JP2013057052A - Coloring material, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring material excellent in dyeability and also excellent in heat resistance, and a method for manufacturing the same, which can provide the coloring material in a high purity and in a high yield.SOLUTION: The coloring material is represented by formula (1) (wherein A is an a-valent organic group whose carbon atom directly bonding with N does not make a π-bond, the organic group is an aliphatic hydrocarbon group at least directly bonding with N and having a saturated aliphatic hydrocarbon group on the terminal or an aromatic group having the aliphatic hydrocarbon group, and the carbon chain may contain O, S, N; Bis a monovalent anion, and a plurality of Bmay be identical or different; Rto Rare each independently a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and Rand R, and Rand Rmay bond to form a ring structure; Aris a divalent aromatic group which may have a substituent; a plurality of Rto Rand Armay be identical or different; and a is an integer of ≥2, b is 0 or 1; when b is 0, there is no bond; and a plurality of b may be identical or different).

Description

  The present invention relates to a novel color material excellent in heat resistance and dyeability, and a method for producing the same.

  Many dyes are known today and are largely distinguished as natural and synthetic dyes. Such synthetic dyes include, for example, aniline blue, fuchsin or methyl orange, but most synthetic dyes have an aromatic or heterocyclic ring and are ionic (eg, all water-soluble dyes) or nonionic Or a disperse dye (for example, a disperse dye). In the case of ionic dyes, a distinction is made between anionic (anionic) dyes and cationic (cationic) dyes.

  The cationic dye is composed of an organic cation having a positive charge delocalized over a conjugated bond and usually an inorganic anion. These are usually dyes in which an optionally substituted amino group participates in resonance. Therefore, the selection of the cationic dye often depends on the number and type of anions which are counter ions. Examples of counter anions include chloride ions, bromide ions, iodide ions, perchlorate ions, tetrafluoroborate ions, Examples include hexafluorophosphate ions, alkyl or aryl sulfate ions, tosylate ions, acetic acid or oxalate ions.

  The cationic dyes rhodamine, safranin or Victoria blue usually have chloride ions or tosylic acid as counter ions. However, these compounds have insufficient heat resistance.

  An example is known in which chloride ions or aryl sulfate ions are used as a counter anion of a triarylmethane dye in order to improve the heat resistance of the triarylmethane dye (for example, Patent Document 1).

  In Patent Document 2, as a means for obtaining a stable colored composition for a color filter having excellent color characteristics and heat resistance, light resistance, and solvent resistance, a triarylmethane basic dye and an organic sulfonated compound having at least two sulfone groups A salt-forming compound consisting of

In Patent Document 3, as a means for obtaining a colored resin composition having excellent light resistance and satisfying light resistance, a sulfonated product of a dye skeleton such as phthalocyanine or anthraquinone is used as a counter anion, and a triarylmethane skeleton that is a cation and a salt The method of forming has been reported.
However, the salt-forming compounds of the dyes and counter anions described in Patent Documents 1 to 3 have insufficient heat resistance and dyeing properties to fibers, and have a problem of discoloration.

  Patent Document 4 describes a polysiloxane dye highly crosslinked by a polysiloxane containing at least 10 Si atoms. However, since the polysiloxane dye described in Patent Document 4 is a mixture in which an unreacted compound having only one dye skeleton and a dye having a different degree of polymerization exist due to its synthesis method, On the other hand, the fiber was dyed with the pigment, and the properties of the fiber dyed with the pigment were not stable. In addition, it is difficult to separate only a dye having a specific polymerization degree, and there is a problem that productivity is poor.

JP 2008-304766 A JP 2011-7847 A WO2009 / 107734 Special table 2010-526897 gazette

  The present invention has been made in view of the above circumstances, and is a coloring material excellent in dyeability and heat resistance, and a coloring material obtained from the coloring material with high purity and high yield. An object is to provide a manufacturing method.

  The coloring material according to the present invention is a compound represented by the following general formula (I).

(In general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and may contain O, S and N in the carbon chain, and B ⁻ represents a monovalent anion. And a plurality of B ⁻ may be the same or different, and R ^{1 to} R ⁵ may each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Represents a good aryl group, and R ² and R ³ , R ⁴ and R ⁵ may combine to form a ring structure, and Ar ¹ represents a divalent aromatic group which may have a substituent. The 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, no bond exists. A plurality of b may be the same or different. )

In the coloring material according to the present invention, the anion (B ⁻ ) in the general formula (I) is an organic anion having a sulfonate group (—SO ₃ ^— group) from the viewpoint of dyeing property and heat resistance. preferable.

  In the coloring material according to the present invention, the organic anion is preferably an anion represented by the following general formula (II) from the viewpoint of dyeing property and heat resistance.

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

  The method for producing a coloring material represented by the general formula (I) according to the present invention comprises a step of subjecting a compound represented by the following general formula (A) and a compound represented by the following general formula (B) to a condensation reaction. It is characterized by having.

