TWI550030B - Color material and method for producing the same - Google Patents

Description

Color material and manufacturing method thereof

The present invention relates to a novel color material excellent in heat resistance and color rendering property and a method of producing the same.

Currently, a variety of dyes are known, mostly distinguished by natural dyes and synthetic dyes. Examples of the synthetic dye include aniline blue, magenta, and methyl orange. Most of the synthetic dyes have an aromatic or heterocyclic ring and are ionic (for example, all water-soluble dyes) or nonionic compounds (for example, Any of the disperse dyes). Further, in the case of an ionic dye, there is a difference between an anionic (anionic) dye and a cationic (cationic) dye.

The above cationic dye contains an organic cation having a positive charge which is delocalized throughout a conjugated bond and an anion which is usually inorganic. Again, these are typically dyes in which the substituted amine group participates in resonance. Therefore, the amount of the cationic dye is preferably selected depending on the amount or type of the anion as the counter ion. Examples of the relative anion include chloride ion, bromide ion, iodide ion, perchlorate ion, and tetrafluoroborate ion. , hexafluorophosphate ion, alkyl or aryl sulfate ion, p-toluenesulfonic acid ion, acetic acid or oxalate ion.

Rose red, saffron or Victoria blue as cationic dyes usually have chloride ions or p-toluenesulfonic acid as relative ions. However, the heat resistance of these compounds is not sufficient.

It is known to increase the durability of the triarylmethane dye to heat. An example in which a chloride ion or an aryl sulfate ion is used in the relative anion of the triarylmethane dye (for example, Patent Document 1).

Patent Document 2 discloses that a triarylmethane-based basic dye and at least two are included as means for obtaining a colored coloring composition for color filters excellent in color properties, heat resistance, light resistance, and solvent resistance. a salt-forming compound of an organic sulfonate of sulfhydryl.

Further, in Patent Document 3, as a means for obtaining a colored resin composition which is excellent in light resistance and also satisfies light resistance, a sulfonate of a pigment skeleton such as phthalocyanine or hydrazine is used as a relative anion, and a cation as a cation is reported. A method in which a base methane skeleton is subjected to salt formation.

However, the dyes described in Patent Documents 1 to 3 and the salt-forming compounds having a relative anion have problems of heat resistance and coloring of the fibers, which are not sufficient to cause discoloration.

Patent Document 4 describes a polyoxyalkylene dye which is highly crosslinked by a polyoxyalkylene containing at least 10 Si atoms. However, the polyoxyalkylene dye described in Patent Document 4 is a mixture of only one unreacted compound having a pigment skeleton or a dye having a different degree of polymerization according to the synthesis method. Therefore, as described in the following comparative examples, The solvent may cause a part of the dissolution residue, and on the other hand, the fiber colored by the pigment may be partially discolored by washing, and the physical properties are not stable. Further, there is a problem that it is difficult to separate only the pigment having a specific degree of polymerization and the productivity is poor.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2008-304766

Patent Document 2: Japanese Patent Special Closed 2011-7847

Patent Document 3: International Publication No. 2009/107734

Patent Document 4: Japanese Patent Laid-Open Publication No. 2010-526897

The present invention has been made in view of the above-described actual circumstances, and an object of the invention is to provide a color material which is excellent in color rendering properties and excellent in heat resistance, and a method for producing a color material which can obtain the color material in high purity and high yield.

The color material of the present invention is characterized in that it is a compound represented by the following formula (I).

(In the formula (I), the carbon atom to which the A system and N are directly bonded does not have an a-valent organic group having a π bond, and the organic group represents a ring having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N. aliphatic hydrocarbon group, or at the N-terminus of directly bonded saturated aliphatic hydrocarbon having at least the aromatic group, the carbon chain may contain O, S, N.B ^- represents a monovalent anion, a plurality of B ^- may be identical or R ¹ to R ⁵ each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ² and R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring structure. Ar ¹ represents a divalent polycyclic aromatic group which may have a substituent, and a plurality of R ¹ to R ⁵ and Ar ¹ may be the same or different.

a represents an integer of 2 or more. b is 0 or 1, and when b is 0, there is no key. A plurality of b may be the same or different).

In the color material of the present invention, the anion (B ^- ) in the above formula (I) is preferably an organic anion having a sulfonate group (-SO ₃ ^- group) in terms of coloring property and heat resistance.

In the color material of the present invention, the organic anion is preferably an anion represented by the following formula (II) in terms of coloring property and heat resistance.

(In the formula (II), Ar ² is a monovalent aromatic group which may have a substituent).

The method for producing a color material represented by the formula (I) of the present invention is characterized by comprising the step of subjecting a compound represented by the following formula (A) to a compound represented by the following formula (B): .

[Chemical 3]

(In the above formula (A), the above formula (B) and the above formula (I), the carbon atom to which the A system and N are directly bonded does not have an a-valent organic group having a π bond, and the organic group means at least The cyclic aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N or the aromatic group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N may contain O, S, and N in the carbon chain. B ^- represents a monovalent anion, and a plurality of B ^- may be the same or different. R ¹ to R ⁵ each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ² and R ³ R ⁴ and R ⁵ may also be bonded to form a ring structure. Ar ¹ represents a divalent polycyclic aromatic group which may have a substituent, and Ar ^{1 '} is a monovalent polycyclic aromatic group in which hydrogen is bonded to Ar ¹ . The plurality of R ¹ to R ⁵ , Ar ¹ and Ar ^{1 '} may be the same or different.

a represents an integer of 2 or more. b is 0 or 1, and when b is 0, there is no key. A plurality of b may be the same or different).

According to the present invention, it is possible to provide a color material which is excellent in coloring property and excellent in heat resistance, and a manufacturer which can obtain the color material of the color material in high purity and high yield. law.

Hereinafter, the color material of the present invention and a method for producing the same will be described in detail.

[color material]

The color material of the present invention is characterized in that it is a compound represented by the following formula (I).

