKA (made by BASF Corporation), Ajisper (Manufactured by Ajinomoto Fine Technology Co., Ltd.) and Disperbyk (manufactured by BYK Chemical Co., Ltd.).

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 (P). 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 salt (1) 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 thereof is preferably 0.5% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 80% by mass or less based on the total amount of the coloring agent (A). . When the pigment (P) is contained, the content thereof is preferably 1% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 70% by mass or less based on the total amount of the coloring agent (A). Further, it is preferably 35 mass% or more and 50 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 mass% based on the total amount of the solid content component. % or more and 50% by mass or less. When the content of the colorant (A) is within the above range, a desired spectral or color density 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 color hardening composition of the present invention. The total amount of the solid content component and the content of each component 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. The alkali-soluble resin is preferably a copolymer comprising a structural unit derived from at least one monomer (Ba) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides.

Examples of the 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 has a carbon number of 2 to 4. a copolymer of a cyclic ether structure and an ethylenically unsaturated bond monomer (Bb) (hereinafter sometimes referred to as "(Bb)"); a resin [K2] (Ba) and (Bb), and a (Ba) Copolymerized monomer (Bc) (but different from (Ba) and (Bb)) (hereinafter, sometimes referred to as "(Bc)") copolymer; copolymer [K3] (Ba) and (Bc) copolymerization Resin [K4] a resin obtained by reacting a copolymer of (Ba) and (Bc) with (Bb); a resin [K5] by copolymerizing (Bb) with (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.

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; maleic acid and fubutene; Diacid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1, Unsaturated dicarboxylic acid such as 2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid or 1,4-cyclohexene dicarboxylic acid; methyl-5-lower 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 - a bicyclic unsaturated compound containing a carboxyl group such as a olefin, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl neighbor Phthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl Unsaturated dicarboxylic anhydride such as tetrahydrophthalic anhydride or 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono[2-(methyl)propene oxiranylethyl An unsaturated mono[(methyl)propenyloxyalkyl] ester of a polyvalent carboxylic acid of 2 or more or more such as an ester or a mono[2-(methyl) propylene oxyethyl] phthalate; 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 from the viewpoint of copolymerization reactivity or solubility of the obtained resin in an aqueous alkaline solution.

(Bb) means, for example, 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, a propylene oxide ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. A polymeric compound.

(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 notation such as "(meth)acrylonitrile" and "(meth)acrylate" has the same meaning.

(Bb), for example, a monomer (Bb1) having an oxirane group and an ethylenically unsaturated bond (hereinafter, the monomer may be referred to as "(Bb1)"), and having an oxypropylene group and a monomer (Bb2) having an ethylenically unsaturated bond (hereinafter, referred to as "(Bb2)"), a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (Bb3) (hereinafter, This monomer is 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, referred to as "(Bb1-2)").

(Bb1-1) is preferably a monomer having a glycidyl group and an ethylenically unsaturated bond, and specific examples thereof include glycidyl (meth)acrylate and β-methylglycidyl (meth)acrylate. , (meth)acrylic acid β-ethyl glycidyl ester, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α- Methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxy) Methyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl) ) styrene, 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris (glycidol) Oxymethyl)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) ; manufactured by Daicel Co., Ltd.), a compound represented by formula (II), a compound represented by formula (III), and the like.

In the formulae (II) and (III), 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 independently of each other represent a single bond, * -R ^c -, * -R ^c -O-, * -R ^c -S- or * -R ^c -NH-.

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

* indicates the key with O]

Examples of the alkyl group 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 in 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 and 4-hydroxybutyl .

Examples of R ^a and R ^b include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a hydroxyalkyl group having 1 to 4 carbon atoms. Preferred examples thereof include a hydrogen atom, a methyl group, an ethyl group, and a hydroxymethyl group. The hydroxyethyl group and the 2-hydroxyethyl group are more preferably a hydrogen atom and a methyl group.

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

Examples of X ^a and X ^b include a single bond, * -R ^c -, * -R ^c -O-, * -R ^c -S- and * -R ^c -NH-, and preferably a single bond, * -R ^c - and * -R ^c -O-, more preferably a single bond and * -R ^c -O-, and further preferably a single bond, a methylene group, an exoethyl group, * -CH ₂ -O - and * -CH ₂ CH ₂ -O-, particularly preferably a single bond and * -CH ₂ CH ₂ -O- (* indicates a bond with O).

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

Examples of the compound represented by the formula (III) include a compound represented by any one of the formulae (III-1) to (III-15), and among them, preferred are the formula (III-1) and the formula (III). -3), a compound represented by formula (III-5), formula (III-7), formula (III-9) and formula (III-11) to formula (III-15), more preferably enumerated formula (III) -1), a compound represented by the formula (III-7), the formula (III-9) and the formula (III-15).

The compound represented by the formula (II) and the compound represented by the formula (III) may be used singly or in combination, and the compound represented by the formula (II) may be used in combination with the compound represented by the formula (III). When the above is used in combination, the content of the compound represented by the formula (II) and the compound represented by the formula (III) is, on a molar basis, preferably from 5:95 to 95:5, more preferably 10: 90~90:10, and further preferably 20:80~80:20.

As (Bb2), a monomer having an oxypropylene group and a (meth)acryloxy group is preferable. Examples of (Bb2) include 3-methyl-3-methylpropenyloxymethyl propylene oxide, 3-methyl-3-propenyloxymethyl propylene oxide, and 3-ethyl-3- Methyl propylene methoxymethyl propylene oxide, 3-ethyl-3-propenyl methoxymethyl propylene oxide, 3-methyl-3-methyl propylene methoxyethyl propylene oxide, 3- Methyl-3-propenyloxyethyl propylene oxide, 3-ethyl-3- Methyl propylene oxiranyl ethyl propylene oxide and 3-ethyl-3-propenyl ethoxyethyl propylene oxide.

As (Bb3), a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group is preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V #150, manufactured by Osaka Organic Chemical Co., Ltd.), and tetrahydrofurfuryl methacrylate.

(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 composition.