(In the general formula (A), the general formula (B), and the general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, The group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and O, S, and N are present in the carbon chain. It included which may be .B ^- represents a monovalent anion, a plurality of B ^- good be different even in the same .R ¹ to R ⁵ each independently represent a hydrogen atom, substituted Represents an optionally substituted alkyl group or an optionally substituted aryl group, and R ² and R ³ , R ⁴ and R ⁵ may combine to form a ring structure, Ar ¹ represents a substituent And Ar ^{1 ′} is a monovalent aromatic group in which hydrogen is bonded to Ar ^1. A 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, no bond exists. A plurality of b may be the same or different. )

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the coloring material which is excellent in dyeing property and excellent in heat resistance, and the coloring material which can obtain the said coloring material with high purity and a high yield can be provided.

FIG. 4 is an absorption spectrum of the coloring material A of Example 1, the coloring material C of Example 3, and Basic Blue 7. FIG.

Hereinafter, the coloring material and the manufacturing method thereof according to the present invention will be described in detail.
[Color material]
The coloring material according to the present invention is a compound represented by the following general formula (I).

(In general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and may contain O, S and N in the carbon chain, and B ⁻ represents a monovalent anion. And a plurality of B ⁻ may be the same or different, and R ^{1 to} R ⁵ may each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Represents a good aryl group, and R ² and R ³ , R ⁴ and R ⁵ may combine to form a ring structure, and Ar ¹ represents a divalent aromatic group which may have a substituent. The 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, no bond exists. A plurality of b may be the same or different. )

The color material according to the present invention is excellent in dyeability and heat resistance. The reason is unclear, but is estimated as follows.
Conventionally, there has been a problem that heat resistance is generally low. As a means for overcoming this problem, a technique using a dye as a salt-forming compound has been used. For example, as a technique for salting a triarylmethane dye, there is a technique using a divalent anion as a counter anion (for example, Patent Document 2). According to this method, since the divalent counter anion can form an ionic bond with two dye cations, the heat resistance is improved as compared with the dye alone. However, even with such a method, sufficient heat resistance could not be obtained. Moreover, since the structure of the cation was not changed, the solubility in water was not basically reduced.
The coloring material of the present invention is a divalent or higher cation in which a cation portion having color developability has a structure represented by the following general formula (IV). Unlike the conventional triarylmethane basic dyes and xanthene basic dyes, the cation moiety represented by the general formula (IV) does not substantially dissolve in water even if it is a chloride thereof.
When the conventional monocation consisting of only one triarylmethane skeleton and the binding species constituting the anion are considered to be only ionic bonds, the binding species constituting the salt-forming product consisting of a divalent or higher cation of the present invention is In addition to the ionic bond, it can be considered that the structure includes a covalent bond linking monocations. Therefore, a salt-forming product composed of a divalent or higher cation having a structure represented by the following general formula (IV) has a stronger binding species in the whole component than a conventional salt-forming product composed of one triarylmethane skeleton. As a result of the increase, it is presumed that the stability becomes high, it becomes difficult to hydrate, and the heat resistance is also improved. Furthermore, since the structure represented by the general formula (IV) has a large molecular weight due to the influence of the linking group A and becomes more hydrophobic, it is substantially soluble in water in combination with the stability of the bond. It is estimated that it will not. For this reason, even if it is a case where it wash | cleans using water or a detergent, it is estimated that there is no color fading and it is excellent in dyeing property.
In the colorant represented by the general formula (I), since the hydrocarbon of the linking group A directly bonded to the cationic coloring site does not have a π bond, The color characteristics such as transmittance hardly change 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 in the formula (I).)

  In the general formula (I), b is an integer of 0 or 1. When b is 0, it has a triarylmethane skeleton represented by the following formula (V).

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

  Moreover, when b is 1, it has a xanthene skeleton represented by the following formula (VI).

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

  A plurality of b may be the same or different. That is, for example, it may be a cation moiety having only a triarylmethane skeleton or a plurality of xanthene skeletons, or may be a cation moiety containing both a triarylmethane skeleton and a xanthene skeleton in one molecule. From the viewpoint of color purity, a cation moiety having only the same skeleton is preferable. On the other hand, the color material of the general formula (I) can be adjusted to a desired color by using a cation moiety containing both a triarylmethane skeleton and a xanthene skeleton, and by combining substituents described later.

A in the general formula (I) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) has no π bond, and the organic group is saturated at least at the terminal directly bonded to N. An aliphatic hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group is represented, and O (oxygen atom), S (sulfur atom), and N (nitrogen atom) are present in the carbon chain. It may be included. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as the color tone and transmittance of the cationic coloring portion are not affected by the linking group A and other coloring portions, Similar colors can be retained.
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is linear, branched or cyclic unless the terminal carbon atom directly bonded to N has a π bond. The carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and the carbon chain contains O, S, and N. Also good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
The aromatic group having an aliphatic hydrocarbon group in A is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N. And may have a substituent, and may be a heterocyclic ring containing O, S, and N.
Especially, it is preferable that A contains a cyclic | annular aliphatic hydrocarbon group or an aromatic group from the point of the robustness of frame | skeleton.
Among the cyclic aliphatic hydrocarbon groups, a bridged alicyclic hydrocarbon group is preferable from the viewpoint of skeleton fastness. The bridged alicyclic hydrocarbon group means a polycyclic aliphatic hydrocarbon group having a bridged structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane and adamantane. Among the bridged alicyclic hydrocarbon groups, norbornane is preferable. Moreover, as an aromatic group, the group containing a benzene ring and a naphthalene ring is mentioned, for example, Among these, the group containing a benzene ring is preferable.
From the viewpoint of easy availability of raw materials, A is preferably divalent. For example, when A is a divalent organic group, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an aromatic group substituted with 2 alkylene groups having 1 to 20 carbon atoms such as a xylylene group Etc.

