TW201302924A - Pigment composition, pigment dispersion and colored resin composition - Google Patents

Abstract

A fine monoazo pigment is enabled to achieve excellent crystal stability and sufficient dispersion stability at the same time. This pigment composition is composed of at least one monoazo pigment represented by general formula (1) and at least one compound represented by one of general formulae (2)-(5). AA General formula.

Description

Pigment composition, pigment dispersion, and coloring resin composition

The present invention relates to a monoazo pigment composition, and a pigment dispersion containing the same, and a coloring resin composition, for example, for inkjet inks and toners for electronic photographs.

Conventionally, as a yellow pigment for inkjet printing or electronic photographing, for example, a diazo pigment such as CI Pigment Yellow 12, the same pigment 13, the same pigment 17 and the same pigment 83; CI Pigment Yellow 1, the same pigment are mainly used. 65 and a monoazo pigment such as pigment 74; and a condensed azo pigment such as CI Pigment Yellow 93, the same pigment 95, and the same pigment 128.
Among these pigments, although the diazo pigment has good transparency and coloring power, it has a problem of low light resistance.
Further, although the condensed azo pigment is excellent in heat resistance and light resistance, it is expensive. Further, the condensed azo pigment is inferior to the diazo pigment or the monoazo pigment in terms of coloring power.
Monoazo pigments are better in light fastness or safety than diazo pigments. Further, the monoazo pigment is more excellent in coloring power than the condensed azo pigment, and can be produced at a lower cost than the condensed azo pigment. In particular, CI Pigment Yellow 74 is excellent in hue or sharpness, and has been widely used as a yellow pigment for inkjet printing or electronic photographs in recent years.
However, many monoazo pigments have poor crystal stability. Specifically, depending on the conditions of use, the monoazo pigment may have an undesired condition such as primary particle growth due to the influence of heat or solvent. Therefore, for example, if a dispersion in which a monoazo pigment is dispersed in a liquid medium is stored for a long period of time, an undesired situation such as an increase in viscosity or a precipitate may occur. These undesired conditions will eventually become the cause of the reduction in the color or sharpness of the printed matter.
Various reviews have been made to improve the crystal stability of monoazo pigments.
A coloring composition for image recording containing a yellow monoazo pigment is described in, for example, Japanese Laid-Open Patent Publication No. Hei 10-158555, and No. Hei 10-171165. In the synthesis of the yellow monoazo pigment, the following components are coupled: a plurality of diazo components obtained by diazotizing a different aromatic structure; and a couplant component, specifically a phenyl group substituted by a specific functional group. The hydrogen atom may also be acetanilide. Thereby, CI Pigment Yellow 74 and the pigments different in structure are formed at the same time. According to this method, a pigment having a small primary particle diameter and excellent heat resistance can be obtained.
An electronic photograph or a composition for inkjet printing containing a yellow monoazo pigment is described in Japanese Laid-Open Patent Publication No. 2004-083779. In the method for producing a composition, when a diazo component is coupled with a couplant component, an interfacial surfactant having a specific structure is added to the reaction liquid to form a monoazo pigment having a small primary particle size and a high degree of crystallization. Then, a fatty acid ester is added to the liquid after the coupling reaction to surface-treat the pigment. According to this method, a pigment having a small primary particle diameter and excellent heat resistance can be obtained.

In recent years, the use of inkjet printing and electronic photographs has increased the level of image quality required for printed matter. Therefore, it is required to uniformly disperse the ink or the carbon powder used for such use in addition to the fineness of the pigment.
However, in general, the finer the pigment particles, the stronger the tendency of the particles to aggregate with each other. Therefore, it is difficult to obtain a uniform dispersion state, and for example, even if a uniform dispersion state is obtained, it is difficult to maintain the state for a long period of time. Although the method described in the above document can obtain a pigment having a small primary particle diameter and good crystal stability, the dispersion stability of the ink containing the pigment or the carbon powder pigment is insufficient.
Thus, it is difficult for the fine monoazo pigment to simultaneously achieve good crystal stability and sufficient dispersion stability. Accordingly, an object of the present invention is to achieve a good crystal stability and sufficient dispersion stability for a fine monoazo pigment.
According to a first aspect of the present invention, there is provided a pigment composition comprising: at least one monoazo pigment represented by each of the following general formula (1); and each of the following general formulas (2) to ( 5) At least one compound represented by one of them.


(wherein X ¹ to X ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, a carboxyl group, One of a nitro group, a sulfonic acid group, a carbamic acid group, an amine sulfonyl group, and a trifluoromethyl group. The adjacent two of X ¹ to X ⁵ are bonded to each other, and two of the benzene rings are bonded thereto. The carbon atom may form a heterocyclic moiety together, or a hydrogen atom bonded to a ring atom of the heterocyclic moiety may be substituted.
X ⁶ to X ¹⁰ each independently represent one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an acetamino group, a carboxyl group and a sulfonic acid group. The adjacent two of X ⁶ to X ¹⁰ are bonded to each other, and the two carbon atoms of the benzene ring bonded thereto may form a hetero ring moiety, or the hydrogen atom of the ring atom bonded to the hetero ring moiety may be substituted. )

(In the formula, A represents one of -CO- and -SO ₂ -. R ¹ represents one of the following: a hydrogen atom; an alkyl group having a carbon number of 20 or less having a substituent; or a substitution An alkenyl group having a carbon number of 20 or less; and an aryl group having a carbon number of 20 or less which may have a substituent.
Y ¹ represents -SO ₂ NH-R ² -NR ³ R ⁴ -, -CONH-R ⁵ -NR ⁶ R ⁷ -, -SO ₂ NH-R ⁸ -SO ₃ H, -CONH-R ⁹ -SO ₃ H, -SO ₂ NH-R ¹⁰ -COOH, -CONH-R ¹¹ -COOH, and one of the groups represented by the following general formula (3). Wherein R ² , R ⁵ and R ⁸ to R ¹¹ each independently represent one of the following: an alkylene group having a carbon number of 20 or less having a substituent group; and an alkylene group having a carbon number of 20 or less having a substituent group And an arylene group having a carbon number of 20 or less which may have a substituent group. R ³ , R ⁴ , R ⁶ and R ⁷ each independently represent one of the following: a hydrogen atom; an alkyl group having a carbon number of 20 or less having a substituent; or an alkenyl group having a carbon number of 20 or less having a substituent. And an aryl group having a carbon number of 20 or less having a substituent. R ³ and R ⁴ or R ⁶ and R ⁷ are bonded to each other, and the nitrogen atom bonded thereto or the like forms a heterocyclic moiety together, or a part of a carbon atom which is a ring atom of the heterocyclic moiety is subjected to another nitrogen atom, an oxygen atom or The sulfur atom may be substituted or the hydrogen atom of the ring atom bonded to the heterocyclic moiety may be substituted. )


(wherein Y ² and Y ³ each independently represent one of -OH-, -NH-R ¹² -NR ¹³ R ¹⁴ -, -NH-R ¹⁵ -SO ₃ H and -NH-R ¹⁶ -COOH Wherein R ¹² , R ¹⁵ and R ¹⁶ each independently represent one of the following: an alkylene group having a carbon number of 20 or less having a substituent; or an alkenyl group having a carbon number of 20 or less having a substituent; And an arylene group having a carbon number of 20 or less of the substituent group. R ¹³ and R ¹⁴ each independently represent one of the following: a hydrogen atom; or an alkyl group having a carbon number of 20 or less having a substituent; An alkenyl group having a carbon number of 20 or less; and an aryl group having a carbon number of 20 or less having a substituent group. R ¹³ and R ¹⁴ are bonded to each other, and a nitrogen atom bonded thereto or the like forms a heterocyclic moiety together, or A part of the carbon atom of the ring atom of the heterocyclic moiety may be replaced by another nitrogen atom, an oxygen atom or a sulfur atom, or the hydrogen atom of the ring atom bonded to the heterocyclic moiety may be substituted.

(In the formula, Y ⁴ represents a single bond, -CONH-R ¹⁷ -, -SO ₂ NH-R ¹⁸ -. R ¹⁷ and R ¹⁸ each independently represent one of the following: may also have a substituent An alkylene group having a carbon number of 20 or less; an alkenyl group having a carbon number of 20 or less having a substituent; and an arylene group having a carbon number of 20 or less having a substituent.
Y ⁵ represents one of -SO ₃ H and -COOH. )

(wherein R ¹⁹ and R ²⁰ each independently represent one of the following: a hydrogen atom; an alkyl group having a carbon number of 20 or less having a substituent; and an alkenyl group having a carbon number of 20 or less; It may also have one of the aryl groups having a carbon number of 20 or less of the substituent group.
Y ⁶ represents -SO ₂ NH-R ²¹ -NR ²² R ²³ -, -CONH-R ²⁴ -NR ²⁵ R ²⁶ -, -SO ₂ NH-R ²⁷ -SO ₃ H, -CONH-R ²⁸ -SO ₃ H, -SO ₂ NHR ²⁹ -COOH and -CONH-R ³⁰ -COOH. R ²¹ , And R ²⁷ to R ³⁰ each independently represent one of the following: an alkylene group having a carbon number of 20 or less having a substituent group; an alkenyl group having a carbon number of 20 or less having a substituent; and An arylene group having a carbon number of 20 or less. R ²² , R ²³ , R ²⁵ and R ²⁶ each independently represent one of the following: a hydrogen atom; an alkyl group having a carbon number of 20 or less having a substituent; and an alkenyl group having a carbon number of 20 or less having a substituent. And an aryl group having a carbon number of 20 or less having a substituent. R ²² and R ²³ or R ²⁵ and R ²⁶ are bonded to each other, and a nitrogen atom bonded thereto or the like forms a heterocyclic moiety together, or a part of a carbon atom which is a ring atom of the heterocyclic moiety is subjected to another nitrogen atom, an oxygen atom or The sulfur atom may be substituted or the hydrogen atom of the ring atom bonded to the heterocyclic moiety may be substituted. )
According to a second aspect of the present invention, there is provided a pigment dispersion comprising the pigment composition of the first aspect and a liquid medium.
According to a third aspect of the present invention, an inkjet ink comprising a pigment dispersion of a second aspect is provided.
According to a fourth aspect of the present invention, there is provided a colored resin composition comprising the pigment composition of the first aspect and a binder resin.
According to a fifth aspect of the present invention, there is provided a carbon powder for an electronic photograph comprising the colored resin composition of the fourth aspect.
In the first to fifth aspects, the total content of the at least one compound represented by any one of the above general formulas (2) to (5) is represented by each of the general formula (1). The ratio of the content of the at least one type of monoazo pigment to the total content of the at least one compound represented by one of the general formulas (2) to (5) is preferably 0.1. Up to 40% by mole. Further, the average primary particle diameter of the pigment composition is preferably 200 nm or less.
The compound contained in the above pigment composition has a specific structure, which has an effect of improving the crystal stability of the monoazo pigment and further improving the dispersion stability. Therefore, the pigment composition can achieve better crystal stability and dispersion stability as compared with the monoazo pigment which is not used together with the compound having the specific configuration. Further, since the compound having such a specific structure is not affected by the preparation method of the pigment composition, a good effect can be imparted, and thus a pigment composition having a good effect can be produced by various methods.