Examples of (Bc) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and tributyl (meth)acrylate. Ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate , cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in the technical field) In some cases, it is sometimes referred to as "dicyclopentyl (meth) acrylate" as a conventional name. Further, it may be called "tricyclodecyl (meth) acrylate" or trimethyl (meth) acrylate [ 5.2.1.0 ^2,6 ]decene-8-yl ester (in the technical field, sometimes referred to as "dicyclopentenyl (meth) acrylate" as a customary name), biphenyl (meth) acrylate Pentyloxyethyl ester, (meth)acrylic acid Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate and (meth)acrylic acid (meth) acrylate such as benzyl ester; (hydroxy) (meth) acrylate such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate; diethyl maleate a dicarboxylic acid diester such as diethyl fumarate or diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene , 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5 -(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]g 2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di (2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[ 2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methyl double Ring [2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis ( a bicyclic unsaturated compound such as cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide, N-cyclohexylmethyleneimine, N-benzyl Isobutyleneimine, N-butylenediamine-3-butylimide imide benzoate, N-butylenediamine-4-butyleneimine Butyrate, N-butanediamine-6-butylenediamine hexanoate, N-butylenediamine-3-oxenimide propionate and N- (9-Acridine) dicarbonyl ruthenium imide such as maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and Vinyl-containing aromatic compounds such as methoxystyrene; vinyl nitriles such as acrylonitrile and methacrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; acrylamide, methacrylamide, etc. Vinylamine Vinyl acetate ester; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-hexadiene and the like.

In the above, (Bc) is preferably a vinyl group-containing aromatic compound, a dicarbonyl quinone imine derivative, or a bicyclic unsaturated compound from the viewpoint of copolymerization reactivity and heat resistance. Specifically, styrene, vinyl toluene, benzyl (meth)acrylate, tricyclo[5.1.02 ^2,6 ]decane-8-yl ester, N-phenyl cis is preferred. Butyleneimine, N-cyclohexylmethyleneimine, N-benzyl maleimide, bicyclo [2.2.1] hept-2-ene.

In the resin [K1], the ratio derived from the respective structural units is preferably such that the resin is formed. In all the structural units of [K1],

Structural unit derived from (Ba): 2~60 mol%

Structural unit derived from (Bb): 40 to 98% by mole; more preferably

Structural unit derived from (Ba): 10~50 mol%

The structural unit derived from (Bb): 50 to 90 mol%.

When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable composition, the developability in forming a colored pattern, and the solvent resistance of the obtained color filter tend to be excellent.

The resin [K1] can be referred to, for example, the method described in the "Experimental Method for Polymer Synthesis" (Taijin Takashi, Issue: Chemical Co., Ltd., 1st Edition, 1st brush, issued on March 1, 1972). It is produced by reference to the documents described 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 oxygen is replaced by nitrogen, for example, thereby making it a deoxidizing gas atmosphere. A method of heating and keeping warm while stirring. Further, the polymerization initiator, the solvent and the like used herein are not particularly limited, and can be used for a general user in the field. 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 used as a solvent to dissolve each monomer, and a solvent (E) to be described later may be mentioned.

The obtained copolymer may be directly used as a solution after the reaction, or a concentrated or diluted solution may be used, or may be extracted as a solid (powder) by a method such as reprecipitation. In the polymerization, the solvent contained in the colored curable composition of the present invention is used as a solvent, and the solution after the reaction can be directly used in the preparation of the color hardening composition of the present invention, so that the present invention can be used. The manufacturing steps of the color hardening composition are simplified and preferred.

In the resin [K2], the ratio derived from the respective structural units is preferably among all the structural units constituting the resin [K2],

Structural unit derived from (Ba): 2~45mol%

Structural unit derived from (Bb): 2~95 mol%

Structural unit derived from (Bc): 1 to 65 mol%; more preferably

Structural unit derived from (Ba): 5~40 mol%

Structural unit derived from (Bb): 5~80 mol%

The structural unit derived from (Bc): 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 composition, the developability in forming a colored pattern, and the solvent resistance and heat resistance of the obtained color filter are 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 derived from the respective structural units is preferably among all the structural units constituting the resin [K3],

Structural unit derived from (Ba): 2~60 mol%

Structural unit derived from (Bc): 40 to 98% by mole; more preferably

Structural unit derived from (Ba): 10~50 mol%

Structural unit derived from (Bc): 50 to 90 mol%.

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), a cyclic ether having 2 to 4 carbon atoms of (Bb) and a carboxylic acid having (Ba) and / or carboxylic anhydride addition.

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 derived from the respective structural units is preferably the same ratio as those listed in the resin [K3].

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

After the production of the copolymer of (Ba) and (Bc), the gas atmosphere in the flask is replaced with air from nitrogen, and the reaction catalyst of (Bb), a carboxylic acid or a carboxylic anhydride and a cyclic ether (for example, tris(dimethyl) Alkylmethyl)phenol and the like, and a polymerization inhibitor (for example, hydroquinone or the like) are placed in a flask, for example, at 60 to 130 ° C for 1 to 10 hours, whereby a resin can be produced [K4 ].

The amount of use as (Bb) is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (Ba). By adjusting the amount of use of (Bb) to the above range, the storage stability of the colored curable composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern are The tendency to balance well. 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), more preferably (Bb1-1).

The amount of the reaction catalyst 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 amount of use of the polymerization inhibitor 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 reaction temperature can be appropriately adjusted in consideration of the production equipment, the heat release amount of the polymerization, and the like in the same manner as the polymerization conditions.

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 concentrated or diluted solution may be used, or a solid (powder) may be used by extraction by a method such as reprecipitation.

In the first stage, the ratio of the structural units derived from (Bb) and (Bc) is preferably the total number of moles relative to all structural units constituting the copolymer of (Bb) and (Bc), respectively

Structural unit derived from (Bb): 5~95 mol%

Structural unit derived from (Bc): 5 to 95% by mole; more preferably

Structural unit derived from (Bb): 10~90 mol%

The structural unit derived from (Bc): 10 to 90 mol%.

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

In the second stage, the amount of (Ba) used as the copolymer of the above (Bb) and (Bc) is preferably 5 to 80 moles relative to (Bb) 100 moles. Since the reactivity of the cyclic ether is high and it is difficult to remain unreacted (Bb), (Bb) used as the resin [K5] is preferably (Bb1), more preferably (Bb1-1).

