JP5546156B2 - Dye compound, pigment dispersant containing the dye compound, pigment composition, and pigment dispersion - Google Patents

Description

  The present invention relates to a novel dye compound, a pigment dispersant containing the compound, a pigment composition containing the pigment dispersant, and a dispersion thereof.

  Azo pigments have a wide range of uses as colorants, and are widely used in fields such as paints, inkjet inks, electrophotographic toners, and color filters. When used in such fields, pigments must be finely dispersed in various media in order to improve spectral characteristics such as coloring power and transparency. However, in general, when the azo pigment is made finer, crystal growth or transition is likely to occur due to thermal history or contact with a solvent in the dispersion process or the subsequent manufacturing process, which causes problems such as a decrease in coloring power and transparency. End up. In order to improve such problems, various pigment compositions and pigment dispersants constituting the same have been proposed. For example, a pigment composition in which a different azo dye is added as a pigment dispersant to an azo pigment has been proposed (see Patent Documents 1 and 2).

  In addition, an example using Solsperse (registered trademark) (manufactured by Lubrizol) as a pigment dispersant is disclosed (see Patent Document 3). However, these pigment compositions and pigment dispersants have not been able to obtain a sufficient dispersion effect when dispersed in organic solvents, particularly nonpolar solvents such as styrene monomers.

  On the other hand, pyrazolone azo compounds have been proposed for various chemical structures as yellow to red colorants for a long time. For example, a water-soluble pyrazolone azo compound has been proposed as a colorant for dyeing and printing (see Patent Document 4). Further, an azo compound having excellent heat resistance and light resistance and excellent solubility in water or an organic solvent has been disclosed (see Patent Document 5). However, when these compounds were used as pigment dispersants, they were easily dissolved in water by contact with water in the pigment dispersion step and the subsequent production steps, and did not function as pigment dispersants.

  Further, pyrazolone azo compounds have been proposed as photosensitive materials for color filters and silver salt photographs (see Patent Documents 6 and 7). However, these are satisfactory for the application, but a sufficient effect as a pigment dispersant in a nonpolar solvent cannot be obtained.

Japanese Patent No. 04069873 JP 2007-262382 A International Publication No. 99-42532 Pamphlet British Patent No. 1211804 JP 2005-263925 A JP 2006-3873 A Japanese Patent Laid-Open No. 2-271353

  The present invention aims to solve the above-described problems. That is, an object of the present invention is to provide a dye compound and a pigment dispersant that have high solubility in an organic solvent and improve the dispersibility of an azo pigment in an organic solvent.

  Another object of the present invention is to provide an azo pigment composition having good dispersibility in an organic solvent.

  The object is solved by the present invention described below. That is, the present invention provides a dye compound represented by the following general formula (1).

［一般式（１）中、Ｒ₁は、水素原子、アルキル基、アリール基又はアラルキル基を表し、Ｒ₂は、ＣＯＯＲ₈基又はＣＯＮＲ₉Ｒ₁₀基を表し（Ｒ₈及びＲ₉は、アルキル基、アリール基又はアラルキル基を表し、Ｒ₁₀は、水素原子、アルキル基、アリール基又はアラルキル基を表す。）、Ｒ₃乃至Ｒ₇はそれぞれ独立して、水素原子、ハロゲン原子、トリフルオロメチル基、アセチルアミノ基、スルファモイル基、アルキル基、アルコキシ基、ＣＯＯＲ₁₁基、ＣＯＮＲ₁₂Ｒ₁₃基（Ｒ₁₁及びＲ₁₂はそれぞれ独立して、アルキル基、アリール基又はアラルキル基を表し、Ｒ₁₃は、水素原子、アルキル基、アリール基又はアラルキル基を表す。）、スルホン酸基、カルボン酸基、スルホン酸塩基又はカルボン酸塩基を表す。但し、一般式（１）中には、スルホン酸基、カルボン酸基、スルホン酸塩基及びカルボン酸塩基からなる群から選ばれる官能基が１つ又は２つ存在する。］

[In the general formula (1), R ₁ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, R ₂ represents COOR ₈ group or CONR ₉ R ₁₀ group (R ₈ and R ₉ are alkyl group, an aryl group or an aralkyl group, R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.), R ₃ to R ₇ each independently represent a hydrogen atom, a halogen atom, trifluoromethyl group, an acetylamino group, a sulfamoyl group, an alkyl group, an alkoxy group, COOR ₁₁ group, CONR ₁₂ R ₁₃ group (R ₁₁ and R ₁₂ each independently represents an alkyl group, an aryl group or an aralkyl group, R ₁₃ is Represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.) Represents a sulfonic acid group , a carboxylic acid group , a sulfonic acid group or a carboxylic acid group. However, in general formula (1), scan sulfonic acid group, a carboxylic acid group, a functional group selected from the group consisting of sulfonate and carboxylate groups are present one or two. ]

  The present invention also provides a pigment dispersant and an azo pigment composition containing at least a dye compound having a structure represented by the general formula (1).

  The present invention provides a dye compound that has low solubility in water and high solubility in organic solvents, particularly nonpolar solvents. Since the dye compound represented by the general formula (1) according to the present invention has a high affinity for an azo pigment, it can be used as a pigment dispersant to improve the dispersibility of the azo pigment and to have a good color tone. A pigment composition can be provided. Furthermore, by using the pigment composition, a pigment dispersion excellent in dispersibility in an organic solvent and a good color tone, particularly a pigment dispersion of a styrene monomer is provided.

It is a figure showing the < ¹ > H NMR spectrum in room temperature and 400 MHz in chloroform-d of the pigment | dye compound (30) concerning this invention.