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 can be mentioned, among which a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a straight chain having 1 to 5 carbon atoms. A chain or branched alkyl group is more preferred from the viewpoint of ease of production and raw material procurement. Especially, it is especially preferable that the alkyl group in R < ¹ > -R < ⁵ > is an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group, and examples of the substituted alkyl group include a benzyl group.
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 that the aryl group may have include an alkyl group and a halogen atom.

R ² and R ³ , R ⁴ and R ⁵ are combined to form a ring structure. R ² and R ³ , R ⁴ and R ⁵ form a ring structure through a nitrogen atom. Say. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

Among them, from the viewpoint of chemical stability, R ^{1 to} R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ² and R ³ , or R ⁴ and R ^5. Thus, it is preferable to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

R ^{1 to} R ⁵ can each independently have the above structure. Among them, R ¹ is preferably a hydrogen atom from the viewpoint of color purity, and R ² to R ² are preferably from the viewpoint of ease of production and raw material procurement. More preferably, all R ⁵ are the same.

The divalent aromatic group in Ar ¹ is not particularly limited. The aromatic group may be a heterocyclic group in addition to an aromatic hydrocarbon group composed of a carbocyclic ring. As an aromatic hydrocarbon in the aromatic hydrocarbon group, in addition to a benzene ring, condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring; biphenyl, terphenyl, Examples thereof include chain polycyclic hydrocarbons such as diphenylmethane, triphenylmethane, and stilbene. The chain polycyclic hydrocarbon may have O, S, and N in the chain skeleton such as diphenyl ether. On the other hand, the heterocyclic ring in the heterocyclic group includes 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole and pyrazole; 6-membered heterocycles such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine and pyrazine. And condensed polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like. These aromatic groups may have a substituent.

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

Ar ¹ is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group composed of a condensed polycyclic carbocycle having 10 to 14 carbon atoms. Among these, a phenylene group or a naphthylene group is more preferable because the structure is simple and the raw material is inexpensive.

A plurality of R ^{1 to} R ⁵ and Ar ¹ in one molecule may be the same or different. In the case where a plurality of R ^{1 to} R ⁵ and Ar ¹ are the same, the color development site exhibits the same color development, so that the same color as the single color development site can be reproduced, which is preferable from the viewpoint of color purity. On the other hand, when at least one of R ^{1 to} R ⁵ and Ar ¹ is a different substituent, a color obtained by mixing plural types of monomers can be reproduced and adjusted to a desired color. it can.

In the color material according to the present invention, the anion portion is a monovalent anion having a structure represented by (B ⁻ ). Since the color material of the present invention has a monovalent anion, it has high solubility in an alcohol solvent or a ketone solvent, and it is also possible to prepare a color material solution with a high concentration. Can be used.
B ⁻ is not particularly limited as long as it is a monovalent anion, and may be an organic anion or an inorganic anion. Here, the organic anion represents an anion containing at least one carbon atom. The inorganic anion represents an anion containing no carbon atom. For example, halide ions such as fluoride ion, chloride ion, bromide ion, iodide ion, nitrate ion (NO ⁻ ), perchloric acid Ion (ClO ₄ ⁻ ) and the like.

When B < ^- > is an organic anion, the structure is not particularly limited. Among these, an organic group having an anionic substituent is preferable.
Examples of the anionic substituent 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 or imidate group such as, -SO ₃ ^{-, _{-CF 2 SO 3 -, -COO -}} , -CF 2 COO - substituents, and the like.
Among them, ease and manufacturing cost of raw materials available, from the viewpoint high effect of maintaining the color-developed state is stabilized cations by high acidity, and imidate _{^{groups, -SO 3 -, -CF 2 SO}} 3 - are preferred, further It is preferably —SO ₃ ^— (sulfonato group).

It does not specifically limit as an organic group by which an anionic substituent is substituted. Examples of the organic group include a linear, branched, or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, and a group in which these are combined, and these include O, Heterogeneous atoms such as S and N may be contained, a carbonyl group, a carboxy group, an oxycarbonyl group and an amide group may be contained, and a hydrogen atom may be substituted. Examples of the substituent that the organic group may have include a halogen atom.
Examples of the organic group in which the anionic substituent is substituted include cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, bicyclo [2,2,2] hexane, bicyclo [3,2,3] octane, adamantane, and the like. Hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, pyrene, triphenylene, fluorene, furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, triazine, indole, purine, quinoline, isoquinoline, xanthene, carbazole, etc. Group compounds, and further may have a substituent such as a halogen atom or an alkyl group.
Among them, the organic group to be substituted with the anionic substituent is preferably a monocyclic or polycyclic aromatic hydrocarbon group or a group in which these are combined from the viewpoint of easy introduction of the anionic substituent.