(In the formula (I), the carbon atom to which the A system and N are directly bonded does not have an a-valent organic group having a π bond, and the organic group represents a ring having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N. aliphatic hydrocarbon group, or at the N-terminus of directly bonded saturated aliphatic hydrocarbon having at least the aromatic group, the carbon chain may contain O, S, N.B ^- represents a monovalent anion, a plurality of B ^- may be identical or R ¹ to R ⁵ each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ² and R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring structure. Ar ¹ represents a divalent polycyclic aromatic group which may have a substituent, and a plurality of R ¹ to R ⁵ and Ar ¹ may be the same or different.

a represents an integer of 2 or more. b is 0 or 1, and when b is 0, there is no key. A plurality of b may be the same or different).

The color material of the present invention is excellent in coloring property and heat resistance. Although the reason is not clear, it is estimated as follows.

Conventionally, there is usually a problem of low heat resistance. As means for overcoming this problem, a method of forming a dye into a salt compound is used. For example, as a method of forming a salt of a triarylmethane dye, there is a method of using a divalent anion as a relative anion (for example, Patent Document 2). According to this method, since the divalent counter anion can form an ionic bond with the two dye cations, the heat resistance is improved as compared with the use of only the dye. However, even with this method, sufficient heat resistance cannot be obtained. Further, since the structure of the cation does not change, the solubility in water is not substantially lowered.

The cation portion having color developability of the color material of the present invention has a divalent or higher cation having a structure represented by the following formula (IV). The cationic moiety represented by the general formula (IV) is different from the conventional triarylmethane basic dye or It is a basic dye that does not substantially dissolve in water even if it is a chloride.

In consideration of the case where the bond type of the monocation and the anion constituting only one conventional triarylmethane skeleton is only an ionic bond, the bond species constituting the salt formation of the cation containing two or more valences of the present invention, in addition to the ionic bond It can be considered to include a structure in which a covalent bond of a single cation is bonded to each other. Therefore, it is inferred that a salt formation product containing a cation of two or more valences having a structure represented by the following formula (IV) contains only one conventional triarylmethane skeleton. The salt formation product increases the type of the bond by the entire constituent element, and as a result, the stability becomes high, the hydration is difficult, and the heat resistance is also improved. Further, it is estimated that the structure represented by the general formula (IV) has a structure including a cyclic aliphatic hydrocarbon group or an aromatic group, and thus the molecular weight is increased by the influence of the linking group A, and the hydrophobicity is changed. It is high and therefore interacts with the stability of the bond to become substantially insoluble in water. Therefore, it is estimated that even when it is washed with water or detergent, it does not fade, and the coloring property is excellent.

Further, since the hydrocarbon of the linking group A in which the color material represented by the above formula (I) is directly bonded to the cationic coloring portion does not have a π bond, the color tone or penetration of the cationic coloring portion is obtained. The rate of isochromatic properties hardly changes before and after the introduction of the linking group A.

(In the formula (IV), A, R ¹ to R ⁵ , Ar ¹ , a and b are the same as those in the formula (I).

b in the above formula (I) is an integer of 0 or 1. When b is 0, it has a triarylmethane skeleton represented by the following formula (V). The triarylmethane skeleton shows a blue color.

(In the formula (V), A, R ¹ to R ⁵ , Ar ¹ , a and b are the same as those in the formula (I)).

Further, when b is 1, it has the following formula (VI) skeleton.

(In the formula (VI), A, R ¹ to R ⁵ , Ar ¹ , a and b are the same as those in the formula (I).

A plurality of b may be the same or different. That is, for example, it may have only a plurality of triarylmethane skeletons or only a plurality of The cation portion of the skeleton may also contain a triarylmethane skeleton in one molecule. The cation part of both skeletons. In terms of color purity, it is preferred to have only the cationic portion of the same skeleton. On the other hand, by setting it to contain a triarylmethane skeleton and The cationic portion of both of the skeletons, and the coloring material of the general formula (I) can be adjusted to a desired color by a combination of the following substituents.

The carbon atom in the above-mentioned general formula (I) in which the carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group represents a saturated aliphatic group at least at the terminal directly bonded to N The cyclic aliphatic hydrocarbon group of the hydrocarbon group or the aromatic group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N may contain O (oxygen atom), S (sulfur atom), and N (nitrogen atom) in the carbon chain. Since the carbon atom directly bonded to N does not have a π bond, the color tone or transmittance of the cationic color-developing portion is not affected by the linking group A or other color-developing portions, and can be maintained with the monomer. The same color. Further, since A has a cyclic aliphatic hydrocarbon group or an aromatic group, the cationic skeleton is excellent in robustness and excellent in heat resistance.

In A, if at least the carbon atom at the end of the direct aliphatic bond group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N does not have a π bond, the carbon atom other than the terminal may have no The saturated bond may have a substituent, and the carbon chain may include O, S, and N. For example, a carbonyl group, a carboxyl group, an oxycarbonyl group, a guanamine group or the like may be contained, and the hydrogen atom may be further substituted with a halogen atom or the like.

Further, the aromatic group having the above aliphatic hydrocarbon group in A may, for example, be a monocyclic or polycyclic aromatic group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, may have a substituent, or may contain O, Heterocyclic ring of S and N.

As the cyclic aliphatic hydrocarbon group, in view of the solidity of the skeleton, a bridged alicyclic hydrocarbon group is preferred. The bridged alicyclic hydrocarbon group refers to a polycyclic aliphatic hydrocarbon group having a bridge structure in an aliphatic ring and having a polycyclic structure, and examples thereof include: Alkane, bicyclo[2,2,2]octane, adamantane, and the like. It is preferred to have a bridged alicyclic hydrocarbon group alkyl. In addition, examples of the aromatic group include a group including a benzene ring and a naphthalene ring, and among them, a group containing a benzene ring is preferred.

In the case of the linking group A, the carbon atom directly bonded to N is electronically stable, and the stability of the cationic skeleton is preferably a cyclic aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal.

A is preferably two valences from the viewpoint of the ease of obtaining raw materials. For example, when A is a divalent organic group, two alkyl groups having 1 to 20 carbon atoms such as a straight chain, a branched or a cyclic alkyl group having 1 to 20 carbon atoms or a benzodiamethylene group may be mentioned. A group substituted with an aromatic group or the like.