The pigment composition of one aspect of the present invention comprises: at least one monoazo pigment represented by the above general formula (1) (hereinafter sometimes referred to as a monoazo pigment in the present aspect); At least one compound represented by any one of the formulas (2) to (5) (hereinafter sometimes referred to as a heterologous skeleton compound).
First, the monoazo pigment represented by the above general formula (1) will be described.
The halogen atom of X ¹ to X ¹⁰ of the general formula (1) may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The alkyl group having 1 to 5 carbon atoms of X ¹ to X ¹⁰ of the general formula (1) may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group or a tertiary group. Butyl, pentyl, isopentyl, secondary pentyl, neopentyl and the like. However, it is not limited to these examples.
The alkoxy group having 1 to 5 carbon atoms of X ¹ to X ^{10 in} the general formula (1) may, for example, be a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tertiary butoxy group or a pentyloxy group. Neopentyloxy and the like. However, it is not limited to these examples.
The alkoxycarbonyl group having 1 to 5 carbon atoms of X ¹ to X ^{10 in} the general formula (1) may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a tertiary butoxycarbonyl group or a pentyloxycarbonyl group. However, it is not limited to these examples.
The adjacent two of X ¹ to X ¹⁰ are bonded to each other, and the two carbon atoms of the benzene ring after the combination thereof may form a heterocyclic ring portion.
The number of rings of each heterocyclic moiety is preferably from 1 to 2, more preferably 1. The number of ring atoms in each ring is preferably from 5 to 7, preferably 5 or 6.
When the heterocyclic moiety contains a plurality of rings, if one ring of the same ring contains an atom other than a carbon atom as a part of the ring atom, the remaining ring contains only a carbon atom as a ring atom, or contains a carbon atom and a carbon atom. Other than the atom can be used as a carbon atom. The atom other than the carbon atom is, for example, a nitrogen atom, an oxygen atom or a sulfur atom. The ring containing a carbon atom other than a carbon atom is a ring of carbon atoms, and the number of ring atoms other than the carbon atom is, for example, 1 to 2. When the heterocyclic moiety contains a plurality of rings, for example, among the other rings, the ring containing the two carbon atoms of the benzene ring as a ring atom contains an atom other than a carbon atom as a part of the remaining ring atom.
Among the ring atoms of the heterocyclic moiety, two adjacent ring atoms other than the two carbon atoms of the benzene ring may be bonded to each other by a single bond or by a double bond.
The hydrogen atom bonded to the ring atom of the hetero ring moiety may be replaced by an alkyl group such as a methyl group. When two hydrogen atoms are bonded to one ring atom, the hydrogen atoms may be replaced by one oxygen atom. That is, the heterocyclic moiety may also contain a carbonyl group.
X ¹ to X ⁵ , X ¹ and X ² are bonded to each other, or X ² and X ³ are bonded to each other, or It may be combined with X ⁴ or X ⁴ and X ⁵ may be combined with each other. Among X ⁶ to X ¹⁰ , X ⁶ and X ⁷ are bonded to each other, or X ⁷ and X ⁸ are bonded to each other, or X ⁸ and X ⁹ are bonded to each other, or X ⁹ and X ¹⁰ may be bonded to each other. Preferably, X ² and X ³ or X ³ and X ⁴ are bonded to each other, or X ⁷ and X ⁸ or X ⁸ and X ⁹ are bonded to each other.
The heterocyclic moiety may, for example, be anthracene, benzimidazolone, benzofuranyl, benzothienyl, pyrrolyl, imidazolidinium, imidazolidinone, benzimidazolidine, benzimidazolone, piperidine. And piperazine, piperazine dione, quinoxaline or quinoline to remove 2 or 4 hydrogen atoms. However, it is not limited to these examples.
Examples of the compound having a heterocyclic moiety in the compound represented by the general formula (1) are shown below.