The resin [K6] is a resin obtained by further reacting a resin [K5] with a carboxylic acid anhydride. It is produced by reacting a hydroxyl group produced by a reaction of a cyclic ether derived from (Bb) with a carboxylic acid or a carboxylic acid anhydride of (Ba) with a carboxylic acid anhydride.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetrahydrogen. Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene Anhydride, etc. The amount of the carboxylic anhydride used is 1 mole based on the amount of (Ba) used, preferably 0.5 to 1 mole.

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 ]Derivatives such as oxime ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (methyl) Glycidyl acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo(5.4- ^diethyl phthalate)/(meth)acrylic acid/N-ring Hexyl-m-butylene iminoimide copolymer, 3,4-epoxytricyclo[5.4.1.0 ^2,6 ]decyl (meth)acrylic acid/N-cyclohexyl-n-butylene Imine/2-hydroxyethyl (meth)acrylate copolymer, 3,4-epoxytricyclo(5.4-diethyl)[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic/vinyltoluene copolymer Resin such as 3-methyl-3-(meth)acryloxymethyl propylene oxide/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth) acrylate / (methyl Acrylic copolymer, styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/(meth)acrylic acid Resin such as polymer [K3]; resin obtained by adding (meth)acrylic acid copolymer/(meth)acrylic acid copolymer to glycidyl (meth)acrylate, p-trimethyl decyl (meth)acrylate / Styrene / (meth)acrylic acid copolymer addition of (meth)acrylic acid glycidyl ester resin, p-trimethyl decyl (meth) acrylate / benzyl (meth) acrylate / (methyl) a resin such as a resin obtained by adding an acrylic acid copolymer to glycidyl (meth)acrylate [K4]; a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate and (methyl) a resin obtained by reacting acrylic acid, a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate with (meth)acrylic acid [ K5]; reacting a copolymer of tricyclodecyl (meth) acrylate/glycidyl (meth) acrylate with (meth)acrylic acid to further obtain the obtained resin together with tetrahydrophthalic anhydride A resin such as a resin obtained by the reaction [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 coloring curable 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 hardness of the coating film formed of the colored curable composition is improved, the residual film ratio during development is also high, and the solubility of the unexposed portion in the developer is good, and The tendency of the resolution of the color pattern to increase.

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

The content of the resin (B) is preferably from 1 to 65% by mass, more preferably from 2 to 60% by mass, even more preferably from 2 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. Further, the resin (B) may be more than the salt (1) or less.

<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. A (meth) acrylate compound is mentioned.

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

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(a). Acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like.

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 second season. Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate , pentaerythritol nine (meth) acrylate, tris(2-(methyl) propylene methoxyethyl) isocyanate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol Modified dipentaerythritol hexa(meth) acrylate, propylene glycol modified pentaerythritol tetra(meth) acrylate, propylene glycol modified dipentaerythritol hexa(meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate And caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc., among them, 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 or more and 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.

The content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 5:95 to 80:20, more preferably 9:91 by mass. 80:20.

Further, the total ratio of the salt (1) to the resin (B) and the content of the polymerizable compound (C) [the total of the salt (1) and the resin (B): the polymerizable compound (C)] is based on the mass basis. Good for 70:30~40:60, better 70:30~50:50.

When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of formation of 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 can generate an active 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, an alkylphenol 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 structure represented by the formula (d1). Hereinafter, * indicates a keying key.

The above O-indenyl ruthenium compound may, for example, be N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imide or N-benzylideneoxy group- 1-(4-Phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane- 1-keto-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1 -imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethoxy) Benzobenzyl}-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzamide) -9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine and N-benzylidene-1-(9-ethyl-6-(2-methylphenyl) Further, fluorenyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, and the like, Irgacure (registered trademark) OXE01, OXE02 (above manufactured by BASF Corporation) And commercial products such as N-1919 (made by Aidike). 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 alkylphenol compound is, for example, a compound having a structure represented by the formula (d2) or a structure represented by the formula (d3). In these structures, the benzene ring may have a substituent.

As a compound having a structure represented by the formula (d2), 2-methyl-2- can be mentioned Lolinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-(4- Phenylphenyl)-2-benzylbutan-1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- A commercially available product such as Irgacure 369, 907 or 379 (manufactured by BASF Corporation) may be mentioned as the phenyl group) phenyl] butan-1-one.

Examples of the compound having the structure represented by the formula (d3) 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)propan-1-one Oligomer, α,α-diethoxyacetophenone, benzoin dimethyl ketal, and the like.

In terms of sensitivity, the alkylphenol compound is preferably a compound having a structure represented by the formula (d2).

The biimidazole compound is preferably a compound represented by the formula (d5).

[In the formula (d5), R ¹³ to R ¹⁸ represent an aryl group having 6 to 10 carbon atoms which may have a substituent]

Examples of the aryl group of R ¹³ to R ¹⁸ include a phenyl group, a tolylmethyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferred.

Examples of the substituent 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 a chlorine atom is preferred. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and a butyl group. The oxy group or the like is preferably a methoxy group.

As the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro) can be mentioned. Phenyl)-4,4',5,5'-tetraphenylbiimidazole (refer to Japanese Patent Laid-Open No. Hei 6-75372, Japanese Patent Laid-Open No. Hei 6-75373, etc.), 2, 2'-double ( 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 ( An imidazole compound in which a phenyl group is substituted with a carbonyl alkoxy group at a 4, 4', 5, 5'-position and a 4, 4', 5, 5'-position (refer to Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204, etc.) Patent Publication No. 7-10913, etc.). Among them, the compound represented by the following formula and the mixture thereof are preferred.

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 And 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri Wait.

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

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl phthalate, and 4- Phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, a benzophenone compound such as 2,4,6-trimethylbenzophenone; an anthraquinone compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine and camphorquinone; 10-butyl-2-chloroacridine Ketones, benzoin, methyl phenylglyoxylate, and titanocene compounds.

It is preferred to use these in combination with a polymerization initiation aid (D1) (hereinafter, an amine) to be described later.

The polymerization initiator (D) preferably comprises an alkylphenol compound selected from the group consisting of 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 0.1 to 40 parts by mass, more preferably 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 polymerizable compound. In the case where the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).

