TW201529741A - Triarylmethane-based colored composition - Google Patents

Abstract

The subject of the invention is to provide a colored composition which has higher heat resistance than the conventional colored compositions. That is, the invention relates to compounds represented by the following formula (1). (In the formula, each of R1 to R4 and R14 independently represents a hydrogen atom; an alkyl group having 1 to 30 carbons; a phenyl group, a naphthyl group, or a benzyl group which has a substituent or non-substituent. Each of R5 to R7 independently represents a hydrogen atom or a methyl group. Each of R8 to R13 independently represents an alkyl group having 1 to 21 carbons, an aryl group, a hydroxyl group, a nitro group, a sulfo group, or an alkoxy group having 1 to 3 carbons. A1 represents: having at least one group of -N(R15)-, -O-, -OCO-, -COO-, or an arylene group in the chain, and an alkylene group having 1 to 21 carbons which is substituted by a hydroxyl group; an alkylene group having 1 to 21 carbons which has at least one group of -N(R15)-, -O-, -OCO-, -COO-, or an arylene group in the chain; or an alkylene having 1 to 21 carbons. A2 represents -NH- or -O-. R15 represents a hydrogen atom; an alkyl group having 1 to 30 carbons; a phenyl group, a naphthyl group, or a benzyl group which has a substituent or non-substituent. An<SP>-</SP> represents an aryl group having an electron-withdrawing substituent, an anion of a sulfonyl group or a halogenated alkyl group which has an electron-withdrawing substituent).

Description

Triarylmethane coloring composition

The present invention relates to a triarylmethane-based coloring compound, a polymer containing a monomer unit derived from the compound, and a colored composition containing the polymer.

As a method of forming a color pixel in the production of a color filter such as a liquid crystal display element or a solid-state image sensor, a dyeing method or a dye dispersion method using a dye in a colorant, and pigment dispersion using a pigment are known. Method, electrodeposition method, printing method, etc. In recent years, as a characteristic of a color filter, it is particularly required to improve brightness and contrast. According to the pigment dispersion method using a pigment, since the heat resistance and the light resistance are higher than that of the dye, the deterioration in the heating step at the time of panel production is small, and a color pixel having high long-term reliability can be obtained. Therefore, the current pigment dispersion method has become the mainstream. However, in the case of using a pigment, since the pigment itself has a relatively large particle diameter, there is a problem that the contrast is lowered due to scattering of light. Attempts have also been made to granulate pigments, but there are limits to microparticles, and it has also been a problem to ensure dispersion stability of finely divided pigments.

On the other hand, as a method for eliminating such a problem, a method of forming a color pixel using a dye is currently under study. Light scattering in the case of dyes It is suppressed, so the contrast is improved. However, when the dye is compared with a pigment, the heat resistance is lower, and depending on the type, there is a dye having sublimation properties, and thus there are problems such as reduction in brightness, fading, and change in hue. Therefore, in the method of using a dye, it is required to eliminate this problem. Regarding the color filter, various kinds of coloring resin compositions using a triarylmethane-based pigment as a dye have been reported, for example, in Japanese Patent Laid-Open No. 2011-116801.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open 2011-116801

A conventional colored resin composition using a triarylmethane-based dye cannot obtain a heat resistance in a practical range. Accordingly, an object of the present invention is to provide a coloring composition having higher heat resistance than conventional coloring compositions.

The present inventors have conducted diligent research in view of the above circumstances, and as a result, found that a triarylmethane-based compound having an anion having a specific structure as a counter anion and having an ethylenically unsaturated bond, or a single derived from the compound The polymer of the bulk unit is used as a dye to obtain a colored composition excellent in heat resistance, and the present invention has been completed. In addition, at this time, an ethylenically unsaturated bond is introduced into the conventionally known triarylmethane-based compound, and as a result, the reaction does not proceed, and the intended triarylmethane-based compound having an ethylenically unsaturated bond cannot be obtained. Therefore, the inventor Efforts have been made to find a method for efficiently synthesizing a triarylmethane-based compound having an ethylenically unsaturated bond.

In other words, the present invention relates to a compound represented by the following formula (1) (hereinafter sometimes referred to simply as a compound of the present invention).

(wherein R ₁ to R ₄ and R ₁₄ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted phenyl group, a naphthyl group or a benzyl group, and R ₅ to R _7; Each independently represents a hydrogen atom or a methyl group, and R ₈ to R ₁₃ each independently represent an alkyl group having 1 to 21 carbon atoms, an aryl group, a hydroxyl group, a nitro group, a sulfo group or an alkoxy group having 1 to 3 carbon atoms; ₁ represents a carbon number of 1 to 21 having at least one group of -N(R ₁₅ )-, -O-, -OCO-, -COO- or an aryl group in the chain and having a hydroxyl group as a substituent. An alkyl group having from 1 to 21 carbon atoms having at least one group of -N(R ₁₅ )-, -O-, -OCO-, -COO- or an aryl group in the chain; having a hydroxyl group as a substituent The alkyl group having 1 to 21 carbon atoms; or the alkyl group having 1 to 21 carbon atoms; A ₂ represents -NH- or -O-; and R ₁₅ represents a hydrogen atom and an alkyl group having 1 to 30 carbon atoms; a substituent or an unsubstituted phenyl, naphthyl or benzyl group; An ^- represents an anion having an electron withdrawing substituent, a sulfonyl group having a electron withdrawing substituent or an alkyl halide group)"," a polymer containing a monomer unit derived from the compound represented by the above formula (1) (hereinafter sometimes A method of producing a compound represented by the following formula (1) (hereinafter sometimes referred to simply as a production method of the present invention), and a compound represented by the following formula (9) After reacting with a compound represented by the following formula (10), an oxidation reaction or a salt exchange reaction is carried out;

(wherein R ₇ represents a hydrogen atom or a methyl group, and R ₈ to R ₁₃ each independently represent an alkyl group having 1 to 21 carbon atoms, an aryl group, a hydroxyl group, a nitro group, a sulfo group, or an alkane having 1 to 3 carbon atoms; Alkyl; R ₁₄ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted phenyl group, a naphthyl group or a benzyl group; and A ₁ represents a group having -N(R ₁₅ )- in the chain. , -O-, -OCO-, -COO- or at least one group of an aryl group, and having a hydroxyl group as a substituent, a C 1~21 alkyl group; having -N(R ₁₅ )- in the chain , an alkyl group having 1 to 21 carbon atoms of at least one group of -O-, -OCO-, -COO- or an extended aryl group; an alkylene group having 1 to 21 carbon atoms having a hydroxyl group as a substituent; or carbon a 1 to 21 alkylene group, A ₂ represents -NH- or -O-; R ₁₅ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted phenyl group, a naphthyl group or a benzyl group. base),

(wherein R ₁ to R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted phenyl group, a naphthyl group or a benzyl group, and R ₅ to R ₆ are each independently Represents a hydrogen atom or a methyl group,

(wherein, R ₁ to R ₁₄ , A ₁ , and A _{2 are} the same as described above; and An ^- represents an aryl group having an electron-donating substituent, a sulfonyl group having an electron-donating substituent, or an alkyl halide; An anion), "a colored composition containing the compound or the polymer", and "a coloring composition for a color filter containing the compound or the polymer".

When the colored composition containing the compound or polymer of the present invention is heated at 230 ° C for 30 minutes, fading due to heating is small and high. Heat resistant effect. That is, since the polymer and the colored composition of the present invention have a heat resistance superior to that of the conventional coloring composition, an excellent colored cured film can be formed. Therefore, the coloring composition of the present invention can be used for a liquid crystal display device (Liquid Crystal Display (LCD)) or a solid-state imaging device (Charge Coupled Device (CCD), Complementary Metal Oxide Semiconductor (Complementary Metal Oxide Semiconductor) In the use of color filters such as color filters used in CMOS, etc., for printing inks, inkjet inks, and coatings, it is particularly suitable for color filters used in liquid crystal display devices. Further, the colored composition of the present invention can be used as a colored resin molded article by forming into a sheet, a film, a bottle, a cup, or the like by a conventionally known molding method. Therefore, it can also be used for applications such as glasses and contact lenses, and can also be used for the same purpose by forming a multilayer structure of a known resin. In addition to this, for example, it can also be used for an optical film, a hair coloring agent, a marking substance for a compound or a living substance, a material of an organic solar cell, or the like.

[Anion containing an aryl group or a halogenated alkyl group having an electron-donating substituent]

An anion (an anion of the present invention) containing an aryl group or a halogenated alkyl group having an electron-donating substituent represented by An ^{- of} the formula (1) may, for example, be an aryl group having a electron-withdrawing substituent, and having a pull a sulfonyl group of an electron substituent or a halogenated alkyl group such as a sulfonate anion, a nitrogen anion (N ^- ), a quaternary boron anion, a nitrate ion, a phosphate ion, etc., preferably a sulfonate anion, a nitrogen anion a quaternary boron anion, more preferably a quaternary boron anion.

Examples of the electron withdrawing substituent in the aryl group having an electron withdrawing substituent or the sulfonyl group having an electron withdrawing substituent of the anion of the present invention include a halogenated alkyl group having 1 to 3 carbon atoms, a halogen group, and a nitrate. The base or the like is preferably a halogenated alkyl group having 1 to 3 carbon atoms, a halogen group, and particularly preferably a halogen group.

Examples of the halogenated alkyl group having 1 to 3 carbon atoms as the electron-donating substituent include chloromethyl group, trichloromethyl group, 2-chloroethyl group, 2,2,2-trichloroethyl group, and 2- Chloropropyl, 3-chloropropyl, 2-chloro-2-propyl and the like chloroalkyl; bromomethyl, tribromomethyl, 2-bromoethyl, 2,2,2-tribromoethyl, 2 a bromoalkyl group such as bromopropyl, 3-bromopropyl or 2-bromo-2-propyl; iodomethyl, triiodomethyl, 2-iodoethyl, 2,2,2-triiodoethyl, Iodoethyl group such as 2-iodopropyl, 3-iodopropyl or 2-iodo-2-propyl; fluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, 3-fluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl, seven A fluoroalkyl group such as a fluoropropyl group. Among them, a fluoroalkyl group is preferred, and a trifluoromethyl group is preferred.

The halogen group as the electron-donating substituent may, for example, be a fluorine group, a chlorine group, a bromine group or an iodine group, and is preferably a fluorine group.

In the above specific examples, the electron-donating substituent in the aryl group having an electron-withdrawing substituent of the anion of the present invention is preferably a group having a strong electron-withdrawing power, and is preferably a trifluoromethyl group, a fluorine group or a nitrate. More preferably, it is a fluorine group or a nitro group.

In the specific example, the electron-donating substituent in the sulfonyl group having an electron-withdrawing substituent of the anion of the present invention is preferably a trifluoromethyl group, a pentafluoroethyl group or a heptafluoro group. Propyl, fluorine, and the like.

The aryl group in the aryl group having an electron-withdrawing substituent of the anion of the present invention may, for example, be a phenyl group or a naphthyl group, and is preferably a phenyl group.

Specific examples of the aryl group having an electron-withdrawing substituent of the anion of the present invention include, for example, the groups represented by the following formula (11) and formula (12).

(wherein m represents an integer of 1 to 5, and m of R ₄₁ each independently represents a halogenated alkyl group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and * represents a bonding bond)

(wherein k represents an integer of 1 to 7. R ₄₁ and * are the same as described above. k R ₄₁ may be the same or different)

m is usually an integer of 1 to 5, and when R ₄₁ is a halogen atom, m is preferably 2 to 5, more preferably 3 to 5, and still more preferably 5. When R ₄₁ is a nitro group, m is preferably from 1 to 3, more preferably 1. When R ₄₁ is a halogenated alkyl group, m is preferably from 1 to 5.

k is usually an integer of 1 to 7, and when R ₄₁ is a halogen atom, k is preferably 2 to 7. When R ₄₁ is a nitro group, k is preferably from 1 to 3, more preferably 1. When R ₄₁ is a halogenated alkyl group, k is preferably from 1 to 7.

The halogenated alkyl group having 1 to 3 carbon atoms of R ₄₁ in the formula (11) and the formula (12) may be a halogenated group having 1 to 3 carbon atoms with the electron withdrawing substituent in the anion of the invention. The same groups of alkyl groups, and preferred groups are also the same.

The halogen atom in the general formula (11) and the general formula (12) may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among them, a fluorine atom is preferred.

Preferred specific examples of R ₄₁ in the formula (11) and the formula (12) are the same as those in the electron withdrawing substituent in the anion of the invention.

Specific examples of the group represented by the formula (11) include a trifluoromethylphenyl group, a bis(trifluoromethyl)phenyl group, a tris(trifluoromethyl)phenyl group, and a monofluorophenyl group. Difluorophenyl, trifluorophenyl, perfluorophenyl, monochlorophenyl, dichlorophenyl, trichlorophenyl, perchlorophenyl, monobromophenyl, dibromophenyl, tribromophenyl, All-bromophenyl, monoiodophenyl, diiodophenyl, triiodophenyl, allyl iodide, nitrophenyl, dinitrophenyl, trinitrophenyl, etc., preferably difluorophenyl , trifluorophenyl, perfluorophenyl, etc., more preferably perfluorophenyl.

Specific examples of the group represented by the formula (12) include a trifluoromethylnaphthyl group, a bis(trifluoromethyl)naphthyl group, a tris(trifluoromethyl)naphthyl group, and a monofluoronaphthyl group. Difluoronaphthyl, trifluoronaphthyl, perfluoronaphthyl, monochloronaphthyl, dichloronaphthyl, trichloronaphthyl, perchloronaphthyl, monobromonaphthyl, dibromonaphthyl, tribromonaphthyl, All-bromonaphthyl group, monoiodonaphthyl group, diiodonaphthyl group, triiodonaphthyl group, periodophthyl group, nitronaphthyl group, dinitronaphthyl group, trinitronaphthyl group and the like.

In the specific example, the electron-withdrawing substitution in the anion of the present invention The aryl group of the group is preferably a group represented by the formula (11), and specifically, a trifluoromethylphenyl group, a nitrophenyl group, a dinitrophenyl group, a trinitrophenyl group, and a single group are preferable. Fluorophenyl, difluorophenyl, trifluorophenyl, perfluorophenyl, more preferably difluorophenyl, trifluorophenyl, nitrophenyl, perfluorophenyl, and further preferably nitrophenyl, Perfluorophenyl, especially preferably perfluorophenyl.

Examples of the sulfonyl group having an electron-donating substituent in the anion of the present invention include -SO ₂ -CF ₃ , -SO ₂ -C ₂ F ₅ , -SO ₂ -C ₃ F ₇ , -SO ₂ -F , -SO ₂ -Cl, -SO ₂ -Br, -SO ₂ -I, and the like.

The halogenated alkyl group in the anion of the present invention may, for example, be a halogenated alkyl group having 1 to 3 carbon atoms, and examples thereof include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a trichloromethyl group, and a pentachloroethyl group. Heptachloropropyl, tribromomethyl, pentabromoethyl, heptabromopropyl, triiodomethyl, pentaiodoethyl, heptiodopropyl, etc., preferably trifluoromethyl, pentafluoroethyl, seven Fluoropropyl group and the like.

Specific examples of the anion of the aryl group having a chargeable substituent, a sulfonyl group having an electron-donating substituent, or a halogenated alkyl group of the present invention include, for example, the following formula (13) to formula (18). The anion indicated.