The monoazo pigment of the present aspect is not particularly limited, and examples thereof include CI Pigment Yellow 1, Pigment 2, Pigment 3, Pigment 4, Pigment 6, Pigment 9, Pigment 49, Pigment 61, and the same pigment. Pigment 62, same pigment 65, same pigment 73, same pigment 74, same pigment 75, same pigment 97, same pigment 98, same pigment 105, same pigment 111, same pigment 116, same pigment 120, same pigment 130, same pigment 133 , the same pigment 151, the same pigment 154, the same pigment 167, the same pigment 168, the same pigment 169, the same pigment 175, the same pigment 181, the same pigment 194, the same pigment 203, the same pigment 213, CI pigment orange 1, the same pigment 36, Same as pigment 60, same pigment 62, same pigment 64, and the like. Among these pigments, CI Pigment Yellow 74 is particularly suitable in terms of hue, sharpness, and transparency. These monoazo pigments may be used singly or in combination of plural kinds.
The form of the monoazo pigment in this aspect is not particularly limited. Use commercially available pigments directly or in combination. Moreover, these monoazo pigments can also be made fine by acid pasting, salt milling, dry grinding, etc., and can be used as a desired particle size.
The monoazo pigment of this aspect can be synthesized by a conventional method. Representative synthetic methods are exemplified below.
The first example is a method of adding a diazo compound of an aromatic amine to a slurry containing acetophenone. First, acetanilide was dissolved in an alkaline aqueous solution, and this was poured into a previously prepared aqueous acetic acid solution to prepare a suspension. On the other hand, an aromatic amine is added to an acidic aqueous solution to prepare a suspension, which is cooled to 5 ° C or lower, and then sodium nitrite is added to carry out diazotization. After the completion of the diazotization, sulfamic acid was added to the reaction mixture to remove excess nitrous acid, and an aqueous solution of the diazotide was prepared. The above-prepared diazotide is added to the slurry of the acetanilide compound to carry out a coupling reaction, and if necessary, the slurry obtained by heating and stirring is filtered, washed with water, dried, and pulverized to obtain a monocouple. Nitrogen pigment.
The second example is a method of adding an alkaline aqueous solution of an acetanilide compound to an aqueous solution of an aromatic amine in a diazotide. First, the acetanilide compound is dissolved in an alkaline aqueous solution. On the other hand, an aromatic amine is added to an acidic aqueous solution to prepare a suspension, which is cooled to 5 ° C or lower, and then sodium nitrite is added to carry out diazotization. After the completion of the diazotization, sulfamic acid was added to the reaction mixture to remove excess nitrous acid, and an aqueous solution containing acetic acid and sodium hydroxide was further added to prepare an aqueous solution of diazotide. An aqueous solution of the above-prepared acetophenone anilide compound is added to the diazotide aqueous solution to carry out a coupling reaction, and if necessary, the obtained slurry is heated and stirred, and then filtered, washed with water, dried, and pulverized to obtain a monoazo. pigment.
The third example is a method in which an aqueous solution of an aromatic amine diazotide and an acetophenone aniline compound is added to an aqueous solution prepared by previously adding an acid such as acetic acid or a base such as sodium hydroxide. First, the acetanilide compound is dissolved in an alkaline aqueous solution. On the other hand, an aromatic amine is added to an acidic aqueous solution to prepare a suspension, which is cooled to 5 ° C or lower, and then sodium nitrite is added to carry out diazotization. After the completion of the diazotization, sulfamic acid was added to the reaction mixture to remove excess nitrous acid, and an aqueous solution of the diazotide was prepared. Further, an acid such as acetic acid and a base such as sodium hydroxide are added to the reaction vessel to prepare a buffer aqueous solution. The aqueous solution of the above-prepared diazotide and the aqueous solution of the acetanilide compound are added to the buffered aqueous solution to carry out a coupling reaction, and if necessary, the slurry obtained by heating and stirring is filtered, washed with water, dried, and It is pulverized to obtain a monoazo pigment.
The aromatic amine used in this aspect may, for example, be 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-(trifluoromethyl)aniline or 3-(trifluoromethyl). Aniline, 4-(trifluoromethyl)aniline, o-methoxyaniline, m-methoxyaniline, p-methoxyaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-methoxy 4-nitroaniline, 2-methoxy-5-nitroaniline, 4-methoxy-2-nitroaniline, 2-methyl-3-nitroaniline, 2-methyl-4- Nitroaniline, 2-methyl-5-nitroaniline, 2-methyl-6-nitroaniline, 3-methyl-4-nitroaniline, 4-methyl-2-nitroaniline, 4- Methyl-3-nitroaniline, 5-methyl-2-nitroaniline, 2-chloro-4-nitroaniline, 2-chloro-5-nitroaniline, 4-chloro-2-nitroaniline, 4-chloro-3-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-5-nitrobenzenesulfonic acid, 4-amino-2-nitrobenzenesulfonic acid, 4-amino -3-nitrobenzenesulfonic acid, 2-chloro-4-methylaniline, 2-chloro-5-methylaniline, 2-chloro-6-methylaniline, 3-chloro-2-methylaniline, 3 -Chloro-4-methylaniline, 4-chloro-4-methylaniline, 4-chloro-3-methylaniline, 5-chloro-2-methylaniline, 3-amino-4-chlorobenzone Amine, 4-amino-3-chlorobenzoguanamine, 4-amino-3-methoxy-N-phenylbenzenesulfonamide, 4-amino-3-methoxy-N-(4 -carbamidine phenyl)benzoguanamine, dimethylamino terephthalate, dimethyl 5-aminophthalic acid dimethyl, 6-amino-7-chloro-4-methylquinoline- 2(1H)-ketone, 5-aminoisoindoline-1,3-dione, and the like. These may be used singly or in combination of plural kinds.
The ethyl acetophenone compound used in the present aspect may, for example, be acetanilide, o-acetamidine, acetophenone, 2'-chloroacetamidine, 4 '-Chloroacetamidine aniline, N-acetamethylene-o-toluidine, N-acetamidine-p-toluidine, o-acetamidine, methoxyacetamide , 醯 醯 醯 ethoxy aniline, 4'-acetamido acetophenone, 2', 4'-dimethyl acetophenone, 4'-chloro-2'-methyl acetamidine Acetanilide, 5'-chloro-2'-methoxyacetamidine, 4'-chloro-2', 5'-dimethoxyacetamidine, 5-acetamidine- 2-benzimidazolone, N-(7-methoxy-2,3-dicarbonyl-1,2,3,4-tetrahydroquinoxalin-6-yl)-3-oxetamine and the like. These may be used singly or in combination of plural kinds.
When the pigment is refined by acid gelatinization, the monoazo pigment is dissolved in concentrated sulfuric acid, and it is mixed with a large amount of excess water to precipitate fine pigment particles. Thereafter, the filtration and washing with water are repeated and dried, whereby finely divided pigment particles can be obtained.
The method of acid gelatinization is not particularly limited, and for example, a method in which a monoazo pigment is dissolved in 5 to 30 times by weight of sulfuric acid, and the obtained sulfuric acid solution is mixed with water having a weight of 5 to 30 times thereof is used. . In this case, the monoazo pigment is dissolved in the temperature of the sulfuric acid, and is not particularly limited as long as it does not cause a reaction such as decomposition of the raw material or sulfonation, and can be carried out, for example, in the range of 3 to 40 °C. Further, the method of mixing the sulfuric acid solution of the monoazo pigment with water, the temperature, and the like are not particularly limited. In many cases, when the particles are precipitated at a low temperature, the particles tend to be finer than when the particles are precipitated at a high temperature, and therefore it is preferably at 0 ° C to 60 ° C. In the range. If the water used at that time is industrially usable water, it can be used. In order to reduce the temperature at the time of precipitation, it is preferred to use pre-cooled water.
The method of mixing the sulfuric acid solution with water is not particularly limited, and if the monoazo pigment is completely precipitated, it may be mixed by any method. For example, a method of injecting a sulfuric acid solution into ice water prepared in advance may be employed, or a device such as a suction device may be used to continuously deposit a sulfuric acid solution or the like in running water to precipitate.
The slurry obtained by the above method is filtered and washed to remove the acidic component, and then dried and pulverized, whereby the pigment composition of the present aspect can be obtained. When the slurry is filtered, the slurry in which the sulfuric acid solution and the water are mixed may be directly filtered, but when the filter property of the slurry is not good, it may be heated and stirred before filtration. Further, after neutralizing the slurry with the base, it may be filtered.
When the pigment is refined by acid gelatinization, a mixture of at least three components of the monoazo pigment, the water-soluble inorganic salt, and the water-soluble solvent is made into a clay shape, and the mixture is vigorously mixed and stirred using a kneader or the like. The mixture was stirred and mixed in water, and stirred into a slurry by a stirrer. This is filtered to remove water-soluble inorganic salts and water-soluble solvents. The above slurrying, filtration, and water washing are repeated to obtain a finely divided organic pigment.
As the water-soluble inorganic salt, sodium chloride, sodium sulfate, potassium chloride or the like can be used. These inorganic salts are used in an amount of 1 time or more, more preferably 20 times or less, in terms of mass ratio. When the mass of the inorganic salt is less than 1 times the mass of the organic pigment, it is difficult to sufficiently refine the pigment. In addition, when the mass of the inorganic salt is greater than 20 times the mass of the organic pigment, after mixing and stirring, in order to remove the water-soluble inorganic salt and the water-soluble solvent, a large amount of labor is required, and at the same time, the amount of the pigment that can be treated at one time is reduced, so that productivity is produced. The point of view is not appropriate.
Since the above-described method for refining the pigment is often accompanied by heat generation during the mixing and stirring, it is preferred to use a water-soluble organic solvent having a boiling point of about 120 to 250 ° C from the viewpoint of safety. Examples thereof include 2-(methoxymethoxy)ethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, ethylene glycol, and diethylene. Alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1 -Methoxy-2-butanol, 1-ethoxy-2-butanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low molecular weight polypropylene glycol, and the like.
When the pigment is refined by the dry grinding method, the monoazo pigment is dry-pulverized by a pulverizer to be finely pulverized. In this method, the pulverization is carried out by collision or rubbing of the pulverizing medium with each other. The apparatus to be used for the dry grinding is not particularly limited, and examples thereof include a dry pulverizing apparatus in which a pulverization medium such as a bead is contained, that is, a ball mill, a grinder, a vibrating mill, and the like. The dry pulverization using these devices may also decompress the inside of the pulverization container as needed, or may be filled with an inert gas such as nitrogen. Further, after the dry milling, the salt milling or the stirring treatment in the solvent may be carried out.
In the method for miniaturizing the above pigments, the monoazo pigments may be used singly or in combination of plural kinds. Further, the monoazo pigment may be used after being dried and pulverized to form a powder, or may be used in the form of a water-containing cake before drying.
Next, the hetero skeleton compounds (each of at least one compound represented by one of the above general formulas (2) to (5)) will be described.
The heterogeneous skeleton compound functions to increase the crystallinity of the monoazo pigment and further improve the dispersion stability.
R ¹ , R ³ , R ⁴ , R ⁶ and R ^{7 in the} general formula (2), and examples of the alkyl group having 20 or less carbon atoms which may have a substituent group include methyl group, ethyl group, propyl group and butyl group. Base, pentyl, hexyl, heptyl, octyl, decyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, secondary butyl, tert-butyl, two A pentyl group, a tertiary pentyl group, a tertiary octyl group, a neopentyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and the like. However, it is not limited to these examples.
R ¹ , R ³ , R ⁴ , R ⁶ and R ^{7 in the} general formula (2), and examples of the alkenyl group having 20 or less carbon atoms which may have a substituent group include a vinyl group, a 1-propenyl group and an allylic group. Base, 1-butenyl, isopropenyl, isobutenyl, 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-octenyl , 1-octadecyl, cyclopentenyl, cyclohexenyl, 1,3-butadienyl, cyclohexadienyl, cyclopentadienyl, trifluorovinyl, 1-chlorovinyl, 2,2-bromovinyl, 4-hydroxy-1-butenyl and the like. However, it is not limited to these examples.
R ¹ , R ³ , R ⁴ , R ⁶ and R ^{7 in the} general formula (2), and examples of the aryl group having 20 or less carbon atoms which may have a substituent group include a phenyl group, a biphenyl group and a fluorenyl group. Tolyl, fluorenyl, p-cyclohexylphenyl, p-cumenyl, m-carboxyphenyl, and the like. However, it is not limited to these examples.
In the general formula (2), R ³ and R ⁴ or R ⁶ and R ^{7 may} be bonded to each other, and the nitrogen atom to be bonded thereto may form a heterocyclic moiety. A part of the carbon atom of the ring atom of the heterocyclic moiety may be replaced by another nitrogen atom, an oxygen atom or a sulfur atom, or a hydrogen atom of a ring atom bonded to the hetero ring moiety may be substituted. The heterocyclic moiety is, for example, a compound obtained by removing one hydrogen atom from hydrazine, benzimidazolidinone or pyrrole. However, it is not limited to these examples.
With respect to R ² , R ⁵ and R ⁸ to R ^{11 in the} general formula (2), examples of the alkylene group having a carbon number of 20 or less which may have a substituent group include a methylene group, a vinyl group, a trimethylene group and a tetraalkyl group. Methylene, propenyl, ethylmethylene, chloromethylene, dimethylmethylene, bis(trifluoromethyl)methylene, and the like. However, it is not limited to these examples.
With respect to R ² , R ⁵ and R ⁸ to R ^{11 in the} general formula (2), examples of the alkenyl group having 20 or less carbon atoms which may have a substituent group include a vinyl group and a 1-methyl group. A propylene group, a 1-butenbutenyl group, a 2-butenbutenyl group, a 1-extenyl group, a 2-pentenyl group, and the like are extended. However, it is not limited to these examples.
With respect to R ² , R ⁵ and R ⁸ to R ¹¹ of the general formula (2), examples of the arylene group having a carbon number of 20 or less which may have a substituent group include an phenyl group, an exophenyl group, and a phenyl group. Phenyl, 4-methyl-1,2-phenylene, 2-methyl-1,4-phenylene, p,p'-biphenylylene, and the like. However, it is not limited to these examples.
R ¹² , R ¹⁵ and R ^{16 in the} general formula (3), and examples of the alkylene group having a carbon number of 20 or less which may have a substituent group include a methylene group, a vinyl group, a trimethylene group, and a tetramethylene group. , propylene, ethylmethylene, chloromethylene, dimethylmethylene, bis(trifluoromethyl)methylene, and the like. However, it is not limited to these examples.
With respect to R ¹² , R ¹⁵ and R ¹⁶ of the general formula (3), examples of the alkenyl group having 20 or less carbon atoms which may have a substituent group include a vinyl group, a 1-methyl group, and a propenyl group. , 1-butenyl group, 2-butenbutenyl group, 1-endopentenyl group, 2-endopentenyl group, and the like. However, it is not limited to these examples.
R ¹² , R ¹⁵ and R ^{16 in the} general formula (3), and an arylene group having a carbon number of 20 or less which may have a substituent group may, for example, be an exophenyl group, an exophenyl group or a paraphenyl group. 4-methyl-1,2-phenylene, 2-methyl-1,4-phenylene, p,p'-biphenylylene, and the like. However, it is not limited to these examples.
R ¹³ and R ^{14 in the} general formula (3), and examples of the alkyl group having 20 or less carbon atoms which may have a substituent group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. , octyl, decyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, secondary butyl, tert-butyl, secondary pentyl, tertiary pentyl, Tertiary octyl, neopentyl, cyclopropyl, cyclobutyl, cyclopentyl and the like. However, it is not limited to these examples.
R ¹³ and R ^{14 in the} general formula (3), and examples of the alkenyl group having 20 or less carbon atoms which may have a substituent group include a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, and a different basis. Propylene, isobutenyl, 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-octenyl, 1-octadecyl, ring Pentenyl, cyclohexenyl, 1,3-butadienyl, cyclohexadienyl, cyclopentadienyl, trifluorovinyl, 1-chlorovinyl, 2,2-bromovinyl, 4 - hydroxy-1-butenyl and the like. However, it is not limited to these examples.
R ¹³ and R ^{14 in the} general formula (3), and examples of the aryl group having a carbon number of 20 or less which may have a substituent group include a phenyl group, a biphenyl group, a fluorenyl group, a tolyl group, a fluorenyl group, and a cyclohexane group. Phenyl, p-cumenyl, m-carboxyphenyl, and the like. However, it is not limited to these examples.
In the general formula (3), R ¹³ and R ¹⁴ are bonded to each other, and a nitrogen atom to be bonded thereto may form a heterocyclic moiety. A part of the carbon atom of the ring atom of the heterocyclic moiety may be replaced by another nitrogen atom, an oxygen atom or a sulfur atom, or a hydrogen atom of a ring atom bonded to the hetero ring moiety may be substituted. The heterocyclic moiety is, for example, a compound obtained by removing one hydrogen atom from hydrazine, benzimidazolidinone or pyrrole. However, it is not limited to these examples.
With respect to R ¹⁷ and R ^{18 in the} general formula (4), examples of the alkylene group having a carbon number of 20 or less which may have a substituent group include a methylene group, a vinyl group, a trimethylene group, a tetramethylene group, and a propenyl group. Ethylmethylene, chloromethylene, dimethylmethylene, bis(trifluoromethyl)methylene, and the like. However, it is not limited to these examples.
With respect to R ¹⁷ and R ¹⁸ of the general formula (4), examples of the alkenyl group having 20 or less carbon atoms which may have a substituent group include a vinyl group, a methyl group, a methyl group, a propenyl group, and a group. A butenyl group, a 2-butenbutenyl group, a 1-pentenylene group, a 2-endopentenyl group, and the like. However, it is not limited to these examples.
With respect to R ¹⁷ and R ¹⁸ of the general formula (4), examples of the arylene group having a carbon number of 20 or less which may have a substituent group include an phenyl group, an exophenyl group, a paraphenyl group, and a 4-methyl group. Base-1, 2-phenylene, 2-methyl-1,4-phenylene, p,p'-biphenylylene, and the like. However, it is not limited to these examples.
In the general formula (5), each of R ¹⁹ and R ²⁰ independently represents one of the following: a hydrogen atom; an alkyl group having a carbon number of 20 or less having a substituent; and an alkyl group having a carbon number of 20 or less having a substituent. And an aryl group having a carbon number of 20 or less which may have a substituent group.
In the general formula (5), Y ⁶ represents -SO ₂ NH-R ²¹ -NR ²² R ²³ -, -CONH-R ²⁴ -NR ²⁵ R ²⁶ -, -SO ₂ NH-R ²⁷ -SO ₃ H,

-CONH-R ²⁸ -SO ₃ H, -SO ₂ NHR ²⁹ -COOH and -CONH-R ³⁰ - one of the COOH. . R ^{twenty one} , R ^{twenty four} And R ²⁷ To R ³⁰ Each of the following independently represents one of: an alkylene group having a carbon number of 20 or less having a substituent; an alkenyl group having a carbon number of 20 or less having a substituent; and a carbon number of 20 or less having a substituent. Arylene. R ^{twenty two} , R ^{twenty three} , R ²⁵ And R ²⁶ Each of the following independently represents a hydrogen atom; an alkyl group having a carbon number of 20 or less having a substituent; an alkenyl group having a carbon number of 20 or less having a substituent; and a carbon number which may have a substituent group of 20 The following aryl groups. R ^{twenty two} With R ^{twenty three} Or R ²⁵ With R ²⁶ Cooperating with each other, forming a heterocyclic moiety together with a nitrogen atom thereof, or a part of a carbon atom of a ring atom of the heterocyclic moiety is replaced by another nitrogen atom, an oxygen atom or a sulfur atom, or is bonded to the heterocyclic moiety The hydrogen atom of the ring atom may be replaced.
The hetero skeleton compound used in this aspect may be exemplified by the compounds shown below. However, the invention is not limited to the examples. These heterologous skeleton compounds may be used singly or in combination of plural kinds.