  Hereinafter, the dye compound of the present invention will be described in more detail.

  As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have found that the dye compound represented by the general formula (1) has low solubility in water and low solubility in organic solvents. It has been found that the dispersibility of azo pigments in organic solvents is improved. Further, the inventors have found that an azo pigment composition having a good color tone can be provided by using the coloring compound, and have reached the present invention.

  First, the dye compound having the structure represented by the general formula (1) provided in the present invention will be described in detail.

［一般式（１）中、Ｒ₁は水素原子、アルキル基、アリール基、アラルキル基を表し、Ｒ₂はＣＯＯＲ₈基、ＣＯＮＲ₉Ｒ₁₀基を表し（Ｒ₈及びＲ₉はアルキル基、アリール基、アラルキル基を表し、Ｒ₁₀は水素原子、アルキル基、アリール基、アラルキル基を表す。）、Ｒ₃乃至Ｒ₇はそれぞれ独立して、水素原子、ハロゲン原子、トリフルオロメチル基、アセチルアミノ基、スルファモイル基、アルキル基、アルコキシ基、ＣＯＯＲ₁₁基、ＣＯＮＲ₁₂Ｒ₁₃基（Ｒ₁₁及びＲ₁₂はそれぞれ独立してアルキル基、アリール基、アラルキル基を表し、Ｒ₁₃は水素原子、アルキル基、アリール基、アラルキル基を表す。）及びスルホン酸基又はカルボン酸基及びそれらの塩を表す。但し、一般式（１）中には、１つ又は２つのスルホン酸基又はカルボン酸基及びそれらの塩を有する。］

[In the general formula (1), R ₁ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, R ₂ represents a COOR ₈ group or a CONR ₉ R ₁₀ group (R ₈ and R ₉ represent an alkyl group, aryl And R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.) And R _{3 to} R ₇ each independently represent a hydrogen atom, a halogen atom, a trifluoromethyl group, or an acetylamino group. Group, sulfamoyl group, alkyl group, alkoxy group, COOR ₁₁ group, CONR ₁₂ R ₁₃ group (R ₁₁ and R ₁₂ each independently represents an alkyl group, an aryl group, an aralkyl group, R ₁₃ represents a hydrogen atom, an alkyl group, Represents an aryl group, an aralkyl group, and a sulfonic acid group or a carboxylic acid group and salts thereof. However, the general formula (1) has one or two sulfonic acid groups or carboxylic acid groups and salts thereof. ]

  The general formula (1) has one or two sulfonic acid groups, carboxylic acid groups, and salts thereof. The counter ion for forming the salt is not particularly limited. For example, alkali metal ions such as lithium, sodium and potassium, ammonium, methylammonium, dimethylammonium, trimethylammonium, triethylammonium, tetramethylammonium And quaternary ammonium ions such as ethylammonium, n-propylammonium, isopropylammonium, n-butylammonium, and ethanolammonium.

These anionic groups are preferably a carboxylic acid group having a low solubility in water and a salt thereof. In addition, the position of substitution of the anionic group in the molecule is preferably the position of R _{3 to} R _{7 in} the general formula (1) from the viewpoint of ease of synthesis.

Although it does not specifically limit as an alkyl group in R < ₁ > in the said General formula (1), For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec Examples include linear, branched or cyclic alkyl groups such as -butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, and cyclopentyl group.

The aryl group for R ₁ in the general formula (1) is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, and a thienyl group.

Although it does not specifically limit as an aralkyl group in R < ₁ > in the said General formula (1), For example, a benzyl group, a phenethyl group, etc. are mentioned.

The substituent represented by R ₁ in the general formula (1) may further have a substituent. In this case, the following substituents may be substituted. Linear, branched or cyclic such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl Aryl group such as alkyl group, phenyl group, naphthyl group, pyridyl group, triazinyl group, benzothiazolyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, linear, branched or cyclic alkoxy groups such as tert-butoxy group, cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, aryloxy groups such as phenoxy group, naphthyloxy group, methylamino group, ethylamino group, N, N-dimethylamino group, N-ethyl-N-phenylamino group, , N-diphenylamino groups and other amino groups, acetyl groups, benzoyl groups and other acyl groups, carboxylic acid groups, sulfonic acid groups, carbamoyl groups, sulfamoyl groups, nitro groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. Of halogen atoms.

R ₁ in the general formula (1) can be arbitrarily selected from the substituents and hydrogen atoms listed above, but is preferably a phenyl group from the viewpoint of improving solubility in organic solvents and ease of synthesis.

R ₂ in the general formula (1) represents a COOR ₈ group or a CONR ₉ R ₁₀ group.

The alkyl group in R _{8 to} R ₁₀ is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert group. -Linear, branched or cyclic alkyl groups such as butyl, cyclopropyl, cyclobutyl, and cyclopentyl.

The aryl group in R _{8 to} R ₁₀ is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, and a thienyl group.

The aralkyl group in R _{8 to} R ₁₀ is not particularly limited, and examples thereof include a benzyl group and a phenethyl group.

R ₉ and R ₁₀ may form a heterocyclic ring with a nitrogen atom. Specific examples of the heterocyclic ring formed by R ₉ and R ₁₀ together with the nitrogen atom include a piperazine ring, a piperidine ring, a pyrrolidine ring, and a morpholine ring.