The alkyl group in R ¹ to R ⁵ is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms may be mentioned. Among them, a linear or branched alkyl group having a carbon number of 1 to 8 is preferable, and in terms of ease of manufacture and supply of raw materials, More preferably, it is a linear or branched alkyl group having a carbon number of 1 to 5. Among them, the alkyl group in R ¹ to R ⁵ is particularly preferably an ethyl group or a methyl group. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group. Examples of the substituted alkyl group include a benzyl group and the like.

The aryl group in R ¹ to R ⁵ is not particularly limited. For example, a phenyl group, a naphthyl group, etc. are mentioned. Examples of the substituent which the aryl group may have include an alkyl group, a halogen atom and the like.

The combination of R ² and R ³ , R ⁴ and R ⁵ to form a ring structure means that R ² and R ³ , and R ⁴ and R ⁵ form a ring structure via a nitrogen atom. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring and a piperidine ring. A porphyrin ring or the like.

In terms of chemical stability, R ¹ to R ^{5 are} preferably independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ² and R ³ , R ⁴ and R. ^5- bonding forms a pyrrolidine ring, a piperidine ring, A porphyrin ring.

Although R ¹ to R ⁵ can independently obtain the above structures, it is preferable that R ¹ is a hydrogen atom in terms of color purity, and it is more preferable in terms of ease of manufacture and supply of raw materials. R ² to R ^{5 are} all the same.

Ar ¹ represents a divalent polycyclic aromatic group. By using Ar ¹ as a polycyclic aromatic group, the cationic skeleton is excellent in robustness, and thus heat resistance is also excellent. The polycyclic aromatic group constituting the polycyclic aromatic group may be a polycyclic heterocyclic group in addition to the polycyclic aromatic hydrocarbon group having a carbocyclic group. Examples of the polycyclic aromatic hydrocarbon in the polycyclic aromatic hydrocarbon group include a condensed polycyclic aromatic hydrocarbon such as a naphthalene ring, an anthracene ring, and a phenanthrene ring; biphenyl, terphenyl, diphenylmethane, and triphenylmethane; A chain polycyclic aromatic hydrocarbon such as hydrazine. In the chain polycyclic aromatic hydrocarbon, for example, diphenyl ether may have O, S, and N in the chain skeleton. On the other hand, examples of the heterocyclic ring in the polycyclic heterocyclic group include benzofuran, benzothiophene, anthracene, oxazole, coumarin, benzopyrone, quinoline, and isoquinoline. Acridine, 酞 Quinazoline, quinolin A condensed polycyclic heterocyclic ring such as a phenyl group. These polycyclic aromatic groups may have a substituent.

Examples of the substituent which the polycyclic aromatic group may have include an alkyl group having 1 to 5 carbon atoms, a halogen atom, and the like.

Ar ^{1 is} preferably a polycyclic aromatic group having 10 to 20 carbon atoms, more preferably a polycyclic aromatic group having a condensed polycyclic carbon ring having 10 to 14 carbon atoms. Among them, in terms of a simple structure and a low raw material, a naphthyl group is more preferred.

A plurality of R's within one molecule ¹ ~ R ⁵ and Ar ¹ may be identical or different. When a plurality of R ¹ to R ⁵ and Ar ¹ are respectively the same, since the same color is displayed in the coloring portion, the same color as that of the coloring portion can be reproduced, and it is preferable in terms of color purity. On the other hand, in the case where at least one of R ¹ to R ⁵ and Ar ¹ is set to a different substituent, the color in which a plurality of monomers are mixed can be reproduced and adjusted to a desired color.

In the present invention, in the case of obtaining a blue color material excellent in coloring property and heat resistance, in the general formula (I), b is preferably 0, R ¹ is a hydrogen atom, and R ² to R ^{5 are used.} It is an ethyl group and Ar ¹ is a combination of an anthranyl group.

In the color material of the present invention, the anion portion is a monovalent anion having a structure represented by (B ^- ). The color material of the present invention has a high solubility in an alcohol solvent or a ketone solvent by having a monovalent anion, and can also prepare a high concentration color material solution, which can be used for coloring of various substrates. When B ^- is a monovalent anion, it is not particularly limited, and the organic anion may be an inorganic anion. Here, the organic anion means an anion having at least one carbon atom. Further, the inorganic anion means an anion containing no carbon atom, and examples thereof include fluoride ion, chloride ion, bromide ion, halide ion of iodide ion or nitrate ion (NO ^- ), perchlorate ion. (ClO ₄ ^- ) and so on.

In the case where B ^- is an organic anion, the structure thereof is not particularly limited. Among them, an organic group having an anionic substituent is preferred.

Examples of the anionic substituent group, examples thereof ^{_{include: -SO 2 N - SO 2 CH}} 3, -SO 2 N - COCH 3, -SO 2 N - SO 2 CF 3, -SO 2 N - COCF 3, -CF 2 SO ₂ N ^- SO ₂ CH ₃ , -CF ₂ SO ₂ N ^- COCH ₃ , -CF ₂ SO ₂ N ^- SO ₂ CF ₃ , -CF ₂ SO ₂ N ^- COCF _3, etc. 醯imino acid group or -SO ₃ ^- a substituent such as -CF ₂ SO ₃ ^- , -COO-, or -CF ₂ COO ^- .

Among them, in terms of the ease of obtaining raw materials or the manufacturing cost, and the effect of stabilizing the cation by a higher acidity and maintaining the color development state, it is preferably a ruthenium group or -SO ₃ ^- Further, -CF ₂ SO ₃ ^- , further preferably -SO ₃ ^- (sulfonate group).

The organic group substituted with an anionic substituent is not particularly limited. The organic group may, for example, be a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a combination thereof, which may include O, S, N in the carbon chain. The hetero atom may also contain a carbonyl group, a carboxyl group, an oxycarbonyl group or a guanamine group, and a hydrogen atom may be substituted. Examples of the substituent which the organic group may have include a halogen atom and the like.