In the manufacture of the pigment composition of the present aspect, the monoazo pigment and the heterologous skeleton compound may be mixed by any method. The mixing method may, for example, be a method of mixing a previously synthesized monoazo pigment and a heterogeneous skeleton compound in a powder state; a method of mixing the same as a water slurry; and a water slurry of a previously synthesized monoazo pigment; a method of adding a heterogeneous skeleton compound in a powder or solution form; a method of synthesizing a monoazo pigment in the presence of a heterogeneous skeleton compound; and a method of mixing and stirring a pigment composition composed of a monoazo pigment and a heterogeneous skeleton compound by a salt milling method Wait. By any of these methods, a pigment composition having good dispersibility and crystal stability can be obtained.
In the pigment composition of the present aspect, the content of the heterogeneous skeleton compound is preferably in the range of 0.1 to 40 mol% in the total amount of the monoazo pigment and the heterologous skeleton compound. The ratio is more preferably from 0.3 to 30 mol%, and further preferably from 0.5 to 20 mol%. When the ratio is less than 0.1 mol%, the dispersion stability and crystal stability of the obtained pigment composition may be insufficient. On the other hand, when the ratio exceeds 40 mol%, the effect of dispersing stability or the effect of crystal stabilization accompanying an increase in the amount of addition is not obtained, and since the content of the monoazo pigment is lowered, the coloring power may be lowered.
The method for producing the pigment composition of the present aspect is preferably the method of the above exemplified method: a method for synthesizing a monoazo pigment in the presence of a heterogeneous skeleton compound; and obtaining the monoazo pigment by synthesizing a monoazo pigment in a liquid phase. a slurry, a method of adding a heterogeneous skeleton compound; or a method of mixing and stirring a pigment composition composed of a monoazo pigment and a heterogeneous skeleton compound by a salt milling method. Among these methods, a method of synthesizing a monoazo pigment in the presence of a heterogeneous skeleton compound, and a slurry obtained by synthesizing a monoazo pigment in a liquid phase, and a method of adding a heterogeneous skeleton compound are preferred. When the pigment composition is produced by these methods, a pigment composition in which the heterogeneous skeleton compound is uniformly distributed can be obtained. Therefore, good dispersibility and crystal stability can be achieved regardless of the use, and high coloring power or transparency can be achieved.
When synthesizing a monoazo pigment in the presence of a heterogeneous skeleton compound, for example, a heterologous skeleton compound is added to one or more of a base component, a coupling component, and a buffer aqueous solution having a pH of 3 to 6, and the above-exemplified synthesis sheet may be used. The method of the azo pigment produces the pigment composition in the same manner.
In the slurry obtained by synthesizing a monoazo pigment in a liquid phase, when a heterogeneous skeleton compound is added, a slurry containing a monoazo pigment is prepared by the above-described method for synthesizing a monoazo pigment, and a heterogeneous skeleton compound is added before filtration. Thereby, a pigment composition can be produced.
The pigment composition obtained in this aspect may be produced by one of the above methods or may be produced by combining a plurality of methods. Further, the pigment composition prepared by the above method may be further refined by a method such as acid gelatinization, salt milling or dry milling to obtain a desired particle size, and then used. The method at that time can be carried out in the same manner as in the case of the above monoazo pigment.
Further, in any of the above methods, the pigment composition of the present aspect may be added with a resin, a surfactant, or the like as needed. These additives can also be used at any stage of the preparation of the pigment composition. For example, the additives are used in the stage of synthesizing a pigment composition, together with an aromatic amine or an acetamidine compound, or when performing acid gelatinization, salt milling, dry milling, or the like.
The type of the resin to be used at that time is not particularly limited, and examples thereof include a rosin-based resin, an acrylic resin, a styrene-acrylic resin, a polyester resin, a polyester resin, a polyamide resin, and a polyurethane resin. A fluorine resin, a vinyl naphthalene-acrylic resin, a styrene-maleic acid resin, or the like. These resins may be used singly or in combination of plural kinds. Further, these may be used in the range of, for example, 0.1 to 30% by weight, more preferably 1 to 15% by weight, based on the pigment composition.
The kind of the surfactant to be used in the case of using the pigment composition is not particularly limited, and examples thereof include a fatty acid salt, an alkyl sulfate salt, an alkylarylsulfonate, an alkylnaphthalenesulfonate, a dialkylsulfonate, and two. Alkyl sulfosuccinate, alkyl diaryl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalenesulfonic acid formalin condensate , polyoxyethylene alkyl phosphate salt, propylene glycol boron fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block polymer, Sorbitol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene alkylamine, fluorine-based nonionic surfactant, hydrazine The base is a nonionic surfactant, an alkylammonium salt, a quaternary ammonium salt, an alkylpyridinium salt, an alkylimidazolium salt or the like. These surfactants may be used singly or in combination of plural kinds. Further, these may be used in the range of, for example, 0.1 to 30% by weight, more preferably 1 to 15%, for the pigment composition.
The pigment composition prepared by the above method has an average particle diameter of preferably 200 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less. When the average primary particle diameter exceeds 200 nm, the coloring power may be deteriorated in some applications, and sediment may be generated during storage of the dispersion or ink, which is not preferable.
In this aspect, the average primary particle diameter of the pigment composition can be measured using a scanning electron microscope or a transmission electron microscope. The average primary particle diameter of the present specification is a photograph of pigment particles by a scanning electron microscope or a transmission electron microscope, and the particle diameters of the respective primary particles constituting the aggregate are measured. At that time, the maximum particle diameter is set as the primary particle diameter of the particles for each particle. The measurement was carried out for 100 particles encompassed in the same field of view, and the average value obtained was set as the average primary particle diameter.
In the pigment composition of the present aspect, the relative conductivity of the aqueous solution extracted by boiling the pigment composition with ion-exchanged water is preferably less than 200 mS/cm, more preferably less than 150 mS/cm, and further preferably less than 100 mS/cm. The relative conductivity is an index for measuring the content of ionic impurities contained in the pigment composition. In general, the ionic impurities contained in the pigment composition are known to have an effect on the dispersion stability and are preferably reduced as much as possible.
In the method for reducing the ionic impurities contained in the pigment composition, the relative conductivity of the aqueous solution extracted by boiling the pigment composition with ion-exchanged water may be in the above range, and is not particularly limited, and examples thereof include The method of repeating filtration and washing after the preparation of the pigment composition. The type of water to be used at that time is not particularly limited, and it is preferably a substance containing no ionic impurities such as distilled water or ion-exchanged water.
Further, in the pigment composition of the present aspect, the total content of calcium, magnesium and iron is preferably less than 300 ppm, more preferably less than 200 ppm, and further preferably less than 150 ppm. Further, the content of each of the above metal elements is preferably less than 150 ppm, more preferably less than 100 ppm, and still more preferably less than 80 ppm. When the total content of calcium, magnesium, and iron is 300 ppm or more, or when the content of each metal element is 150 ppm or more, when the pigment composition is used for inkjet ink, the ink flow path of the printer or the nozzle portion of the head may be Insoluble matter is generated and becomes a cause of nozzle clogging, which is not preferable.
As a method for measuring the contents of calcium, magnesium and iron, various methods are known, and for example, a solution obtained by adding nitric acid to a pigment composition and decomposing it by microwave is diluted to an appropriate concentration, and an inductively coupled plasma luminescence analysis is used. (ICP) to determine the method.
The method for reducing the content of calcium, magnesium, and iron contained in the pigment composition is not particularly limited, and examples thereof include a method in which a pigment composition is prepared, and then slurryed in an acidic aqueous solution to repeat filtration and washing. The type of the acid to be used at that time is not particularly limited, and examples thereof include sulfuric acid, hydrochloric acid, and acetic acid. Further, the type of water used for the washing is not particularly limited, and is preferably a material containing no ionic impurities such as distilled water or ion-exchanged water.
The pigment dispersion system of the present aspect contains the pigment composition of the present aspect and a liquid medium, which comprises any one of the following: an aqueous pigment dispersion in which the pigment composition of the aspect is dispersed in an aqueous medium; and the pigment composition of the aspect An oily pigment dispersion in which the substance is dispersed in an organic solvent.
The aqueous pigment dispersion system can be prepared by dispersing a mixture of the pigment composition, the aqueous medium, the resin, the surfactant, and the like in the present embodiment as a dispersion treatment. Further, if necessary, an additive may be added to the above-mentioned raw materials to carry out dispersion treatment. When the aqueous pigment dispersion is prepared, the order of addition or the method of addition of each raw material is not particularly limited.
In the case of the aqueous pigment dispersion, the content of the pigment composition is not particularly limited, and is preferably in the range of 5 to 50% by weight, particularly preferably 10 to 40% by weight.
The type or content of the aqueous medium used for producing the aqueous pigment dispersion is not particularly limited, and ion-exchanged water or distilled water from which metal ions or the like are removed is preferably used. The aqueous medium is preferably present in an amount of from 30 to 95% by weight of the aqueous pigment dispersion.
Further, as the aqueous medium, water and a water-soluble solvent may be mixed as needed. The water-soluble solvent is not particularly limited, and examples thereof include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, alcohol ketone, and diethylene glycol. Monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, 1,2-hexanediol, N-methyl-2-oxazolone, substituted oxalidone, 2,4,6-hexyl Triol, tetrafuranol, 4-methoxy-4-methylpentanone, and the like. These may be used singly or in combination of plural kinds. When such a water-soluble solvent is used, the water-soluble solvent is preferably contained in an amount of from 1 to 50% by weight based on the aqueous pigment dispersion.
The resin used for the production of the water-based pigment is not particularly limited as long as it can disperse the pigment composition in an aqueous medium, and for example, a resin which can be used as a pigment composition can be used. These resins may be used singly or in combination of plural kinds. Further, the amount thereof to be used is not particularly limited, and is preferably from 0.5 to 30% by weight, more preferably from 1 to 20% by weight, based on the aqueous pigment dispersion.
Further, the surfactant used for the production of the aqueous pigment dispersion is not particularly limited as long as it can disperse the pigment composition in the aqueous medium, and for example, when the pigment composition is produced, it can be used as an example. A surfactant that can be used. The surfactants may be used singly or in combination of plural kinds. Further, the amount thereof to be used is not particularly limited, and is preferably from 0.5 to 30% by weight, more preferably from 1 to 20% by weight, based on the aqueous pigment dispersion.
Further, when an aqueous pigment dispersion is produced, an additive such as an antifungal agent, a pH adjuster, or an antifoaming agent may be used as needed.
The antifungal agent is used to prevent mildew in the aqueous pigment dispersion. The type of the fungicide is not particularly limited, and examples thereof include sodium dehydroacetate, sodium benzoate, sodium pyridine sulfate-1-oxide, zinc pyridine sulfate-1-oxide, and 1,2-benzisothiazoline. An ammonium salt such as 3-ketone or 1-benzisothiazolin-3-one. These are preferably used in the range of 0.05 to 2% by weight of the aqueous pigment dispersion.
The pH adjuster is used to adjust the pH of the aqueous pigment dispersion to a desired value. The type of the pH adjuster is not particularly limited, and examples thereof include an amine, an inorganic base, ammonia, a buffer, and the like.
Antifoaming agents are used to prevent foaming in the production of aqueous pigments. The kind of the antifoaming agent is not particularly limited, and any commercially available antifoaming agent can be used. For example, Surfynol 104A, Surfynol 104E, Surfynol 104H, Surfynol 104BC, Surfynol 104DPM, Surfynol 104PA, Surfynol 104PG-50, Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485, Surfynol PSA-336 (all Air Products and Chemical) Company system) and so on.
The oily pigment dispersion system can be prepared by dispersing a mixture of a pigment composition, an organic solvent, a dispersant or the like in the present embodiment as a dispersion treatment. Further, if necessary, an additive may be added to the above-mentioned raw materials to carry out dispersion treatment. When the oily pigment dispersion is prepared, the order of addition or the method of addition of each raw material is not particularly limited.
In the case of the oily pigment dispersion, the content of the pigment composition is not particularly limited, and is preferably in the range of 5 to 50% by weight, particularly preferably 10 to 40% by weight.