As the polymerization initiation aid (D1), an amine compound, an alkoxy oxime compound, and 9-oxosulfuric acid can be cited. Compounds, carboxylic acid compounds, and the like.

The amine compound may, for example, be an alkanolamine such as triethanolamine, methyldiethanolamine or triisopropanolamine; methyl 4-dimethylaminobenzoate or ethyl 4-dimethylaminobenzoate; -Amino benzoate such as isoamyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; N, N -Dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michlerone), 4,4'-bis(diethylamino)benzol An alkylamino benzophenone such as a ketone or a 4,4'-bis(ethylmethylamino)benzophenone or the like. Among them, an alkylaminobenzophenone is preferred, and more preferably 4,4'-bis(diethylamino)benzophenone. Also, EAB-F (made by Hodogaya Chemical Industry Co., Ltd.) Commercial products such as manufacturing).

Examples of the alkoxyfluorene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

As the above 9-oxygen sulfur The compound may, for example, be 2-isopropyl-9-oxosulfur 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur And 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 methoxyphenylthio group. Acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine And naphthoxyacetic acid and the like.

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

<Solvent (E)>

The solvent (E) is not particularly limited, and those which are usually used in the field may be used singly or in combination of two or more.

Examples of the solvent (E) include an ester solvent (a solvent containing -COO- in the molecule and 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 (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO-, -COO-free in the molecule), alcohol solvent (containing OH in the molecule, without -O -, -CO- and -COO- solvents), aromatic hydrocarbon solvents, guanamine solvents, and dimethyl hydrazine.

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 acetic acid. Amyl ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate , cyclohexanol acetate and γ-butyrolactone.

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 diethyl ether. 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 ether and Methyl anisole and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-B Ethyl oxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene 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-pentyl Ketone, cyclopentanone, cyclohexanone and isophorone.

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

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

As the guanamine solvent, N,N-dimethylformamide, N,N-dimethylacetamide can be cited. And N-methylpyrrolidone and the like.

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

Among them, preferred are propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-di Methylformamide, N-methylpyrrolidone, etc., more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, 4-hydroxy-4-methyl-2-pentanone and N-methylpyrrolidine ketone.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass based on the total amount of the coloring curable composition. In other words, the solid content of the colored curable 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 is improved when the colored curable composition is applied, and the color density is insufficient when the color filter is formed, so that the display characteristics are improved.

<Leveling agent (F)>

Examples of the leveling agent (F) include a polyfluorene-based surfactant, a fluorine-based surfactant, and the like. These may also have a polymerizable group in 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 (trade name; manufactured by Toray 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 (Mitto Advanced Materials Day) The company is manufactured by).

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 Dickson (DIC) Co., Ltd.), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic 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.).

The polyoxo-based surfactant may be a polyfluorene-based surfactant having a fluorine atom. 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 Dianesei Co., Ltd.).

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 or less based on the total amount of the coloring curable composition. Further, it is preferably 0.005% by mass or more and 0.07% by mass or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>

The colored curable composition of the present invention 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 Composition>

The color hardening composition of the present invention can be, for example, a salt (1), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and other coloring agents and solvents as needed ( E), a leveling agent (F), a polymerization starting aid (D1), and other components are prepared by mixing.

When the pigment (P) is contained, it is preferred to mix the pigment (P) with a part or all of the solvent (E) in advance, and to disperse it by using a bead mill or the like until 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 obtained pigment dispersion liquid, the remaining components are mixed so as to have a specific concentration, whereby a desired color hardening composition can be prepared.

The salt (1) is preferably prepared by dissolving in part or all of the solvent (E) in advance. Preferably, the solution is filtered by a filter having a pore diameter of about 0.01 to 1 μm.

In the case of using the dye (A1), the dye (A1) may be dissolved in a part or all of the solvent (E) to prepare a solution. Preferably, the solution is further filtered by a filter having a pore diameter of about 0.01 to 1 μm.

Preferably, after mixing the above components, the obtained mixture is filtered through a filter having a pore diameter of about 0.01 to 10 μm.

<Method for Producing Coating Film and Color Filter>

The coating film and the color filter of the present invention are each formed of the coloring composition described above. The color filter of the present invention may also have a colored pattern.

Examples of the method for producing the colored pattern include a photolithography method, an inkjet method, a printing method, and the like, and a photolithography method is preferable. The photolithography method is a method in which the colored curable composition is applied onto a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask to be developed. In the method for forming the colored pattern described above, a coating film which is a cured product of the colored composition layer can be formed without using a photomask at the time of exposure and/or without development. The colored pattern or the coated film can be used as a color filter.

The film thickness of the coating film or the color filter is not particularly limited and may be depending on the purpose or use. The appropriate adjustment is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, quartz glass, borosilicate glass, aluminosilicate glass, a glass plate such as soda lime glass coated with cerium oxide on the surface, or polycarbonate, polymethyl methacrylate, or poly can be used. A resin plate such as ethylene terephthalate or the like, and an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. Further color filter layers, resin layers, transistors, circuits, and the like may be formed on the substrates.

The formation of pixels of various colors by photolithography can be performed by well-known or conventional devices or conditions. For example, it can be produced as follows.

First, the colored curable composition is applied onto a substrate, dried by heating (prebaking), and/or dried under reduced pressure, whereby volatile components such as a solvent are removed and dried to obtain a smooth colored composition layer.

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

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 coloring composition layer is not particularly limited, and can 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 coloring 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 in the exposure, a light source that emits light having a wavelength of 250 to 450 nm is preferable. For example, for light that does not reach 350 nm, filtering is used to cut off the wavelength region. The sheet was cut off, and the light in the vicinity of 436 nm, around 408 nm, and around 365 nm was selectively extracted using a band pass filter that extracts the wavelength regions. Examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

It is preferable to uniformly irradiate the parallel light to the entire exposed surface or to align the correct position of the mask with the substrate on which the colored composition layer is formed. Therefore, it is preferable to use an exposure device such as a mask aligner or a stepper.

The colored composition layer after the exposure is brought into contact with the developer to develop, thereby forming a colored pattern on the substrate. The unexposed portion of the colored composition layer is dissolved in the developer by development to remove it.