  For the purpose of preventing color change by anions, it is preferable to use 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 organic groups composed of condensed polycyclic carbocycles such as naphthalene, tetralin, indene, fluorene, anthracene, phenanthrene; biphenyl, terphenyl, diphenylmethane, and triphenyl. Organic groups consisting of chain polycyclic hydrocarbons such as methane and stilbene; Organic groups consisting of 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, pyran, pyrone, pyridine, pyridazine, Aromatic compounds composed of 6-membered heterocycles such as pyrimidine and pyrazine; condensed polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline Organic group, and the like made.

Moreover, as an organic group substituted with an anionic substituent, a skeleton derived from an azo dye, anthraquinone dye, triphenylmethane dye, xanthene dye and phthalocyanine dye, indigo dye, which is an organic compound or an organometallic compound, is used. Also good. Alternatively, conventionally known acid dyes, direct dyes, and acid mordant dyes may be used.
When a dye-derived skeleton, acid dye, direct dye, acid mordant 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 general formula (I) is desired. Can be adjusted.

Among the anions having a skeleton derived from a dye, anions represented by the following general formula (III) are preferable from the viewpoint of improving heat resistance.
When the anion of the general formula (III) is used as the anion part of the color material of the present invention, the color material can be adjusted to a desired color by combination with the cation part.

(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 with an aromatic ring. doing.)

  In the colorant according to the present invention, the organic anion is preferably an anion represented by the following general formula (II) from the viewpoint of improving heat resistance.

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

  When the anion of the above general formula (II) is used as the anion part of the color material of the present invention, since the anion is colorless or pale yellow, the resulting color material is a cation represented by the general formula (I) It has the feature that it is easy to retain the unique color of the.

The aromatic group in Ar ² is not particularly limited. The aromatic group may be a heterocyclic ring in addition to an aromatic hydrocarbon group composed of a carbocyclic ring. As aromatic hydrocarbon group, in addition to benzene ring, condensed polycyclic aromatic hydrocarbon groups such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring; biphenyl, terphenyl, diphenylmethane, triphenyl Examples thereof include chain polycyclic hydrocarbon groups such as methane and stilbene. The chain polycyclic hydrocarbon group may have a heteroatom such as O or S in the chain skeleton such as diphenyl ether. On the other hand, examples of the heterocyclic ring include 5-membered heterocyclic rings such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; 6-membered heterocyclic rings such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, and pyrazine; benzofuran and thionaphthene. , Indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like. These aromatic groups may have a substituent.

  As a substituent which an aromatic group has, a C1-C5 alkyl group, a halogen atom, etc. are mentioned.

Ar ² is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group composed of a condensed polycyclic carbocycle having 10 to 14 carbon atoms. Among these, a phenylene group or a naphthalene group is more preferable because the structure is simple and the raw material is inexpensive.

In the coloring material of the present invention, a plurality of anions (B ⁻ ) may be the same or different, and organic anions and inorganic anions can be used in combination.

The coloring material according to the present invention can be used after being dissolved in a solvent. Examples of the solvent for dissolving the coloring material according to the present invention include methanol, N-methylpyrrolidone (NMP), γ-butyrolactone, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF) and the like.
On the other hand, the coloring material according to the present invention is dispersed in a solvent having a solubility of the coloring material at 23 ° C. of 0.1 (mg / 10 g solvent) or less, that is, a solvent that does not substantially dissolve or is hardly soluble. Can be used. In this case, since it is dispersed in the solvent while maintaining its agglomerated state, the heat resistance is higher than when it is used after being dissolved in the solvent. Among them, a solvent having a solubility of the coloring material at 23 ° C. of 0.01 (mg / 10 g solvent) or less is preferable, and a solvent that does not substantially dissolve the coloring material is more preferable. Since the coloring material according to the present invention is a normal salt, there is no problem that the dispersion does not proceed properly as in the case where an acidic salt is used, or the problem that the dispersion gels during storage, dispersibility and dispersion. High stability.

In the present invention, a solvent having a colorant represented by the general formula (I) having a solubility of the colorant at 23 ° C. of 0.1 (mg / 10 g solvent) or less can be simply determined by the following evaluation method. Can be determined.
Into a 20 mL sample tube, 10 g of the solvent to be evaluated is added, 0.1 g of the coloring material is further added, the lid is covered, shaken well for 20 seconds, and then allowed to stand in a 23 ° C. water bath for 10 minutes. 5 g of this supernatant liquid is filtered to remove insoluble matters. The absorbance spectrum of a solution obtained by further diluting the obtained filtrate 1000 times is measured with a UV-visible spectrophotometer (for example, UV-2500PC manufactured by Shimadzu Corporation) using a 1 cm cell, and the absorbance at the maximum absorption wavelength is obtained. At this time, if the absorbance at the maximum absorption wavelength is less than 2, the solvent has a colorant represented by the general formula (I) having a solubility of the colorant at 23 ° C. of 0.1 (mg / 10 g solvent) or less. It can be evaluated that it is a solvent (slightly soluble solvent).