The substituent represented by R _{8 to} R ₁₀ may further have a substituent. In this case, the following substituents may be substituted. Linear, branched or cyclic such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl Aryl group such as alkyl group, phenyl group, naphthyl group, pyridyl group, triazinyl group, benzothiazolyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, linear, branched or cyclic alkoxy groups such as tert-butoxy group, cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, aryloxy groups such as phenoxy group, naphthyloxy group, methylamino group, ethylamino group, N, N-dimethylamino group, N-ethyl-N-phenylamino group, , N-diphenylamino groups and other amino groups, acetyl groups, benzoyl groups and other acyl groups, carboxylic acid groups, sulfonic acid groups, carbamoyl groups, sulfamoyl groups, nitro groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. Of halogen atoms.

R ₂ in the general formula (1) is preferably a CONR ₉ R ₁₀ group in that it is difficult to hydrolyze. R ₉ can be arbitrarily selected from the substituents and hydrogen atoms listed above, and R ₁₀ can be arbitrarily selected from the substituents listed above, but the solubility in organic solvents is improved and the solubility in water is reduced. Therefore, R ₉ and R ₁₀ are an alkyl group, preferably represents an aryl group and aralkyl group, further the total number of carbon atoms of R ₉ and R ₁₀ are more preferably may be 10 or more.

Examples of the halogen atom in R _{3 to} R ₇ in the general formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group in R _{3 to} R ₇ in the general formula (1) is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and isobutyl. And linear, branched or cyclic alkyl groups such as a group, sec-butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group and cyclopentyl group.

The alkoxy group in R _{3 to} R ₇ in the general formula (1) is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, Examples thereof include linear, branched or cyclic alkoxy groups such as isobutoxy group, sec-butoxy group, tert-butoxy group, cyclopropoxy group, cyclobutoxy group and cyclopentyloxy group.

R _{3 to} R ₇ in the general formula (1) may be a COOR ₁₁ group or a CONR ₁₂ R ₁₃ group.

The alkyl group in R _{11 to} R ₁₃ is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert group. -Linear, branched or cyclic alkyl groups such as butyl, cyclopropyl, cyclobutyl, and cyclopentyl.

The aryl group in R _{11 to} R ₁₃ is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, and a thienyl group.

The aralkyl group in R _{11 to} R ₁₃ is not particularly limited, and examples thereof include a benzyl group and a phenethyl group.

R ₁₂ and R ₁₃ may form a heterocyclic ring with a nitrogen atom. Specific examples of the heterocyclic ring formed by R ₁₂ and R ₁₃ together with the nitrogen atom include a piperazine ring, a piperidine ring, a pyrrolidine ring, and a morpholine ring.

The substituent represented by R _{11 to} R ₁₃ may further have a substituent. In this case, the following substituents may be substituted. Linear, branched or cyclic such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl Aryl group such as alkyl group, phenyl group, naphthyl group, pyridyl group, triazinyl group, benzothiazolyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, linear, branched or cyclic alkoxy groups such as tert-butoxy group, cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, aryloxy groups such as phenoxy group, naphthyloxy group, methylamino group, ethylamino group, N, N-dimethylamino group, N-ethyl-N-phenylamino group, , N-diphenylamino groups and other amino groups, acetyl groups, benzoyl groups and other acyl groups, carboxylic acid groups, sulfonic acid groups, carbamoyl groups, sulfamoyl groups, nitro groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. Of halogen atoms.

R _{3 to} R ₇ in the general formula (1) may be the sulfonic acid group, carboxylic acid group and salts thereof.

The combination of the substituents R _{3 to} R _{7 in} the general formula (1) is low in solubility in water and easy to synthesize, so any one is a carboxylic acid group and a salt thereof, and the rest The case where four are hydrogen atoms is preferable.

  As shown in the following scheme, the molecular structure represented by the general formula (1) has tautomers having a structure such as the following general formula (3). It is within the scope of the right of the invention.

［一般式（３）中のＲ₁乃至Ｒ₇は一般式（１）におけるＲ₁乃至Ｒ₇と各々同意義を有する。］

[Formula (3) R ₁ to R ₇ in having a R ₁ to R ₇ in the general formula (1) each as defined above. ]

  Next, the manufacturing method of the pigment | dye compound which has a structure represented by the said General formula (1) of this invention is demonstrated below.

  The dye compound represented by the general formula (1) according to the present invention can be synthesized according to a known method. An example of a synthesis scheme is shown below.

［一般式（５）乃至（１０）中のＲ₁乃至Ｒ₁₀は、前記一般式（１）におけるＲ₁乃至Ｒ₁₀と同意義を有する。］

[R _{1 to} R _{10 in} General Formulas (5) to (10) have the same meanings as R _{1 to} R ₁₀ in General Formula (1). ]

  First, Step 1 for producing a compound represented by the general formula (6) by cyclization with the compound (4) and hydrazine represented by the general formula (5) will be described. The manufacturing method of the said General formula (6) by the cyclization reaction of the process 1 is compoundable by the well-known manufacturing method mentioned below (for example, Journal of Medicinal Chemistry, Vol.44, No.22, pp.3730-). 3745 (2001).).

  The compound (4) used in the present invention is commercially available and can be easily obtained. Various hydrazines represented by the general formula (5) are commercially available and can be easily obtained. Moreover, it is easily compoundable by a well-known method (For example, experiment chemistry course 14. Synthesis and reaction of an organic compound [III], 1573-1584). Specifically, although not particularly limited, for example, hydrazine, methyl hydrazine, ethyl hydrazine, n-propyl hydrazine, isopropyl hydrazine, n-butyl hydrazine, isobutyl hydrazine, sec-butyl hydrazine, tert-butyl hydrazine, Examples thereof include cyclopropyl hydrazine, cyclobutyl hydrazine, cyclopentyl hydrazine, phenyl hydrazine, phenethyl hydrazine, naphthyl hydrazine, and benzyl hydrazine.