(wherein R ₄₁ and m are the same as described above. m R ₄₁ may be the same or different)

(wherein R ₄₁ and k are the same as described above. k R ₄₁ may be the same or different)

(wherein R ₄₁ and k are the same as described above. k R ₄₁ may be the same or different)

(wherein R ₄₂ to R ₄₅ each independently represent a halogenated alkyl group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and m ₁ to m ₄ each independently represent an integer of 1 to 5. m ₁ R ₄₂ may be used. The same or different, m ₂ R ₄₃ , m ₃ R ₄₄ and m ₄ R _{45 can} also be the same or different)

(wherein R ₄₆ each independently represents a halogenated alkyl group having 1 to 3 carbon atoms or a halogen atom, and at least one of the four R ₄₆ represents a halogenated alkyl group having 1 to 3 carbon atoms)

(wherein R ₄₇ and R ₄₈ each independently represent a halogenated alkyl group having 1 to 3 carbon atoms or a halogen atom, and R ₄₇ and R _{48 may} form a halogenated alkyl group having 2 to 3 carbon atoms)

The combination of R ₄₁ and m in the formula (13) is, for example, a combination described in the following table. Further, the m R ₄₁ are independent, and preferably m R _{41 are the} same.

Preferable examples of the anion represented by the formula (13) include the following anions.

The combination of R ₄₁ and m in the general formula (14) and the general formula (15) is, for example, a combination described in the following table. Further, the m R ₄₁ are independent, and preferably m R _{41 are the} same.

Preferred specific examples of the anion represented by the general formula (14) and the general formula (15) For example, the following anions can be mentioned.

The halogenated alkyl group having 1 to 3 carbon atoms of R ₄₂ to R ₄₅ in the formula (16) may be the same as the halogenated alkyl group in the anion of the present invention, and preferred groups are also the same.

The halogen atom of R ₄₂ to R ₄₅ in the formula (16) may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among them, a fluorine atom is preferred.

The combination of R ₄₂ to R ₄₅ and m ₁ to m ₄ in the formula (16) is, for example, a combination described in the following table.

Preferable examples of the anion represented by the formula (16) include the following anions.

Among them, the following anions are preferred.

More preferably, it is an anion described below.

The halogenated alkyl group of R ₄₆ of the formula (17) may be the same as the halogenated alkyl group of the anion of the present invention, and preferred groups are also the same.

The halogen atom of R ₄₆ in the formula (17) may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among them, a fluorine atom is preferred.

Preferable specific examples of the anion represented by the formula (17) include CF ₃ BF ₃ ^- , C ₂ F ₅ BF ₃ ^- , C ₃ F ₇ BF ₃ ^- , B (CF ₃ ) ₄ B ^- , B (C ₂ F ₅ ) ₄ B ^- , B(C ₃ F ₇ ) ₄ B ^- and the like.

The halogenated alkyl group of R ₄₇ of the formula (18) may be the same as the halogenated alkyl group of the anion of the present invention, and preferred groups are also the same.

The halogen atom of R ₄₈ of the formula (18) includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom is preferred.

Examples of the halogenated alkyl group having 2 to 3 carbon atoms formed by R ₄₇ and R _{48 of} the formula (18) include a tetrafluoroethyl group and a hexafluoropropyl group.

Preferable specific examples of the anion represented by the formula (18) include the following anions.

The anion of the present invention is preferably an anion represented by the formula (16), the formula (17) or the formula (18), more preferably an anion represented by the formula (16). In the above specific examples, the following anions are preferred.

Among them, the following anions are more preferred.

[Compound of the present invention]

The compound of the present invention is a compound represented by the formula (1).

The alkyl group having 1 to 30 carbon atoms of R ₁ to R ₄ and R ₁₄ in the formula (1) may be linear or branched or cyclic, preferably an alkyl group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, isobutyl group, second butyl group, tert-butyl group, and n-pentyl group. , 1-ethylpropyl, 2-methylbutyl, 1,2-dimethylpropyl, cyclopentyl, isopentyl, second pentyl, third pentyl, neopentyl, n-hexyl, 2-methylpentyl, 1-ethylbutyl, 1,2-dimethylbutyl, 2,3-dimethylbutyl, cyclohexyl, isohexyl, second hexyl, third hexyl, neohexyl , 2-heptyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, seventeen Alkyl, octadecyl, nonadecyl, arachyl, eicosyl, behenyl, behenyl, docosyl, tetracosyl , dipentadecyl, hexadecyl, hexadecyl, octadecyl, octacosyl, octadecyl, isoheptyl, isooctyl, isodecyl, isoindole Base, is undecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, iso Heptadecyl, iso-octadecyl, isodecyl, iso-arachiyl, iso-eicosyl, iso-octadecyl, iso-docosyl, iso-tris-trialkyl, hetero-di Tetradecyl, iso-pentadecyl, iso-hexadecyl, iso-heptadecyl, iso-octadecyl, iso-dodecyl, iso-t-octadecyl, 1-methyl Hexyl, 1-ethylheptyl, 1-methylheptyl, 1-cyclohexylethyl, 1-heptyloctyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl , 2,6-Dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,3-dimethylcyclohexyl , 3,3,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, 2-ethylhexyl, 1-adamantyl, 2-adamantyl, etc., preferably methyl, ethyl, N-propyl, isopropyl, n-butyl, 1-methylpropyl, isobutyl, t-butyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl 1,2-dimethylpropyl, cyclopentyl, isopentyl, second pentyl, third amyl, neopentyl, n-hexyl, 2-methylpentyl, 1-ethylbutyl, 1,2-dimethylbutyl, 2,3- Methylbutyl, cyclohexyl, isohexyl, cyclohexyl second, third hexyl, neohexyl and the like, more preferably methyl, ethyl, n-propyl, isopropyl and the like.

The phenyl group, naphthyl group or benzyl group of R ₁ to R ₄ and R ₁₄ of the formula (1) may have one to five, preferably one to three, substituents. Examples of the substituent include methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, isobutyl, t-butyl, t-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 1,2-dimethylpropyl, cyclopentyl, isopentyl, second pentyl, third pentyl, neopentyl, n-hexyl, 2 -methylpentyl, 1-ethylbutyl, 1,2-dimethylbutyl, 2,3-dimethylbutyl, cyclohexyl, isohexyl, second hexyl, third hexyl, neohexyl, etc. An alkyl group having 1 to 6 carbon atoms; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a sulfonic acid group; a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a third butoxy group, Alkoxy group having 1 to 6 carbon atoms such as hexyloxy group; hydroxyalkyl group such as hydroxyethyl group or hydroxypropyl group; methoxyethyl group, ethoxyethyl group, ethoxypropyl group, butoxyethyl group, etc. Alkoxyalkyl group having 2 to 10 carbon atoms; hydroxyalkoxy group having 1 to 6 carbon atoms such as 2-hydroxyethoxy group; carbon number such as 2-methoxyethoxy group and 2-ethoxyethoxy group Alkoxy alkoxy group of 2 to 10; sulfoalkyl group having 1 to 6 carbon atoms such as 2-sulfoethyl group; carboxymethyl group, carboxyethyl group, carboxypropyl group, a carboxyalkyl group having 2 to 7 carbon atoms such as a butyl group, a carboxypentyl group or a carboxyhexyl group; a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group, a cyanopentyl group, a cyanohexyl group, etc. A cyanoalkyl group having 2 to 7 carbon atoms.

In the specific examples of R ₁ to R ₄ and R ₁₄ , a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 1-methylpropyl group, an isobutyl group, and a second group are preferable. Base, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 1,2-dimethylpropyl, cyclopentyl, isopentyl, second pentyl, third Pentyl, neopentyl, n-hexyl, 2-methylpentyl, 1-ethylbutyl, 1,2-dimethylbutyl, 2,3-dimethylbutyl, cyclohexyl, isohexyl, The second hexyl group, the third hexyl group, the neohexyl group and the like are more preferably a methyl group, an ethyl group, a n-propyl group or an isopropyl group, and more preferably a methyl group or an ethyl group.

R ₅ to R _{7 in the} formula (1) represent a hydrogen atom or a methyl group, preferably a hydrogen atom.

The alkyl group having 1 to 21 carbon atoms of R ₈ to R ₁₃ in the formula (1) may be linear or branched or cyclic, preferably an alkyl group having 1 to 12 carbon atoms, more preferably It is an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, isobutyl group, second butyl group, tert-butyl group and n-pentyl group. , 1-ethylpropyl, 2-methylbutyl, 1,2-dimethylpropyl, cyclopentyl, isopentyl, second pentyl, third pentyl, neopentyl, n-hexyl, 2-methylpentyl, 1-ethylbutyl, 1,2-dimethylbutyl, 2,3-dimethylbutyl, cyclohexyl, isohexyl, second hexyl, third hexyl, neohexyl , 2-heptyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, seventeen Alkyl, octadecyl, nonadecyl, arachidyl, eicosyl, icosyl, isoheptyl, isooctyl, isodecyl, isodecyl, isodecyl, iso Dodecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isodecyl, iso-arachi , iso-eicosyl, isohexadecyl, 1-methylhexyl, 1-ethylheptyl, 1-methylheptyl, 1-cyclohexylethyl, 1 -heptyloctyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,6-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 3,5 - dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, 2- Ethylhexyl or the like, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, isobutyl, t-butyl, t-butyl, n-pentyl , 1-ethylpropyl, 2-methylbutyl, 1,2-dimethylpropyl, cyclopentyl, isopentyl, second pentyl, third pentyl, neopentyl, n-hexyl, 2-methylpentyl, 1-ethylbutyl, 1,2-dimethylbutyl, 2,3-dimethylbutyl, cyclohexyl, isohexyl, second hexyl, third hexyl, neohexyl More preferably, it is a methyl group, an ethyl group, a n-propyl group, an isopropyl group or the like.

The aryl group of R ₈ to R ₁₃ in the formula (1) may, for example, be an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group, and a phenyl group is preferred.

The alkoxy group having 1 to 3 carbon atoms of R ₈ to R ₁₃ in the formula (1) may, for example, be a methoxy group, an ethoxy group, a n-propoxy group or an isopropoxy group.

The alkyl group having 1 to 30 carbon atoms of R ₁₅ in the formula (1) is the same as the alkyl group having 1 to 30 carbon atoms of R ₁ to R ₄ and R ₁₄ , and the preferred group is also the same. .

The substituted or unsubstituted phenyl, naphthyl or benzyl group of R ₁₅ of the formula (1) may, for example, be a substituted or unsubstituted phenyl group with the above R ₁ to R ₄ and R ₁₄ . The groups described in the naphthyl group or the benzyl group are the same, and the preferred groups are also the same.

Carbon atoms in A ₁ of formula (1) is 1 to 21 extending in the alkyl chain has chain an arylene group include phenylene, naphthyl stretch, preferably phenylene.

A ₁ of the formula (1) has at least one group of -N(R ₁₅ )-, -O-, -OCO-, -COO- or an extended aryl group in the chain, and has a hydroxyl group as a substituent. Carbon number of at least one group having a carbon number of 1 to 21 and an alkyl group having -N(R ₁₅ )-, -O-, -OCO-, -COO- or an aryl group in the chain 1~ Alkyl group having 1 to 21 carbon atoms in the alkyl group of 21, "alkyl group having 1 to 21 carbon atoms having a hydroxyl group as a substituent" and "alkyl group having 1 to 21 carbon atoms" are linear It is preferably in the form of a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, and preferably a carbon number of 1 to 3. Specific examples thereof include a methylene group, an ethylidene group, a propyl group, a methyl group ethyl group, a butyl group, a 1-methyl propyl group, a 2-methyl propyl group, and a pentyl group. Methyl butyl, 1,2-dimethylpropyl, 1-ethyl propyl, hexyl, methyl pentyl, heptyl, octyl, thiol, thiol, Undecyl, n-dodecyl, n-tridecyl, tetradecyl, n-pentadecyl, heptadecyl, heptadecyl, octadecyl, succinyl An alkyl group, a rhizoma base, a perylene oxide group, etc., preferably a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc., more preferably a methylene group or a stretching group. Ethyl, propyl, especially preferably ethyl.

A ₁ of the formula (1) has at least one group of -N(R ₁₅ )-, -O-, -OCO-, -COO- or an extended aryl group in the chain, and has a hydroxyl group as a substituent. Examples of the alkylene group having 1 to 21 carbon atoms include a group represented by the following formula (6-1) to formula (6-4).

-N(R ₁₅ )-R ₅₁ -(CH ₂ ) _p1 - (6-1)

(wherein R ₁₅ is the same as described above. R ₅₁ represents an alkylene group having 1 to 7 carbon atoms having a hydroxyl group as a substituent or an exoaryl group having a carbon number of 6 to 10 having a hydroxyl group as a substituent, and p1 represents An integer from 1 to 3)

-N(R ₁₅ )-R ₅₁ -X ₁ -(CH ₂ ) _p2 - (6-2)

(wherein R ₁₅ and R _{51 are} the same as described above. X ₁ represents -O-, -OCO- or -COO-, and p2 represents an integer of 1 to 3)

-R ₅₂ -(CH ₂ )p3- (6-3)

(wherein R ₅₂ represents a aryl group having 6 to 10 carbon atoms having a hydroxyl group as a substituent, and p3 represents an integer of 1 to 3)

-R ₅₁ -X ₁ -(CH ₂ ) _p4 - (6-4)

(wherein R ₅₁ and X _{1 are} the same as described above. p4 represents an integer of 1 to 3)

Examples of the alkylene group having a carbon number of 1 to 7 having a hydroxyl group as a substituent of R ₅₁ of the formula (6-1), the formula (6-3) and the formula (6-4): a hydroxy group A group, a hydroxyl group, an ethyl group, a hydroxy group, a hydroxy group, a hydroxy group, a hydroxy group, a hydroxy group, a hydroxy group, a hydroxy group, a hydroxy group, a hydroxy group, a hydroxy group, a hydroxy group, and a cycloheptyl group.

Examples of the aryl group having 6 to 10 carbon atoms having a hydroxyl group as a substituent of R ₅₁ of the formula (6-1), the formula (6-3) and the formula (6-4): Base, dihydroxyphenylene, hydroxynaphthyl, dihydroxynaphthyl and the like.

The aryl group having 6 to 10 carbon atoms having a hydroxyl group as a substituent of R ₅₂ of the formula (6-3) may be the same group as the exoaryl group having a hydroxyl group as a substituent of the above R ₅₁ .

Preferred examples of the group represented by the formula (6-1) include, for example, -NH-C ₆ H ₉ (OH)-CH ₂ -, -NH-C ₆ H ₉ (OH)-C ₂ H. _5- , -NH-C ₆ H ₉ (OH)-C ₃ H ₇ -, -NH-C ₄ H ₃ (OH)-CH ₂ -, -NH-C ₄ H ₃ (OH)-C ₂ H ₅ -, -NH-C ₄ H ₃ (OH)-C ₃ H ₇ -, -NH-CH ₂ -CH(OH)-CH ₂ -, -NH-CH ₂ -CH(OH)-C ₂ H ₅ - , -NH-CH ₂ -CH(OH)-C ₃ H ₇ -, -N(CH ₃ )-C ₆ H ₉ (OH)-CH ₂ -, -N(CH ₃ )-C ₆ H ₉ (OH )-C ₂ H ₅ -, -N(CH ₃ )-C ₆ H ₉ (OH)-C ₃ H ₇ -, -N(CH ₃ )-C ₄ H ₃ (OH)-CH ₂ -, -N (CH ₃ )-C ₄ H ₃ (OH)-C ₂ H ₅ -, -N(CH ₃ )-C ₄ H ₃ (OH)-C ₃ H ₇ -, -N(CH ₃ )-CH ₂ - CH(OH)-CH ₂ -, -N(CH ₃ )-CH ₂ -CH(OH)-C ₂ H ₅ -, -N(CH ₃ )-CH ₂ -CH(OH)-C ₃ H ₇ - Wait.