  Further, in the above evaluation method, an absorption spectrum is measured in the same manner as described above without diluting the obtained filtrate, and the absorbance at the maximum absorption wavelength is obtained. At this time, if the absorbance at the maximum absorption wavelength is less than 2, the solvent can be evaluated as a solvent that does not substantially dissolve the coloring material represented by the general formula (I).

  Examples of the solvent having a solubility of the coloring material at 23 ° C. of 0.1 (mg / 10 g solvent) or less include, in addition to water, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methoxy Examples include ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate.

[Production method of coloring material]
Although the manufacturing method of the color material represented by general formula (I) is not specifically limited, For example, after manufacturing a cation part with the following method, it can obtain by introduce | transducing a counter anion as needed.
As one method, the manufacturing method of the coloring material represented by the following general formula (I) according to the present invention includes a compound represented by the following general formula (A), a compound represented by the following general formula (B), and It has the process of making a condensation reaction.

(In the general formula (A), the general formula (B), and the general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, The group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and O, S, and N are present in the carbon chain. It included which may be .B ^- represents a monovalent anion, a plurality of B ^- good be different even in the same .R ¹ to R ⁵ each independently represent a hydrogen atom, substituted Represents an optionally substituted alkyl group or an optionally substituted aryl group, and R ² and R ³ , R ⁴ and R ⁵ may combine to form a ring structure, Ar ¹ represents a substituent And Ar ^{1 ′} is a monovalent aromatic group in which hydrogen is bonded to Ar ^1. A 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, no bond exists. A plurality of b may be the same or different. )

In the method for producing a coloring material according to the present invention, a triarylmethane skeleton or a xanthene skeleton is formed by dehydration condensation between Ar ^{1 ′} of the general formula (A) and the carbonyl group of the general formula (B). At the same time, the linking group A is introduced. According to the production method, color materials having different degrees of polymerization do not occur, and unreacted substances are easily separated because their skeletons are greatly different, and the color material according to the present invention has high purity and high yield. Can be obtained at

(Compound represented by the following general formula (A))
First, a compound represented by the following general formula (A), which is a precursor compound of the cation moiety, is synthesized. Moreover, a commercial item may be used for the compound represented by general formula (A).

(In the formula (A), A, R ¹ and a are the same as those in the general formula (I). Ar ^{1 ′} is a structure in which hydrogen is bonded to Ar ¹ in the general formula (I).)

The method for synthesizing the compound represented by the general formula (A) is not particularly limited. For example, the halogenated aromatic compound into which the desired substituent Ar ^{1 ′} is introduced and the a valence into which the desired substituent A is introduced. The amine compound can be obtained by reacting in a solvent using palladium acetate or the like as a catalyst in the presence of a base.

The amount of the halogenated aromatic compound used in the above reaction varies depending on the desired valence (a). For example, when a = 2, it is 1.5 to 10 molar equivalents relative to the amine compound. It is preferable that it is 1.5 to 3.0 molar equivalent, and further 1.8 to 2.2 molar equivalent suppresses the formation of by-products and improves the reaction yield. It is preferable from the point of making it.
Although the reaction temperature in the said reaction does not have a restriction | limiting in particular, Usually, it is about 100-150 degreeC, and it is preferable that it is 130-145 degreeC from the point which suppresses a side reaction. Moreover, there is no restriction | limiting in particular in the reaction pressure of the said reaction, but normal pressure-0.1 MPa are desirable, and normal pressure is further more desirable. In addition, the reaction time in the above reaction may vary depending on the amount of synthesis, reaction temperature, etc., and thus cannot be generally specified, but is usually set in the range of 6 to 72 hours, preferably 6 to 48 hours.

  Although it does not specifically limit as a base used for the said reaction, For example, metal alkoxide, metal amide, etc. other than sodium hydroxide, potassium hydroxide, potassium carbonate etc. are mentioned. Among them, it is preferable to use a strong base with low nucleophilicity from the viewpoint of suppressing side reactions and improving the yield of the base generator. For example, potassium-t-butoxide, sodium-t-butoxide, lithium-t- Butoxide, lithium diisopropylamide, potassium hexamethyldisilazide, lithium tetramethylpiperidide and the like are preferably used. Among strong bases having low nucleophilicity, it is more preferable to use potassium t-butoxide.

  The addition amount of the base is not particularly limited, but is usually 2.0 to 4.0 molar equivalents relative to the amine compound, and 2.5 to 3.5 molar equivalents improves the reaction yield. It is preferable from the point.

(Synthesis of cation moiety)
The cation part of the coloring material represented by the general formula (I) is obtained by subjecting the compound represented by the general formula (A) and the compound represented by the following general formula (B) to a condensation reaction. Is synthesized. For example, it can be obtained as a chloride in the cation moiety by reacting in a solvent using a chlorinating agent such as phosphorus oxychloride. A commercial item can be used for the compound represented by the following general formula (B).