The type or content of the organic solvent used to produce the oily pigment dispersion is not particularly limited. Examples thereof include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol; acetone, methyl ethyl ketone, methyl n-propanone, methyl isopropanone, and methyl group. Butanone, methyl isobutyl ketone, methyl n-pentanone, diethyl ketone, ethyl n-acetone, ethyl isopropanone, ethyl n-butanone, ethyl isobutyl ketone, di-n-acetone, diisobutyl ketone , ketones such as cyclohexanone, methylcyclohexanone, isophorone; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, acetic acid Ester such as octyl, methyl lactate, lactate propyl, and butyl acetate; alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol; ethylene glycol monomethyl ether and ethylene glycol Monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol single Propyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropyl Glycol ethers such as alcohol monoethyl ether, dipropylene glycol dipropyl ether, and tripropylene glycol monomethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol Monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol single a diol acetate such as butyl ether acetate or dipropylene glycol monomethyl ether acetate; a saturated hydrocarbon such as n-hexane, isohexane, n-decane, isodecane, dodecane or isododecane; Unsaturated hydrocarbons such as alkene, 1-heptene, and 1-octene; cyclic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, cyclododecane, and decahydronaphthalene; cyclohexene, a cyclic unsaturated hydrocarbon such as cycloheptene, cyclooctene, 1,3,5,7-cyclooctenetetraene or cyclododecene; an aromatic hydrocarbon such as benzene, toluene or xylene; and the like. The organic solvent is preferably contained in an amount of from 30 to 95% by weight based on the oil pigment dispersion. These may be used singly or in combination of plural kinds.
The dispersing agent used for the production of the oily pigment dispersion is not particularly limited, and examples thereof include a carboxylic acid ester containing a hydroxyl group, a salt of a long-chain polyamine guanamine and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, and a long a salt of a polyamine amide and a polar acid ester, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyacrylate, a condensate or a salt of a polyallylamine and a polyester having a free carboxylic acid, and a poly Ether ester type anionic surfactant, salt of naphthalene carboxylic acid famarin condensate, salt of aromatic carboxylic acid formalin condensate, polyoxyethylene alkyl phosphate, polyoxyethylene alkyl phenyl ether, stearylamine Acetate and the like. These may be used singly or in combination of plural kinds. The amount of use is not particularly limited and is preferably from 0.5 to 30% by weight, more preferably from 1 to 20% by weight, based on the oil pigment dispersion.
The dispersing machine for producing the pigment dispersion of the present aspect is not particularly limited, and examples thereof include a horizontal type sand mixer, an upright type sand mixer, a ring ball mill, a grinder, a micro jet homogenizer, a high speed mixer, and homogenization. Machines, homogenizers, ball mills, ink shakers, roll mills, ballast mills, ultrasonic dispersers, etc., can use all dispersers or mixers commonly used to make dispersions.
Further, before dispersion by a dispersing machine, pre-dispersion using an ink mixer such as a kneader or a three-roll mill, or solid dispersion such as a two-roll mill may be performed. Further, after dispersing in a dispersing machine, the step of preserving after being kept at a temperature of 30 to 80 ° C for several hours to one week, or post-treatment by using an ultrasonic disperser or a conflict-type beadless disperser It is effective for imparting dispersion stability to pigment dispersions. Further, after dispersing in a dispersing machine, the treatment may be carried out by a centrifugal separator. This treatment is effective for removing coarse particles contained in the pigment dispersion.
The inkjet ink of this aspect contains the pigment dispersion of the present aspect, and includes both an aqueous inkjet ink using the above aqueous pigment dispersion and an oily inkjet ink using the above oily pigment dispersion.
The aqueous inkjet ink according to this aspect can be produced by uniformly mixing an aqueous medium, a resin, a surfactant, other additives, or the like by the aqueous pigment dispersion.
In the aqueous inkjet ink of the present aspect, the content of the pigment composition is not particularly limited, and is preferably from 1 to 10% by weight, more preferably from 2 to 7% by weight, based on the aqueous inkjet ink.
The type or content of the aqueous medium used for producing the aqueous inkjet ink is not particularly limited, and ion-exchanged water or distilled water from which metal ions or the like are removed is preferably used. The aqueous medium is preferably present in an amount of from 60 to 99% by weight of the aqueous pigment dispersion.
Further, as the aqueous medium, in order to prevent drying and solidification of the ink in the nozzle portion of the printer head, it is possible to use a water-soluble solvent as needed for stable discharge. The type of the water-soluble solvent is not particularly limited, and examples thereof include a water-soluble solvent which can be used in the production of an aqueous pigment dispersion. These may be used singly or in combination of plural kinds. When such a water-soluble solvent is used, the water-soluble solvent is preferably contained in an amount of from 1 to 50% by weight based on the aqueous inkjet ink.
When the aqueous inkjet ink of this aspect is prepared, a resin may be used to impart fixability to the printed matter of the pigment composition. The type of the resin is not particularly limited, and examples thereof include a resin which can be used in the production of the aqueous pigment dispersion, or an oil-in-water emulsion thereof. Among these, when the oil-in-water emulsion is used, it is preferable to obtain a low-viscosity aqueous inkjet ink and a recording material having good water resistance. These resins may be used singly or in combination of plural kinds. The resin is preferably contained in an amount of from 0.5 to 10% by weight, more preferably from 1 to 5% by weight, based on the aqueous inkjet ink. When the content is less than 0.5%, the effect of fixing the pigment composition is insufficient. When the content is more than 15%, the ink viscosity may increase or the discharge stability may be lowered, which is not preferable. These resins can be used by neutralizing an acidic functional group with a pH adjuster such as ammonia, an amine or an inorganic base as needed.
When the aqueous inkjet ink of this aspect is prepared, in order to impart dispersion stability to the pigment composition in the ink, a surfactant may be used as needed. The type of the surfactant is not particularly limited, and examples thereof include a surfactant which can be used in the production of an aqueous pigment dispersion. The surfactant is preferably contained in an amount of from 0.5 to 10% by weight, more preferably from 1 to 5% by weight, based on the aqueous inkjet ink.
When the aqueous inkjet ink of this aspect is produced, a drying accelerator, a penetrating agent, an antifungal agent, a chelating agent, a pH adjuster, or the like can be used as the other additive.
The drying accelerator can be used for accelerating drying when printing aqueous inkjet inks. The type of the drying accelerator is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, and isopropyl alcohol. These may be used singly or in combination of plural kinds. Further, the content is preferably from 1 to 50% by weight of the aqueous inkjet ink.
Further, when the printed object is a permeable substrate such as paper, a penetrating agent can be used in order to promote the penetration of the ink into the substrate and accelerate the drying of the surface. Examples of the penetrating agent include water-soluble solvents such as diethylene glycol monobutyl ether, alkene glycol, and alkylene glycol, or polyethylene glycol lauryl ether, sodium lauryl sulfate, and dodecylbenzene. A surfactant such as sodium sulfonate, sodium oleate or sodium di-(2-ethylalkyl)-sulfosuccinate. If the amount of use is 5% by weight or less of the aqueous inkjet ink, a sufficient effect is obtained. If the amount is more than this amount, the viscosity of the ink is increased, or ink bleed or paper is detached, which is not preferable.
The antifungal agent can be used to prevent mildew in the aqueous inkjet ink. The type of the antifungal agent is not particularly limited, and examples thereof include an antifungal agent which can be used in the production of an aqueous pigment dispersion. These are preferably used in the range of 0.05 to 1.0% by weight of the aqueous inkjet ink.
The chelating agent can be used to prevent metal ions contained in the aqueous inkjet ink from being precipitated in the nozzle portion of the printer head or in the ink. The type of the chelating agent is not particularly limited, and examples thereof include ethylene diamine tetraacetic acid, sodium salt of ethylene diamine tetraacetic acid, diammonium salt of ethylene diamine tetraacetic acid, and tetraammonium salt of ethylene diamine tetraacetic acid. These are preferably used in the range of 0.005 to 0.5% by weight of the aqueous inkjet ink.
Further, in order to adjust the pH of the aqueous inkjet ink to a desired value, a pH adjuster can be used. The type of the pH adjuster is not particularly limited, and examples thereof include a pH adjuster which can be used in the production of an aqueous pigment dispersion.
The oil-based inkjet ink according to this aspect can be produced by uniformly mixing an organic solvent, a resin, a dispersant, or other additives by adding the above-mentioned oily pigment dispersion.
In the oil-based inkjet ink of the present aspect, the content of the pigment composition is not particularly limited, and is preferably from 1 to 10% by weight, and more preferably from 2 to 7% by weight, based on the oil-based inkjet ink.
The kind of the organic solvent used for the production of the oil-based inkjet ink is not particularly limited, and for example, an organic solvent which can be used in the production of the oil-based pigment dispersion can be used. The content of the organic solvent is not particularly limited and is preferably from 80 to 97% by weight of the oil-based inkjet ink. These organic solvents may be used singly or in combination of plural kinds.
When the oily inkjet ink of this aspect is produced, a resin can be used to impart fixability of the pigment composition to the printed matter. The type of the resin is not particularly limited, and examples thereof include petroleum resin, casein, shellac, rosin resin, rosin ester resin, cellulose resin, natural rubber, synthetic rubber, cyclized rubber, chlorinated rubber, and oxidized rubber. , hydrochloric acid rubber, phenol resin, terpineol phenol resin, alkyd resin, polyester resin, unsaturated polyester resin, amine resin, epoxy resin, vinyl resin, polychlorinated resin, polyallylamine resin, chlorine Vinyl-vinyl acetate resin, styrene-vinyl acetate resin, vinyl chloride resin, acrylic resin, methacrylic resin, urethane resin, sulfhydryl resin, fluororesin, drying oil, synthetic dryness Oil, maleic acid resin, polyamide resin, polyimide resin, benzoguanamine resin, melamine resin, urea resin, butyral resin, benzofuran-indene resin, xylene resin, anti-butene Diacid resin, polyolefin, chlorinated polypropylene, wax-latex resin, styrene-acrylic resin, styrene-maleic acid resin, and the like. These may be used singly or in combination of plural kinds. The amount of use is not particularly limited and is preferably from 1 to 15% by weight, and more preferably from 3 to 8% by weight, of the oil-based inkjet ink.
When the oil-based inkjet ink of this aspect is prepared, in order to impart dispersion stability to the pigment composition in the ink, a dispersing agent may be used as needed. The type of the dispersant is not particularly limited, and examples thereof include a dispersant which can be used in the production of an oil pigment dispersion. These may be used singly or in combination of plural kinds. The amount of use is not particularly limited and is preferably from 0.1 to 15% by weight, and more preferably from 0.5 to 10% by weight, based on the oil-based inkjet ink.
The oily inkjet ink of this aspect may further comprise an additive. Examples of the additive include a wetting agent, a deaerator/defoaming agent, a preservative, and an antioxidant.
When the inkjet ink is prepared by mixing the above raw materials, the method of mixing the raw materials is not particularly limited, and a high-speed disperser, an emulsifier, or the like may be used in addition to a stirrer generally using a blade. At this time, the order of addition or the mixing method of the raw materials is not particularly limited.
Further, by filtering and mixing the inkjet ink prepared by mixing the respective raw materials with a filter, coarse particles contained in the ink can be removed. The filter pore size used at that time should be 1 μm or less, and more preferably 0.65 μm or less.
The colored resin composition of the present aspect contains the pigment composition of the present aspect, a binder resin, and, if necessary, a charge control agent and a release agent to be described later, and can be used as, for example, a toner for electronic photographs. The colored resin composition of the present aspect can be sufficiently mixed with the pigment composition and the binder resin of the present aspect by a mixer, and then melt-mixed and stirred by a hot mixing mixer to be cooled and solidified.
The toner for electronic photographs (hereinafter, simply referred to as carbon powder for electronic photographs) can be produced by a conventionally known production method such as a pulverization method or a polymerization method. In the production example of the pulverization method, the colored resin composition is coarsely pulverized by a pulverizer, and if necessary, it is mixed with an additive other than the one described later, and then finely pulverized and classified.
Further, the production method of the polymerization method is carried out in a monomer, and a pigment composition, a polymerization initiator, and an additive as needed are dissolved or dispersed to prepare an oil phase. The oil phase is mixed with an aqueous phase containing a dispersant or the like to form an oil droplet, and a radical polymerization reaction is promoted, followed by washing, drying, and mixing with an external additive to produce a carbon powder. When the carbon powder of this aspect is produced by a polymerization method, it can be produced by a conventional method such as a suspension polymerization method, an emulsion polymerization method, a dissolution suspension method, or an ester elongation polymerization method. Further, when the carbon powder is produced by the above polymerization method, the colored resin composition can be used as a raw material and processed.
The binder resin used for producing the colored resin composition and the carbon powder of the present invention is not particularly limited, and examples thereof include a styrene-p-chlorostyrene copolymer, a styrene-vinyltoluene copolymer, and a styrene-vinyl group. Naphthalene copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-a-chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl Ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-茚Copolymer, polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, vinyl acetate, sulfhydryl resin, polyester resin, polyurethane , furan resin, epoxy resin, xylene resin, polyvinyl butyral resin, terpene resin, benzofuran-indene resin, petroleum resin, and the like. Among them, a polyester resin or a styrene copolymer is particularly preferably used. Among the above-mentioned binder resins, the pigment composition of the present aspect is particularly preferable for the polyester resin, and the pigment composition is uniformly and finely dispersed in the binder resin, which is suitable.
Examples of the alcohol component constituting the polyester resin include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, and 2,3-butanediol. , 1,4-butenediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3- Hexanediol, bisphenol A, hydrogenated bisphenol A, 1,4-bis(hydroxymethyl)cyclohexane, diols such as bisphenol derivatives represented by the following general formula (9), glycerol , polyglycerols such as diglycerol, sorbitol, sorbitan, tributol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol These are used alone or in combination of plurals.