  Although this step can be performed without a solvent, it is preferably performed in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction. Examples thereof include water, alcohols such as methanol, ethanol and propanol, esters such as methyl acetate, ethyl acetate and propyl acetate, diethyl ether. , Ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, amides such as N, N-dimethylformamide and N, N-dimethylimidazolidinone, and nitriles such as acetonitrile and propionitrile And acids such as hydrochloric acid, formic acid, acetic acid and propionic acid. Moreover, the said solvent can mix and use 2 or more types of solvents, and the mixing ratio in the case of mixing use can be defined arbitrarily. The reaction solvent is used in an amount of 0.1 to 1000 times by mass, preferably 0.5 to 100 times by mass, more preferably 1.0 to 20 times by mass, relative to compound (4). .

  The reaction temperature in this step is -80 ° C to 250 ° C, preferably -50 ° C to 200 ° C, more preferably -20 ° C to 150 ° C. Usually the reaction is complete within 24 hours.

  Next, the compound represented by the general formula (6) is esterified with the alcohol represented by the general formula (7) or amidated with the amine represented by the general formula (8), and the general formula ( Step 2 for producing the compound represented by 9) will be described. Step 2 can be synthesized by a known method as in Step 1. Specifically, a method using a dehydration condensing agent such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (for example, Journal of Organic Chemistry, Vol. 2525-2528 (1961).), Fisher-ester synthesis (e.g., Journal of Organic Chemistry, Vol. 71, No. 8, pp. 3332-3334 (2006).) And the Schotten-Baumann method (e.g., Chemical Reviews, Vol.52, No.2, pp.237-416 (1953).) And the like.

  Various alcohols represented by the general formula (7) used in the present invention are commercially available and can be easily obtained. Specifically, although not particularly limited, for example, methanol, ethanol, n-propanol, isopropanol, cyclopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, phenol, naphthol, benzyl alcohol Etc.

  Various amines represented by the general formula (8) used in the present invention are commercially available and can be easily obtained. Specifically, although not particularly limited, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, cyclopropylamine, cyclobutylamine N, N-dimethylamine, N, N-diethylamine, N, N-di (n-propyl) amine, N, N-di (n-butyl) amine, N, N-di (2-ethylhexyl) amine, N, N-dicyclohexylamine, aniline, benzylamine, phenethylamine, N, N-benzylphenylamine and the like can be mentioned.

  Although this step can be performed without a solvent, it is preferably performed in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, N and N -Amides such as dimethylformamide and N, N-dimethylimidazolidinone, and nitriles such as acetonitrile and propionitrile. Moreover, the said solvent can mix and use 2 or more types of solvents, and the mixing ratio in the case of mixing use can be defined arbitrarily. The amount of the reaction solvent used is in the range of 0.1 to 1000 times by mass, preferably 0.5 to 100 times by mass, more preferably 1.times. With respect to the compound represented by the general formula (6). 0 to 20 times mass.

  The reaction temperature in this step is -80 ° C to 250 ° C, preferably -50 ° C to 200 ° C, more preferably 0 ° C to 100 ° C. Usually the reaction is complete within 24 hours.

  Next, Step 3 for forming an azo bond with the coupler represented by the general formula (9) and the aniline analog represented by the general formula (10) to form a dye will be described. Step 3 can be performed by a known method. Specifically, the method shown below is mentioned, for example. First, in a methanol solvent, the amine derivative represented by the general formula (10) is reacted with a diazotizing agent such as sodium nitrite in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid to convert to a corresponding diazonium salt. . Further, this diazonium salt is coupled with the compound represented by the general formula (9) to produce a dye compound represented by the general formula (1).

  For the compounds represented by the general formulas (1), (6) and (9) obtained in the respective steps, ordinary organic compound isolation and purification methods can be used. The isolation and purification methods include, for example, a method of acidifying with hydrochloric acid or the like in an aqueous medium and acid precipitation, a recrystallization method or reprecipitation method using an organic solvent, column chromatography using silica gel or the like. These methods can be obtained with high purity by performing purification alone or in combination of two or more.

The dye compound represented by the general formula (1) can be synthesized by the production method. Table 1 below shows the pigment compounds (11) to (37) as specific examples of the present invention, but is not limited to the following examples. In Table 1, “Ph” represents an unsubstituted phenyl group, “Bn” represents an unsubstituted benzyl group, and “*” represents a binding site of the substituent. In addition, pigment compound (11)-(16), (19), (36), (37) is described as a reference example.

  Next, the pigment dispersant and the pigment composition of the present invention will be described. The coloring compound of the present invention has high affinity with pigments, particularly azo pigments, and has high solubility in a dispersion medium, so that it can be used alone or in combination of two or more as a pigment dispersant.

  The pigment composition of the present invention is used for paints, inks, toners, and resin molded articles, and is characterized by containing at least one dye compound according to the present invention as a pigment dispersant.

  Examples of the pigment that can be used in the present invention include monoazo pigments, disazo pigments, and polyazo pigments. Among these, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 180. Among them, C.I represented by the following formula (2): I. Pigment Yellow 155 is more preferable because the dispersion effect of the dye compound represented by the general formula (1) of the present invention is high. The above pigments may be used alone or in combination of two or more.

  These may be crude pigments, or may be prepared pigment compositions as long as they do not significantly inhibit the effect of the pigment dispersant of the present invention.