(R ^{2 to} R ⁵ and e in the formula (B) are the same as those in the general formula (I).)

The amount of the compound represented by the general formula (B) used in the above reaction varies depending on the desired valence (a). For example, when a = 2, 1.5 to 4.0 molar equivalents, more preferably 1.5 to 3.0 molar equivalents, and even more preferably 1.8 to 2.2 molar equivalents by-product. From the point which suppresses the production | generation of and improves a reaction yield.
The reaction temperature in the above reaction is not particularly limited, but is usually about 110 to 150 ° C, and preferably 110 to 120 ° C from the viewpoint of suppressing side reactions. Moreover, there is no restriction | limiting in particular in the reaction pressure of the said reaction, but normal pressure-0.1 MPa are desirable, and normal pressure is further more desirable. The reaction time in the above reaction may vary depending on the amount of synthesis, reaction temperature, etc., and thus cannot be generally stated, but is usually set in the range of 1 to 10 hours, preferably 1 to 5 hours.

  The amount of phosphorus oxychloride added is not particularly limited, but is usually 1.5 to 3.0 molar equivalents and 1.8 to 3.0 molar equivalents relative to the compound (A). This is preferable from the viewpoint of improving the yield.

  The color material represented by the general formula (I) is obtained as a cation moiety chloride by the reaction. Moreover, the coloring material represented by the general formula (I) having the desired anion part is obtained by mixing the chloride of the cation part obtained by the reaction and the desired anion part in a solvent.

  Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.

(Synthesis Example 1: Synthesis of Intermediate 1)
Wako Pure Chemical Industries, Ltd. 1-iodonaphthalene 18.7 g (73.4 mmol), sodium tert-butoxide 9.88 g (102.8 mmol), Tokyo Chemical Industry Co., Ltd. p-xylenediamine 5.0 g (36.7 mmol) ), Aldrich 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 0.27 g (0.57 mmol), Wako Pure Chemical Industries, Ltd. palladium acetate 0.054 g (0.28 mmol), xylene The mixture was dispersed in 36 mL and reacted at 130-135 ° C. for 24 hours. After completion of the reaction, the mixture was cooled to room temperature and the precipitated crystals were filtered and washed with methanol. Subsequently, it was washed with water and dried to obtain 9.79 g (yield 69%) of Intermediate 1 represented by the following chemical formula (1).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 389 (+),
Elemental analysis value: CHN actual measurement value (86.72%, 6.54%, 6.97%); theoretical value (86.56%, 6.23%, 7.21%)

(Example 1: Synthesis of coloring material A)
Intermediate 1 10.0 g (25.7 mmol), toluene 100 mL, Wako Pure Chemical Industries, Ltd. phosphorus oxychloride 7.89 g (51.5 mmol) were added and stirred. Next, 16.2 g (49.9 mmol) of 4,4′-bis (diethylamino) benzophenone manufactured by Tokyo Chemical Industry Co., Ltd. was added, and the mixture was refluxed for 5 hours and cooled. After completion of the reaction, toluene was decanted. 100 mL of water was added and the resinous precipitate was filtered. The cake was dispersed with dilute hydrochloric acid, filtered, washed with water, and dried to obtain 18.4 g (yield 66%) of Coloring Material A represented by the following chemical formula (2).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 501 (+), divalent element analysis value: CHN measured value (78.02%, 7.13%, 7.11%); theoretical value (78.26%) , 7.32%, 7.82%)

(Example 2: Synthesis of coloring material B)
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 were added and stirred at 50-55 ° C. 3.19 g (2.97 mmol) of the coloring material A obtained in Example 1 was added, and the mixture was stirred at 50 to 55 ° C. for 1 hour. Methanol in the solution was concentrated with an evaporator, 100 mL of water was added, and the precipitate was collected by filtration and washed with water. The cake was dried to obtain 3.33 g (yield 83%) of coloring material B represented by the following chemical formula (3).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 502 (+), divalent, 171 (-) monovalent Element analysis value: CHN measured value (75.18%, 7.11%, 6.15%); Theoretical value (74.97%, 6.89%, 6.24%)

(Synthesis Example 2: Synthesis of Intermediate 2)
Wako Pure Chemical Industries, Ltd. 1-iodonaphthalene 15.2 g (60 mmol), Mitsui Chemicals, Inc. norbornanediamine (NBDA) (CAS No. 56602-77-8) 4.63 g (30 mmol), sodium-tert- Butoxide 8.07 g (84 mmol), Aldrich 2-dicyclohexylphosphino-2 ′, 6 ′,-dimethoxybiphenyl 0.09 g (0.2 mmol), Wako Pure Chemical Industries, Ltd. Palladium acetate 0.021 g (0.1 mmol) ) And xylene were dispersed in 30 mL and reacted at 130-135 ° C. for 48 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted with water. Next, it was dried over magnesium sulfate and concentrated to obtain 8.5 g of intermediate 2 represented by the following chemical formula (4) (yield 70%).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 407 (M + H),
Elemental analysis value: CHN actual measurement value (85.47%, 8.02%, 6.72%); theoretical value (85.26%, 8.11%, 6.63%)