Examples of the organic group substituted by the above anionic substituent include cyclopropane, cyclobutane, cyclopentane, cyclohexane, and lower Alkane, bicyclo[2,2,2]hexane, bicyclo[3,2,3]octane, adamantane and other hydrocarbons; benzene, naphthalene, anthracene, phenanthrene, anthracene, triazine, hydrazine, furan, thiophene, Pyrrole, imidazole, pyran, pyridine, pyrimidine, pyridyl ,three , hydrazine, hydrazine, quinoline, isoquinoline, An aromatic compound such as carbazole may further have a substituent such as a halogen atom or an alkyl group.

The organic group substituted with an anionic substituent is preferably a monocyclic or polycyclic aromatic hydrocarbon group and a combination thereof in terms of ease of introduction of the anionic substituent.

In the case where the anion does not cause a color change, it is preferably used in an organic group having an absorption maximum in a wavelength region of 400 nm or less. Examples of the organic group having an absorption maximum in a wavelength region of 400 nm or less include an organic group containing a condensed polycyclic carbocyclic ring such as naphthalene, tetralin, anthracene, anthracene, an anthracene or a phenanthrene; and a biphenyl group. An organic group of a chain polycyclic hydrocarbon such as triphenyl, diphenylmethane, triphenylmethane or hydrazine; containing furan, thiophene, pyrrole, 5-membered heterocyclic organic group such as azole, thiazole, imidazole or pyrazole, including pyran, pyrone, pyridine, hydrazine Pyrimidine, pyridyl a 6-membered heterocyclic aromatic compound; comprising benzofuran, benzothiophene, anthracene, oxazole, coumarin, benzopyrone, quinoline, isoquinoline, acridine, anthracene Quinazoline, quinolin An organic group such as a condensed polycyclic heterocyclic ring such as a phenyl group.

Further, as the organic group substituted with an anionic substituent, an azo dye, an anthraquinone dye, a triphenylmethane dye derived from an organic compound or an organometallic compound can be used. Dye and phthalocyanine dye, skeleton of indigo dye. Alternatively, conventionally known acid dyes, direct dyes, and acid mord dyes can also be used.

When a dye-derived skeleton or an acid dye, a direct dye, an acid mord dye or the like is used, the color tone of the obtained color material changes, and the color tone of the color material represented by the above formula (I) can be adjusted to Required.

Among the anions having a skeleton derived from a dye, an anion represented by the following formula (III) is preferred from the viewpoint of improving heat resistance.

As the anion portion of the color material of the present invention, when an anion of the formula (III) is used, the color material can be adjusted to a desired color by a combination with the above cation portion.

(In the general formula (III), M represents two hydrogen atoms or Cu, Mg, Al, Ni, Co, Fe or Zn. The sulfonate group (-SO ₃ ^- group) is substituted by an aromatic ring).

Further, in the color material of the present invention, the organic anion is preferably an anion represented by the following formula (II) in terms of improving heat resistance.

(In the formula (II), Ar ² is a monovalent aromatic group which may have a substituent).

When the anion of the color material of the present invention is used in the case of using the anion of the above formula (II), since the anion is colorless or pale yellow, the color material produced has an easy to maintain the cation represented by the general formula (I). Inherent The characteristics of color.

The aromatic group in Ar ² is not particularly limited. The aromatic group may be a heterocyclic ring in addition to the aromatic hydrocarbon group containing a carbocyclic ring. Examples of the aromatic hydrocarbon group include a condensed polycyclic aromatic hydrocarbon group such as a naphthalene ring, a naphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring, and a phenanthrene ring, and a biphenyl ring; a biphenyl group; a biphenyl group; a chain polycyclic hydrocarbon group such as triphenylmethane or hydrazine. In the chain polycyclic hydrocarbon group, for example, diphenyl ether may have a hetero atom such as O or S in the chain skeleton. On the other hand, examples of the hetero ring include furan, thiophene, and pyrrole. 5-membered heterocyclic ring such as azole, thiazole, imidazole or pyrazole; pyran, pyrone, pyridine, pyrone, hydrazine Pyrimidine, pyridyl 6-membered heterocyclic ring; benzofuran, benzothiophene, anthracene, oxazole, coumarin, benzopyrone, quinoline, isoquinoline, acridine, anthracene Quinazoline, quinolin A condensed polycyclic heterocyclic ring such as a phenyl group. These aromatic groups may have a substituent.

Examples of the substituent of the aromatic group include an alkyl group having 1 to 5 carbon atoms, a halogen atom, and the like.

Ar ^{2 is} preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having a condensed polycyclic carbon ring having 10 to 14 carbon atoms. Among them, in terms of a simple structure and a low raw material, a phenyl or naphthyl group is more preferred.

In the color material of the present invention, the plurality of anions (B ^- ) may be the same or different, and an organic anion may be used in combination with an inorganic anion.

The color material of the present invention can be used by being dissolved in a solvent. Examples of the solvent for dissolving the color material of the present invention include methanol, N-methylpyrrolidone (NMP, N-Methylpyrrolidone), γ-butyrolactone, and dimethyl hydrazine (DMSO, Dimethylsulfoxide), N,N-dimethylformamide (DMF, N, N-dimethylformamide) and the like.

On the other hand, the color material of the present invention can be used by dispersing a solvent having a solubility of the above-mentioned color material at 23 ° C of 0.1 (mg/10 g solvent) or less, that is, a substantially insoluble solvent or a poorly soluble solvent. . In this case, since it is dispersed in a solvent while maintaining its agglomerated state, heat resistance is higher than when it is dissolved in a solvent and used. Among them, a solvent having a solubility of the color material of 23 ° C or less is preferably 0.01 (mg/10 g solvent) or less, and more preferably a solvent which does not substantially dissolve the color material. Since the color material of the present invention is a normal salt, if an acidic salt is used, there is no problem that the dispersion is not promoted preferentially or the dispersion is gelled during storage, and the dispersibility and dispersion stability are high.

Further, in the present invention, the solvent having a solubility of the color material of 23 ° C in the dispersion of the color material represented by the general formula (I) of 0.1 (mg/10 g solvent) or less can be determined by the following evaluation method. Easy judgment.