  The mass composition ratio of the pigment to the pigment dispersant in the pigment composition of the present invention is preferably 100: 0.5 to 100: 10. More preferably, it is 100: 1 to 100: 5. If the amount of the pigment dispersant is too small, the target dispersion effect is small. If the amount is too large, the dispersion effect is obtained, but the color dispersion of the pigment dispersant increases, resulting in a problem of reduced sharpness.

  The pigment composition of the present invention can be produced by a wet method or a dry method. Considering that the dye compound of the present invention has high solubility in an organic solvent, production by a wet method capable of easily producing a uniform pigment composition is preferable. Specifically, for example, it is obtained as follows. The pigment dispersant and, if necessary, the resin are dissolved in the dispersion medium, and the pigment powder is gradually added while stirring to fully adjust the dispersion medium. Furthermore, by applying mechanical shearing force with a disperser such as a kneader, roll mill, ball mill, paint shaker, dissolver, attritor, sand mill, high speed mill, etc., the pigment dispersant is adsorbed on the surface of the pigment particles and the pigment is stably and even Can be finely dispersed into fine particles.

  The resin that can be used in the pigment composition of the present invention is determined according to the intended use of the pigment composition and is not particularly limited. Specifically, for example, polystyrene, styrene copolymer, polyacrylic acid, polymethacrylic acid, polyacrylate, polymethacrylate, acrylate copolymer, methacrylate copolymer, polyester, polyvinyl ether, polyvinyl methyl ether, polyvinyl alcohol, Polyvinyl butyral is mentioned. Other examples include polyurethane and polypeptides. Two or more of these dispersion media can be mixed and used. The pigment composition produced by the method of the present invention can be isolated using conventional methods, for example, by filtration, decanting or centrifuging. The solvent can also be removed by washing.

  The pigment composition of the present invention may further contain an auxiliary agent during production. Specifically, for example, surface active agents, pigments and non-pigment dispersants, fillers, standardizers, resins, waxes, antifoaming agents, antistatic agents, dustproofing agents, extenders, dark colorants ( shading colorants), preservatives, drying inhibitors, rheology control additives, wetting agents, antioxidants, UV absorbers, light stabilizers, or combinations thereof.

  In addition, the pigment dispersant of the present invention may be added in advance when the crude pigment is produced.

  Next, the pigment dispersion of the present invention will be described.

  The pigment dispersion of the present invention comprises the above pigment composition and an organic solvent. The pigment composition may be dispersed in an organic solvent, or each component of the pigment composition may be dispersed in an organic solvent.

  The pigment dispersion of the present invention is obtained, for example, as follows. If necessary, the pigment dispersant and the resin are dissolved in the dispersion medium, and the pigment or the pigment composition powder is gradually added while stirring to fully adjust the dispersion medium. Furthermore, by applying mechanical shearing force with a dispersing machine such as a ball mill, paint shaker, dissolver, attritor, sand mill, high speed mill, etc., the pigment dispersant is adsorbed on the surface of the pigment particles, and the pigment is stably made into fine particles. Can be finely dispersed.

  The organic solvent that can be used in the pigment dispersion of the present invention is determined according to the intended use of the pigment dispersion and is not particularly limited. Specifically, for example, alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol, cyclohexanol, methyl cellosolve, cellosolve, diethylene glycol, ethers such as diethyl ether, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone Such as ketones, esters such as methyl acetate, ethyl acetate, propyl acetate, hydrocarbons such as hexane, octane, petroleum ether, cyclohexane, benzene, toluene, xylene, styrene, carbon tetrachloride, trichloroethylene, tetrabromoethane, etc. Halogenated hydrocarbons, acetals such as methylal and diethyl acetal, organic acids such as formic acid, acetic acid and propionic acid, or nitropropene, nitrobenzene and dimethyl Triethanolamine, monoethanolamine, pyridine, dimethyl sulfoxide, sulfur-nitrogen-containing organic compounds such as dimethylformamide.

  The organic solvent that can be used in the pigment dispersion of the present invention may be a polymerizable monomer. Specifically, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4 dichlorostyrene, p-ethylstyrene, 2,4 -Dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn- Dodecylstyrene, ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl iodide, vinyl acetate, vinyl propionate, vinyl benzoate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid -N-octyl, dodecyl methacrylate, methacryl 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methyl acrylate, ethyl acrylate, acrylic acid n-butyl, isobutyl acrylate, propyl acrylate, acrylic acid n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl methyl ketone, vinyl hexyl ketone, Mention may be made of methyl isopropenyl ketone, vinyl naphthalene, acrylonitrile, methacrylonitrile, acrylamide.

  The resin that can be used in the pigment dispersion of the present invention is determined according to the intended use of the pigment composition and is not particularly limited. Specifically, for example, polystyrene, styrene copolymer, polyacrylic acid, polymethacrylic acid, polyacrylate, polymethacrylate, acrylate copolymer, methacrylate copolymer, epolyester, polyvinyl ether, polyvinyl methyl ether, polyvinyl alcohol And polyvinyl butyral. Other examples include polyurethane and polypeptides. Two or more of these resins can be mixed and used.

  The pigment dispersion of the present invention can be used, for example, for producing an electrophotographic toner. As a method for producing toner particles, all conventionally used methods can be used. Specific examples include a pulverization method, a suspension polymerization method, and an emulsion polymerization method.

  As explained above, the dye compound of the present invention is particularly preferably used as a dispersant for azo pigments. The dye compound of the present invention is not only used as a pigment dispersant, but also applied to electronic materials such as colorants for inkjet inks and thermal transfer recording sheets, dyes for optical recording, and dyes for color filters. I can do it.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to these. In the text, “parts” and “%” are based on mass unless otherwise specified.