As the developer, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration in the aqueous solution of the basic compound 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 may be inclined at an arbitrary angle during development.

It is preferred to carry out water washing after development.

Further, it is preferred to post-bake the developed coloring composition layer. 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 salt of the present invention has high NMP resistance, it can be used as a material for producing a color-curable composition which is excellent in NMP-resistant coating film and color filter. The color filter can be used as a color filter used in a display device (a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state imaging device.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the examples. In the example, the "%" and "parts" of the content or usage are only A quality benchmark is required unless otherwise stated.

In the following, NMR was measured by an FT-NMR apparatus (trade name "MR-400") manufactured by Agilent Technologies, Inc. ¹ H-NMR was dissolved in Strontium II at room temperature, pulse width of 5.8 μs (45° pulse), extraction time of 3.5 seconds, waiting time of 3.5 seconds, and cumulative number of times of 16 times. The measurement was carried out in methyl hydrazine, and the signal of deuterated dimethyl hydrazine was used as an internal standard of chemical shift (δ 2.50). 19F-NMR was dissolved in deuterated dimethyl ether at room temperature, pulse width of 4.75 μs (45° pulse), take-in time of 0.84 seconds, waiting time of 3.6 seconds, and cumulative number of times of 32 times. The measurement was carried out in Kiah. The separately measured signal of hexafluorobenzene was used as an external standard for chemical shift (δ -163.0).

In the following, the structure of the reaction product was confirmed by mass analysis (LC; Model 1200 manufactured by Agilent Technologies, MASS; LC/MSD type of Agilent Technologies, Inc.).

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene of the resin was carried out under the following conditions by the SEC method.

Device: HLC-8120 manufactured by Tosoh Corporation

Column: TSKgel α4000+α3000+α2500+TSK protection column

Column temperature: 40 ° C

Solvent: 50 mM LiBr/DMF

Flow rate: 1.0 mL/min

Solid content concentration of the test liquid: 0.1% by mass

Injection volume: 50μL

Detector: RI

Standard material for calibration: TSK standard polystyrene

F-1, F-4, F-288, A-2500, A-500, A-5000

[Synthesis Example 1]

To a flask under a nitrogen atmosphere, 158 parts of a 0.4 M ammonia tetrahydrofuran solution (manufactured by Sigma-Aldrich Japan Co., Ltd.) was placed. The flask was immersed in a dry ice / 2-propanol bath to be cooled, and 10.0 parts of nonafluorobutanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while stirring the above-mentioned ammonia tetrahydrofuran solution. In the flask. After the completion of the dropwise addition, the mixture was further stirred for one hour while stirring. After the completion of the stirring, after warming to room temperature, 8.95 parts of water and 17.9 parts of dichloromethane were added to the obtained mixture, and the obtained reaction mixture was transferred to a separating funnel, and hydrochloric acid was added to the mixture until water. The layer is neutral and the organic layer and the aqueous layer are separated. The recovered organic layer was washed with 17.9 parts of saturated brine, and dried over anhydrous magnesium sulfate. The obtained organic layer was subjected to distillation and further dried to obtain 3.92 parts of a reaction product in a yield of 38%.

With respect to the above reaction product, it was confirmed to be nonafluorobutanesulfonamide based on the analysis results described below.

MS (ESI) (m/z) 298 (-)

¹ H-NMR δ 9.14 (br, 2H)

¹⁹ F-NMR δ -76.3(t), -110.1(t), -117.2(t), -121.7(td)

[Synthesis Example 2]

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to make a nitrogen atmosphere, and 10.0 parts of sodium p-vinylbenzenesulfonate salt hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto. 1.84 parts of N,N-dimethylformamide and 72.5 parts of acetonitrile. The flask was placed in an ice bath, and 11.8 parts of sulfinium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the mixture while stirring the mixture.

After completion of the dropwise addition, the obtained mixture was heated to 70 ° C, kept at this temperature for 3 hours, and further an aqueous sodium hydrogencarbonate solution was added.

Further using an aqueous solution of sodium hydrogencarbonate and ethyl acetate to obtain a reaction mixture obtained The liquid separation was carried out to recover the organic layer. The organic layer was washed with 18% by mass of brine and dried over anhydrous magnesium sulfate. The obtained organic layer was further subjected to distillation and drying under reduced pressure, whereby 8.32 parts of p-vinylbenzenesulfonium chloride was obtained in a yield of 82%.

Next, a suitable amount of nitrogen gas was introduced into a flask having a dropping funnel and a stirrer to thereby make it into a nitrogen atmosphere, and 10.0 parts of nonafluorobutsulfonamide synthesized in Synthesis Example 1, 118 parts of dichloromethane, and triethyl group were added. 13.3 parts of amine. The flask was placed in an ice bath, and while stirring the mixture obtained, 14.0 parts of p-vinylbenzenesulfonyl chloride was added dropwise to the mixture.

After the dropwise addition for 2 hours, the mixture was warmed to room temperature, and further stirred for 5 hours, and then ion-exchanged water was added. The organic layer was recovered from the obtained reaction mixture, and the organic layer was washed with ion-exchanged water and dried by adding anhydrous magnesium sulfate. The obtained organic layer was filtered and purified by column chromatography to obtain 11.7 parts of the reaction product in a yield of 63%.

From the analysis results described below, it was confirmed that the reaction product was a triethylamine salt of (p-vinylphenyl) nonafluorobutylsulfonimide represented by the formula (M-1).

MS (ESI) (m/z) 103 (+), 464 (-)

¹ H-NMR δ 8.83 (br, 1H), 7.73 (d, J = 8.3 Hz, 2H), 7.58 (d, J = 8.3 Hz, 2H), 6.79 (dd, 1H), 5.96 (d, 1H), 5.38 (d, 1H), 3.09 (q, 6H), 1.17 (t, 9H)

¹⁹ F-NMR δ-76.3(t), -109.0(t), -117.0(t), -121.6(t)

[Synthesis Example 3]

Appropriate amount of nitrogen in a flask with a reflux condenser, a dropping funnel and a stirrer Gas, thereby making it a nitrogen atmosphere, in which 10.0 parts of sodium p-vinylbenzenesulfonate hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.84 parts of N,N-dimethylformamide, and acetonitrile were added. 72.5 servings. The flask was placed in an ice bath, and 11.8 parts of sulfinium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the mixture while stirring the mixture. After the completion of the dropwise addition, the obtained mixture was heated to 70 ° C, and the temperature was maintained for 3 hours, and further an aqueous sodium hydrogencarbonate solution was added. Thereafter, the obtained reaction mixture was subjected to liquid separation using an aqueous sodium hydrogencarbonate solution and ethyl acetate, and the organic layer was collected. The organic layer was washed with 18% by mass of brine and dried over anhydrous magnesium sulfate. The obtained organic layer was subjected to distillation, followed by drying under reduced pressure, whereby 8.32 parts of p-vinylbenzenesulfonium chloride was obtained in a yield of 82%.