(Example 3: Synthesis of coloring material C)
Intermediate 2 8.46 g (20.8 mmol), Tokyo Chemical Industry 4,4′-bis (dimethylamino) benzophenone 13.5 g (41.6 mmol) 60 mL of toluene were added and 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 completion of the reaction, toluene was decanted. The resinous precipitate was dissolved by adding chloroform (40 mL), water (40 mL) and concentrated hydrochloric acid, 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 colorant C represented by the following chemical formula (5).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 511 (+), divalent and elemental analysis values: CHN measured value (78.13%, 7.48%, 7.78%); theoretical value (78.06%) , 7.75%, 7.69%)

(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 coloring material D of Comparative Example 1.

(Comparative Example 2: Synthesis of coloring 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. Next, 5.0 g (9.73 mmol) of Basic Blue 7 (CI-42595) manufactured by Tokyo Chemical Industry Co., Ltd. was added and stirred at room temperature for 1 hour. The reaction solution was collected by filtration under reduced pressure and washed with water. The cake was dried under reduced pressure to obtain 3.0 g (yield 92%) of a coloring 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-sulfonate disodium manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in 50 mL of water and 50 mL of methanol. Next, 5.0 g (9.73 mmol) of Basic Blue 7 (CI-42595) manufactured by Tokyo Chemical Industry Co., Ltd. was added and stirred at room temperature for 1 hour. The reaction solution was collected by filtration under reduced pressure and washed with water. The cake was dried under reduced pressure to obtain 5.2 g (yield 86%) of a coloring material F represented by the following chemical formula (8).

(Comparative Example 4: Synthesis of Color Material G)
In Comparative Example 3, in place of naphthalene-2,6-sulfonate disodium, Direct Chemical 86 3.92 g (5.02 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was used in the same manner as in Comparative Example 3, except that the following chemical formula ( Color material G shown in 9) was obtained.

(Comparative Example 5: Synthesis of coloring material H)
According to the method described in Patent Document 4, 12 molybdophosphate of a polysiloxane dye was synthesized to obtain a coloring 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 this dye was completely precipitated, and a blue color was formed in the solution. 2N sodium hydroxide aqueous solution was added until it did not remain at all and was not restored for several hours. The precipitate was filtered off, washed with ion exchange water three times, and dried at 60 ° C. under reduced pressure (0.1 kPa). 45.23 g (94.7%) of deprotonated BB7 was isolated as an almost black powder.

  Separately, 50 ml of 3-iodopropyl-trimethoxysilane manufactured by Sigma-Aldrich and 2.0 ml (2.95 g; 10.2 mmol) of absolute ethanol solution were mixed and stirred at room temperature for 60 hours under argon. Subsequently, the solvent was distilled off under reduced pressure to obtain 3-iodopropyl-triethoxysilane. The obtained 3-iodopropyl-triethoxysilane was dissolved in 50 ml of anhydrous acetonitrile, 2.389 g (5 mmol) of the deprotonated BB7 was added, and the solution was heated under reflux for 24 hours under argon. The solvent is distilled off and the semi-solid residue is washed several times with methyl-t-butyl ether under a stream of argon until the filtrate is almost colorless to remove excess alkylating agent and unreacted desorbing. The protonated dye was removed to obtain silanized BB7 as a solid residue. 1 g of the silanized BB7 was dissolved in 25 ml of absolute ethanol to obtain a silanized BB7 solution.

  25 ml of the silanized BB7 solution was added to a mixed solvent consisting of 150 ml of ethanol (96%), 50 ml of water and 30 g of 25% aqueous ammonia solution, and vigorously stirred at room temperature for 24 hours. After formation of seed particles, the mixture was centrifuged. After the residue was dispersed in ethanol (80%), washing and centrifugation were repeated three times, and then the solvent was removed to obtain a residue. The residue was dispersed in dimethyl sulfoxide (DMSO), added to 400 ml of deionized water, stirred, and 12 molybdophosphoric acid / n hydrate was further added to obtain a coloring material H of Comparative Example.

<Evaluation of color change of colorant>
Color materials A and C obtained in Example 1 and Example 3, and 10 mg each were dissolved in 100 mL of methanol and diluted 20 times to obtain a measurement solution. The absorption spectrum was measured with a Hitachi spectrophotometer U-3500 using a 1 cm quartz cell.
Further, as a control product, BB7, 10 mg as a monomer, was dissolved in 100 mL of methanol and diluted 20 times to obtain a measurement solution, and an absorption spectrum was measured in the same manner as described above. The results are shown in FIG.
From the results of FIG. 1, it is clear that the coloring materials A and C have almost the same peak shape as BB7 having no linking group, and the color hardly changes.
As described above, the color material represented by the general formula (I) in which the carbon atom directly bonded to N has the linking group A having no π bond has the same color as the color material of the monomer having no linking group. It became clear to have.