Preferred examples of the group represented by the formula (6-2) include, for example, -NH-CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) ₂ -, -NH-CH ₂ - CH(OH)-CH ₂ -O-(CH ₂ ) ₃ -, -NH-CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) ₄ -, -N(CH ₃ )-CH ₂ - CH(OH)-CH ₂ -O-(CH ₂ ) ₂ -, -N(CH ₃ )-CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) ₃ -, -N(CH ₃ ) -CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) ₄ -, -NH-CH ₂ -CH(OH)-CH ₂ -OCO-(CH ₂ ) ₂ -, -NH-CH ₂ - CH(OH)-CH ₂ -OCO-(CH ₂ ) ₃ -, -NH-CH ₂ -CH(OH)-CH ₂ -OCO-(CH ₂ ) ₄ -, -N(CH ₃ )-CH ₂ - CH(OH)-CH ₂ -OCO-(CH ₂ ) ₂ -, -N(CH ₃ )-CH ₂ -CH(OH)-CH ₂ -OCO-(CH ₂ ) ₃ -, -N(CH ₃ ) -CH ₂ -CH(OH)-CH ₂ -OCO-(CH ₂ ) ₄ -, -NH-CH ₂ -CH(OH)-CH ₂ -COO-(CH ₂ ) ₂ -, -NH-CH ₂ - CH(OH)-CH ₂ -COO-(CH ₂ ) ₃ -, -NH-CH ₂ -CH(OH)-CH ₂ -COO-(CH ₂ ) ₄ -, -N(CH ₃ )-CH ₂ - CH(OH)-CH ₂ -COO-(CH ₂ ) ₂ -, -N(CH ₃ )-CH ₂ -CH(OH)-CH ₂ -COO-(CH ₂ ) ₃ -, -N(CH ₃ ) -CH ₂ -CH(OH)-CH ₂ -COO-(CH ₂ ) ₄ -.

Preferred examples of the group represented by the formula (6-3) include, for example, -C ₄ H ₃ (OH)-CH ₂ -, -C ₄ H ₃ (OH)-C ₂ H ₅ -, - C ₄ H ₃ (OH)-C ₃ H ₇ -, -C ₄ H ₂ (OH) ₂ -CH ₂ -, -C ₄ H ₂ (OH) ₂ -C ₂ H ₅ -, -C ₄ H ₂ ( OH) ₂ -C ₃ H ₇ -etc.

Preferred examples of the group represented by the formula (6-4) include, for example, -CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) ₂ -, -CH ₂ -CH(OH) -CH ₂ -O-(CH ₂ ) ₃ -, -CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) ₄ -, -CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) ₂ -, -CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) ₃ -, -CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) ₄ -, -CH ₂ -CH(OH)-CH ₂ -OCO-(CH ₂ ) ₂ -, -CH ₂ -CH(OH)-CH ₂ -OCO-(CH ₂ ) ₃ -, -CH ₂ -CH(OH)-CH ₂ -OCO-(CH ₂ ) ₄ -, -CH ₂ -CH(OH)-CH ₂ -OCO-(CH ₂ ) ₂ -, -CH ₂ -CH(OH)-CH ₂ -OCO-(CH ₂ ) ₃ -, -CH ₂ -CH(OH)-CH ₂ -OCO-(CH ₂ ) ₄ -, -CH ₂ -CH(OH)-CH ₂ -COO-(CH ₂ ) ₂ -, -CH ₂ -CH ( OH)-CH ₂ -COO-(CH ₂ ) ₃ -, -CH ₂ -CH(OH)-CH ₂ -COO-(CH ₂ ) ₄ -, -CH ₂ -CH(OH)-CH ₂ -COO- (CH ₂ ) ₂ -, -CH ₂ -CH(OH)-CH ₂ -COO-(CH ₂ ) ₃ -, -CH ₂ -CH(OH)-CH ₂ -COO-(CH ₂ ) ₄ -, and the like.

A ₁ of the formula (1) "having an alkyl group having 1 to 21 carbon atoms of at least one group having -NR ₁₅ -, -O-, -OCO-, -COO- or an extended aryl group in the chain" For example, a group represented by the following general formula (7-1) to general formula (7-9) can be given.

-N(R ₁₅ )-R ₅₅ - (7-1)

(wherein, R ₅₅ represents an alkylene group having 1 to 21 carbon atoms)

-N(R ₁₅ )-(CH ₂ ) _p5 -OCO-R ₅₃ -COO-(CH ₂ ) _p6 - (7-2)

(wherein R ₁₅ is the same as described above. R ₅₃ represents a phenyl group, an alkylene group having 1 to 7 carbon atoms, and p5 and p6 each independently represent an integer of 1 to 3)

-N(R ₁₅ )-(C ₂ H ₄ O) _p7 -(CH ₂ ) _p8 - (7-3)

(wherein R ₁₅ is the same as described above. p7 represents an integer from 1 to 9, and p8 represents an integer from 1 to 3)

-N(R ₁₅ )-(CH ₂ CH(CH ₃ )O) _p9 -R ₅₄ - (7-4)

(wherein R ₁₅ is the same as described above. p9 represents an integer of 1 to 9, and R ₅₄ represents a branched alkyl group having 1 to 4 carbon atoms)

-(CH ₂ ) _p5 -OCO-R ₅₃ -COO-(CH ₂ ) _p6 - (7-5)

(wherein R ₅₃ , p5 and p6 are the same as described above)

-(C ₂ H ₄ O) _p5 -(CH ₂ ) _p6 - (7-6)

(where p7 and p9 are the same as described above)

-(CH ₂ CH(CH ₃ )O) _p9 -R ₅₄ - (7-7)

(where p9 and R _{54 are} the same as described above)

-(CH ₂ ) _p12 -OCO-(CH ₂ ) _p13 - (7-8)

(wherein p12 and p13 each independently represent an integer from 1 to 4)

-(CH ₂ ) _p12 -COO-(CH ₂ ) _p13 - (7-9)

(wherein p12 and p13 each independently represent an integer from 1 to 4)

R in the general formula (7-1) ₅₅ alkylene group having a carbon number 1 to 21 include: a -N (R ₁₅₎ and "chain thereon in the general formula (1) A ₁ of a group having the same group as described in the alkyl group of -, -O-, -OCO-, -COO- or at least one of the aryl groups of the alkyl group having 1 to 21 carbon atoms. The group is also the same.

The alkylene group having a carbon number of 1 to 7 having a hydroxyl group as a substituent of R ₅₃ of the formula (7-2) and the formula (7-5) may be exemplified by having a hydroxyl group as a substituent with the R ₅₁ The same group of carbon atoms of 1 to 7 alkyl groups.

The branched alkyl group having 1 to 4 carbon atoms represented by the above formula (7-4) and R _{54 of} the formula (7-7) may, for example, be a methylmethylene group or a methyl group-extended ethyl group. Methyl extended propyl and the like.

The p12 and p13 of the general formula (7-8) and the general formula (7-9) are independent The ground is preferably 2 to 3, more preferably 2.

Specific examples of the group represented by the formula (7-1) include -NH-CH ₂ -, -NH-C ₂ H ₄ -, -NH-C ₃ H ₆ -, -NH- C ₄ H ₈ -, -NH-C ₅ H ₁₀ -, -NH-C ₆ H ₁₂ -, -NH-C ₇ H ₁₄ -, -NH-C ₈ H ₁₆ -, -NH-C ₉ H ₁₈ - , -NH-C ₁₀ H ₂₀ -, -NH-C ₁₁ H ₂₂ -, -NH-C ₁₂ H ₂₄ -, -NH-C ₁₃ H ₂₆ -, -NH-C ₁₄ H ₂₈ -, -NH-C ₁₅ H ₃₀ -, -NH-C ₁₆ H ₃₂ -, -NH-C ₁₇ H ₃₄ -, -NH-C ₁₈ H ₃₆ -, -NH-C ₁₉ H ₃₈ -, -NH-C ₂₀ H ₄₀ -, -NH-C ₂₁ H ₄₂ -, -N(CH ₃ )-CH ₂ -, -N(CH ₃ )-C ₂ H ₄ -, -N(CH ₃ )-C ₃ H ₆ -, -N(CH ₃ )-C ₄ H ₈ -, -N(CH ₃ )-C ₅ H ₁₀ -, -N(CH ₃ )-C ₆ H ₁₂ -, -N(CH ₃ )-C ₇ H ₁₄ -, -N (CH ₃ )-C ₈ H ₁₆ -, -N(CH ₃ )-C ₉ H ₁₈ -, -N(CH ₃ )-C ₁₀ H ₂₀ -, -N(CH ₃ )-C ₁₁ H ₂₂ -, -N(CH ₃ )-C ₁₂ H ₂₄ -, -N(CH ₃ )-C ₁₃ H ₂₆ -, -N(CH ₃ )-C ₁₄ H ₂₈ -, -N(CH ₃ )-C ₁₅ H ₃₀ -, -N(CH ₃ )-C ₁₆ H ₃₂ -, -N(CH ₃ )-C ₁₇ H ₃₄ -, -N(CH ₃ )-C ₁₈ H ₃₆ -, -N(CH ₃ )-C ₁₉ H ₃₈ -, -N(CH ₃ )-C ₂₀ H ₄₀ -, -N(CH ₃ )-C ₂₁ H ₄₂ -, -N(C ₂ H ₅ )-CH ₂ -, -N (C ₂ H ₅ )-C ₂ H ₄ -, -N(C ₂ H ₅ )-C ₃ H ₆ -, -N (C ₂ H ₅ -C ₄ H ₈ -, -N(C ₂ H ₅ )-C ₅ H ₁₀ -, -N(C ₂ H ₅ )-C ₆ H ₁₂ -, etc., preferably -NH-CH ₂ -, - NH-C ₂ H ₄ -, -NH-C ₃ H ₆ -, -NH-C ₄ H ₈ -, -NH-C ₅ H ₁₀ -, -NH-C ₆ H ₁₂ -, etc., more preferably -NH -CH ₂ -, -NH-C ₂ H ₄ -, -NH-C ₃ H ₆ -, -NH-C ₄ H ₈ -.

Specific examples of the group represented by the formula (7-2) include, for example, -NH-CH ₂ CH ₂ -O-CO-C ₆ H ₄ -CO-O-CH ₂ CH ₂ -, - NH-CH ₂ CH ₂ -O-CO-C ₆ H ₁₀ -CO-O-CH ₂ CH ₂ -

-N(CH ₃ )-CH ₂ CH ₂ -O-CO-C ₆ H ₄ -CO-O-CH ₂ CH ₂ -, -N(CH ₃ )-CH ₂ CH ₂ -O-CO-C ₆ H ₁₀ -CO-O-CH ₂ CH ₂ -etc.

Specific examples of the group represented by the formula (7-3) include -NH-(CH ₂ CH ₂ O)-CH ₂ CH ₂ -, -NH-(CH ₂ CH ₂ O) ₂ -CH ₂ CH ₂ -, -NH-(CH ₂ CH ₂ O) ₃ -CH ₂ CH ₂ -, -NH-(CH ₂ CH ₂ O) ₄ -CH ₂ CH ₂ -, -NH-(CH ₂ CH ₂ O) ₅ -CH ₂ CH ₂ -, -NH-(CH ₂ CH ₂ O) ₆ -CH ₂ CH ₂ -, -NH-(CH ₂ CH ₂ O) ₇ -CH ₂ CH ₂ -, -NH- (CH ₂ CH ₂ O) ₈ -CH ₂ CH ₂ -, -NH-(CH ₂ CH ₂ O) ₉ -CH ₂ CH ₂ -, -N(CH ₃ )-(CH ₂ CH ₂ O)-CH ₂ CH ₂ -, -N(CH ₃ )-(CH ₂ CH ₂ O) ₂ -CH ₂ CH ₂ -, -N(CH ₃ )-(CH ₂ CH ₂ O) ₃ -CH ₂ CH ₂ -, -N (CH ₃ )-(CH ₂ CH ₂ O) ₄ -CH ₂ CH ₂ -, -N(CH ₃ )-(CH ₂ CH ₂ O) ₅ -CH ₂ CH ₂ -, -N(CH ₃ )-( CH ₂ CH ₂ O) ₆ -CH ₂ CH ₂ -, -N(CH ₃ )-(CH ₂ CH ₂ O) ₇ -CH ₂ CH ₂ -, -N(CH ₃ )-(CH ₂ CH ₂ O) ₈ -CH ₂ CH ₂ -, -N(CH ₃ )-(CH ₂ CH ₂ O) ₉ -CH ₂ CH ₂ -, and the like.

Specific examples of the group represented by the formula (7-4) include -NH-(CH ₂ CH(CH ₃ )O)-CH ₂ CH(CH ₃ )-, -NH-(CH ₂ CH(CH ₃ )O) ₂ -CH ₂ CH(CH ₃ )-, -NH-(CH ₂ CH(CH ₃ )O) ₃ -CH ₂ CH(CH ₃ )-, -NH-(CH ₂ CH (CH ₃ )O) ₄ -CH ₂ CH(CH ₃ )-, -NH-(CH ₂ CH(CH ₃ )O) ₅ -CH ₂ CH(CH ₃ )-, -NH-(CH ₂ CH(CH ₃ )O) ₆ -CH ₂ CH(CH ₃ )-, -NH-(CH ₂ CH(CH ₃ )O) ₇ -CH ₂ CH(CH ₃ )-, -NH-(CH ₂ CH(CH ₃ ) O) ₈ -CH ₂ CH(CH ₃ )-, -NH-(CH ₂ CH(CH ₃ )O) ₉ -CH ₂ CH(CH ₃ )-, -NH-CH(CH ₃ )CH ₂ -O- CH ₂ CH(CH ₃ )-, -N(CH ₃ )-(CH ₂ CH(CH ₃ )O)-CH ₂ CH(CH ₃ )-, -N(CH ₃ )-(CH ₂ CH(CH ₃ O) ₂ -CH ₂ CH(CH ₃ )-, -N(CH ₃ )-(CH ₂ CH(CH ₃ )O) ₃ -CH ₂ CH(CH ₃ )-, -N(CH ₃ )-( CH ₂ CH(CH ₃ )O) ₄ -CH ₂ CH(CH ₃ )-, -N(CH ₃ )-(CH ₂ CH(CH ₃ )O) ₅ -CH ₂ CH(CH ₃ )-, -N (CH ₃ )-(CH ₂ CH(CH ₃ )O) ₆ -CH ₂ CH(CH ₃ )-, -N(CH ₃ )-(CH ₂ CH(CH ₃ )O) ₇ -CH ₂ CH(CH ₃ )-, -N(CH ₃ )-(CH ₂ CH(CH ₃ )O) ₈ -CH ₂ CH(CH ₃ )-, -N(CH ₃ )-(CH ₂ CH(CH ₃ )O) ₉ -CH ₂ CH(CH ₃ )-, -N(CH ₃ )-CH(CH ₃ )CH ₂ -O-CH ₂ CH(CH ₃ )-, and the like.

Specific examples of the group represented by the formula (7-5) include -CH ₂ CH ₂ -O-CO-C ₆ H ₄ -CO-O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CO-C ₆ H ₁₀ -CO-O-CH ₂ CH ₂ -.