Next, a suitable amount of nitrogen gas was introduced into a flask having a dropping funnel and a stirrer to form a nitrogen atmosphere, and 10.0 parts of trifluoromethanesulfonamide (manufactured by Tokyo Chemical Industry Co., Ltd.), 243 parts of dichloromethane, and three were added. Ethylamine 24.8 parts.

The flask was placed in an ice bath, and while stirring the mixture obtained, 17.7 parts of p-vinylbenzenesulfonyl chloride was added dropwise to the mixture, and the flask was placed in an ice bath for 2 hours. Thereafter, the obtained mixture was warmed to room temperature, ion-exchanged water was added, and the organic layer was recovered from the obtained reaction mixture. The organic layer was washed with ion-exchanged water and dried by anhydrous magnesium sulfate. After the obtained organic layer was filtered, purification was carried out by column chromatography to obtain 23.2 parts of the reaction product in a yield of 80%.

From the analysis results described below, it was confirmed that the reaction product was a triethylamine salt of (p-vinylphenyl)trifluoromethanesulfonimide represented by the formula (M-2).

MS (ESI) (m/z) 103 (+), 314 (-)

¹ H-NMR δ 8.83 (br, 1H), 7.72 (d, 1H), 7.58 (d, 1H), 6.79 (dd, 1H), 5.95 (d, 1H), 5.39 (d, 1H), 3.09 (m) , 6H), 1.17 (t, 9H)

¹⁹ F-NMR δ -73.8(s)

[Synthesis Example 4]

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make it into a nitrogen atmosphere, and 10.0 parts of (p-vinylphenyl) nonafluorobutanesulfonate triethylamine salt was placed. 27.0 parts of cyclohexanone and 7.5 parts of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred and heated to 100 °C.

Next, using a dropping funnel, a solution of 0.12 part of α,α'-azoisobutyronitrile (manufactured by Kanto Chemical Co., Ltd.) dissolved in cyclohexanone was added dropwise to the obtained mixture in 15 minutes. After the dropwise addition of α,α'-azoisobutyronitrile, the obtained mixture was kept at the same temperature for 3 hours, and then cooled to room temperature.

After 106 parts of acetone was added to the obtained reaction solution, the mixture was stirred, and the obtained mixed liquid droplet was added to 3300 parts of hexane to precipitate a polymer.

The precipitated polymer was washed with hexane and further dried to obtain a polymer (12.9 parts, yield: 73%).

According to ¹ H-NMR analysis, it was found that the obtained polymer had a structural unit represented by the formula (P-1), and the ratio of p to q was 1:1.2. Hereinafter, this polymer is referred to as polymer 1. The polymer 1 had a weight average molecular weight Mw of 12,000, a number average molecular weight Mn of 8,500, and a molecular weight distribution of 1.4.

[Synthesis Example 5]

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make it into a nitrogen atmosphere, and 10.0 parts of (p-vinylphenyl) nonafluorobutanesulfonate triethylamine salt was placed. 19.1 parts of cyclohexanone and 19.6 parts of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were heated to 100 ° C while stirring. Next, using a dropping funnel, a solution of 0.10 part of α,α'-azoisobutyronitrile (manufactured by Kanto Chemical Co., Ltd.) dissolved in cyclohexanone was added dropwise to the obtained mixture in 15 minutes. After the dropwise addition of α,α'-azoisobutyronitrile, the obtained mixture was kept at the same temperature for 3 hours, and then cooled to room temperature.

To the reaction solution, 221 parts of acetone was added and stirred, and the obtained mixed liquid droplet was added to 4,850 parts of hexane to precipitate a polymer. The precipitated polymer was washed with hexane and further dried to obtain 22.6 parts of a polymer (yield 77%).

According to ¹ H-NMR analysis, it was found that the polymer had a structural unit represented by the formula (P-2), and the ratio of p to q in the formula (P-2) was 1:6.7. Hereinafter, this polymer is referred to as polymer 2. The polymer 2 had a weight average molecular weight Mw of 10,000, a number average molecular weight Mn of 7,500, and a molecular weight distribution of 1.4.

[Synthesis Example 6]

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, and 10.0 parts of (p-vinylphenyl)trifluoromethanesulfonimide triethylamine salt was placed. Further, 13.1 parts of cyclohexanone and 13.5 parts of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were heated to 100 ° C while stirring. Next, in the flask, a solution of 0.15 parts of α,α'-azoisobutyronitrile (manufactured by Kanto Chemical Co., Ltd.) dissolved in cyclohexanone was added dropwise to the obtained solution using a dropping funnel for 15 minutes. In the mixture. After the dropwise addition of α,α'-azoisobutyronitrile, the obtained mixture was kept at the same temperature for 3 hours, and then cooled to room temperature.

To the obtained reaction solution, 110 parts of acetone was added, and the obtained mixed liquid droplet was added to 4,850 parts of hexane, whereby the polymer was precipitated. The precipitated polymer was washed with hexane and further dried to obtain 17.2 parts of a polymer (yield: 74%).

According to ¹ H-NMR analysis, it was found that the above polymer had a structural unit represented by the formula (P-3), and the ratio of p to q in the formula (P-3) was 1:2.3. Hereinafter, this polymer is referred to as polymer 3.

The polymer 3 had a weight average molecular weight Mw of 23,000, a number average molecular weight Mn of 11,000, and a molecular weight distribution of 2.1.