<Evaluation of solubility in methanol>
Methanol (manufactured by Kanto Chemical Co., Ltd.) so that 0.05 g of each of coloring materials A to H of Examples 1 to 3 and Comparative Examples 1 to 5 is put in a sample tube bottle and the total weight excluding the sample tube bottle is 1.0 g. Was added. A magnetic stirrer was put into this, and the mixture was stirred at room temperature for 1 hour, and it was discriminated whether the coloring material was dissolved by visual observation. If it was dissolved, it was rated as ◯, and if insoluble matter could be confirmed, it was marked as x.

<Heat resistance evaluation>
(1) Evaluation of thermal decomposition temperature About 5 mg of each of the coloring materials A to H of Examples 1 to 3 and Comparative Examples 1 to 5 was put in a quartz pan, and a differential type differential thermal balance (TG) manufactured by Rigaku Corporation. -DTA) Using TG8120, a quartz pan was used as a reference for alumina, and the temperature was increased to 800 ° C at a heating rate of 5 ° C / min. The extrapolated temperature of the peak of the obtained TG curve was taken as the decomposition point, and the temperature at the decomposition point was taken 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 each of the coloring materials A to H of Examples 1 to 3 and Comparative Examples 1 to 5 was placed in a quartz pan, and a differential type differential thermal balance (TG) manufactured by Rigaku Corporation. -DTA) Using TG8120, a quartz pan as a reference was heated to 230 ° C. with alumina at a temperature rising rate of 20 ° C./min, and kept at the same temperature for 60 minutes after reaching 230 ° C., and then the weight loss rate was measured. 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 x 100 (%)

<Dyeing property evaluation>
(1) Dyeing on cloth 0.5 g of colorant A of Example 1 was added to 10 ml of methanol to obtain a methanol solution of colorant A. 0.1 ml of the methanol solution was dropped on the cloth, the methanol was removed with a dryer, and the coloring material A was dyed on the cloth.
Further, the color materials B to H were dyed on the cloth in the same manner as described above except that the color materials B to H were used instead of the color material A, respectively.

(2) Evaluation with water The cloth dyed with the coloring materials A to H was washed with running water at 20 ° C. for 10 minutes, visually observed for color fading, and evaluated according to the following evaluation criteria.
[Evaluation criteria]
○: There was no color fading.
Δ: Color fading was confirmed.
X: No color remained.

(3) Evaluation by detergent After the cloth dyed with coloring materials A to H is immersed in a detergent containing a surfactant for 5 minutes, it is washed with running water at 20 ° C. for 5 minutes, and color fading is observed visually. Evaluation was performed according to the same evaluation criteria as the evaluation with water.
Each evaluation result is shown in Table 1.

[Summary of results]
It became clear that the coloring materials A to C of Examples 1 to 3 represented by the general formula (I) are excellent in dyeing property and heat resistance.
The color material of Comparative Example 1, which is a conventional triarylmethane dye, was inferior in heat resistance and dyeability. Although heat resistance and dyeing property were improved by replacing anions as in Comparative Examples 2 to 4, it was insufficient and discolored easily by household detergent.
Although the color material of Comparative Example 5 contains a cation having a structure in which a triarylmethane dye is polymerized with siloxane, it is a mixture of pigments having different degrees of polymerization, and therefore has insufficient heat resistance and dyeability. There was an undissolved residue in methanol.

Claims (4)

A coloring material represented by the following general formula (I).
(In general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and may contain O, S and N in the carbon chain, and B ⁻ represents a monovalent anion. And a plurality of B ⁻ may be the same or different, and R ^{1 to} R ⁵ may each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Represents a good aryl group, and R ² and R ³ , R ⁴ and R ⁵ may combine to form a ring structure, and Ar ¹ represents a divalent aromatic group which may have a substituent. The 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, no bond exists. A plurality of b may be the same or different. ) The coloring material according to claim 1, wherein the anion (B ⁻ ) in the general formula (I) is an organic anion having a sulfonate group (—SO ₃ ^— group). The anion in the general formula (I) (B ^-) is an anion represented by the following formula (II), the colorant according to claim 1 or 2.
(In general formula (II), Ar ² is a monovalent aromatic group which may have a substituent.) The manufacturing method of the coloring material represented by the following general formula (I) which has a process with which the compound represented by the following general formula (A) and the compound represented by the following general formula (B) are condensation-reacted.
(In the general formula (A), the general formula (B), and the general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, The group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and O, S, and N are present in the carbon chain. It included which may be .B ^- represents a monovalent anion, a plurality of B ^- good be different even in the same .R ¹ to R ⁵ each independently represent a hydrogen atom, substituted Represents an optionally substituted alkyl group or an optionally substituted aryl group, and R ² and R ³ , R ⁴ and R ⁵ may combine to form a ring structure, Ar ¹ represents a substituent And Ar ^{1 ′} is a monovalent aromatic group in which hydrogen is bonded to Ar ^1. A 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, no bond exists. A plurality of b may be the same or different. )