Specific examples of the group represented by the above formula (7-6) include -(CH ₂ CH ₂ O)-CH ₂ CH ₂ -, -(CH ₂ CH ₂ O) ₂ -CH ₂ CH ₂ -, -(CH ₂ CH ₂ O) ₃ -CH ₂ CH ₂ -, -(CH ₂ CH ₂ O) ₄ -CH ₂ CH ₂ -, -(CH ₂ CH ₂ O) ₅ -CH ₂ CH ₂ - , -(CH ₂ CH ₂ O) ₆ -CH ₂ CH ₂ -, -(CH ₂ CH ₂ O) ₇ -CH ₂ CH ₂ -, -(CH ₂ CH ₂ O) ₈ -CH ₂ CH ₂ -, - (CH ₂ CH ₂ O) ₉ -CH ₂ CH ₂ -.

Specific examples of the group represented by the formula (7-7) include -(CH ₂ CH(CH ₃ )O)-CH ₂ CH(CH ₃ )-, -(CH ₂ CH(CH) ₃ )O) ₂ -CH ₂ CH(CH ₃ )-, -(CH ₂ CH(CH ₃ )O) ₃ -CH ₂ CH(CH ₃ )-, -(CH ₂ CH(CH ₃ )O) ₄ - CH ₂ CH(CH ₃ )-, -(CH ₂ CH(CH ₃ )O) ₅ -CH ₂ CH(CH ₃ )-, -(CH ₂ CH(CH ₃ )O) ₆ -CH ₂ CH(CH ₃ )-,-(CH ₂ CH(CH ₃ )O) ₇ -CH ₂ CH(CH ₃ )-, -(CH ₂ CH(CH ₃ )O) ₈ -CH ₂ CH(CH ₃ )-, -(CH ₂ CH(CH ₃ )O) ₉ -CH ₂ CH(CH ₃ )-, -CH(CH ₂ )CH ₂ -O-CH ₂ CH(CH ₃ )-, and the like.

Specific examples of the group represented by the formula (7-8) include -CH ₂ -OCO-CH ₂ -, -(CH ₂ ) ₂ -OCO-(CH ₂ ) ₂ -, -( CH ₂ ) ₃ -OCO-(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -OCO-(CH ₂ ) ₄ -, -CH ₂ -OCO-(CH ₂ ) ₂ -, -CH ₂ -OCO-( CH ₂ ) ₃ -, -CH ₂ -OCO-(CH ₂ ) ₄ -, -(CH ₂ ) ₂ -OCO-(CH ₂ ) ₃ -, -(CH ₂ ) ₂ -OCO-(CH ₂ ) ₄ - , -(CH ₂ ) ₃ -OCO-(CH ₂ ) ₄ -, -(CH ₂ ) ₂ -OCO-CH ₂ -, -(CH ₂ ) ₃ -OCO-CH ₂ -, -(CH ₂ ) ₄ - OCO-CH ₂ -, -(CH ₂ ) ₃ -OCO-(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -OCO-(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -OCO-(CH _{2 3} - and the like, wherein -CH ₂ -OCO-CH ₂ -, -(CH ₂ ) ₂ -OCO-(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -OCO-(CH ₂ ) ₃ - , -(CH ₂ ) ₄ -OCO-(CH ₂ ) ₄ -, more preferably -(CH ₂ ) ₂ -OCO-(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -OCO-(CH ₂ ) ₃ -, preferably -(CH ₂ ) ₂ -OCO-(CH ₂ ) ₂ -.

Specific examples of the group represented by the formula (7-9) include -CH ₂ -COO-CH ₂ -, -(CH ₂ ) ₂ -COO-(CH ₂ ) ₂ -, -( CH ₂ ) ₃ -COO-(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -COO-(CH ₂ ) ₄ -, -CH ₂ -COO-(CH ₂ ) ₂ -, -CH ₂ -COO-( CH ₂ ) ₃ -, -CH ₂ -COO-(CH ₂ ) ₄ -, -(CH ₂ ) ₂ -COO-(CH ₂ ) ₃ -, -(CH ₂ ) ₂ -COO-(CH ₂ ) ₄ - , -(CH ₂ ) ₃ -COO-(CH ₂ ) ₄ -, -(CH ₂ ) ₂ -COO-CH ₂ -, -(CH ₂ ) ₃ -COO-CH ₂ -, -(CH ₂ ) ₄ - COO-CH ₂ -, -(CH ₂ ) ₃ -COO-(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -COO-(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -COO-(CH _{2 3} - and the like, wherein -CH ₂ -COO-CH ₂ -, -(CH ₂ ) ₂ -COO-(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -COO-(CH ₂ ) ₃ - , -(CH ₂ ) ₄ -COO-(CH ₂ ) ₄ -, more preferably -(CH ₂ ) ₂ -COO-(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -COO-(CH ₂ ) ₃ -, preferably -(CH ₂ ) ₂ -COO-(CH ₂ ) ₂ -.

Formula (1) A ₁ is a "carbon atoms having a hydroxyl group as a substituent 1 to 21 alkylene group" include, for example, by the following general formula (8-1) a group represented by like.

-R ₅₆ -(CH ₂ ) _p10 - (8-1)

(wherein R ₅₆ represents an alkylene group having 1 to 7 carbon atoms having a hydroxyl group as a substituent, and p10 represents an integer of 1 to 4)

The alkylene group having a carbon number of 1 to 7 having a hydroxyl group as a substituent of R ₅₆ of the formula (8-1) can be exemplified by a carbon number of 1 to 7 having a hydroxyl group as a substituent as the substituent of R ₅₁ . The same group of alkyl groups.

Specific examples of the group represented by the formula (8-1) include -C ₆ H ₉ (OH)-CH ₂ -, -C ₆ H ₉ (OH)-C ₂ H ₅ -, -C ₆ H ₉ (OH)-C ₃ H ₇ -, -CH ₂ -CH(OH)-CH ₂ -, -CH ₂ -CH(OH)-C ₂ H ₅ -, -CH ₂ -CH(OH )-C ₃ H ₇ -, -CH ₂ -CH(OH)-C ₄ H ₉ -, and the like.

A ₁ in the formula (1) is preferably a carbon number of 1 to 21 having at least one group of -N(R ₁₅ )-, -O-, -OCO-, -COO- or an extended aryl group in the chain. Alkyl. Among them, a group represented by the above formula (7-1) and a group represented by the formula (7-9) are preferable, and specifically, -NH-CH ₂ -, -NH- is preferable. C ₂ H ₄ -, -NH-C ₃ H ₆ -, -NH-C ₄ H ₈ -, -NH-C ₅ H ₁₀ -, -NH-C ₆ H ₁₂ -, -NH-C ₇ H ₁₄ - , -NH-C ₈ H ₁₆ -, -NH-C ₉ H ₁₈ -, -NH-C ₁₀ H ₂₀ -, -NH-C ₁₁ H ₂₂ -, -NH-C ₁₂ H ₂₄ -, -NH-C ₁₃ H ₂₆ -, -NH-C ₁₄ H ₂₈ -, -NH-C ₁₅ H ₃₀ -, -NH-C ₁₆ H ₃₂ -, -NH-C ₁₇ H ₃₄ -, -NH-C ₁₈ H ₃₆ -, -NH-C ₁₉ H ₃₈ -, -NH-C ₂₀ H ₄₀ -, -NH-C ₂₁ H ₄₂ -, -CH ₂ -COO-CH ₂ -, -(CH ₂ ) ₂ -COO-(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -COO-(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -COO-(CH ₂ ) ₄ -, -CH ₂ -COO-(CH ₂ ) ₂ -, -CH _2- COO-(CH ₂ ) ₃ -, -CH ₂ -COO-(CH ₂ ) ₄ -, -(CH ₂ ) ₂ -COO-(CH ₂ ) ₃ -, -(CH ₂ ) ₂ -COO-( CH ₂ ) ₄ -, -(CH ₂ ) ₃ -COO-(CH ₂ ) ₄ -, -(CH ₂ ) ₂ -COO-CH ₂ -, -(CH ₂ ) ₃ -COO-CH ₂ -, -( CH ₂ ) ₄ -COO-CH ₂ -, -(CH ₂ ) ₃ -COO-(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -COO-(CH ₂ ) ₂ -, -(CH ₂ ) ₄ - COO-(CH ₂ ) ₃ -etc., more preferably -NH-CH ₂ -, -NH-C ₂ H ₄ -, -NH-C ₃ H ₆ -, -NH-C ₄ H ₈ -CH ₂ - COO-CH ₂ -, -(CH ₂ ) ₂ -COO-(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -COO-(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -COO-(CH ₂ ) ₄ -, etc. More preferably, it is -NH-C ₂ H ₄ -, -(CH ₂ ) ₂ -COO-(CH ₂ ) ₂ -, and the like.

A ₂ in the formula (1) is preferably -O-.

The compound of the present invention is more preferably a compound represented by the following formula (1').

(wherein R ₁ to R ₄ , R ₇ , A ₁ and An ^{- are} the same as described above)

Preferred combinations of the above R ₁ to R ₄ , R ₇ and A ₁ include the combinations described in the following tables. In addition, p11 A ₁ represents an integer column, p12 and p13 1 ~ 12 are each independently an integer of 1 to 4. Further, each of R ₁ to R _{4 is} independent, and it is preferred that the above R ₁ to R _{4 are the} same.

Further, the combination of the table used in conjunction with An ^- include the following anions.

[Method for Producing Compound of the Present Invention]

The compound of the present invention can be produced by reacting a compound represented by the following formula (9) with a compound represented by the following formula (10) or by expressing the following formula (20); The compound is reacted with a compound obtained by reacting aminonaphthalene and a compound represented by the following formula (10), followed by an oxidation reaction and a salt exchange reaction.

(wherein R ₇ to R ₁₄ , A ₁ , and A _{2 are} the same as described above)

(wherein, R ₁ to R _{6 are} the same as described above)

(wherein R ₂₀ represents a leaving group, and R ₇ , A ₁ , and A _{2 are} the same as described above)

[Reaction of a compound represented by the formula (9) with a compound represented by the formula (10)]

In the reaction between the compound represented by the formula (9) and the compound represented by the formula (10), the compound represented by the formula (9) and the compound represented by the following formula (10) are placed in a solvent. The reaction is usually carried out in the presence of an acid at a temperature of usually from 50 ° C to 80 ° C, preferably from 60 ° C to 80 ° C, for from 1 hour to 10 hours, preferably from 1 hour to 5 hours.

The acid may, for example, be sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid or camphorsulfonic acid, and is preferably p-toluenesulfonic acid. The amount of the acid used is such that the concentration in the reaction liquid is from 1 w/v% to 10 w/v%, preferably from 1 w/v% to 5 w/v%.

The solvent may, for example, be tetrahydrofuran (THF), dioxane, acetone, N,N-Dimethylformamide (DMF) or N-methyl-2-pyrrolidone ( An organic solvent such as N-methyl-2-pyrrolidone, NMP), toluene, cyclohexane, dichloromethane or chloroform, preferably THF, toluene or the like. These solvents may be used alone or in combination of two or more. The amount of the reaction solvent used is usually from 1 to 50 times, preferably from 1 to 20 times, based on the total capacity of the compound represented by the formula (9) and the compound represented by the formula (10). .

The compound represented by the formula (10) is used in an amount of from 1 mol to 1.5 mol, based on 1 mol of the compound represented by the formula (9).

The compound represented by the above formula (9) is represented by the formula (10) In the reaction of the compound, a polymerization inhibitor known per se can also be used. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, p-benzoquinone, phenothiazine, and phenylenediamine. The amount of the polymerization inhibitor used may be any range generally used in the field.

Preferable specific examples of the compound represented by the above formula (9) include compounds represented by the following formula (9').

(wherein R ₇ and A _{1 are} the same as described above)

A preferred combination of R ₇ and A ₁ in the formula (9') is a combination of the combinations described in the compound represented by the above formula (1').

Preferable specific examples of the compound represented by the above formula (10) include compounds represented by the following formula (10').

(wherein, R ₁ to R _{4 are} the same as described above)

A preferred combination of R ₁ to R ₄ in the formula (10') is a combination of the combinations described in the compound represented by the above formula (1').

[Method for Producing Compound represented by General Formula (9)]

The compound represented by the above formula (9) can be synthesized, for example, as follows.

In other words, the compound represented by the following formula (9-1) is subjected to a dehydrogenation reaction with a compound represented by the following formula (9-2), or a compound represented by the following formula (9-1) The compound represented by the formula (9) is synthesized by subjecting a compound represented by the following formula (9-3) to a dehydration reaction.

(wherein R ₈ to R _{14 are} the same as described above)

(wherein R ₇ and A _{2 are} the same as described above. A ₁₁ represents at least one group having -O-, -OCO-, -COO- or an extended aryl group in the chain, and having a hydroxyl group as a substituent a alkyl group having 1 to 21 carbon atoms; an alkyl group having 1 to 21 carbon atoms having at least one group of -O-, -OCO-, -COO- or an extended aryl group in the chain; a substituent having a carbon number of 1 to 21; or an alkyl group having a carbon number of 1 to 21)

(wherein R ₇ and A _{2 are} the same as described above. A ₁₂ represents at least one of -N(R ₁₅ )-, -O-, -OCO-, -COO- or an extended aryl group in the chain. a group having a hydroxyl group of 1 to 21 having a hydroxyl group as a substituent; having at least one of -N(R ₁₅ )-, -O-, -OCO-, -COO- or an extended aryl group in the chain a group having a C 1~21 alkyl group; a C 1~21 alkyl group having a hydroxyl group as a substituent; or a C 1~21 alkyl group)

A (9-2) a compound represented by the general formula -O having in the chain ₁₁ -, - OCO -, - COO- group or at least one arylene group, and a hydroxyl group as a substituent having a carbon group Examples of the alkylene group of 1 to 21 include a group represented by the following formula (6-1') (a group obtained by removing a -N(R ₁₅ )- group from the formula (6-1)) And a group represented by the formula (6-3) and the formula (6-4) described in the item of A ₁ . Specific examples of the groups include a group represented by the formula (6-1) and a group represented by the formula (6-3) and the formula (6-4). Group.

-R ₅₁ -(CH ₂ )p1- (6-1')

(wherein R ₅₁ and p1 are the same as described above)

A (9-2) a compound represented by the general formula -O having in the chain ₁₁ -, - OCO -, - at least one group having a carbon number of an arylene group is COO- or extension of alkoxy having 1 to 21 The group represented by the formula (7-5) to the formula (7-6) described in the item of the above A ₁ may be exemplified, and specific examples thereof may be the same.

A (9-2) a compound represented by the general formula ₁₁ carbon atoms having a hydroxyl group as the alkylene group having 1 to 21 carbon atoms and an alkylene group having 1 to 21 substituents of A ₁ include the item The group described in the above may also be exemplified by the same group.

At least one group of A ₁₂ of the compound represented by the formula (9-3) having -N(R ₁₅ )-, -O-, -OCO-, -COO- or an extended aryl group in the chain And having at least one of a C 1~21 alkyl group having a hydroxyl group as a substituent, and having -N(R ₁₅ )-, -O-, -OCO-, -COO- or an aryl group in the chain The alkyl group having 1 to 21 carbon atoms of the group, the alkylene group having 1 to 21 carbon atoms having a hydroxyl group as a substituent, and the alkylene group having 1 to 21 carbon atoms can be exemplified as the above A ₁ The groups having the same groups as described in the above items may be exemplified by the same groups.