10 g of the solvent to be evaluated was placed in a 20 mL sample vial, and 0.1 g of the above color material was placed, and the lid was fully shaken for 20 seconds, and then allowed to stand in a water bath at 23 ° C for 10 minutes. The supernatant was filtered 5 g to remove insolubles. The absorption spectrum of the obtained filtrate is further diluted 1000 times by a UV-visible spectrophotometer (for example, UV-2500PC manufactured by Shimadzu Corporation) using a 1 cm cuvette to determine the maximum absorption wavelength. Absorbance. At this time, if the absorbance in the maximum absorption wavelength is less than 2, Then, the solvent was evaluated as a solvent having a solubility of the color material at 23 ° C in which the color material represented by the general formula (I) was dispersed to 0.1 (mg/10 g solvent) or less (solvent which is poorly soluble).

Further, in the above evaluation method, the absorbance spectrum was measured in the same manner as described above without diluting the obtained filtrate, and the absorbance at the maximum light absorption wavelength was determined. At this time, if the absorbance in the maximum absorption wavelength is less than 2, it can be evaluated that the solvent is substantially insoluble in the color material represented by the general formula (I).

The solvent having a solubility of the above-mentioned color material at 23 ° C of 0.1 (mg/10 g solvent) or less, for example, ethyl acetate, butyl acetate, methyl methoxypropionate, ethoxy propylene, etc. Ethyl acetate, ethyl lactate, ethyl methoxyacetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-ethyl-1-acetic acid butyl ester, 3-methoxybutyl acetate, A An ester solvent such as butyl oxyacetate, ethyl ethoxyacetate or ethyl celecoxib acetate.

[Manufacturing method of color material]

The method for producing the color material represented by the formula (I) is not particularly limited. For example, it can be obtained by introducing a counter anion as needed after the cation portion is produced by the following method.

As a method, the method for producing a color material represented by the following formula (I) of the present invention is characterized by comprising a compound represented by the following formula (A) and a formula represented by the following formula (B) The step of the compound undergoing a condensation reaction.

(In the above formula (A), the above formula (B) and the above formula (I), the carbon atom to which the A system and N are directly bonded does not have an a-valent organic group having a π bond, and the organic group means at least a cyclic aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end directly bonded to N or an aromatic group having a saturated aliphatic hydrocarbon group at a terminal directly bonded to N, and the carbon chain may include O, S, N. ^- represents a monovalent anion, and a plurality of B ^- may be the same or different. R ¹ to R ⁵ each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, R ² and R ³ , R ⁴ and R ⁵ may also be bonded to form a ring structure. Ar ¹ represents a divalent polycyclic aromatic group which may have a substituent, and Ar ^{1 '} is a monovalent polycyclic aromatic group in which hydrogen is bonded to Ar ¹ . The plurality of R ¹ to R ⁵ , Ar ¹ and Ar ^{1 '} may be the same or different.

a represents an integer of 2 or more. b is 0 or 1, and when b is 0, there is no key. A plurality of b may be the same or different).

The method for producing a color material of the present invention is as follows: a triarylmethane skeleton is formed by dehydration condensation between Ar ^{1 '} of the general formula (A) and a carbonyl group of the general formula (B) or At the same time as the skeleton, the linking group A is introduced. According to this production method, the color materials having different degrees of polymerization do not occur, and the unreacted materials are easily separated due to the large difference in the skeleton, and the color material of the present invention can be obtained with high purity and high yield.

(Compound represented by the following formula (A))

First, a compound represented by the following formula (A) which is a precursor of a cationic moiety is synthesized. Further, a commercially available product can also be used as the compound represented by the formula (A).

(In the formula (A) A, R ^1, and a general formula (I) the same .Ar ^{1 'based} on the Ar of the general formula (I) have the structure ¹ as hydrogen bonding).

The method for synthesizing the compound represented by the formula (A) is not particularly limited. For example, in the presence of a base, palladium acetate or the like is used as a catalyst, and a halogenated aromatic compound having a desired substituent Ar ^{1 '} introduced therein is introduced. The a-valent amine compound having the desired substituent A is reacted in a solvent, whereby a compound represented by the formula (A) can be obtained.

The amount of the halogenated aromatic compound used in the above reaction varies depending on the desired valence number (a). For example, when a = 2 is used, it is preferably 1.5 to 10 moles with respect to the amine compound. The equivalent of the ear, more preferably 1.5 to 3.0 mole equivalents, thereby suppressing the formation of by-products and improving the yield of the reaction. In general, it is preferably 1.8 to 2.2 mole equivalents.

The reaction temperature in the above reaction is not particularly limited, but is usually about 100 to 150 ° C, and is preferably 130 to 145 ° C in terms of suppressing side reactions. Further, the reaction pressure of the above reaction is not particularly limited, and it is preferably from normal pressure to 0.1 MPa, and more preferably atmospheric pressure. Further, the reaction time in the above reaction may vary depending on the amount of synthesis or the reaction temperature, and the like, but it is not generally described. However, it is usually 6 to 72 hours, preferably 6 to 48 hours.

The base to be used in the reaction is not particularly limited. For example, in addition to sodium hydroxide, potassium hydroxide or potassium carbonate, a metal alkoxide or a metal decylamine may be mentioned. Among them, from the viewpoint of suppressing side reactions and increasing the yield of the alkali generating agent, it is preferred to use a strong base having a low nucleophilicity. For example, potassium third potassium butoxide, sodium third butoxide, and the like are preferably used. Lithium tributylate, lithium diisopropylamide, potassium hexamethyldioxanamide, lithium tetramethylpiperidine, and the like. Among the strong bases having a lower nucleophilicity, potassium butoxide is more preferably used.

The amount of the base to be added is not particularly limited, but is usually 2.0 to 4.0 moles per equivalent of the amine compound, and is preferably 2.5 to 3.5 moles per equivalent of the reaction yield.

(synthesis of cationic part)

The cation portion of the color material represented by the above formula (I) is obtained by subjecting a compound represented by the above formula (A) to a compound represented by the following formula (B) to carry out a condensation reaction to synthesize a cation portion. For example, using a chlorinating agent such as phosphorus oxychloride The reaction is carried out in a solvent, whereby it can be obtained as a chloride of a cationic portion. A commercially available product can be used as the compound represented by the following formula (B).