The obtained reaction product was identified by a plurality of analysis methods using the following apparatuses. That is, the analyzer used was ¹ H nuclear magnetic resonance spectroscopy (ECA-400, manufactured by JEOL Ltd.), high performance liquid chromatography (LC-20A, manufactured by Shimadzu Corporation), LC / TOF MS ( LC / MSD TOF, manufactured by Agilent Technologies). In addition, when performing mass spectrometry, electrospray ionization (ESI) was used as a method for ionizing the dye compound.

[Example 1]
The dye compound of the present invention was synthesized by the following method.

<Synthesis Example 1>
[Synthesis of Dye Compound (14)]

  First, compound (39) was synthesized using compounds (1) and (38). To 8.1 parts of the compound (38), 150 parts of acetic acid and 10 parts of the compound (1) were added and stirred at 100 ° C. for 5 hours. After completion of the reaction, the reaction mixture was concentrated, and the solid precipitated by recrystallization was filtered to obtain 13 parts of Compound (39) (yield 86%).

  Next, the compound (41) was synthesized using the compound (40) and the obtained compound (39). To 20 parts of compound (39), 60 parts of compound (40) and 0.1 part of concentrated sulfuric acid were added and stirred at 130 ° C. for 5 hours. After completion of the reaction, the reaction solution was distilled under reduced pressure, the residue was washed with 200 parts of hexane, and the precipitated solid was separated by filtration to obtain 20 parts of Compound (41) (yield 70%).

  Next, a dye compound (14) was synthesized using the compound (42) and the obtained compound (41). To 4.0 parts of the compound (42), 20 parts of methanol and 4.8 parts of concentrated hydrochloric acid were added and cooled to 10 ° C. or lower with ice. To this solution, 1.7 parts of sodium nitrite dissolved in 4.0 parts of water was added and reacted at the same temperature for 1 hour. Next, 0.30 part of sulfamic acid was added and the mixture was further stirred for 20 minutes (diazonium salt solution). 35 parts of methanol was added to 7.3 parts of compound (41) and the mixture was cooled to 10 ° C. or less with ice, and the diazonium salt solution was added. Thereafter, a saturated aqueous sodium acetate solution was added to adjust the pH to 5 to 7, and the mixture was reacted at 10 ° C. or lower for 2 hours. After completion of the reaction, 10 parts of the dye compound (14) was obtained by purification by a recrystallization method (yield 84%).

[Analytical result of dye compound (14)]
[1] ¹ H NMR (400 MHz, DMSO-d6, room temperature): δ [ppm] = 7.93 (2.0 H, d), 7.86 (1.0 H, d), 7.76 (1.0 H D), 7.59-7.45 (3.0H, m), 7.37-7.26 (2.0H, m), 4.37-4.25 (2.0H, m), 1 .80-1.68 (1.0 H, m), 1.58-1.20 (8.0 H, m), 1.00-0.81 (6.0 H, m)
[2] Mass spectrometry (ESI-TOF): m / z = 521.15 (M-Na) ⁻
[3] HPLC results: purity = 99 area%, retention time 25.2 minutes, electron absorption spectrum λ _max = 407 nm (0.1 mM TFA solution-MeOH)

<Synthesis Example 2>
[Synthesis of Dye Compound (30)]

  Compound (39) was synthesized in the same manner as in Synthesis Example 1.

  Next, a compound (44) was synthesized using the compound (43) and the obtained compound (39). To 40 parts of the compound (39), 600 parts of chloroform, 66 parts of the compound (43) and 37 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride were added and stirred at 25 ° C. for 5 hours. After completion of the reaction, the mixture was extracted with chloroform and purified by column chromatography to obtain 50 parts of compound (44) (yield 65%).

  Next, a dye compound (30) was synthesized using the compound (45) and the obtained compound (44). To 5.0 parts of the compound (45), 25 parts of methanol and 7.4 parts of concentrated hydrochloric acid were added and cooled to 10 ° C. or lower with ice. To this solution, 2.6 parts of sodium nitrite dissolved in 7.8 parts of water was added and reacted at the same temperature for 1 hour. Next, 0.53 part of sulfamic acid was added and the mixture was further stirred for 20 minutes (diazonium salt solution). 75 parts of methanol was added to 15 parts of the compound (44) and the mixture was cooled to 10 ° C. or less with ice, and the diazonium salt solution was added. Thereafter, a saturated aqueous sodium acetate solution was added to adjust the pH to 5 to 7, and the mixture was reacted at 10 ° C. or lower for 2 hours. After completion of the reaction, 17 parts of the dye compound (30) was obtained by purification by a recrystallization method (yield 80%). The obtained dye compound was subjected to a purity test by HPLC and then subjected to NMR analysis and mass spectrometry to determine the structure. The analysis results are shown below. The NMR spectrum of the dye compound (30) by NMR analysis is shown in FIG.

[Analysis Results for Dye Compound (30)]
[1] ¹ H NMR (400 MHz, chloroform-d, room temperature): δ [ppm] = 7.99 (1.0 H, d), 7.88-7.71 (2.9 H, m), 7.46 (1.0H, t), 7.16-7.08 (2.8H, m), 6.93 (0.9H, t), 3.68-3.51 (1.0H, m), 3 .50-3.33 (1.0H, m), 3.24 (1.9H, d), 1.81-0.71 (30.0H, m)
[2] Mass spectrometry (ESI-TOF): m / z = 596.33 (M-Na) ⁻
[3] HPLC results: purity = 99 area%, retention time 31.6 minutes, electron absorption spectrum λ _max = 402 nm (0.1 mM TFA solution-MeOH)

<Synthesis Example 3>
In accordance with the method described in Synthesis Example 1 or 2, dye compounds (11) to (13), (15) to (29), and (31) to (37) described in Table 1 were obtained. The structures of these dye compounds were confirmed by HPLC analysis, mass spectrometry and NMR analysis in the same manner as the dye compounds (14) and (30) described above.