The reaction of the compound represented by the above formula (9-1) with the compound represented by the formula (9-2) or the formula (9-3) is usually carried out in a solvent at usually 20 ° C to 50 ° C. Preferably, the reaction is carried out at 30 ° C to 45 ° C for 10 minutes to 180 minutes, preferably 10 minutes to 60 minutes. Examples of the solvent include ethers such as diethyl ether, diisopropyl ether, ethyl methyl ether, tetrahydrofuran, 1,4-dioxane, and dimethoxyethane; for example, acetone, dimethyl ketone, and methyl ethyl Ketones such as ketone, diethyl ketone, 2-hexanone, t-butyl methyl ketone, cyclopentanone, cyclohexanone; for example, methyl chloride, dichloromethane, chloroform, dichloromethane, dichloroethane, trichloro a halogenated hydrocarbon such as ethane or chlorobenzene; for example, a hydrocarbon such as n-hexane, benzene, toluene or xylene; an ester such as ethyl acetate, butyl acetate or methyl propionate; a nitrile such as acetonitrile; for example, N, Amidoxime such as N-dimethylformamide, etc. Preferred are ethers, halogenated hydrocarbons, and hydrocarbons, and more preferred are tetrahydrofuran, dichloromethane, toluene, and the like. These solvents may be used alone or in combination of two or more. The reaction solvent is usually used in an amount of from 1 to 50 times the total capacity of the compound represented by the formula (9-1) and the compound represented by the formula (9-2) or the formula (9-3). The amount is preferably from 1 to 20 times.

The compound represented by the formula (9-2) or the formula (9-3) is used in an amount of usually 1 mol to 2 mol, preferably 1 mol, per mol of the compound represented by the formula (9-1). An amount of 1.5 mol.

[Reaction of aminonaphthalene, a compound represented by the formula (10) and a compound represented by the formula (20)]

In the reaction of the aminonaphthalene with the compound represented by the formula (10), the aminonaphthalene and the compound represented by the formula (10) are preferably used in an aqueous acid solution at 60 ° C to 100 ° C, preferably 80. The reaction is usually carried out at a temperature of from ° C to 100 ° C for from 1 hour to 10 hours, preferably from 1 hour to 5 hours.

The aqueous acid solution may, for example, be an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution or an aqueous solution of nitric acid. Among them, an aqueous hydrochloric acid solution is preferred. The concentration of the aqueous acid solution is usually from 1% to 40%, preferably from 5% to 10%.

In this case, the compound represented by the formula (10) is used in an amount of 1 mol to 1.5 mol based on 1 mol of the aminonaphthalene.

The aminonaphthalene is preferably 1-aminonaphthalene. Preferable specific examples of the compound represented by the formula (10) include the compounds represented by the above formula (10').

The reaction of the compound obtained by reacting the aminonaphthalene and the compound represented by the formula (10) (the compound represented by the above formula (21)) with the compound represented by the formula (20) is as long as it is in a solvent. The reaction is usually carried out at a temperature of from -20 ° C to 50 ° C, preferably from 0 ° C to 30 ° C, for usually from 1 hour to 10 hours, preferably from 1 hour to 2 hours.

The solvent may, for example, be tetrahydrofuran (THF), dioxane, acetone, N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), toluene, cyclohexane. An organic solvent such as dichloromethane or chloroform, preferably THF, toluene or the like. These solvents may be used alone or in combination of two or more. The amount of the reaction solvent used is usually from 1 to 50 times, preferably from 1 to 20 times, based on the total capacity of the compound represented by the formula (21) and the compound represented by the formula (20). .

The compound represented by the formula (20) is used in an amount of from 1 mol to 1.5 mol based on 1 mol of the compound represented by the formula (21).

In the reaction of the compound represented by the above formula (21) with the compound represented by the formula (20), a polymerization inhibitor known per se can also be used. Polymerization inhibition Examples of the agent include hydroquinone, p-methoxy phenol, p-benzoquinone, phenothiazine, and phenylenediamine. The amount of the polymerization inhibitor used may be any range generally used in the field.

Examples of the leaving group represented by R _{20 of} the formula (20) include a carbonyloxymethyl group, a carbonyloxyethyl group, a carbonyloxy n-propyl group, a carbonyloxyisopropyl group, and a carbonyloxy-n-butyl group. A carbonyloxyalkyl group such as a carbonyloxyisobutyl group or a carbonyloxythird butyl group, preferably a carbonyloxyisobutyl group, a carbonyloxyisopropyl group or the like, more preferably a carbonyloxyisobutyl group.

Preferable specific examples of the compound represented by the formula (20) include compounds represented by the following formula (20').

(wherein R ₂₀ , R ₇ , and A _{1 are} the same as described above)

A preferred combination of R ₇ and A ₁ in the formula (20') is a combination of the combinations described in the compound represented by the above formula (1').

The compound represented by the formula (20) can be synthesized by a condensation reaction with a chloroformate which is known per se. In other words, the compound represented by the following formula (20-1) and the compound represented by the following formula (20-2) are reacted in a solvent at a temperature of usually 10 ° C to 30 ° C in the presence of a base. can. Further, R ₇ , A ₁ , A ₂ and R ₂₀ in the formula (20-1) are the same as described above.

Examples of the base in the synthesis of the compound represented by the above formula (20) include ammonia, ethylamine, diethylamine, pyridine, and triethylamine. Pyridine, aniline, pyridine, pyrrole, etc., preferably triethylamine or the like. The amount of the compound represented by the formula (20) is usually from 1 mol to 1.5 mol.

The solvent in the synthesis of the compound represented by the above formula (20) is the same solvent as the solvent described in the reaction of the aminonaphthalene with the compound represented by the formula (10).

[oxidation reaction]

The oxidation reaction in the method for producing a compound of the present invention is carried out by reacting a compound represented by the formula (9) with a compound of the following formula (10) in the presence of an oxidizing agent in a solvent. a compound obtained by reacting the compound represented by the compound or a compound obtained by reacting a compound represented by the following formula (20) with a compound obtained by reacting an aminonaphthalene and a compound represented by the following formula (10) ( Hereinafter, these compounds may be simply referred to as triarylmethane compounds of the production method of the present invention.

The oxidation reaction is carried out at a temperature of usually 10 ° C to 40 ° C, preferably 20 ° C to 30 ° C for 1 hour to 48 hours, preferably 6 hours to 24 hours.

Examples of the oxidizing agent include organic oxidizing agents such as chloranil, dichlorodicyanobenzoquinone, N-2,4,6-trinitrophenyl-N', N'-phenyldifluorene, or lead dioxide. , An inorganic oxidizing agent such as manganese dioxide, potassium permanganate, potassium chromate or selenium dioxide. Further, it can also be carried out by a system in which chloranil, a metal complex, and hydrogen peroxide are combined. In terms of ease of handling, a lanthanide-based oxidizing agent is preferred, and among them, chloranil is preferred. The amount of the oxidizing agent used is 1 mol to 5 mol, preferably 1 mol to 2 mol, per mol of the triarylmethane compound of the production method of the present invention.

In the oxidation reaction, it is preferred to allow hydrochloric acid to coexist and pass through the chloride salt. The hydrochloric acid is used in an amount of usually 1 mol to 50 mol, preferably 1 mol to 10 mol, per mol of the triarylmethane compound of the production method of the present invention.

The solvent to be used in the oxidation reaction is preferably the same solvent as the solvent used in the reaction of the compound represented by the above formula (9-1) and the compound represented by the formula (9-2). The solvent is also the same. The total amount of the triarylmethane-based compound to be used in the production method of the present invention is usually from 1 to 50 times, preferably from 1 to 20 times.

[salt exchange reaction]

The salt exchange reaction in the method for producing a compound of the present invention is carried out by reacting a salt of an anion or a halogenated alkyl group having an electron-withdrawing substituent of the present invention with an oxidation-reacted invention of the present invention. The triarylmethane-based compound of the production method is contacted in a solvent.

The salt exchange reaction is carried out at usually 10 ° C to 50 ° C, preferably 20 ° C to 30 ° C for 1 hour to 10 hours, preferably 1 hour to 6 hours.

The salt of the anion containing an aryl group having an electron-donating substituent, a sulfonyl group having an electron-donating substituent or a halogenated alkyl group of the present invention may be exemplified by the anion and sodium. The salt, the salt of potassium, the salt of lithium, etc. are preferably a salt of potassium or lithium. The anion of the aryl group having an electron withdrawing substituent, a sulfonyl group having an electron withdrawing substituent or a halogenated alkyl group of the present invention, relative to 1 mol of the triarylmethane compound of the production method of the present invention by oxidation reaction The amount of the salt used is usually an amount of 1 mol.

In the method for producing a compound of the present invention, the oxidation reaction and the salt exchange reaction may be continuously carried out, and the reaction may be carried out in one step. In this case, the aryl group having an electron withdrawing substituent, a sulfonyl group having an electron withdrawing substituent or an alkyl halide having the electron withdrawing substituent of the present invention may be added to the reaction solution after the oxidation reaction. The anion salt may be reacted at the temperature and time of the salt exchange reaction.

[Polymer of the present invention]

The polymer of the present invention is a polymer containing a monomer unit derived from the compound of the present invention.

The weight average molecular weight (Mw) of the polymer of the present invention is usually 2,000 to 100,000, preferably 2,000 to 50,000, more preferably 2,000 to 30,000. Further, the degree of dispersion (Mw/Mn) is usually from 1.00 to 5.00, preferably from 1.00 to 3.00.

The polymer of the present invention may be a homopolymer or a copolymer as long as it contains a monomer unit derived from the compound represented by the above formula (1), and is preferably a copolymer.

For example, the monomer unit derived from the compound represented by the above formula (1) and one type or two kinds are derived from the following general formula (2), general formula (3), and general formula ( 4) Copolymerization of monomer units of the compound represented by the formula (5) Things.

Wherein R ₆₁ represents a hydrogen atom or a methyl group, and R ₆₂ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon number of 7 ~13 arylalkyl group, carbon number 2-9 alkoxyalkyl group, carbon number 3-9 alkoxy alkoxyalkyl group, carbon number 7-13 aryloxyalkyl group, carbon number 5 a morpholinoalkyl group of ~7, a trialkylsulfanyl group having a carbon number of 3 to 9, an alicyclic hydrocarbon group having an oxygen atom or a carbon number of 6 to 10, and a dialkyl group having a carbon number of 3 to 9 An aminoalkyl group, a fluoroalkyl group having 1 to 18 carbon atoms or an N-alkylene phthalimide group having 1 to 6 carbon atoms, a group represented by the following formula (2-1)

(wherein R ₆₅ represents an alkylene group having 1 to 3 carbon atoms; R ₆₆ represents a phenyl group having a hydroxyl group as a substituent or unsubstituted, or an alkyl group having 1 to 3 carbon atoms, and q represents an integer of 1 to 3; a group represented by the following formula (2-2)

(wherein, R ₆₇ to R ₆₉ represent an alkyl group having 1 to 3 carbon atoms; R ₇₀ represents an alkylene group having 1 to 3 carbon atoms), and a group represented by the following formula (2-3)

(wherein, l represents an integer from 1 to 6, and R ₇₁ represents a phenyl or cyclohexyl group)]

(wherein R ₆₁ is the same as described above. R ₆₃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₆₄ represents a hydrogen atom or a dialkylaminoalkyl group having 3 to 7 carbon atoms; a hydroxyalkyl group of 1 to 6. R ₆₃ and R ₆₄ may also form a morpholinyl group with the adjacent nitrogen atom)

(wherein R ₃₁ represents a phenyl group, a pyrrolidinyl group, and R ₆₁ is the same as described above)

(wherein R ₃₃ represents a nitrogen atom or an oxygen atom, and when R ₃₃ is an oxygen atom, j represents 0, and when R ₃₃ is a nitrogen atom, j represents 1. R ₃₂ represents a hydrogen atom, and carbon number is 1 to 20 Alkyl group, hydroxyalkyl group having 1 to 10 carbon atoms, halogenated alkyl group having 1 to 10 carbon atoms, alkylcycloalkyl group having 1 to 10 carbon atoms, halogenated cycloalkyl group having 6 to 7 carbon atoms, carbon number 6 An aryl group of ~10, an aryl group having 6 to 10 carbon atoms having a carbon number of 1 to 6 as a substituent, or a halogenated aryl group having 6 to 10 carbon atoms)

R ₆₁ in the formula (2) is preferably a methyl group.

The alkyl group having 1 to 18 carbon atoms of R ₆₂ in the formula (2) may be linear or branched or cyclic, and examples thereof include a methyl group, an ethyl group, a n-propyl group and an isopropyl group. , n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, isopentyl, second pentyl, third pentyl, neopentyl, n-hexyl, isohexyl, second hexyl , third hexyl, 3-methylpentyl, 2-methylpentyl, 1,2-dimethylbutyl, n-heptyl, isoheptyl, second heptyl, n-octyl, isooctyl, Second octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, positive Heptadecyl, n-octadecyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotetradecane Base, cyclooctadecyl and the like.

The hydroxyalkyl group having 1 to 10 carbon atoms of R ₆₂ in the formula (2) may, for example, be a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group or a hydroxyhexyl group.

The aryl group having 6 to 10 carbon atoms of R ₆₂ in the formula (2) may, for example, be a phenyl group or a naphthyl group.

Examples of the arylalkyl group having 7 to 13 carbon atoms of R ₆₂ in the formula (2) include a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group, and the like. Preferably, it is a benzyl group.

The alkoxyalkyl group having 2 to 9 carbon atoms of R ₆₂ of the formula (2) may, for example, be a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group or a methoxy group. Pentyl, methoxyhexyl, methoxyheptyl, methoxyoctyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, Ethoxyhexyl, ethoxyheptyl, propoxymethyl, propoxyethyl, propoxypropyl, propoxybutyl, propoxypentyl, propoxyhexyl and the like.

The alkoxyalkoxyalkyl group having 3 to 9 carbon atoms of R ₆₂ of the formula (2) may, for example, be a methoxymethoxymethyl group, a methoxymethoxyethyl group or a methoxymethoxy group. Propyl, ethoxymethoxymethyl, ethoxymethoxyethyl, ethoxymethoxypropyl, propoxymethoxymethyl, propoxymethoxyethyl, propoxy Methoxypropyl, ethoxyethoxymethyl, ethoxyethoxyethyl, ethoxyethoxypropyl, ethoxyethoxymethyl, ethoxyethoxy B Base, ethoxyethoxypropyl, propoxyethoxymethyl, propoxyethoxyethyl, propoxyethoxypropyl and the like.

The aryloxyalkyl group having 7 to 13 carbon atoms of R ₆₂ of the formula (2) may, for example, be a phenoxymethyl group, a phenoxyethyl group, a phenoxypropyl group, a naphthyloxymethyl group or a naphthyloxy group. Ethyl, naphthyloxypropyl and the like.

Examples of the morpholinoalkyl group having 5 to 7 carbon atoms of R ₆₂ in the formula (2) include a morpholinylmethyl group, a morpholinylethyl group, and a morpholinylpropyl group.

Examples of the trialkylsulfanyl group having 3 to 9 carbon atoms of R ₆₂ of the formula (2) include a trimethyldecyl group, a tolylethyl decyl group, a tripropyl decyl group, and a dimethyl ethyl decyl group. , diethylmethyl fluorenyl and the like.

The alicyclic hydrocarbon group having 6 to 10 carbon atoms of the oxygen group of R ₆₂ in the formula (2) may, for example, be a dicyclopentenyloxyethyl group or the like.

The alicyclic hydrocarbon group having 6 to 10 carbon atoms which does not contain oxygen in the R ₆₂ of the formula (2) may, for example, be a cyclohexyl group, an isobornyl group or a dicyclopentyl group.

The dialkylaminoalkyl group having 3 to 9 carbon atoms of R ₆₂ of the formula (2) may, for example, be dimethylaminomethyl, dimethylaminoethyl, dimethylaminopropyl or the like. Ethylaminomethyl, diethylaminoethyl, diethylaminopropyl, dipropylaminomethyl, dipropylaminoethyl, dipropylaminopropyl, and the like.