[Example 1]

Polymer 1 (10.0 parts) was dissolved in 159 parts of dimethyl hydrazine to prepare a solution of polymer 1. Victoria Pure Blue BOH (CI-42595) (cationic dye represented by formula (Q-1); manufactured by Hodogaya Chemical Industry Co., Ltd.) to be derived from the formula (M-1) in the polymer 1. The amount of the structural unit of the compound represented is 90 mol%, added to the solution of the above polymer 1, under reduced pressure by an evaporator (pressure: 900 hPa), 40 ° C, The obtained mixture was stirred for 30 minutes.

To the obtained solution, 1600 parts of water was added, and the precipitate was collected by filtration. The precipitate was washed with water and dried under reduced pressure to obtain a salt 1 (9.1 parts, yield: 42%) of the formula (Q-2).

Salt 1 (0.097g) was dissolved in acetonitrile, with a volume of 100cm ³ of a solution, the solution was further diluted with acetonitrile by 2cm ^3, diluted with a volume of 250cm ³ of a solution (concentration of salt 1: 0.0078g / L) . The absorption spectrum of the diluted solution was measured using a spectrophotometer (quartz cell, optical path length: 1 cm), and as a result, λmax = 618 nm and the maximum absorbance was 1 (arbitrary unit).

[Embodiment 2]

Polymer 2 (10.0 parts) was dissolved in 310 parts of dimethyl hydrazine, thereby preparing a solution of polymer 2. The cationicity represented by the above formula (Q-1) is a ratio of 90 mol% relative to the amount of the structural unit derived from the compound represented by the formula (M-1) in the polymer 2. The dye was added to the solution of the above polymer 2, and the obtained mixture was stirred for 30 minutes under reduced pressure (pressure: 900 hPa) at 40 ° C by an evaporator. 3100 parts of water was added to the obtained reaction liquid, and the precipitate was collected by filtration. The precipitate was washed with water and dried under reduced pressure to obtain a salt 2 (20.0 parts, yield: 57%) of the formula (Q-3).

2 salt (0.099 g) was dissolved in acetonitrile, whereby a solution having a volume of 100cm ^3, the solution was further diluted by 2cm ³ of acetonitrile, diluted with a volume of 250cm ³ of a solution (the concentration of salt 2: 0.0079g / L). The absorption spectrum of the diluted solution was measured using a spectrophotometer (quartz cell, optical path length: 1 cm), and as a result, λmax = 621 nm and the maximum absorbance was 0.7 (arbitrary unit).

[Comparative Example 1]

Polymer 3 (10.0 parts) was dissolved in 159 parts of dimethyl hydrazine, whereby a solution of polymer 3 was prepared. The cation represented by the above formula (Q-1) is a ratio of 90 mol% relative to the amount of the structural unit derived from the compound represented by the above formula (M-2) in the polymer 3. The dye was added to the solution of the above polymer 3, and the obtained mixture was stirred for 30 minutes under reduced pressure (pressure: 900 hPa) at 40 ° C using an evaporator. To the obtained mixture, 1600 parts of water was added, and the precipitate was collected by filtration. The precipitate was washed with water and dried under reduced pressure to obtain a salt 3 (16.4 parts, yield 71%) of the formula (R-2).

The salt of 3 (0.050 g) was dissolved in acetonitrile, whereby a solution having a volume of 50cm ^3, and further the solution was diluted by ion-exchanged water 2cm ^3, thereby obtaining a volume of 250cm ³ of the diluted solution (concentration of salt 3 :0.0080g/L). The absorption spectrum of the diluted solution was measured using a spectrophotometer (quartz cell, optical path length: 1 cm), and as a result, λmax = 610 nm and the maximum absorbance was 1.6 (arbitrary unit).

[Synthesis Example 8]

An appropriate amount of nitrogen gas was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to form a nitrogen atmosphere, and 141 parts of ethyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.) and propylene glycol monomethyl ether B were placed. 178 parts of an acid ester (manufactured by Tokyo Chemical Industry Co., Ltd.) was heated to 85 ° C while stirring.

Next, 38 parts of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 25 parts of E-DCPA (manufactured by Daicel Co., Ltd.), and cyclohexyl maleimide (Italy Chemical Industry Co., Ltd.) were added dropwise over 5 hours. Manufactured: 137 parts, 50 parts of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and a mixed solution of 338 parts of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.).

Furthermore, a mixture of 5 parts of 2,2-azobisisobutyronitrile (manufactured by Kanto Chemical Co., Ltd.) dissolved in 88 parts of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 6 hours. Solution. After the completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a resin having a B-type viscosity (23 ° C) of 23 mPas, a solid content of 25.6% by mass, and a solution acid value of 28 mg-KOH/g. B-1. Resin B-1 had a weight average molecular weight Mw of 8,000 and a molecular weight distribution of 2.1.

[Measurement of Solubility]

With respect to the salts 1 to 3, the solubility per 100 parts of ethyl lactate [EL] described in Table 1 was confirmed. The results obtained are shown in Table 1.

[Example 3]

By coloring agent (A): salt 1 15 parts; resin (B): resin (B-1) 12 parts; polymerizable compound (C): photocurable monomer

(NK Ester A9550; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 13 copies; Polymerization initiator (D): photopolymerization initiator (OXE01; manufactured by BASF Japan Co., Ltd.) 3.4 parts; solvent (E): 4-hydroxy-4-methyl-pentanone 73 parts; solvent (E): 10 parts of propylene glycol monomethyl ether; solvent (E): 70 parts of propylene glycol monomethyl ether acetate; leveling agent (F): polyether modified polyoxylized oil

(Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.027 parts; fluorine-based surfactant (Megafac F-554; manufactured by Di Ai Sheng (DIC) Co., Ltd.) 0.036 parts; antioxidant (G): (Sumilizer GP; Sumitomo Chemical Co., Ltd.) 1.7 parts; and decane coupling agent (H): (KBM-503; manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts

The coloring curable composition 1 was obtained by mixing.