(R ² to R ⁵ and b in the formula (B) are the same as those in the formula (I)).

The amount of the compound represented by the formula (B) used in the above reaction varies depending on the desired valence (a), for example, when the ratio is a = 2, relative to the above formula (A) It is preferably 1.5 to 4.0 mole equivalents, more preferably 1.5 to 3.0 mole equivalents, and further preferably 1.8 to 2.2 moles in terms of suppressing formation of by-products and increasing reaction yield. .

The reaction temperature in the above reaction is not particularly limited, but is usually about 110 to 150 ° C, and is preferably 110 to 120 ° C in terms of suppressing side reactions. Further, the reaction pressure of the above reaction is not particularly limited, and it is preferably from normal pressure to 0.1 MPa, and more preferably atmospheric pressure. Further, the reaction time in the above reaction may vary depending on the amount of synthesis or the reaction temperature, and the like, but it is usually not from 1 to 10 hours, and is preferably in the range of from 1 to 5 hours.

The amount of the phosphorus oxychloride added is not particularly limited, and is usually from 1.5 to 3.0 mol equivalents based on the compound (A), and is preferably from 1.8 to 3.0 mol equivalents in terms of improving the reaction yield.

The color material represented by the formula (I) is obtained by the above reaction as a chloride of a cationic portion. Further, the chloride of the cation portion obtained by the above reaction and the desired anion portion are mixed in a solvent, whereby a color material represented by the formula (I) having a desired anion portion can be obtained.

(Example)

Hereinafter, the present invention will be specifically described by explaining the embodiments. However, the present invention is not limited by the description.

(Synthesis Example 1: Synthesis of Intermediate 1)

1-iodo naphthalene 18.7 g (73.4 mmol), sodium butoxide sodium 9.88 g (102.8 mmol) manufactured by Wako Pure Chemical Co., Ltd., and p-xylenediamine 5.0 g (36.7 mmol) manufactured by Tokyo Chemical Co., Ltd. , 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl 0.27 g (0.57 mmol) manufactured by Aldrich, and palladium acetate 0.054 g (0.28 mmol) manufactured by Wako Pure Chemical Co., Ltd. Disperse in 36 mL of xylene and carry out the reaction at 130-135 ° C for 24 hours. After completion of the reaction, the mixture was cooled at room temperature, and the precipitated crystals were filtered and washed with methanol. Then, it was washed with water and dried to obtain 9.79 g (yield 69%) of the intermediate 1 represented by the following chemical formula (1).

The obtained compound was confirmed to be the target compound based on the analysis results described below.

‧MS(ESI)(m/z):389(+), ‧ Elemental analysis values: CHN measured values (86.72%, 6.54%, 6.97%); theoretical values (86.56%, 6.23%, 7.21%)

(Example 1: Synthesis of Color Material A)

10.0 g (25.7 mmol) of Intermediate 1, 100 mL of toluene, and 7.89 g (51.5 mmol) of phosphorus oxychloride manufactured by Wako Pure Chemical Industries, Ltd. were added and stirred. Then, 16.2 g (49.9 mmol) of 4,4'-bis(diethylamino)diphenyl ketone manufactured by Tokyo Chemical Industry Co., Ltd. was added and refluxed for 5 hours to be cooled. After the reaction was completed, toluene was decanted. 100 mL of water was added and the resin-like precipitate was filtered. The cake was dispersed and filtered by dilute hydrochloric acid, washed with water, and dried to obtain 18.4 g (yield 66%) of the color material A represented by the following chemical formula (2).

The obtained compound was confirmed to be the target compound based on the analysis results described below.

‧MS(ESI)(m/z): 501(+), 2 price

‧ Elemental analysis values: CHN measured values (78.02%, 7.13%, 7.11%); theoretical values (78.26%, 7.32%, 7.82%)

Chemical formula (2)

(Example 2: Synthesis of color material B)

It was added to 1.15 g (5.94 mmol) of sodium p-toluenesulfonate manufactured by Tokyo Chemical Industry Co., Ltd., 33 mL of methanol, and 33 mL of water, and stirred at 50-55 °C. 3.19 g (2.97 mmol) of the color material A obtained in Example 1 was added, and the mixture was stirred at 50 to 55 ° C for 1 hour. The methanol in the solution was concentrated by an evaporator, 100 mL of water was added, and the precipitate was collected by filtration, and washed with water. The filter cake was dried to obtain 3.33 g (yield 83%) of the color material B represented by the following chemical formula (3).

The obtained compound was confirmed to be the target compound based on the analysis results described below.

‧MS(ESI)(m/z): 502(+), 2 price, 171(-)1 price

‧ Elemental analysis values: CHN measured values (75.18%, 7.11%, 6.15%); theoretical values (74.97%, 6.89%, 6.24%)

Chemical formula (3)

(Synthesis Example 2: Synthesis of Intermediate 2)

The production of 1-iodonaphthalene 15.2 g (60 mmol) and Mitsui Chemicals Co., Ltd. manufactured by Wako Pure Chemical Co., Ltd. Cyclohexane diamine (NBDA, Norbornane Diamine) (CAS No. 56602-77-8) 4.63 g (30 mmol), sodium butoxide sodium 8.07 g (84 mmol), 2-dicyclohexylphosphino-2 from Aldrich ',6',-dimethoxybiphenyl 0.09 g (0.2 mmol), and palladium acetate 0.021 g (0.1 mmol) manufactured by Wako Pure Chemical Co., Ltd. were dispersed in 30 mL of xylene and carried out at 130-135 °C. Reaction for 48 hours. After completion of the reaction, it was cooled at room temperature and water was added for extraction. Then, it was dried and concentrated by magnesium sulfate, whereby 28.5 g (yield 70%) of the intermediate represented by the following chemical formula (4) was obtained.

The obtained compound was confirmed to be the target compound based on the analysis results described below.