The fluoroalkyl group having 1 to 18 carbon atoms of R ₆₂ of the formula (2) may, for example, be 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3 ,3-tetrafluoropropyl, 2,2,3,3,4,4-hexafluoropropyl, 2,2,3,3,4,4,5,5-octafluoropentyl, 3,3, 4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoroindolyl; 2-(heptadecafluorooctyl)ethyl and the like.

The N-alkylene phthalimido group having 1 to 6 carbon atoms of R ₆₂ of the formula (2) may, for example, be 2-phthalimidoethyl, 2-tetrahydrophthalene Formamidine ethyl and the like.

The alkylene group having 1 to 3 carbon atoms of R ₆₅ in the formula (3) may, for example, be a methylene group, an ethylidene group or a propyl group, and is preferably an ethyl group.

Formula (3) having a hydroxyl group as substituent R or unsubstituted phenyl group include hydroxyphenyl, phenyl and the like _66.

The alkyl group having 1 to 3 carbon atoms of R ₆₆ in the formula (3) may, for example, be a methyl group, an ethyl group or a propyl group.

Specific examples of the group represented by the formula (3) include 2-hydroxy-3-phenoxymethyl, 2-hydroxy-3-phenoxyethyl, 2-hydroxy-3-phenoxypropyl a group, a methyltrimethylene glycol group, a methyltriethylene glycol group, a methyltripropylene glycol group, etc., among which 2-hydroxy-3-phenoxypropyl group, methyltripropylene glycol group, methyl group are preferred. Triethylene glycol group and the like.

The alkyl group having 1 to 3 carbon atoms of R ₆₇ to R ₆₉ in the formula (2-2) may, for example, be a methyl group, an ethyl group or a propyl group, and is preferably a methyl group.

The alkylene group having 1 to 3 carbon atoms of R ₇₀ in the formula (2-2) may, for example, be a methylene group, an exoethyl group or a propyl group.

Specific examples of the group represented by the formula (2-2) include a trimethylammoniummethyl group, a trimethylammoniumethyl group, a triethylammoniummethyl group, and a triethylammoniumethyl group.

Preferable examples of the group represented by the formula (2-3) include the following groups.

Preferable specific examples of the formula (2) include methacrylic acid, benzyl methacrylate, hydroxyethyl methacrylate, methyl methacrylate, etc., among which methacrylic acid and benzyl methacrylate are preferred. Wait.

The alkyl group having 1 to 3 carbon atoms of R ₆₃ in the formula (3) may, for example, be a methyl group, an ethyl group or a propyl group.

The dialkylaminoalkyl group having 3 to 9 carbon atoms of R ₆₄ of the formula (3) may, for example, be dimethylaminomethyl, dimethylaminoethyl, dimethylaminopropyl or the like. Ethylaminomethyl, diethylaminoethyl, diethylaminopropyl, dipropylaminomethyl, dipropylaminoethyl, dipropylaminopropyl, and the like.

The alkyl group of 1 to 3 may be the same as the above R ₆₃ .

The hydroxyalkyl group having 1 to 6 carbon atoms of R ₆₄ in the formula (3) may, for example, be a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group or a hydroxyhexyl group, and preferably a hydroxy group B. base.

Preferred examples of the general formula (3) include (meth)acrylamide, N,N-dimethylpropenamide, hydroxyethyl(meth)acrylamide, 4-propenylmorphomorpholine. Wait.

Preferable specific examples of the formula (4) include styrene, α-methylstyrene, and N-vinylpyrrolidone.

The alkyl group having 1 to 20 carbon atoms of R ₃₂ in the formula (5) may be linear or branched or cyclic, and examples thereof include a methyl group, an ethyl group, a n-propyl group and an isopropyl group. , n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, isopentyl, second pentyl, third pentyl, neopentyl, n-hexyl, isohexyl, second hexyl , third hexyl, 3-methylpentyl, 2-methylpentyl, 1,2-dimethylbutyl, n-heptyl, isoheptyl, second heptyl, n-octyl, isooctyl, Second octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, positive Heptadecyl, n-octadecyl, nonadecyl, peanut, and the like.

Examples of the hydroxyalkyl group having 1 to 10 carbon atoms of R ₃₂ in the formula (5) include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, and a hydroxyl group. Octyl, hydroxyindenyl, hydroxyindenyl, and the like.

Examples of the halogenated alkyl group having 1 to 10 carbon atoms of R ₃₂ in the formula (5) include a chloromethyl group, a chloroethyl group, a chloro-n-propyl group, a chloroisopropyl group, a chloro-n-butyl group, and a chloro-t-butyl group. , chloro-n-pentyl, chloro-n-hexyl, chloro-n-heptyl, chloro-n-octyl, chloro-n-decyl, chloro-n-decyl, fluoromethyl, fluoroethyl, fluoro-n-propyl, fluoroisopropyl, fluorine Butyl, fluoro-t-butyl, fluoro-n-pentyl, fluoro-n-hexyl, fluoro-n-heptyl, fluoro-n-octyl, fluoro-n-decyl, fluoro-n-decyl, and the like.

Examples of the alkylcycloalkyl group having 1 to 10 carbon atoms of R ₃₂ in the formula (5) include a methylcyclohexyl group, an ethylcyclohexyl group, a propylcyclohexyl group, and a butylcyclohexyl group.

Examples of the halogenated cycloalkyl group having 6 to 7 carbon atoms of R ₃₂ in the formula (5) include a chlorocyclohexyl group, a fluorocyclohexyl group, a bromocyclohexyl group, a chlorocycloheptyl group, a fluorocycloheptyl group, and a bromocycloheptyl group.

Examples of the aryl group having 6 to 10 carbon atoms of R ₃₂ in the formula (5) include a phenyl group and a naphthyl group.

The aryl group having 6 to 10 carbon atoms which has an alkyl group having 1 to 6 carbon atoms and a substituent of R ₃₂ in the formula (5) may, for example, be a methylphenyl group, an ethylphenyl group or a n-propylphenyl group. Butylphenyl, n-pentylphenyl, n-hexylphenyl and the like.

Examples of the halogenated aryl group having 6 to 10 carbon atoms of R ₃₂ in the formula (5) include a chlorophenyl group, a fluorophenyl group, a chloronaphthyl group, and a fluoronaphthyl group.

Preferable specific examples of the general formula (5) include maleic anhydride, maleic imine, N-methyl maleimide, N-ethyl maleimide, n-butyl maleate Amine, N-octylmaleimide, N-dodecylmaleimide, N-(2-ethylhexyl)maleimide, N-(2-hydroxyethyl)male Yttrium, N-(2-chlorohexyl)maleimide, N-cyclohexylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(2-B Cyclohexyl)maleimide, N-(2-chlorocyclohexyl)maleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide N-(2-ethylphenyl)maleimide, N-(2-chlorophenyl)maleimide, and the like.

Specific examples of the copolymer of the present invention include the following combinations of monomer units, of which combination 1 is preferred.

In the combination 1, a copolymer comprising a compound represented by the formula (1) and two compounds represented by the formula (2) is preferred. In the case of the compound represented by the above formula (2), the compound of the formula (2) wherein R ₆₁ is a hydrogen atom or a methyl group and R ₆₂ is a hydrogen atom, and R in the formula (2) ₆₁ is a compound wherein a hydrogen atom or a methyl group and R ₆₂ is an arylalkyl group having 7 to 13 carbon atoms.

a monomer unit derived from a compound represented by the formula (1) and a monomer unit derived from a compound represented by the formula (2), the formula (3), the formula (4) or the formula (5) The weight ratio may be appropriately set depending on the type of the monomer unit to be used, and the monomer unit derived from the compound represented by the formula (1) is usually from 1% by weight to 90% based on the total weight of the polymer obtained. The weight % is preferably 5% by weight to 85% by weight.

Preferable specific examples of the copolymer of the present invention include a monomer unit derived from the compound represented by the formula (1) and one or two kinds of compounds derived from the compound represented by the following formula (2'). The polymer of the monomer unit.

(wherein R ₆₁ is the same as described above. R' ₆₂ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon number. 7 to 13 arylalkyl groups, carbon number 2 to 9 alkoxyalkyl groups)

The R' ₆₂ has an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 13 carbon atoms, and a carbon number of 2 to 9 Specific examples of the alkoxyalkyl group include the same groups as those of the above R ₆₂ .

The R' _{62 is} preferably a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an arylalkyl group having 7 to 13 carbon atoms, and the like, and more preferably a hydrogen atom or an arylalkyl group having 7 to 13 carbon atoms.

A preferred combination of R ₆₁ and R' ₆₂ in the compound represented by the formula (2') is as follows.

[Method for Producing Polymer of the Present Invention]

The polymer of the present invention is produced, for example, as follows. That is, the polymer of the present invention can be obtained by carrying out a polymerization reaction known per se by using the compound of the present invention as a monomer. In the case where the polymer of the present invention is a copolymer, the compound of the present invention and the formula (2), formula (3), formula (4) or formula are used as long as they are polymerized. (5) One or two kinds of the compounds to be represented may be obtained by mixing the ratio of the monomer units derived from the respective monomers in the finally obtained polymer as described above, and then performing polymerization.

The polymerization reaction is carried out, for example, as follows. That is, the polymerization reaction is carried out by using the compound of the present invention represented by the formula (1), and optionally, the formula (2), the formula (3), the formula (4) or the pass. One or two kinds of the compounds represented by the formula (5) are dissolved in a suitable solvent having a capacity of 1 to 10 times the total capacity of the compound, for example, toluene, 1,4-dioxane, tetrahydrofuran. In isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether acetate or the like, 0.01 to 30% by weight of a polymerization initiator, for example, azo, relative to the total amount of the dissolved compound. Butyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionate), 2,2'-azobis ( The reaction is carried out at 50 ° C to 150 ° C for 1 hour to 20 hours in the presence of 2-methylbutyronitrile, benzoyl peroxide, and lauric acid peroxide. After the reaction, it can also be treated in accordance with the usual method for obtaining a polymer.

[Coloring composition 1

The colored composition of the present invention contains at least one of the compounds or polymers of the present invention.

This colored composition can form an excellent colored cured film having heat resistance. Therefore, the colored composition of the present invention can be used for coloring pixel formation of color filters and the like used in liquid crystal display devices (LCDs) or solid-state imaging devices (CCD, CMOS, etc.), printing inks, inkjet inks, paints, and the like. Use, especially suitable for color filters for liquid crystal display devices. Furthermore, the colored composition of the present invention can also be used A known molding method is used to form a molded article of a colored resin by forming into a sheet, a film, a bottle, a cup, or the like. Therefore, it can also be used for applications such as glasses and colored contact lenses, and can also be used for the same purpose by forming a multilayer structure of a known resin. In addition to this, for example, it can also be used for an optical film, a hair dye, a labeling substance for a compound or a living substance, or a material of an organic solar cell.

The colored resin may be directly used as the compound or polymer of the present invention, or the compound or polymer of the present invention may be used in combination with other polymers. The other polymer is not particularly limited, and is preferably a homopolymer derived from a compound represented by the above formula (2), formula (3), formula (4) or/and formula (5) or The copolymer is more preferably a homopolymer. In the case of mixing with other polymers, the mixing ratio thereof may be appropriately set according to the color of the desired coloring resin. The colored resin exhibits an excellent effect of reducing the elution of the dye even when it comes into contact with a solvent.

The colored composition of the present invention may optionally contain a pigment, a polymerization initiator, a solvent, a binder resin, a radical polymerizable monomer, an oligomer or a crosslinking agent, and the coloring composition contains a coloring composition. The compound or polymer of the present invention is from 1% to 50% by weight, preferably from 5% to 30% by weight. In addition, the weight of the coloring composition herein means the weight of the solid component other than a solvent, and the following meaning is the same in this invention.

The pigment may be a pigment for producing a blue or green colored pattern, and examples thereof include a phthalocyanine-based pigment. Examples of the phthalocyanine-based pigment include pigments containing magnesium, titanium, iron, cobalt, nickel, copper, zinc, and aluminum in the center metal, and specific examples thereof include Color Index (CI) Pigment Blue 15, CI Pigment Blue 15:1. CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:5, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 17:1, CI Pigment Blue 75 , CI Pigment Blue 79, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58, Chloroaluminum Phthalocyanine, Hydroxy Aluminum Phthalocyanine, Aluminium Phthalocyanine Oxide, Zinc Phthalocyanine, Preferably, CI Pigment Blue 15, CI Pigment Blue 15:6, Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Green 58, and more preferably CI Pigment Blue 15:6, CI Pigment Green 58.

The content of the pigment is from 10% by weight to 50% by weight, preferably from 10% by weight to 30% by weight, based on the weight of the coloring composition.

In the case where the colored composition of the present invention contains the pigment, it is preferred to contain a pigment dispersant. Examples of the pigment dispersant include polyamine-amine and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly(A). A acrylate, a (meth)acrylic copolymer, a naphthalenesulfonic acid famarin condensate, a polyoxyalkylene alkyl phosphate, a polyoxyalkyleneamine, an alkanolamine or the like. The pigment dispersant may be used singly or in combination of two or more. The content is usually from 1% by weight to 80% by weight, preferably from 10% by weight to 60% by weight, based on the weight of the pigment.

As the polymerization initiator, a known thermal polymerization initiator, a photopolymerization initiator, preferably a photopolymerization initiator can be used. Specific examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin dimethyl ketal, and 1-(4-isopropylphenyl). 2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl-phenyl ketone 2-methyl-2-morpholinyl (4-thiomethylphenyl) Acetophenones such as propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone; benzoin, benzoin isopropyl ether, benzoin isobutyl ether Anthraquinone; a fluorenylphosphine oxide such as 2,4,6-trimethylbenzhydryldiphenylphosphine oxide; phenyl oxime, methyl phenyl glyoxyester; diphenyl Methyl ketone, methyl O-benzoyl benzoate, 4-phenyl benzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzylidene-4' -methyl-diphenyl sulfide, benzoated benzophenone, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 3,3'-dimethyl a benzophenone system such as 4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2, Thiophenone series such as 4-dichlorothioxanthone; amino benzophenone series such as Michler's Ketone and 4,4'-diethylaminobenzophenone; 1-[4- (phenylthio)phenyl]-1,2-octanedione 2-(O-benzhydrylhydrazine), 1-[6-(2-methylbenzylidene)-9-ethyl-9H - oxazol-3-yl]ethanone-O-acetamidopurine and other oxime esters; 10-butyl-2-chloroacridone, 2-ethylhydrazine, 9,10- , Camphorquinone and the like.

The polymerization initiator may be used alone or in combination of two or more. The content is from 1% by weight to 50% by weight, preferably from 5% by weight to 30% by weight, based on the weight of the coloring composition.

The solvent may be appropriately selected depending on the components contained in the coloring composition. Specific examples thereof include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyrate B. Ester, butyl butyrate, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, methoxy Butyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate, Methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2 Methyl methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, Ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solution Fibrous acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like. The amount of the solvent is such that the concentration of the colored composition of the present invention is from 10% by weight to 80% by weight in the solvent.

The binder resin may be dissolved in an alkaline developer used in the production of a color filter, and examples thereof include an ethylenically unsaturated monomer having at least one carboxyl group or a hydroxyl group, or the ethylenically unsaturated monomer. A copolymer of a body and an ethylenically unsaturated monomer having an aromatic hydrocarbon group or an aliphatic hydrocarbon group; a compound having an epoxy group such as a side chain or a terminal of the copolymer; or a compound obtained by adding an acrylate. These compounds may be used alone or in combination of two or more.