[Example 2]
The dye compound obtained in the present invention was evaluated by the following method.

<Solubility Evaluation of Dye Compound>
The solubility of the dye compound in the styrene monomer at a temperature of 25 ° C. was measured. The solubility was evaluated as follows.
A: Solubility in styrene monomer is 1% or more B: Solubility in styrene monomer is 0.1% or more and less than 1% C: Solubility in styrene monomer is less than 0.1% Solubility in styrene monomer is 1% or more Was judged to be sufficient solubility.

<Evaluation of water transferability of dye compound>
The coloring of the aqueous layer was visually evaluated when the styrene solution of the coloring compound at a temperature of 25 ° C. was brought into contact with water. Water transferability was evaluated as follows.
A: The water layer is colorless B: The water layer is slightly colored C: The water layer is clearly colored If the water layer is not clearly colored, it is judged that there is no practical problem with water migration.

  Table 2 shows the evaluation results of the types of the dye compounds, the solubility of the dye compounds, and the water transferability.

[Comparative Example 1]
Examples of comparative dye compound (46) and comparative pigment dispersant (47) “Solsperse 24000SC (registered trademark) (manufactured by Lubrizol)” disclosed in Patent Document 2 were evaluated for solubility and water migration. Evaluation was performed in the same manner as in 2.

  The evaluation results are shown in Table 2.

  From Table 2, it was confirmed that the present invention provides a dye compound having high solubility in a nonpolar organic solvent and low water transferability.

[Example 3]
The pigment dispersion of the present invention was prepared by the following method.

<Preparation Example 1 of Pigment Dispersion>
18.0 parts of the azo pigment represented by the formula (2), 0.18 part of the dye compound (11) as a pigment dispersant, 180 parts of styrene monomer, 130 parts of glass beads (φ1 mm) are mixed with a paint shaker. It was dispersed for 3 hours and filtered through a mesh to obtain a pigment dispersion (101).

<Preparation Example 2 of Pigment Dispersion>
The pigment dispersions (101) to (127) were obtained in the same manner as in Preparation Example 1 of the pigment dispersion, except that the dye compound (11) was changed to the dye compounds (12) to (37). It was.

<Pigment Dispersion Preparation Example 3>
A pigment dispersion (128) was obtained in the same manner as in Preparation Example 1 for the pigment dispersion, except that 0.18 part of the dye compound (11) was changed to 0.08 part of the dye compound (30). .

<Preparation Example 4 of Pigment Dispersion>
A pigment dispersion (129) was obtained in the same manner as in Preparation Example 1 for pigment dispersion, except that 0.18 part of the dye compound (11) was changed to 2 parts of the dye compound (30).

[Comparative Example 2]
A comparative pigment dispersion was prepared in the following manner.

<Preparation Example 1 for Comparative Pigment Dispersion>
A comparative pigment dispersion (130) was obtained in the same manner as in Preparation Example 1 of the pigment dispersion of Example 3 except that the dye compound (11) was not added.

<Preparation Example 2 for Comparative Pigment Dispersion>
The same procedure was performed except that the dye compound (11) used in the preparation example of the pigment dispersion was changed to the comparative dye compound (46) and the comparative pigment dispersant (47). Pigment dispersions (131) and (132) were obtained.

[Example 4]
The color tones of the pigment dispersions (101) to (129) obtained in the present invention were evaluated by the following methods.

The pigment dispersion was applied to art paper by the bar coat method (Bar No. 10), air-dried all day and night, and measured with SpectroLino (manufactured by Gretag Machbeth). The color tone was evaluated as follows.
A: OD (Y) is 1.6 or more B: OD (Y) is 1.5 or more, less than 1.6 C: OD (Y) is less than 1.5 OD (Y) value is 1.5 or more If so, it was judged that the color tone was good.

  Table 3 shows the evaluation results of the pigment dispersion type, the pigment dispersant type, and the color tone of the pigment dispersion.

[Comparative Example 3]
Comparative pigment dispersions (130) to (132) were evaluated in the same manner as in Example 4. The evaluation results are shown in Table 3.

  From Table 3, the coloring compound of the present invention gives an azo pigment dispersion having a good color tone. From this, it was confirmed that it is useful as a coloring compound for an azo pigment dispersant.

[Example 5]
Yellow toner particles were produced by the following method using the pigment dispersion obtained in the present invention.

<Manufacture of yellow toner particles>
710 parts of ion-exchanged water and 450 parts of 0.1 mol / l-Na ₃ PO ₄ aqueous solution were added to a 2-liter four-necked flask equipped with a high-speed stirring device TK-homomixer (made by Tokushu Kika Kogyo Co., Ltd.). Was adjusted to 12000 rpm and heated to 60 ° C. To this, 68 parts of a 1.0 mol / l-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing Ca ₃ (PO ₄ ) ₂ as a minute hardly water-soluble dispersion stabilizer.

-Pigment dispersion (120) of Example 3 132 parts-Styrene monomer 46 parts-n-Butyl acrylate monomer 34 parts-Polar resin 10 parts [Polycondensate of propylene oxide modified bisphenol A and isophthalic acid ( Tg = 65 ° C., Mw = 10000, Mn = 6000)]
Ester wax 25 parts (peak temperature of maximum endothermic peak in DSC measurement = 70 ° C., Mn = 704)
・ 2 parts of aluminum salicylate compound (Bontron E-88 manufactured by Orient Chemical Co., Ltd.)
-Divinylbenzene monomer 0.1 part The said prescription was heated at 60 degreeC, and it melt | dissolved and disperse | distributed uniformly at 5000 rpm using TK-homomixer. In this, 10 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved to prepare a polymerizable monomer composition.