‧ MS (ESI) (m / z): 407 (M + H), ‧ elemental analysis value: CHN measured value (85.47%, 8.02%, 6.72%); theoretical value (85.26%, 8.11%, 6.63%)

Chemical formula (4)

(Example 3: Synthesis of color material C)

8.46 g (20.8 mmol) of Intermediate 2, 4,4'-bis(dimethylamino)diphenyl ketone manufactured by Tokyo Chemical Industry Co., Ltd. 13.5 g (41.6 mmol), and 60 mL of toluene were stirred at 45-50 ° C. . 6.38 g (51.5 mmol) of phosphorus oxychloride manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise, refluxed for 2 hours and cooled. After the reaction was completed, toluene was decanted. 40 mL of chloroform, 40 mL of water, and concentrated hydrochloric acid were added to dissolve the resinous precipitate, and the chloroform layer was separated. The chloroform layer was washed with water, dried over magnesium sulfate, and concentrated. 65 mL of ethyl acetate was added to the concentrate and refluxed. After cooling, the precipitate was filtered to obtain 15.9 g (yield 70%) of the color material C represented by the following chemical formula (5).

The obtained compound was confirmed to be the target compound based on the analysis results described below.

‧MS(ESI)(m/z): 511(+), 2 price

‧ Elemental analysis values: CHN measured values (78.13%, 7.48%, 7.78%); theoretical values (78.06%, 7.75%, 7.69%)

[Chem. 17] Chemical formula (5)

(Comparative Example 1: color material D)

Basic Blue 7 (CI-42595) (BB7) manufactured by Tokyo Chemical Industry Co., Ltd. represented by the following chemical formula (6) was used as the color material D of Comparative Example 1.

(Comparative Example 2: Synthesis of color material E)

0.97 g (5.02 mmol) of sodium p-toluenesulfonate manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in 50 mL of water and 50 mL of methanol. Then, 5.0 g (9.73 mmol) of Basic Blue 7 (CI-42595) manufactured by Tokyo Chemical Industry Co., Ltd. was added, and the mixture was stirred at normal temperature for 1 hour. The reaction solution was filtered under reduced pressure and washed with water. The cake was dried under reduced pressure to obtain 3.0 g (yield: 92%) of the color material E represented by the following chemical formula (7).

(Comparative Example 3: Synthesis of color material F)

1.62 g (5.02 mmol) of naphthalene-2,6-sulfonic acid disodium salt manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in 50 mL of water and 50 mL of methanol. Then, 5.0 g (9.73 mmol) of Basic Blue 7 (CI-42595) manufactured by Tokyo Chemical Industry Co., Ltd. was added, and the mixture was stirred at normal temperature for 1 hour. The reaction solution was filtered under reduced pressure and washed with water. The filter cake was dried under reduced pressure to give 5.2 g (yield: 86%) of the color material F represented by the following chemical formula (8).

(Synthesis of color material G of Comparative Example 4)

In Comparative Example 3, except that 3.92 g (5.02 mmol) of Direct Blue 86 manufactured by Tokyo Chemical Industry Co., Ltd. was used instead of naphthalene-2,6-sulfonic acid disodium salt, In the same manner as in Example 3, the color material G represented by the following chemical formula (9) was obtained.

(Comparative Example 5: Synthesis of color material H)

According to the method described in Patent Document 4, 12 phosphomolybdate of a polysiloxane dye was synthesized to obtain a color material H.

51.52 g of Basic Blue 7 (BB7) manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in 750 ml of ion-exchanged water, and then, under stirring, the deprotonated form of the pigment was completely precipitated, and no blue residue remained in the solution. The color was added to a 2N aqueous sodium hydroxide solution for several hours until it could not be restored to its original state. The precipitate was separated by filtration, washed three times with ion-exchanged water, and dried at 60 ° C under reduced pressure (0.1 kPa). 45.23 g (94.7%) of the deprotonated BB7 was made into a substantially black powder and separated.

In contrast, 50 ml of 3-iodopropyltrimethoxydecane manufactured by Sigma-Aldrich Co., Ltd. was mixed with 2.0 ml (2.95 g; 10.2 mmol) of an anhydrous alcohol solution, and stirred under argon at room temperature. After an hour, the solvent was distilled off under reduced pressure to give 3-iodopropyltriethoxydecane. Dissolving the obtained 3-iodopropyltriethoxydecane in 50 ml of anhydrous acetonitrile, plus 2.289 g (5 mmol) of the above deprotonated BB7 was introduced, and the solution was heated while refluxing under argon for 24 hours. The solvent was distilled off, and the semi-solid residue was washed several times with methyl tributyl ether under a stream of argon until the filtrate became substantially colorless, and the excess alkylating agent and unreacted deprotonated pigment were removed. Obtained decaneated BB7 as a solid residue. 1 g of this decylated BB7 was dissolved in 25 ml of absolute alcohol to obtain a decaneated BB7 solution.

To a mixed solvent containing 150 ml of ethanol (96%), 50 ml of water and 30 g of a 25% aqueous ammonia solution, 25 ml of a decaneated BB7 solution was added, and the mixture was vigorously stirred at room temperature for 24 hours. After the seed particles were formed, the mixture was centrifuged. After the residue was dispersed in ethanol (80%), the mixture was washed three times and centrifuged, and then the solvent was removed to obtain a residue. The residue was dispersed in dimethyl hydrazine (DMSO), added to 400 ml of deionized water and stirred, and further, a color material H of a comparative example was obtained by adding 12 phosphomolybdic acid ‧n hydrate .

<Color color evaluation of color materials>

Each of 10 mg of the color materials A and C obtained in Example 1 and Example 3 was dissolved in 100 mL of methanol, and diluted to 20 times as a measurement solution. The absorbance spectrum was measured by a Hitachi spectrophotometer U-3500 using a 1 cm quartz cuvette.

Further, as a control, 10 mg of BB7 as a monomer was dissolved in 100 mL of methanol, and the mixture was diluted to 20 times as a measurement solution, and the absorption spectrum was measured by the same method as above. The results are shown in Fig. 1.

As is clear from the results of Fig. 1, the color materials A and C have substantially the same peak shape as the BB7 having no linking group, and the color hardly changes.

Thus, it is understood that the color material represented by the formula (I) having the linking group A in which the carbon atom directly bonded to N does not have a π bond has the same color as the color material of the monomer having no linking group.