Specific examples of the carboxyl group-containing ethylenically unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; Acid, maleic acid Unsaturated dicarboxylic acids (anhydrides) such as anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, and unsaturated polycarboxylic acids of more than 3 yuan ( Anhydrides; 2-(methyl)propenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl 2-hydroxypropyl phthalate, 2-propene oxime Ethyl ethyl 2-hydroxyethyl phthalic acid and the like.

The content of the binder resin is from 10% by weight to 50% by weight, preferably from 20% by weight to 50% by weight, based on the weight of the coloring composition.

Examples of the radical polymerizable monomer or oligomer include polyethylene glycol diacrylate (the number of ethyl groups being 2 to 14), and polyethylene glycol dimethacrylate (b. The number of bases is 2 to 14), trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate , trimethylolpropane ethoxy triacrylate, trimethylolpropane ethoxy trimethacrylate, trimethylolpropane propoxy triacrylate, trimethylolpropane propoxy trimethyl Acrylate, tetramethylol methane triacrylate, tetramethylol methane trimethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, polypropylene glycol diacrylate The number of propyl groups is 2 to 14), polypropylene glycol dimethacrylate (the number of propyl groups is 2 to 14), dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol Acrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate (Ethyloxy group is 40 or less), propoxylated pentaerythritol tetraacrylate (with a propoxy group of 40 or less), ethoxylated trimethylolpropane triacrylate (having an ethoxy group of 40 or less), Propoxylated trimethylolpropane triacrylate Ester (propoxy group of 40 or less), bisphenol A polyoxyethylene ethyl diacrylate, bisphenol A polyoxyethylene ethyl dimethacrylate, bisphenol A dioxoethyl diacrylate, double Phenol A dioxoethyl dimethacrylate, bisphenol A trioxoethyl diacrylate, bisphenol A trioxoethyl dimethacrylate, bisphenol A decahydrate ethyl diacrylate , bisphenol A oxirane ethyl dimethacrylate, isocyanuric acid ethoxylated triacrylate, polycarboxylic acid (phthalic anhydride, etc.) and a compound having a hydroxyl group and an ethylenically unsaturated group An ester of (acrylic acid-β-hydroxyethyl ester, methacrylic acid-β-hydroxyethyl ester, etc.), an alkyl ester of acrylic acid or methacrylic acid (methyl acrylate, methyl methacrylate, ethyl acrylate, methyl group) Ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, etc.), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate Ester, phenoxyethyl acrylate, phenoxyethyl methacrylate, N,N-dimethyl decylamine, N-N-dimethylaminoethyl acrylate, a quaternary chloride obtained from chloromethane using N-N-N-dimethylaminoethyl hydride, a quaternary chloride obtained from methyl chloride, and N,N-dimethylaminopropyl acrylamide using chloromethane, Propylene decylmorpholine, N-isopropylacrylamide, N,N-diethyl acrylamide, and the like.

The crosslinking agent may, for example, be: (a) an epoxy resin; (b) a melamine compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group and a decyloxymethyl group; a compound, a glycoluril compound or a urea compound; (c) a phenol compound, a naphthol compound or a hydroxyquinone compound substituted with at least one substituent selected from the group consisting of a methylol group, an alkoxymethyl group and a decyloxymethyl group, wherein Preferably, it is a multifunctional epoxy resin.

The content of the crosslinking agent is from 10% by weight to 50% by weight, preferably from 20% by weight to 50% by weight, based on the weight of the coloring composition.

The coloring composition of the present invention may contain, in addition to the components described above, a polymerization inhibitor, a surfactant, an additive, etc., and these are not particularly limited as long as they are known per se, and the amount used is usually The amount used in the field is not limited.

The coloring composition of the present invention is prepared by mixing the above-described components.

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.

[Examples]

Example 1 Method for Producing Compound of the Present Invention

(1) Synthesis of a naphthalene derivative (compound 3) having a methacryl group

To a 1 L round-bottomed flask equipped with a stirring apparatus, 21.5 g (150 mmol) of 1-aminonaphthalene (Compound 1: manufactured by Tokyo Chemical Industry Co., Ltd.) and isocyanatoethyl methacrylate (Compound 2: and Manufactured by Wako Pure Chemical Industries, Ltd., 25.6 g (165 mmol) and dichloromethane (manufactured by Wako Pure Chemical Industries, Ltd.) 450 ml, and the inside was subjected to nitrogen substitution, and then reacted at 40 ° C for 15 minutes to give a white solid. Thereafter, the mixture was further stirred at 40 ° C for 1 hour, and then cooled to 10 ° C. The white solid was collected by filtration and washed with a small portion of dichloromethane. The obtained solid was dried under reduced pressure to give 38.3 g of a urea (Comp. 3) (yield: 86%).

(2) Construction of triarylmethane skeleton

Add 10 mg of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) and 19.9 g (60 mmol) of urea (Compound 3) to a 2 L round bottom flask equipped with a stirring device, and add THF (Wako Pure Chemical Industries Co., Ltd.) ) Manufactured) 1100 ml for dissolution. 4,4'-(dimethylamino)benzhydrol (4,4'-(dimethylamino)benzhydrol) (Compound 4: manufactured by Tokyo Chemical Industry Co., Ltd.) 19.5 g (72 mmol) and p-toluene acid. Monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 27.4 g (144 mmol) was stirred at 65 ° C for 3 hours. Thereafter, after cooling to 10 ° C, the THF solution was removed by decantation, and dichloromethane and ion-exchanged water were added to the residual oil component, followed by extraction and water washing. After the organic layer was washed with a 2% aqueous solution of K ₂ CO ₃ , the mixture was extracted with 1 mol/L hydrochloric acid, and 25% of NaOH was added to the obtained aqueous layer for neutralization, and the precipitated solid was extracted with dichloromethane. After washing with water and drying with sodium sulfate, the mixture was concentrated under reduced pressure to yield 20.9 g of white solid. The green-white solid was washed with THF, filtered, and dried under reduced pressure to yield 9.1 g of pale blue solid. In addition, the solid which precipitated and concentrated the filtrate at the time of the filtration was washed with THF again, and the mixture was further filtered, dried under reduced pressure, and 2.8 g of a pale blue solid was collected. The obtained pale blue solids were combined to obtain 11.8 g of a triarylmethane derivative (Compound 5) (yield: 36%).

(3) Oxidation reaction and salt exchange reaction

Into a 1 L round bottom flask equipped with a stirring apparatus, 11.0 g (20 mmol) of the triarylmethane derivative (Compound 5), 330 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), and dichloromethane (Wako Pure Chemicals Co., Ltd.) were added. After the production of the product (manufactured by the company), 220 ml (220 mmol) of 1 mol/L hydrochloric acid and 4.9 g (20 mmol) of chloranil (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred at room temperature for 4 hours. Then, 14.9 g (corresponding to 20 mmol) of a lithium salt of tetrakis(pentafluorophenyl)borate (IV) (manufactured by Tosoh Finechem Co., Ltd.) was added thereto, and the mixture was stirred at room temperature for 12 hours. Thereafter, the aqueous layer was removed by liquid separation, and the organic layer was washed with a 3% K ₂ CO ₃ aqueous solution, washed with water, dried over sodium sulfate, and concentrated under reduced pressure to give a dark blue solid (Comp. 7). (Yield 91%).

Comparative Example 1 Method for producing triarylmethane derivative having chloride ion as an anion

In the same manner as in Example 1, except that the lithium salt of tetrakis(pentafluorophenyl)borate (IV) was not added, the experiment was carried out to obtain a dark blue solid (compound 6) of 11.7 g. (Yield 100%).

Example 2 Method for producing the compound of the present invention

(1) Synthesis of a triarylmethane derivative having an amine group (Compound 8)

In a 1 L round bottom flask equipped with a stirring device, 14.3 g (100 mmol) and 4,4'-(dimethylamino)diphenyl were added to 1-aminonaphthalene (Compound 1: manufactured by Tokyo Chemical Industry Co., Ltd.). Methanol (Compound 4: manufactured by Tokyo Chemical Industry Co., Ltd.) 29.7 g (111 mmol), 200 ml of ion-exchanged water, and 41 ml of concentrated hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were reacted at 90 ° C for 2 hours. After cooling the reaction liquid to 50 ° C, a solid solution was obtained by adding 200 ml of a 13% sodium hydroxide aqueous solution. Further, the reaction After stirring the solution in an ice water bath for 30 minutes, the solid was collected by filtration and washed with ion-exchanged water. The obtained solid was dried under reduced pressure, and then recrystallized from isopropyl alcohol to obtain 36.3 g (yield: 92%) of the triarylmethane derivative (compound 8).

(2) Synthesis of a triarylmethane derivative (compound 11) having a methacryl group

In a 300 ml round bottom flask equipped with a stirring device, NK ester (NK Ester) SA (succinic acid-2-methylpropenyloxyethyl ester, manufactured by Shin-Nakamura Chemical Co., Ltd.) was added in an amount of 11.5 g (50 mmol). 5.6 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) and THF (manufactured by Wako Pure Chemical Industries, Ltd.) 100 ml, and cooled to 10 °C. 50 ml of a 7.5 g (55 mmol) THF solution of isobutyl chloroformate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise thereto, and the mixture was stirred at 10 ° C for 1 hour. The resulting hydrochloride of trimethylamine was filtered to obtain a corresponding mixed anhydride (Compound 10) in THF. In a 500 ml round bottom flask equipped with a stirring device, 19.8 g (50 mmol) of a triarylmethane derivative (Compound 8) and 100 ml of THF were added, and a previously prepared THF solution of the compound 10 was added dropwise thereto, and the reaction was carried out at 60 ° C. 2 hours. After removing THF from the reaction liquid by concentration under reduced pressure, dichloromethane (Wako Pure Chemical Industries Co., Ltd.) Manufactured) 200 ml of redissolved, washed with water, and concentrated under reduced pressure. The obtained crude product was purified by a silica gel column to obtain 15.0 g (yield: 49%) of a triarylmethane derivative (compound 11) having a methacrylic acid group.

(3) Oxidation reaction and salt exchange reaction

To a 500 ml round bottom flask equipped with a stirring device, 5.0 g (8.2 mmol) of a triarylmethane derivative (compound 11) having a methacryl group, and 100 ml of a toluene (manufactured by Wako Pure Chemical Industries, Ltd.) and dichloride were added. After 150 ml of methane (manufactured by Wako Pure Chemical Industries, Ltd.), 17 ml (17 mmol) of 1 mol/L hydrochloric acid and 3.0 g (12.3 mmol) of chloranil (manufactured by Wako Pure Chemical Industries, Ltd.) were further added and stirred at room temperature. 1 hour. To the solution, 6.1 g (corresponding to 8.2 mmol) of a lithium salt of tetrakis(pentafluorophenyl)borate (IV) (manufactured by Tosoh Finechem Co., Ltd.) was added thereto, and the mixture was stirred at room temperature for 22 hours. Thereafter, the aqueous layer was removed from the stirred solution by liquid separation, and the obtained organic layer was washed with a 3% K ₂ CO ₃ aqueous solution, washed with water, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified using a silica gel column to obtain (Comp. 13) (1.

Comparative Example 2 Method for producing triarylmethane derivative having chloride ion as an anion

In the same manner as in Example 2 except that the lithium salt of tetrakis(pentafluorophenyl)borate (IV) was not added, the experiment was carried out to obtain a dark blue solid (Compound 12) 4.5 g. (yield 85%)

Comparative Example 3 Method for producing a compound of the present invention from Basic Blue 7.

To a 200 mL round bottom flask equipped with a stirring device, 2.6 g (5 mmol) of Basic Blue 7 (manufactured by Tokyo Chemical Industry Co., Ltd.) and dichloromethane (manufactured by Wako Pure Chemical Industries, Ltd.) 20 ml were added. After it was dissolved, 0.9 g (5.5 mmol) of 2-isocyanatoethyl methacrylate (Compound 2: manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at room temperature. Then, the obtained solution was stirred at room temperature for 3 hours, and further stirred under reflux for 1 hour. Then, the solution was washed with water, dried over sodium sulfate, and concentrated under reduced pressure to give a dark blue solid (3.2 g). When the obtained dark blue solid was measured by ¹ H-nuclear magnetic resonance (NMR), it was confirmed that the triarylmethane derivative (compound 5) was not obtained as a target product, and it was found to be a mixture of raw materials.

That is, from the results, it was found that even if the isocyanatoethyl methacrylate was directly introduced into Basic Blue 7, the reaction did not proceed, and the target triarylmethane derivative could not be obtained.

Comparative Example 4 Method for producing a compound of the present invention using phosphorus oxychloride as a condensing agent

In a 200 mL round bottom flask equipped with a stirring device, 10 mg of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.), urea (compound 3) 2.0 g (6.7 mmol), 4, 4'- (two) were added. Ethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in an amount of 0.2 g (6.7 mmol) and toluene (manufactured by Wako Pure Chemical Industries, Ltd.) in 50 ml, and then the inside was purged with nitrogen. After the solution was warmed to 45 ° C, 1.0 g (6.7 mmol) of phosphorus oxychloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. Then, the temperature of the solution was raised to 70 ° C and stirred for 1 hour, and then the solvent was distilled off under reduced pressure. Dichloromethane (manufactured by Wako Pure Chemical Industries, Ltd.) and water were added to a round bottom flask for solvent extraction, washed with water, dried over sodium sulfate, and concentrated under reduced pressure to give a blue-green oil (4.2 g). The blue-green oil was measured by ¹ H-NMR, and it was found to be a complex mixture. Therefore, each component was separated by a column, but a triarylmethane derivative (compound 5) as a target was hardly confirmed.

The production method is a conventional method for synthesizing a triarylmethane-based compound using a benzophenone derivative and an N-alkylnaphthylamine as a raw material, but it is known that naphthylamine having a plurality of carbonyl groups in the molecule is derived. In the case of the object, the target triarylmethane-based compound is hardly obtained, and only a complicated mixture is formed. In other words, it has been found that the target triarylmethane derivative cannot be obtained by a method using phosphorus oxychloride as a condensing agent which is widely recognized as a synthesis method of a triarylmethane-based compound.

Example 3 Evaluation of heat resistance of Compound 7 (monomer) (230 ° C, 0.5 hour)

The heat resistance of the compound 7 obtained in Example 1 was evaluated as follows.

(1) Synthesis of dye-free polymers

98.5 g of propylene glycol monomethyl ether acetate was placed in a 500 ml round bottom flask equipped with a stirring device, a condenser, a thermometer, and a nitrogen introduction tube, and heated under a nitrogen stream until the internal temperature reached 90 °C. Then, 186.2 g of benzyl methacrylate, 25.6 g of methacrylic acid, and dimethyl 2,2'-azobis(2-methylpropionate) (and pure light) were added dropwise to the round bottom flask over 2 hours. A solution obtained by mixing 33.9 g of a polymerization initiator V-601) and 98.5 g of propylene glycol monomethyl ether acetate produced by the pharmaceutical industry. Thereafter, the resulting solution was allowed to react at 90 ° C for 2 hours. Then, the temperature was raised to 100 ° C and the reaction was carried out for 1 hour. After the reaction, the mixture was cooled to room temperature, and 171.5 g of propylene glycol monomethyl ether acetate was added thereto, followed by dilution to obtain a pale yellow transparent polymer solution. This was taken as polymer A. Further, the concentration of the nonvolatile component of the polymer A was 35.9%.

(2) Adjustment of dye monomer mixed solution

0.5 g of the compound 7, 52.9 g of the polymer A, and 3.2 g of propylene glycol monomethyl ether acetate were mixed to prepare a dye monomer mixed solution B.