[Example 4]

By coloring agent (A): salt 2 36 parts; resin (B): resin (B-1) 2.0 parts; polymerizable compound (C): photocurable monomer (NK Ester A9550; Xinzhongcun Chemical Industry Co., Ltd. (manufactured by Ltd.) 19 parts; polymerization initiator (D): photopolymerization initiator (OXE01; manufactured by BASF Japan Co., Ltd.) 4.8 parts; solvent (E): 4-hydroxy-4-methyl-pentanone 105 a solvent (E): 15 parts of propylene glycol monomethyl ether; solvent (E): 145 parts of propylene glycol monomethyl ether acetate; Leveling agent (F): polyether modified polyoxyl oil

(Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.039 parts; fluorine-based surfactant (Megafac F-554; manufactured by Di Ai Sheng (DIC) Co., Ltd.) 0.053 parts; antioxidant (G): (Sumilizer GP; Sumitomo Chemical Co., Ltd.) 2.4 parts; and decane coupling agent (H): (KBM-503; manufactured by Shin-Etsu Chemical Co., Ltd.) 0.7 parts

The coloring curable composition 2 was obtained by mixing.

[Comparative Example 2]

By coloring agent (A): salt 3 15 parts; resin (B): resin (B-1) 12 parts; polymerizable compound (C): photocurable monomer (NK Ester A9550; Xinzhongcun Chemical Industry Co., Ltd. Made by Ltd.) 14 parts; polymerization initiator (D): photopolymerization initiator

(OXE01; manufactured by BASF Japan Co., Ltd.) 3.4 parts; solvent (E): 4-hydroxy-4-methyl-pentanone 73 parts; solvent (E): propylene glycol monomethyl ether 10 parts; solvent (E): propylene glycol 71 parts of monomethyl ether acetate; leveling agent (F): polyether modified polyoxylized oil

(Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.027 parts; fluorine-based surfactant (Megafac F-554; manufactured by Di Ai Sheng (DIC) Co., Ltd.) 0.037 parts; Antioxidant (G): (Sumilizer GP; Sumitomo Chemical Co., Ltd.) 1.7 parts; and decane coupling agent (H): (KBM-503; manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts

The coloring curable composition 3 was obtained by mixing.

[Production of color filter]

The colored curable composition 1 was applied onto a 5 cm square glass substrate (#1737; manufactured by Corning Incorporated) by spin coating, and then prebaked at 100 ° C for 3 minutes to form a color. Composition layer 1. After cooling, the colored composition layer 1 was exposed to light at an exposure amount of 150 mJ/cm ² (365 nm basis) using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). No reticle is used in this exposure. The exposed coloring composition layer 1 was baked in an oven at 230 ° C for 20 minutes, and then baked to prepare a color filter 1 (having a film thickness of 2 to 4 μm). The colored curable composition 2 and the colored curable composition 3 were used instead of the colored curable composition 1, and the colored composition layer 2, the colored composition layer 3, the color filter 2, and the color filter were produced in the same manner. 3.

[NMP resistance evaluation 1]

A 1.9 cm square was cut out from the central portion of the color filter, and N-methylpyrrole at 80 ° C was measured using a color measuring machine (OSP-SP-200; manufactured by Olympus) for the obtained test piece. The color difference (ΔEab*) before and after the immersion in the ketone for 5 minutes.

With respect to the color filter 1, the color filter 2, and the color filter 3 obtained by the compositions of the third embodiment, the fourth embodiment, and the comparative example 2, the NMP resistance evaluation described above was carried out, and the color difference was observed ( ΔEab*) is 7.8 in the color filter 1 obtained in Example 3, 9.9 in the color filter 2 obtained in Example 4, and the color filter 3 obtained in Comparative Example 2. The middle is 26.3.

[NMP resistance evaluation 2]

Cut out 1.9 cm square from the center of the color filter, for the test obtained The color difference (ΔEab*) before and after the immersion in the N-methylpyrrolidone at 23 ° C for 40 minutes was measured using a color measuring machine (OSP-SP-200; manufactured by Olympus Corporation).

The color filter 2 and the color filter 3 obtained by the compositions of Example 4 and Comparative Example 2 were subjected to the above-mentioned NMP resistance evaluation, and as a result, the color difference (ΔEab*) was obtained in Example 4. It was 1.0 in the color filter 2 and 7.4 in the color filter 3 obtained in Comparative Example 2.

Further, regarding the color difference (ΔEab*), the smaller the value, the higher the NMP resistance.

[Industrial availability]

The salt of the present invention can be used as a material for a color hardening composition which can be made into a color filter excellent in NMP resistance. The color filter can be used as a color filter used in a display device (a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state imaging device.

Claims (10)

A salt comprising (a) a cation represented by the formula (AI), and (b) a polymer having a structural unit derived from the anionic compound represented by the formula (A-II): [In the formula (AI), R ⁴¹ to R ⁴⁸ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a aralkyl group having 7 to 30 carbon atoms having a substituent, R ⁴¹ and R ⁴² , R ⁴³ and R ⁴⁴ , and R ⁴⁵ and R ⁴⁶ may be bonded to each other to form a nitrogen atom together with the bonded nitrogen atom. Rings, R ⁴⁷ and R ⁴⁸ may also be bonded to each other to form a ring together with the carbon atoms bonded thereto] [In the formula (A-II), X represents an alkyl group having 2 or 8 carbon atoms which may be substituted with a fluorine atom; Y represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, carbon a 6 to 20 aryl group, or a combination thereof, wherein the methylene group constituting the above aliphatic hydrocarbon group may be substituted with an oxygen atom, -CO- or -N(R ⁵² )-, wherein The methylene group is not substituted at the same time, and the methylene group at the terminal is not substituted; R ⁵¹ represents a hydrogen atom or a methyl group; and R ⁵² represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, An aryl group having 6 to 20 carbon atoms having a substituent or an aralkyl group having 7 to 30 carbon atoms which may have a substituent. The salt of claim 1, wherein X is a perfluoroalkyl group having 2 to 8 carbon atoms. A salt according to claim 1 or 2 wherein X is perfluorobutyl. A salt according to claim 1 or 2, wherein Y is an exoaryl group having 6 to 20 carbon atoms. A salt according to claim 1 or 2, wherein Y is a phenylene group. A coloring agent comprising the salt of claim 1 or 2. A colored hardening composition comprising the salt of claim 1 or 2, a resin, a polymerizable compound, and a polymerization initiator. A coating film formed from the color hardening composition of claim 7. A color filter formed by the color hardening composition of claim 7. A display device comprising a color filter as in claim 9.