(where, R ^A In the case of ethylene or propylene, x and y are each an integer of 1 or more, and x + y is 2 to 10. )
Examples of the divalent carboxylic acid as the acid component constituting the polyester resin include an aromatic dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid or phthalic anhydride or an anhydride thereof; An aliphatic dicarboxylic acid such as a diacid, azelaic acid or sebacic acid or an anhydride thereof; or a succinic acid or an anhydride thereof substituted with an alkyl group having 16 to 18 carbon atoms; fumaric acid, maleic acid An aliphatic unsaturated dicarboxylic acid such as diacid, methyl maleic acid or itaconic acid or an anhydride thereof. Examples of the trivalent or higher carboxylic acid which is effective as a bridging component include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, butanetricarboxylic acid, hexanetricarboxylic acid, diphenylketonetetracarboxylic acid, and tetrakis (sub. Carboxyl) methane, octylenetetracarboxylic acid, diphenyl ketone tetracarboxylic acid or anhydride thereof. These may be used singly or in combination of plural kinds.
The polyester resin may be a homopolyester or a copolyester synthesized from the above-described alcohol component and acid component, or may be used in combination of two or more kinds.
Further, from the viewpoint of offset resistance and low-temperature fixability, the molecular weight of the polyester resin measured by a gel permeation chromatography (GPC) preferably has a weight average molecular weight (Mw) of 5,000 or more. It should be 10,000 to 1,000,000. The weight average molecular weight (Mw) is more preferably in the range of 20,000 to 100,000. When the weight average molecular weight of the polyester resin is small, the offset resistance of the carbon powder tends to decrease, and if the weight average molecular weight is increased, the fixability tends to decrease, which is not preferable.
Further, the acid value of the polyester resin is preferably from 10 to 60 mgKOH/g, more preferably from 15 to 55 mgKOH/g. When the acid value is less than 10 mgKOH/g, the release agent is not suitable. On the other hand, when the acid value exceeds 60 mgKOH/g, the hydrophilicity of the resin becomes large, and the image density is lowered in a high humidity environment, which is not preferable.
The hydroxyl value of the polyester resin is preferably 20 mgKOH/g or less, more preferably 15 mgKOH/g or less. When the hydroxyl value exceeds 20 mgKOH/g, the hydrophilicity becomes large, and in a high humidity environment, the image density is lowered, which is not preferable.
Further, from the viewpoint of preventing the coagulation of the carbon powder, the glass transition temperature (Tg) of the polyester resin measured by a differential scanning calorimeter (device: DSC-6, manufactured by Shimadzu Corporation) is preferably 50 to 70 ° C, more preferably 50 to 65 ° C.
The carbon powder of this aspect can be added with a charge control agent as needed. By using a charge control agent, a toner having a stable charge can be obtained. The carbon powder of this aspect can be used as a charge control agent using any of the conventional positive or negative charge control agents.
When the carbon powder of the present aspect is a positively charged toner, examples of the positive charge control agent used include an anilic black dye, a triphenylmethane dye, an organotin peroxide, a quaternary ammonium compound, and The quaternary ammonium salt is a styrene ‧ acrylic polymer copolymerized with a styrene ‧ acrylic resin as a functional group, and among them, a quaternary ammonium salt compound is particularly preferable.
The quaternary ammonium salt compound which can be used in this aspect may be a salt-forming compound composed of a quaternary ammonium salt and an organic sulfonic acid or molybdic acid. Naphthalenesulfonic acid is preferably used as the organic sulfonic acid
Further, examples of the negative charge control agent used in the case of the negatively charged toner include a metal complex of a monoazo pigment, and a styrene/acrylic acid copolymerized with a styrene/acrylic resin using a sulfonic acid as a functional group. A polymer, a metal salt compound of an aromatic hydroxycarboxylic acid, a metal complex of an aromatic hydroxycarboxylic acid, a phenolic complex, an oxime compound, or the like. The aromatic hydroxycarboxylic acid is preferably salicylic acid, 3,5-di-tributylbutyl sulphate, 3-hydroxy-2-naphthoic acid or 3-phenylsulphonic acid. Further, examples of the metal used for the metal salt compound include zinc, calcium, magnesium, chromium, aluminum, and the like.
Further, a release agent can be used for the toner of the present aspect. Examples of the release agent include natural ester waxes such as a hydrocarbon wax such as a polypropylene wax, a polyethylene wax, and a Fischer-Tropsch wax, a synthetic ester wax, a palm wax, and a rice bran wax.
In the toner of this aspect, an external additive such as a lubricant, a fluidizer, an abrasive, a conductivity imparting agent, or an image peeling inhibitor may be used as needed. As the external additive, a conventional external additive used in the conventional production of carbon powder can be used. Examples of such external additives are as follows. Examples of the slip agent include polydifluoroethylene and zinc stearate. Examples of the fluidizing agent include telluride, alumina, titania, yttrium aluminum co-oxide, and niobium titanium produced by a dry method or a wet method. Co-oxides, such hydrophobized materials, and the like. In addition, examples of the polishing agent include cerium nitride, cerium oxide, cerium carbide, barium titanate, tungsten carbon, calcium carbonate, and the like, and the like. The conductivity imparting agent may, for example, be tin oxide.
As the fluidizing agent used in the carbon powder of the present aspect, it is preferable to use a yttrium aluminum co-oxide or a niobium-titanium co-oxide fine powder as the above-exemplified. The hydrophobization treatment of the fine powders may be carried out by using a decane coupling agent such as eucalyptus oil or tetramethyldiazide nitrogen, dimethyldichlorodecane or dimethyldimethoxydecane.
The toner of this aspect can also be used as a one-component developer, or can be used as a two-component developer by mixing with a carrier. The two-component developer can also be used in any of the conventional ones. Examples thereof include magnetic powders such as iron powder, ferrite powder, and nickel powder, and those treated with a resin or the like. The resin covering the surface of the carrier may, for example, be a styrene-acrylate copolymer, a styrene-methacrylate copolymer, an acrylate copolymer, a methacrylate copolymer, a fluorine-containing resin, a ruthenium-containing resin, or a polyamide resin. , ionomer resin, polyphenylene sulfide resin, etc., or a mixture thereof. Among these, a ruthenium-containing resin is particularly preferred because it forms less waste toner. The weight average particle diameter of the carriers is preferably in the range of from 30 to 100 mm.
In the case of producing the colored resin composition of the present aspect, any mixer conventionally known, such as a Henschel mixer or a high-speed mixer, may be used as the mixer for mixing the raw materials. Further, the kneader used for melt mixing, stirring, and the like may be a batch kneader such as a heating kneader or a Bamburi mixer, or a continuous mixing agitator such as a single-shaft or a biaxial extruder.
When the colored resin composition is produced, the temperature of the melt-mixing and stirring raw material is preferably from 100 to 200 ° C, more preferably from 120 to 180 ° C. When the temperature is less than 100 ° C, the dispersion of the pigment and/or the pigment composition is insufficient, and when it exceeds 200 ° C, the binder resin is thermally deteriorated, which is not preferable.
The charge control agent may be used by mixing with the raw material in the melt-mixing and stirring step, or after mixing the colored resin composition, or mixing, and then melting and mixing and using the mixture. Among them, when used in the melt-mixing and stirring step, the charge controlling agent can be uniformly dispersed in the colored resin composition, which is more preferable.
Further, the mold release agent may be used by mixing with a raw material in the melt-mixing and stirring step, or after mixing the colored resin composition, or after mixing, and then mixing and stirring the mixture to be used. Among them, when used in the melt-mixing and stirring step, a toner having a high durability can be obtained, which is more preferable.
The details of the present invention are explained in detail below by way of examples, but the invention is not limited to the embodiments. Further, the adhesive resins used in Examples 79 to 90 and Comparative Examples 15 to 18 were as follows.
<bonding resin>
Thermoplastic polyester resin
A polyester resin composed of terephthalic acid, isophthalic acid, isophthalic acid, or propylene oxide added with bisphenol A or ethylene glycol.
Acid value: 10 mgKOH/g, hydroxyl value: 43 mgKOH/g, Tg: 58 °C
MMW: 28200, Mn: 2500
<Preparation of monoazo pigments and pigment compositions>
Manufacturing example 1 <Preparation of monoazo pigment A-01 (CI Pigment Yellow 74)>
67.3 g of 2-methoxy-4-nitroaniline was added to 500 g of water as a diazo component, and the suspension was stirred to prepare a suspension, and ice was further added thereto to adjust the temperature to 5 ° C or lower. 105 g of 35% hydrochloric acid was added thereto, and the mixture was stirred at 5 ° C or lower for 1 hour. Thereafter, an aqueous solution obtained by dissolving 28.0 g of sodium nitrite in 72.0 g of water was added, and the mixture was stirred for 1 hour to carry out diazotization. To the reaction mixture, 0.5 g of sulfamic acid was added to make nitrous acid disappear, and a diazo aqueous solution was prepared.
Further, as a couplant component, 84.5 g of o-acetamidine methoxyaniline and 164 g of a 25% aqueous sodium hydroxide solution were added to 140 g of water, and the mixture was stirred to completely dissolve. This was poured into an aqueous solution in which 82.2 g of 80% acetic acid and 420 g of water were mixed to prepare a couplant slurry.
The above prepared couplant slurry was heated to 40 ° C, and an aqueous solution of diazo was dropped therein over 1 hour. After the completion of the dropwise addition, the temperature was maintained at this temperature for 1 hour to complete the reaction. After the reaction was completed, the slurry was heated to 90 ° C and stirred for 1 hour. Thereafter, the mixture was filtered through a Büchner funnel having a diameter of 285 mm, and washed with 25 liters of ion-exchanged water, dried, and pulverized to obtain 147 g of monoazo pigment A-01 (CI Pigment Yellow 74).
Manufacturing Example 2 <Preparation of monoazo pigment A-02 (CI Pigment Yellow 3)>
In Production Example 1, 67.3 g of 2-methoxy-4-nitroaniline used as a diazo component was changed to 69.0 g of 4-chloro-2-nitroaniline, and the adjacent B was used as a coupling agent component. A single azo pigment A-02 (CI Pigment Yellow) 150 g was obtained in the same manner as in Example 1 except that 84.5 g of methoxyacetanilide was changed to 86.3 g of o-chloroacetamidine.
Manufacturing Example 3 <Preparation of monoazo pigment A-03 (CI Pigment Yellow 49)>
In Production Example 1, 67.3 g of 2-methoxy-4-nitroaniline used as a diazo component was changed to 56.6 g of 4-chloro-2-nitroaniline, and the adjacent B was used as a coupling agent component. The monoazo pigment A was obtained in the same manner as in Example 1 except that 84.5 g of methoxyacetanilide was changed to 110.9 g of 4'-chloro-2'5'-dimethoxyacetamidine anilide. 03 (CI Pigment Yellow 49) 161 g.
Manufacturing Example 4 <Preparation of monoazo pigment A-04 (CI Pigment Yellow 111)>
In Production Example 1, 84.5 g of o-acetamidine methoxyaniline used as a couplant component was changed to 98.6 g of 5'-chloro-2'-methoxyacetamidine anilide, and otherwise In the same manner as in Example 1, 160 g of monoazo pigment A-04 (CI Pigment Yellow 111) was obtained.
Manufacturing Example 5 <Preparation of monoazo pigment A-05 (CI Pigment Yellow 120)>
In Production Example 1, 67.3 g of 2-methoxy-4-nitroaniline used as a diazo component was changed to 83.7 g of 5-aminoisophthalic acid dimethyl, and used as a coupling agent component. A single azo pigment A-05 (CI) was obtained in the same manner as in Example 1 except that 84.5 g of o-acetamethylene methoxyaniline was changed to 95.1 g of 5-acetoxime-2-benzimidazolone. Pigment Yellow 120) 172g.
Manufacturing Example 6 <Modulation of heterogeneous skeleton compound D-02>
The reaction of acetamidine with cyanuric chloride is carried out in an equivalent molar amount, followed by hydrolysis of the equivalent molar N,N-dibutylaminopropylamine to obtain a compound represented by the following formula. D-01.