(3) Heat resistance evaluation

The dye monomer mixed solution B was spin-coated on a 3 Å glass wafer (Eagle XG manufactured by Corning), and dried on a hot plate heated to 90 ° C for 90 seconds. A film having a film thickness of 1 μm was obtained. The obtained film was measured for absorbance (λa) at the maximum absorption wavelength using a spectrophotometer (Spectrophotometer UV-2550 manufactured by Shimadzu Corporation), and then heated on a hot plate heated to 230 ° C for 30 minutes, and then again. The absorbance (λb) was measured. The dye residual ratio (%) was determined from the values of λa and λb by the following formula. The results are shown in Table 1.

Dye residual rate (%) = (λb / λa) × 100

Example 4 Evaluation of heat resistance of Compound 13 (monomer) (230 ° C, 0.5 hour)

An experiment was carried out in the same manner as in Example 3 except that the compound 13 obtained in Example 2 was used as the dye monomer. The results are shown in Table 1 together with the results of Example 3.

Comparative Example 5 Evaluation of heat resistance of a monomer (230 ° C, 0.5 hour)

In addition to using 0.5 g of the compound 6 obtained in Comparative Example 1, 0.5 g of the compound 12 obtained in Comparative Example 2 or Basic Blue 7 (Tokyo Chemical Industry Co., Ltd.) In the same manner as in Example 2 except that 0.5 g of the dye monomer was produced, the dye residual ratio (%) was determined.

The results obtained are shown in Table 1 together with the results of Example 3 and Example 4.

When the heated glass wafer was observed, the dye in Comparative Example 5 was decomposed to become colorless and transparent, whereas the blue film in Example 3 and Example 4 remained. As shown in Table 1, in the case of using a polymerizable blue dye having chloride ions or Basic Blue 7 as a usual blue dye, the dye hardly remains due to heating, and Here, the dye monomers of Examples 3 and 4 remained 70% to 80%, and exhibited excellent heat resistance.

Example 5 Synthesis of dye polymer containing monomer units derived from compound 7

27.9 g of propylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a 200 ml round bottom flask equipped with a stirring device, a condenser, a thermometer, a nitrogen gas introduction tube, and heated to a temperature of 90 under a nitrogen stream. °C so far. Then, 3.0 g of Compound 7, 50.1 g of benzyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 6.9 g of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), and dimethyl 2,2' were mixed. -Azo Bis(2-methylpropionate) (polymerization initiator V-601 manufactured by Wako Pure Chemical Industries Co., Ltd.) 9.6 g, and propylene glycol monomethyl ether acetate 27.9 g (manufactured by Wako Pure Chemical Industries, Ltd.) The mixed solution was added dropwise to the round bottom flask over 2 hours. Thereafter, the resulting solution was allowed to react at 90 ° C for 2 hours. After the reaction, the mixture was cooled to room temperature, and 48.6 g of propylene glycol monomethyl ether acetate was added thereto to be diluted to obtain a dye polymer containing the monomer unit derived from the compound 7 (Compound 7 / Benzyl methacrylate / methacrylic acid = 3.0/50.1/6.9). This dye polymer was used as the dye polymer 1.

Comparative Example 6 Synthesis of dye polymer containing monomer units derived from compound 6

In the same manner as in Example 5, except that 3.0 g of the compound 6 was used instead of 3.0 g of the compound 7, a dye polymer containing a monomer unit derived from the compound 6 was obtained. This dye polymer was used as the dye polymer 2.

Example 6 Evaluation of heat resistance of dye polymer 1 (230 ° C, 0.5 hour)

The heat resistance of the dye polymer 1 obtained in Example 5 was evaluated as follows.

Namely, the dye polymer 1 was spin-coated on a 3 Å glass wafer (Eagle XG manufactured by Corning), and dried on a hot plate heated to 90 ° C for 90 seconds. A film having a film thickness of 1 μm was obtained. The obtained film was measured for absorbance (λa) at the maximum absorption wavelength using a spectrophotometer (Spectrophotometer UV-2550 manufactured by Shimadzu Corporation), and then heated on a hot plate heated to 230 ° C for 30 minutes, and then again. The absorbance (λb) was measured. According to the obtained λa and λb The value of the dye remaining ratio (%) was determined by the following formula. The results are shown in Table 2.

Dye residual rate (%) = (λb / λa) × 100

Comparative Example 7 Evaluation of heat resistance of polymer (230 ° C, 0.5 hour)

In the same manner as in Example 6, except that the dye polymer 2 obtained in Comparative Example 6 was used instead of the dye polymer 1, the dye residual ratio (%) was determined by the same method. The results obtained are shown in Table 2 together with the results of Example 6.

According to the results of Table 2, with respect to the compound 6 having a chloride ion, the residual ratio of the dye polymer containing the monomer unit derived from the compound 6 was not improved. On the other hand, as for the compound 7 which is a dye compound of the invention of the present application, it is known that it is used as a dye monomer as a dye polymer containing a monomer unit derived from the monomer. The dye residual rate becomes higher. From this, it was found that the compound of the present application was further improved in heat resistance by being made into a polymer.

Example 7 Synthesis of dye polymer containing monomer units derived from compound 7

Add propylene glycol monomethyl ether acetate (Daicel) to a 2000 ml round bottom flask equipped with a stirring device, a condenser, a thermometer, and a nitrogen inlet tube. 105 g was produced and heated under a nitrogen stream until the internal temperature reached 95 °C. Then, 15 g of the compound 7, methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 285 g, 2,2'-azobis(methyl 2-methylpropionate) (trade name V-601, 15 g of Wako Pure Chemical Industries, Ltd., and the mixed solution was added dropwise to a round bottom flask at 95 ° C for 2 hours. Thereafter, the resulting solution was allowed to react at 95 ° C for 2 hours. After cooling the reaction liquid to room temperature, it was dissolved in 1000 g of ethyl acetate. The obtained solution was poured into 4600 ml of n-hexane, and the resulting precipitate was collected by filtration, and dried under reduced pressure to give 315 g of a dye polymer containing about 5 parts by weight of Compound 7. This dye polymer was used as the dye polymer 3.

Example 8 Synthesis of a coloring resin containing a dye polymer

0.5 parts by weight of the dye polymer 3 obtained in Example 7 and 99.5 parts by weight of a methyl methacrylate resin (Acrypet MD001 (manufactured by Mitsubishi Rayon)) were melted using a co-rotating twin-screw extruder. Mixing to obtain colored resin particles. Then, the obtained resin pellets were formed into a molded plate of 150 mm × 150 mm × 2 mm in thickness using an electric injection molding machine.

Comparative Example 8 Synthesis of a coloring resin containing a dye polymer

The same procedure as in Example 8 was carried out except that 0.025 parts by weight of Basic Blue 7 was used instead of 0.5 part by weight of the dye polymer 3, and 100 parts by weight of methyl methacrylate resin was used instead of 99.5 parts by weight. Operate and make a molded plate.

Example 9. Comparative Example 9 Dissolution test

The molded sheets produced in Example 8 and Comparative Example 8 were each cut into a size of 40 mm × 30 mm × 2 mm in thickness, and immersed in 50 parts of ethanol and 50 parts of ion-exchanged water. 80 ml of the combined ethanol solution was stored in a thermostat at 40 °C. The spectrophotometer (a spectrophotometer UV-2500 manufactured by Shimadzu Corporation) was taken out from the thermostat, and the spectroscopic spectrum of the aqueous solution of the ethanol impregnated with the resin plate was measured.

The weight of the compound 7 or the basic blue (Basic Blue) 7 eluted into the aqueous ethanol solution was calculated using the absorbance (λa) at the maximum absorption wavelength of the measurement sample and the gram absorbance coefficient (ε) measured in advance, and was calculated by the following formula. The dissolution rate (%) based on the weight of the compound 7 or the basic blue (Basic Blue) 7 contained in the resin plate to be immersed was calculated.

Dissolution rate (%) = [(λa × 0.08 / ε) / (weight of dye contained in the resin sheet)] × 100

* The weight of the dye indicates the weight of Compound 7 or Basic Blue 7.

The results of the impregnation for 200 hours are shown in Table 3 below.

From the results, it was found that the coloring resin obtained by using the polymer of the present invention can suppress the elution of the dye in a solvent as compared with the coloring resin obtained by using the conventional dye.

Claims (15)

a compound represented by the following formula (1); In the formula, R ₁ to R ₄ and R ₁₄ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted phenyl group, a naphthyl group or a benzyl group, and R ₅ to R ₇ are respectively independently represent a hydrogen atom or a methyl group, R ₈ ~ R ₁₃ each independently represent an alkyl group having 1 to 21 carbon atoms, an aryl group, a hydroxyl group, a nitro group, a sulfo group or an alkoxy group having a carbon number of 1 to 3; a ₁ And an alkylene group having from 1 to 21 carbon atoms having at least one group of -NR ₁₅ -, -O-, -OCO-, -COO- or an aryl group in the chain, and having a hydroxyl group as a substituent; a C 1~21 alkyl group having at least one group of -NR ₁₅ -, -O-, -OCO-, -COO- or an aryl group in the chain; a C 1~21 having a hydroxyl group as a substituent An alkyl group; or an alkylene group having 1 to 21 carbon atoms; A ₂ represents -NH- or -O-; R ₁₅ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted Phenyl, naphthyl or benzyl; An ^- represents an anion containing an aryl group having an electron-donating substituent, a sulfonyl group having an electron-donating substituent or a halogenated alkyl group. The compound of claim 1, wherein the electron-donating substituent in An ^- is a halogen atom. The compound of claim 1, wherein the electron-donating substituent in An ^- is a fluorine atom. The compound of claim 1, wherein An ^- is a quaternary boron anion. The compound of claim 1, wherein An ^- is a tetrakis(perfluorophenyl)borate anion. a polymer comprising a monomer unit derived from a compound represented by the following formula (1); In the formula, R ₁ to R ₄ and R ₁₄ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted phenyl group, a naphthyl group or a benzyl group, and R ₅ to R ₇ are respectively independently represent a hydrogen atom or a methyl group, R ₈ ~ R ₁₃ each independently represent an alkyl group having 1 to 21 carbon atoms, an aryl group, a hydroxyl group, a nitro group, a sulfo group or an alkoxy group having a carbon number of 1 to 3; a ₁ And an alkylene group having from 1 to 21 carbon atoms having at least one group of -NR ₁₅ -, -O-, -OCO-, -COO- or an aryl group in the chain, and having a hydroxyl group as a substituent; a C 1~21 alkyl group having at least one group of -NR ₁₅ -, -O-, -OCO-, -COO- or an aryl group in the chain; a C 1~21 having a hydroxyl group as a substituent An alkyl group; or an alkylene group having 1 to 21 carbon atoms; A ₂ represents -NH- or -O-; R ₁₅ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted Phenyl, naphthyl or benzyl; An ^- represents an anion containing an aryl group having an electron-donating substituent, a sulfonyl group having an electron-donating substituent or a halogenated alkyl group. The polymer of claim 6, wherein the electron withdrawing substituent in An ^- is a halogen atom. The polymer of claim 6, wherein the electron withdrawing substituent in An ^- is a fluorine atom. The polymer of claim 6, wherein An ^- is a quaternary boron anion. The polymer of claim 6, wherein An ^- is a tetrakis(perfluorophenyl)borate anion. The polymer of claim 6, wherein the polymer is a copolymer. The polymer according to claim 11, wherein the copolymer is derived from one to two of the following formula (2), formula (3), formula (4) or formula (5). a monomer unit of the monomer represented and a monomer unit derived from the compound represented by the above formula (1) as a constituent component; In the formula, R ₂₁ represents a hydrogen atom or a methyl group, and R ₂₂ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon number of 7~ An arylalkyl group of 13 , an alkoxyalkyl group having 2 to 9 carbon atoms, an alkoxyalkoxyalkyl group having 3 to 9 carbon atoms, an aryloxyalkyl group having 7 to 13 carbon atoms, and a carbon number of 5~ a morpholinoalkyl group of 7 , a trialkylsulfanyl group having 3 to 9 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms containing or not containing oxygen, and a dialkylamino alkane having 3 to 9 carbon atoms a group, a fluoroalkyl group having 1 to 18 carbon atoms, or an N-alkylene phthalic acid imine group having 1 to 6 carbon atoms; a group represented by the following formula (2-1); Wherein R ₂₃ represents an alkylene group having a hydroxyl group as a substituent or an unsubstituted carbon number of 1 to 3, and R ₂₄ represents a phenyl group having a hydroxyl group as a substituent or an unsubstituted group, or an alkyl group having 1 to 3 carbon atoms; a group, q represents an integer of 1 to 3, and a group represented by the following formula (2-2); In the formula, R ₂₅ to R ₂₆ represent an alkyl group having 1 to 3 carbon atoms, R ₂₈ represents an alkylene group having 1 to 3 carbon atoms, or a group represented by the following formula (2-3). Wherein l represents an integer from 1 to 6, and R ₂₉ represents a phenyl or cyclohexyl group; Wherein R ₂₁ is the same as defined above; R ₃₁ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₃ 2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and a carbon number of 3 to 9; An alkylaminoalkyl group or a hydroxyalkyl group having 1 to 6 carbon atoms; R ₃₁ and R ₃₂ may also form a morpholinyl group with the adjacent nitrogen atom; Wherein R ₃₃ represents a phenyl or pyrrolidinyl group, and R ₂₁ is the same as described above; Wherein, R ₃₅ represents a nitrogen atom or an oxygen atom, in R ₃₅ is the case of oxygen atom, j represents 0, at the time of R ₃₅ is the case of a nitrogen atom, j represents 1; R ₃₄ represents a hydrogen atom, a C 1 to 20 An alkyl group, a hydroxyalkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkylcycloalkyl group having 6 to 10 carbon atoms, a halogenated cycloalkyl group having 6 to 7 carbon atoms, and a carbon number of 6~ An aryl group of 10, an aryl group having 6 to 10 carbon atoms having a C 1 to 6 alkyl group as a substituent, or a halogenated aryl group having 6 to 10 carbon atoms. In the method for producing a compound, the compound is represented by the following formula (1), and a compound represented by the following formula (9) is reacted with a compound represented by the following formula (10) to carry out an oxidation reaction. Salt exchange reaction; In the formula, R ₇ represents a hydrogen atom or a methyl group, and R ₈ to R ₁₃ each independently represent an alkyl group having 1 to 21 carbon atoms, an aryl group, a hydroxyl group, a nitro group, a sulfo group or an alkoxy group having 1 to 3 carbon atoms. R ₁₄ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted phenyl group, a naphthyl group or a benzyl group; and A ₁ represents a group having -NR ₁₅ -, -O-, -OCO-, -COO- or at least one group of an aryl group, and having a hydroxyl group as a substituent, a C 1~21 alkyl group; having -NR ₁₅ -, -O-, -OCO- in the chain a C1-C21 alkyl group having at least one group of -COO- or an aryl group; an alkyl group having 1 to 21 carbon atoms having a hydroxyl group as a substituent; or an alkylene group having 1 to 21 carbon atoms , A ₂ represents -NH- or -O-; R ₁₅ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted phenyl group, a naphthyl group or a benzyl group; In the formula, R ₁ to R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted phenyl group, a naphthyl group or a benzyl group, and R ₅ to R ₆ are each independently represented. a hydrogen atom or a methyl group; Wherein R ₁ to R ₁₄ , A ₁ and A _{2 are} the same as described above; An ^- represents an aryl group having a electron-withdrawing substituent, a sulfonyl group having an electron-donating substituent or a halogenated alkyl group. Anion. A coloring composition comprising the compound of claim 1 or the polymer of claim 6 of the patent application. Coloring composition for color filter, which is included in the scope of patent application The compound according to item 1 or the polymer according to item 6 of the patent application.