<Evaluation of solubility in methanol>

0.05 g of the color materials A to H of the examples 1 to 3 and the comparative examples 1 to 5 were respectively added to the sample vial, and methanol (manufactured by Kanto Chemical Co., Ltd.) was added in such a manner that the total weight of the sample vial was 1.0 g. A magnetic stir bar was added thereto, and the mixture was stirred at room temperature for 1 hour, and it was visually judged whether or not the color material was dissolved. When it is dissolved, it is set to ○, and if it is confirmed that it is insoluble, it is set to ×.

<heat resistance evaluation> (1) Evaluation of thermal decomposition temperature

About 5 mg of the color materials A to H of Examples 1 to 3 and Comparative Examples 1 to 5 were placed in a quartz-made pot, and a differential type differential thermal balance (TG-DTA) TG8120 manufactured by Rigaku Co., Ltd. was used. As a reference, alumina was added to a pot made of quartz, and the temperature increase rate was set to 5 ° C / min to 800 ° C for measurement. The peak of the peak of the obtained thermogravimetry (TG, Thermogravimetry) curve is set as the decomposition point, and the temperature in the decomposition point is set as the thermal decomposition temperature. The thermal decomposition temperature can be used as an index indicating heat resistance.

(2) Evaluation of weight reduction rate

About 5 mg of the color materials A to H of Examples 1 to 3 and Comparative Examples 1 to 5, respectively It was placed in a quartz pot, and a differential type differential thermal balance (TG-DTA) TG8120 manufactured by Rigaku Co., Ltd. was used as a reference. The alumina was placed in a pot made of quartz, and the temperature was raised to 20 ° C / min. At 230 ° C, the weight reduction rate was maintained at the same temperature for 60 minutes from the time point of reaching 230 ° C. The weight reduction rate is calculated by the following formula and can be used as an index indicating heat resistance.

Weight reduction rate = (weight before heating - weight after heating) / weight before heating × 100 (%)

<Coloring evaluation> (1) the color of the cloth

0.5 g of the color material A of Example 1 was added, and 10 ml of methanol was added to prepare a methanol solution of the color material A. 0.1 ml of this methanol solution was added dropwise to the cloth, and methanol was removed by a dryer to color the color material A onto the cloth.

Further, the color materials B to H are colored on the cloth in the same manner as described above except that the color materials B to H are used instead of the color materials A.

(2) Evaluation by water

The cloth of the colored material A to H was washed with running water at 20 ° C for 10 minutes, and the color was observed by visual observation, and evaluated according to the following evaluation criteria.

[evaluation benchmark]

○: No color drop.

△: It was confirmed that there was color loss.

×: No color remains.

(3) Evaluation by detergent

The cloth of the colored material A to H was immersed in the detergent containing the surfactant for 5 minutes, and then washed by running water at 20 ° C for 5 minutes, and the color was visually observed, and the evaluation was the same as the above evaluation by water. Benchmarks are evaluated.

The results of each evaluation are shown in Table 1.

[summary of results]

It is understood that the color materials A to C of Examples 1 to 3 represented by the general formula (I) are excellent in coloring property and heat resistance.

The color material of Comparative Example 1 which is a conventional triarylmethane dye is inferior in heat resistance and coloring property. By replacing the anions as shown in Comparative Examples 2 to 4, although heat resistance and coloring properties were improved, they were not sufficient, and the household detergent was easily faded.

In the color material of Comparative Example 5, although the triarylmethane dye contains a cation having a structure polymerized by a siloxane, the heat resistance and coloring property are not sufficient because it is a mixture of pigments having different degrees of polymerization. There is a dissolution residue for methanol.

1‧‧‧Light absorption spectrum of color material A obtained in Example 1

2‧‧‧The absorption spectrum of the color material C obtained in Example 3

Absorption spectrum of 3‧‧‧Basic Blue 7

1 is an absorption spectrum of the color material A of Example 1, the color material C of Example 3, and Basic Blue 7.

Claims (4)

A color material represented by the following general formula (I): (In the formula (I), the carbon atom to which the A system and N are directly bonded does not have an a-valent organic group having a π bond, and the organic group represents a ring having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N. An aliphatic hydrocarbon group may contain O, S, and N in the carbon chain; B ^- represents a monovalent anion, and a plurality of B ^- may be the same or different; and R ¹ to R ⁵ each independently represent a hydrogen atom and an alkyl group which may have a substituent Or a aryl group which may have a substituent, R ² and R ³ , R ⁴ and R ⁵ may also be bonded to form a ring structure; Ar ¹ represents a divalent polycyclic aromatic group which may have a substituent; and a plurality of R ¹ ~R ⁵ and Ar ¹ respectively may be the same or different; a represents an integer of 2 or more; b is 0 or 1, and when b is 0, there is no bond; a plurality of b may be the same or different). The color material of the first aspect of the invention, wherein the anion (B ^- ) in the above formula (I) is an organic anion having a sulfonate group (-SO ₃ ^- group). The color material according to claim 1 or 2, wherein the anion (B ^- ) in the above formula (I) is an anion represented by the following formula (II): (In the formula (II), the Ar ² -based monovalent aromatic group which may have a substituent). A process for producing a color material represented by the following formula (I), which comprises the step of subjecting a compound represented by the following formula (A) to a compound represented by the following formula (B): (In the above formula (A), the above formula (B) and the above formula (I), the carbon atom to which the A system and N are directly bonded does not have an a-valent organic group having a π bond, and the organic group means at least a cyclic aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, wherein the carbon chain may include O, S, and N; B ^- represents a monovalent anion, and the plurality of B ^- may be the same or different; R ¹ ~ R ⁵ each independently represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ² and R ³ , R ⁴ and R ⁵ may be bonded to form a ring structure; Ar ¹ represents that it may have a divalent polycyclic aromatic group of a substituent, Ar ^{1 '} is a monovalent polycyclic aromatic group to which hydrogen is bonded to Ar ¹ ; a plurality of R ¹ to R ⁵ , Ar ¹ and Ar ^{1 '} may be the same It may be different; a represents an integer of 2 or more; b is 0 or 1, and when b is 0, there is no key; a plurality of b may be the same or different).