Next, the indole-2-carboxylic acid was chlorinated with a sulfonium chloride group according to a usual method to obtain 27.0 g of indole-2-carboxychloride, which was obtained from the compound D- obtained in Production Example 6. 01. 300 g of methanol was mixed and heated under reflux for 3 hours.
After completion of the reaction, 1500 g of water and 8 g of sodium hydroxide were added, and the mixture was filtered, washed with water, and dried to obtain 58.0 g of compound D-02 represented by the following formula.
Compound D-02:

Example 1 <Preparation of Pigment Composition P-01>
63.9 g of 2-methoxy-4-nitroaniline was added to 500 g of water as a diazo component, and the suspension was stirred to prepare a suspension, and ice was further added thereto to adjust the temperature to 5 ° C or lower. 105 g of 35% hydrochloric acid was added thereto, and the mixture was stirred at 5 ° C or lower for 1 hour. Thereafter, an aqueous solution obtained by dissolving 28.0 g of sodium nitrite in 72.0 g of water was added, and the mixture was stirred for 1 hour to carry out diazotization. Sulfamic acid was added to the reaction mixture to make nitrous acid disappear, and a diazo aqueous solution was prepared.
Further, as a couplant component, 80.4 g of o-acetamidine methoxyaniline and 164 g of a 25% aqueous sodium hydroxide solution were added to 140 g of water, and the mixture was stirred to be completely dissolved. Further, an aqueous solution of 82.0 g of 80% acetic acid and 420 g of water was prepared and mixed, and 12.4 g of the compound D-02 represented by the above formula was added to the aqueous solution to obtain a suspension containing the compound D-02. The above-prepared couplant solution was injected thereinto to prepare a couplant slurry containing the compound D-02.
The couplant slurry containing the compound D-02 was heated to 40 ° C, and the above adjusted aqueous diazonium solution was added dropwise thereto over 1 hour. After the completion of the dropwise addition, the temperature was maintained at this temperature for 1 hour to complete the reaction. After the reaction was completed, the slurry was heated to 90 ° C and stirred for 1 hour.
Thereafter, the mixture was filtered through a Buchner funnel having a diameter of 285 mm, and washed with 25 liters of ion-exchanged water, and dried and pulverized to obtain 147 g of the pigment composition P-01. The component contained in the pigment composition P-01 was a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-02, and the content of the compound D-02 was 5.0 mol%.
Example 2 <Modulation of Pigment Composition P-02>
In Production Example 1, 63.9 g of 2-methoxy-4-nitroaniline was changed to 65.6 g of 2-nitro-4-chloroaniline, and 80.4 g of o-acetamidine methoxyaniline was changed to ethyl acetate. In the same manner as in Example 1, except that 12.8 g of the compound D-02 was changed to 6.4 g of the compound D-03 represented by the following formula, 136 g of the pigment composition P-02 was obtained. The component of the pigment composition P-02 was CI Pigment Yellow 6 and Compound D-03, and the content of the compound D-03 was 5.0 mol%.

Example 3 <Preparation of Pigment Composition P-03>
In Production Example 1, 63.9 g of 2-methoxy-4-nitroaniline was changed to 69.3 g of 6-amino-7-chloro-4-methylquinoline-2(1H)-one, and 12.4 g. In the same manner as in Example 1, except that the compound D-02 of g was changed to 7.3 g of the compound D-04 represented by the following formula, 166 g of the pigment composition P-03 was obtained. The component contained in the pigment composition P-03 was CI Pigment Yellow 105 and Compound D-04, and the content of the compound D-04 was 5.0 mol%.

Example 4 <Modulation of Pigment Composition P-04>
63.9 g of 2-methoxy-4-nitroaniline was added to 500 g of water as a diazo component, and the suspension was stirred to prepare a suspension, and ice was further added thereto to adjust the temperature to 5 ° C or lower. 105 g of 35% hydrochloric acid was added thereto, and the mixture was stirred at 5 ° C or lower for 1 hour. Thereafter, 28.0 g of sodium nitrite was added to an aqueous solution prepared by adding 72.0 g of water, and the mixture was stirred for 1 hour to carry out diazotization. Sulfamic acid was added to the reaction mixture to make excess nitrous acid disappear, and a diazo aqueous solution was prepared. To the aqueous diazo solution, 5.0 g of the compound D-05 represented by the following formula was added, and the mixture was uniformly stirred to prepare a suspension to obtain a diazo aqueous solution containing the compound D-05.

Further, as a couplant component, 80.4 g of o-acetamidine methoxyaniline and 164 g of a 25% aqueous sodium hydroxide solution were added to 140 g of water, and the mixture was stirred to be completely dissolved. Further, this was poured into an aqueous solution in which 82.0 g of 80% acetic acid and 420 g of water were mixed to prepare a couplant slurry.
The couplant slurry prepared above was heated to 40 ° C, and a diazo aqueous solution containing the compound D-05 was dropped therein over 1 hour. After the completion of the dropwise addition, the temperature was maintained at this temperature for 1 hour to complete the reaction. After the reaction was completed, the slurry was heated to 90 ° C and stirred for 1 hour. Thereafter, it was filtered through a Buchner funnel having a diameter of 285 mm, and washed with ion-exchanged water of 25 liters. Then, it was dried and pulverized to obtain 144 g of the pigment composition P-04. The pigment composition P-04 contained a monoazo pigment A (CI Pigment Yellow 74) and a compound D-05, and the content of the compound D-05 was 5.0 mol%.
Example 5 <Preparation of Pigment Composition P-05>
In Production Example 4, 63.9 g of 2-methoxy-4-nitroaniline used as a diazo component was changed to 65.6 g of 2-nitro-4-chloroaniline, and 5.0 g of the compound D-05 was changed. In the same manner as in Example 4, except that 6.4 g of the compound D-06 represented by the following formula was obtained, 147 g of the pigment composition P-05 was obtained. The pigment composition P-05 contained CI pigment yellow 73 and compound D-06, and the content of the compound D-06 was 5.0 mol%.

Example 6 <Modulation of Pigment Composition P-06>
67.2 g of 2-methoxy-4-nitroaniline was added to 500 g of water as a diazo component, and the suspension was stirred to prepare a suspension, and ice was further added thereto to adjust the temperature to 5 ° C or lower. 105 g of 35% hydrochloric acid was added thereto, and the mixture was stirred at 5 ° C or lower for 1 hour. Thereafter, 28.0 g of sodium nitrite was added to an aqueous solution prepared by adding 72.0 g of water, and the mixture was stirred for 1 hour to carry out diazotization. Sulfamic acid was added in an appropriate amount to the reaction mixture to make excess nitrous acid disappear, and a diazo aqueous solution was prepared.
Further, as a couplant component, 84.5 g of o-acetamidine methoxyaniline and 164 g of a 25% aqueous sodium hydroxide solution were added to 140 g of water, and the mixture was stirred to completely dissolve. Further, an aqueous solution of 82.0 g of 80% acetic acid and 420 g of water was prepared and mixed. Next, an aqueous alkaline solution was poured into the aqueous solution to prepare a couplant slurry. To the couplant slurry, 0.097 g of the compound D-07 represented by the following formula was added to prepare a couplant slurry containing the compound D-07.




The couplant slurry containing the compound D-07 was heated to 40 ° C, and the above adjusted aqueous diazonium solution was added dropwise thereto over 1 hour. After the completion of the dropwise addition, the temperature was maintained at this temperature for 1 hour to complete the reaction. After the reaction was completed, the slurry was heated to 90 ° C and stirred for 1 hour.
Thereafter, it was filtered through a Buchner funnel having a diameter of 285 mm, and washed with ion-exchanged water of 25 liters. Then, it was dried and pulverized to obtain 152 g of the pigment composition P-06. The pigment composition P-06 contained a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-07, and the content of the compound D-07 was 0.05 mol%.
Example 7 <Preparation of Pigment Composition P-07>
In Production Example 6, 66.9 g of 2-methoxy-4-nitroaniline used as a diazo component was changed to 66.9 g, and 84.5 g of o-acetamidine methoxyaniline used as a coupling agent component was used. A pigment composition P-07 of 147 g was obtained in the same manner as in Example 6 except that the compound D-07 was changed to 0.87 g, and the compound D-07 was changed to 0.97 g. The pigment composition P-07 contained a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-07, and the content of the compound D-07 was 0.5 mol%.
Example 8 <Preparation of Pigment Composition P-08>
In Production Example 6, 67.3 g of 2-methoxy-4-nitroaniline used as a diazo component was changed to 65.3 g, and 84.5 g of o-acetamidine methoxyaniline used as a couplant component was used. A pigment composition P-08 of 148 g was obtained in the same manner as in Example 6 except that the compound D-07 was changed to 5.8 g in an amount of 82.1 g. The pigment composition P-08 contained a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-07, and the content of the compound D-07 was 3.0 mol%.
Example 9 <Preparation of Pigment Composition P-09>
In Production Example 6, 71.2 g of 2-methoxy-4-nitroaniline used as a diazo component was changed, and 84.5 g of o-acetamidine methoxyaniline used as a couplant component was used. In the same manner as in Example 6, except that the amount of the compound D-07 was changed to 72.1 g, and the compound D-07 was changed to 29.0 g, 152 g of the pigment composition P-09 was obtained. The pigment composition P-09 contained a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-07, and the content of the compound D-07 was 15.0 mol%.
Example 10 <Preparation of Pigment Composition P-10>
In Production Example 6, 47.1 g of 2-methoxy-4-nitroaniline used as a diazo component was changed, and 84.5 g of o-acetamidine methoxyaniline used as a couplant component was used. A pigment composition P-10 of 153 g was obtained in the same manner as in Example 6 except that the compound D-07 was changed to 58.0 g, and the compound D-07 was changed to 59.7 g. The pigment composition P-10 contained a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-07, and the content of the compound D-07 was 30.0 mol%.
Example 11 <Preparation of Pigment Composition P-11>
In Production Example 6, 63.6 g of 2-methoxy-4-nitroaniline used as a diazo component was changed to 33.6 g, and 84.5 g of o-acetamidine methoxyaniline used as a couplant component was used. A pigment composition P-11 of 157 g was obtained in the same manner as in Example 6 except that the compound D-07 was changed to 46.7 g, and the compound D-07 was changed to 96.7 g. The component contained in the pigment composition P-11 was a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-07, and the content of the compound D-07 was 50.0 mol%.
Example 12 <Preparation of Pigment Composition P-12>
67.2 g of 2-methoxy-4-nitroaniline was added to 500 g of water as a diazo component, and the suspension was stirred to prepare a suspension, and ice was further added thereto to adjust the temperature to 5 ° C or lower. 105 g of 35% hydrochloric acid was added thereto, and the mixture was stirred at 5 ° C or lower for 1 hour. Thereafter, 28.0 g of sodium nitrite was added to an aqueous solution prepared by adding 72.0 g of water, and the mixture was stirred for 1 hour to carry out diazotization. Sulfamic acid was added in an appropriate amount to the reaction mixture to make excess nitrous acid disappear, and a diazo aqueous solution was prepared.
Further, as a couplant component, 84.5 g of o-acetamidine methoxyaniline and 164 g of a 25% aqueous sodium hydroxide solution were added to 140 g of water, and the mixture was stirred to completely dissolve. To the alkaline aqueous solution, 0.05 g of the compound D-08 represented by the following formula was added to prepare a suspension containing the compound D-08. Further, an aqueous solution of 82.0 g of 80% acetic acid and 420 g of water was prepared and mixed. To the aqueous solution, the suspension containing the compound D-08 prepared above was injected to prepare a couplant slurry containing the compound D-08.