  This polymerizable monomer composition was put into the aqueous dispersion medium and granulated for 15 minutes while maintaining the rotation speed of 12000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirring blade, the polymerization was continued for 5 hours at an internal temperature of 60 ° C., and then the internal temperature was raised to 80 ° C. and polymerization was continued for 8 hours. After completion of the polymerization reaction, the residual monomer was distilled off at 80 ° C. under reduced pressure, and then the mixture was cooled to 30 ° C. to obtain a polymer fine particle dispersion.

Next, the polymer fine particle dispersion is transferred to a washing container, and while stirring, dilute hydrochloric acid is added and stirred at pH 1.5 for 2 hours to dissolve the phosphoric acid and calcium compound containing Ca ₃ (PO ₄ ) _2. Thereafter, solid-liquid separation was performed with a filter to obtain polymer fine particles. This was poured into water and stirred to obtain a dispersion again, followed by solid-liquid separation with a filter. The redispersion of polymer fine particles in water and solid-liquid separation were repeated until the phosphoric acid and calcium compound containing Ca ₃ (PO ₄ ) ₂ was sufficiently removed. Thereafter, the polymer fine particles finally solid-liquid separated were sufficiently dried with a dryer to obtain a yellow toner. At this time, the washing solution was not colored.

  From the above results, it was suggested that the pigment dispersion of the present invention is suitable as a pigment dispersion for toner.

  As an application example of the present invention, the dye compound of the present invention can be applied to various uses. That is, the present invention can be applied not only as a pigment dispersant but also to electronic materials such as inkjet inks, colorants for thermal transfer recording sheets, dyes for optical recording, and dyes for color filters.

Claims (16)

A dye compound represented by the following general formula (1).

[In General Formula (1), R ₁ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, R ₂ represents a CONR ₉ R ₁₀ group (R ₉ and R ₁₀ are each independently an alkyl group, R _{3 to} R ₇ each independently represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an acetylamino group, a sulfamoyl group, an alkyl group, an alkoxy group, or a COOR ₁₁ group. CONR ₁₂ R ₁₃ group (R ₁₁ and R ₁₂ each independently represents an alkyl group, an aryl group or an aralkyl group, and R ₁₃ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group), a sulfone. An acid group, a carboxylic acid group, a sulfonate group or a carboxylate group is represented. However, in the general formula (1), one or two functional groups selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a sulfonic acid group, and a carboxylic acid group are present. ] The dye compound according to claim 1, wherein R ₁ in the general formula (1) is an unsubstituted phenyl group. 2. The dye compound according to claim 1 , wherein, in the general formula (1), the total number of carbon atoms of R ₉ and R ₁₀ is 10 or more. The dye compound according to any one of claims 1 to 3 , wherein the general formula (1) has one or two carboxylic acid groups and / or salts thereof. The substitution position of all carboxylic acid groups and / or salts thereof having in its molecule, according to claim 4, characterized in that any position of R ₃ to R ₇ in the general formula (1) Pigment compound. A pigment dispersant characterized by containing at least one dye compound represented by the following general formula (1) .

[In General Formula (1), R ₁ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, R ₂ represents a COOR ₈ group or a CONR ₉ R ₁₀ group (R ₈ and R ₉ are alkyl groups) A group, an aryl group or an aralkyl group, R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.), R _{3 to} R ₇ are each independently a hydrogen atom, a halogen atom or trifluoromethyl. group, an acetylamino group, a sulfamoyl group, an alkyl group, an alkoxy group, COOR ₁₁ group, CONR ₁₂ R ₁₃ group (R ₁₁ and R ₁₂ each independently represents an alkyl group, an aryl group or an aralkyl group, R ₁₃ is Represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.), A sulfonic acid group, a carboxylic acid group, a sulfonic acid group or a carboxylic acid group. However, in the general formula (1), one or two functional groups selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a sulfonic acid group, and a carboxylic acid group are present. ] In the general formula (1), R ₁ Is a non-substituted phenyl group, The pigment dispersant of Claim 6 characterized by the above-mentioned. In the general formula (1), R ₂ Is CONR ₉ R _Ten Group (R ₉ And R _Ten Each independently represents an alkyl group, an aryl group or an aralkyl group. The pigment dispersant according to claim 6 or 7, wherein In the general formula (1), R ₉ And R _Ten The total number of carbon atoms is 10 or more, The pigment dispersant according to claim 8. The pigment dispersant according to any one of Claims 6 to 9, wherein the general formula (1) has one or two carboxylic acid groups and / or salts thereof. The substitution positions of all carboxylic acid groups and / or salts thereof in the molecule are R in the general formula (1). _Three To R ₇ The pigment dispersant according to claim 10, wherein the pigment dispersant is at any one of the positions. A pigment composition comprising the pigment dispersant according to any one of claims 6 to 11 and an azo pigment dispersed by the pigment dispersant. The pigment composition according to claim 12 , wherein a mass composition ratio of the azo pigment to the pigment dispersant is 100: 0.5 to 100: 10. 14. The pigment composition according to claim 12 or 13 , wherein the azo pigment is represented by the formula (2).

A pigment dispersion comprising the pigment composition according to any one of claims 12 to 14 and an organic solvent. The pigment dispersion according to claim 15 , wherein the organic solvent is a styrene monomer.

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