The couplant slurry containing the compound D-08 was heated to 40 ° C, and the above adjusted aqueous diazonium solution was added dropwise thereto over 1 hour. After the completion of the dropwise addition, the temperature was maintained at this temperature for 1 hour to complete the reaction. After the reaction was completed, the slurry was heated to 90 ° C and stirred for 1 hour.
Thereafter, it was filtered through a Buchner funnel having a diameter of 285 mm, and washed with ion-exchanged water of 25 liters. Then, it was dried and pulverized to obtain 151 g of the pigment composition P-12. The pigment composition P-12 contained a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-08, and the content of the compound D-08 was 0.05 mol%.
Example 13 <Preparation of Pigment Composition P-13>
In Production Example 12, 66.9 g of 2-methoxy-4-nitroaniline used as a diazo component was changed to 66.9 g, and 84.5 g of o-acetamidine methoxyaniline used as a couplant component was used. In the same manner as in Example 12 except that 0.054 g of the compound D-08 was changed to 0.50 g, 147 g of the pigment composition P-13 was obtained. The component of the pigment composition P-13 was a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-08, and the content of the compound D-08 was 0.5 mol%.
Example 14 <Preparation of Pigment Composition P-14>
In Production Example 12, 65.3 g of 2-methoxy-4-nitroaniline used as a diazo component was changed to 65.3 g, and 84.5 g of o-acetamidine methoxyaniline used as a couplant component was used. In the same manner as in Example 12 except that 0.05 g of the compound D-08 was changed to 3.0 g, the pigment composition P-14 was obtained in an amount of 145 g. The pigment composition P-14 contained a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-08, and the content of the compound D-08 was 3.0 mol%.
Example 15 <Preparation of Pigment Composition P-15>
In Production Example 12, 67.2 g of 2-methoxy-4-nitroaniline used as a diazo component was changed to 57.2 g, and 84.5 g of o-acetamidine methoxyaniline used as a couplant component was used. The pigment composition P-15 of 139 g was obtained in the same manner as in Example 12 except that the compound D-08 was changed to 75.0 g, and the compound D-08 was changed to 15.0 g. The pigment composition P-15 contained a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-08, and the content of the compound D-08 was 15.0 mol%.
Example 16 <Preparation of Pigment Composition P-16>
In Production Example 12, 67.1 g of 2-methoxy-4-nitroaniline used as a diazo component was changed to 47.1 g, and 84.5 g of o-acetamidine methoxyaniline used as a couplant component was used. The pigment composition P-16 of 127 g was obtained in the same manner as in Example 12 except that the compound D-08 was changed to 29.9 g, and the compound D-08 was changed to 29.9 g. The pigment composition P-16 contained a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-08, and the content of the compound D-08 was 30.0 mol%.
Example 17 <Preparation of Pigment Composition P-17>
In Production Example 12, 63.6 g of 2-methoxy-4-nitroaniline used as a diazo component was changed to 33.6 g, and 84.5 g of o-acetamidine methoxyaniline used as a couplant component was used. The pigment composition P-17 was obtained in the same manner as in Example 12 except that the compound D-08 was changed to 49.9 g, and the compound D-08 was changed to 49.9 g. The pigment composition P-17 contained a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-08, and the content of the compound D-08 was 50.0 mol%.
Example 18 <Preparation of Pigment Composition P-18>
63.2 g of 2-(trifluoromethyl)aniline was added to 500 g of water as a diazo component, and the suspension was stirred to prepare a suspension, and ice was further added thereto to adjust the temperature to 5 ° C or lower. 105 g of 35% hydrochloric acid was added thereto, and the mixture was stirred at 5 ° C or lower for 1 hour. Thereafter, 28.0 g of sodium nitrite was added to an aqueous solution prepared by adding 72.0 g of water, and the mixture was stirred for 1 hour to carry out diazotization. Sulfamic acid is added in an appropriate amount to the reaction mixture to make excess nitrous acid disappear. Next, 4.0 g of the compound D-09 represented by the following formula was added to the aqueous solution, and the mixture was stirred and mixed. Further, water was added, and the amount of the solution was adjusted to 1000 g to prepare a diazo aqueous solution containing the compound D-09.

Further, as a couplant component, 93.3 g of 5-acetoxime-2-benzimidazolone and 164 g of a 25% aqueous sodium hydroxide solution were added to 140 g of water, and the mixture was stirred to completely dissolve. Further, water was added, and the amount of the solution was adjusted to 400 g to prepare an aqueous solution of a coupling agent.
365 g of water was uniformly mixed with 64.0 g of 80% acetic acid and 71.2 g of a 25% aqueous sodium hydroxide solution to prepare a reaction tank aqueous solution. This was heated to 40 ° C, and the temperature was maintained. After maintaining the pH of the reaction vessel at 6.0 or less over 1 hour, the aqueous diazo solution containing the compound D-09 and the aqueous solution of the coupling agent were simultaneously dropped. After completion of the dropwise addition, the mixture was stirred at 40 ° C for 1 hour to complete the reaction. After the reaction was completed, the slurry was heated to 90 ° C and stirred for 1 hour. Thereafter, it was filtered through a Buchner funnel having a diameter of 285 mm, and washed with ion-exchanged water of 25 liters. Then, it was dried and pulverized to obtain 155 g of the pigment composition P-18. The pigment composition P-18 contained CI Pigment Yellow 154 and Compound D-09, and the content of the compound D-09 was 2.0 mol%.
Example 19 <Preparation of Pigment Composition P-19>
66.6 g of 2-methoxy-4-nitroaniline was added to 500 g of water as a diazo component, and the suspension was stirred to prepare a suspension, and ice was further added thereto to adjust the temperature to 5 ° C or lower. 105 g of 35% hydrochloric acid was added thereto, and the mixture was stirred at 5 ° C or lower for 1 hour. Thereafter, 28.0 g of sodium nitrite was added to an aqueous solution prepared by adding 72.0 g of water, and the mixture was stirred for 1 hour to carry out diazotization. Sulfamic acid is added in an appropriate amount to the reaction mixture to make excess nitrous acid disappear. Further, water was added to adjust the amount of the liquid to 1000 g.
Further, as the couplant component, 83.7 g of o-acetamidine methoxyaniline and 164 g of a 25% aqueous sodium hydroxide solution were added to 140 g of water, and the mixture was stirred to completely dissolve. Next, 2.1 g of the compound D-10 represented by the following formula was added to the aqueous solution of the coupling agent and stirred. Further, water was added, and the amount of the solution was adjusted to 400 g to prepare a coupling agent liquid containing the compound D-10.

365 g of water was uniformly mixed with 64.0 g of 80% acetic acid and 71.2 g of a 25% aqueous sodium hydroxide solution to prepare a reaction tank aqueous solution. This was heated to 40 ° C, and the temperature was maintained for one hour, while maintaining the pH of the reaction vessel at 6.0 or less, and simultaneously dropping a diazo aqueous solution and a coupling agent liquid containing the compound D-10. After completion of the dropwise addition, the mixture was stirred at 40 ° C for 1 hour to complete the reaction. After the reaction was completed, the slurry was heated to 90 ° C and stirred for 1 hour. Thereafter, it was filtered through a Buchner funnel having a diameter of 285 mm, and washed with ion-exchanged water of 25 liters. Then, it was dried and pulverized to obtain 147 g of the pigment composition P-19. The component of the pigment composition P-19 was a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-10, and the content of the compound D-10 was 1.0 mol%.
Example 20 <Preparation of Pigment Composition P-20>
63.9 g of 2-methoxy-4-nitroaniline was added to 500 g of water as a diazo component, and the suspension was stirred to prepare a suspension, and ice was further added thereto to adjust the temperature to 5 ° C or lower. 105 g of 35% hydrochloric acid was added thereto, and the mixture was stirred at 5 ° C or lower for 1 hour. Thereafter, 28.0 g of sodium nitrite was added to an aqueous solution prepared by adding 72.0 g of water, and the mixture was stirred for 1 hour to carry out diazotization. Sulfamic acid was added to the reaction mixture in an appropriate amount to remove nitrous acid, and water was further added thereto, and the amount of the solution was adjusted to 1000 g to prepare a diazo aqueous solution.
Further, as a couplant component, 80.4 g of o-acetamidine methoxyaniline and 164 g of a 25% sodium hydroxide aqueous solution were added to 140 g of water, and the mixture was stirred to completely dissolve, and water was further added thereto to prepare a liquid amount of 400 g. , prepared as an aqueous solution of a coupling agent.
365 g of water was uniformly mixed with 64.0 g of 80% acetic acid and 71.2 g of a 25% aqueous sodium hydroxide solution to prepare a reaction tank aqueous solution. 9.1 g of the compound D-11 represented by the following formula was added thereto and uniformly stirred to prepare a suspension. The suspension was heated to 40 ° C, and the temperature was maintained. After maintaining the pH of the reaction vessel at 6.0 or less over 1 hour, the aqueous solution of diazo and the aqueous solution of the coupling agent were simultaneously dropped. After completion of the dropwise addition, the mixture was stirred at 40 ° C for 1 hour to complete the reaction. After the reaction was completed, the slurry was heated to 90 ° C and stirred for 1 hour. Thereafter, it was filtered through a Buchner funnel having a diameter of 285 mm, and washed with ion-exchanged water of 25 liters. Then, it was dried and pulverized to obtain 148 g of the pigment composition P-20. The component contained in the pigment composition P-20 was a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-11, and the content of the compound D-11 was 5.0 mol%.

Example 21 <Modulation of Pigment Composition P-21>
63.9 g of 2-methoxy-4-nitroaniline was added to 500 g of water as a diazo component, and the suspension was stirred to prepare a suspension, and ice was further added thereto to adjust the temperature to 5 ° C or lower. 105 g of 35% hydrochloric acid was added thereto, and the mixture was stirred at 5 ° C or lower for 1 hour. Thereafter, 28.0 g of sodium nitrite was added to an aqueous solution prepared by adding 72.0 g of water, and the mixture was stirred for 1 hour to carry out diazotization. Sulfamic acid was added in an appropriate amount to the reaction mixture to make excess nitrous acid disappear, and a diazo aqueous solution was prepared.
Further, as a couplant component, 80.4 g of o-acetamidine methoxyaniline and 164 g of a 25% aqueous sodium hydroxide solution were added to 140 g of water, and the mixture was stirred to be completely dissolved. This was poured into an aqueous solution in which 82.0 g of 80% acetic acid and 420 g of water were mixed to prepare a couplant slurry.
The above prepared couplant slurry was heated to 40 ° C, and an aqueous solution of diazo was dropped therein over 1 hour. After the completion of the dropwise addition, the temperature was maintained at this temperature for 1 hour to complete the reaction. To the slurry after completion of the reaction, 8.1 g of the compound D-12 represented by the following formula was added, and then the slurry was heated to 90 ° C and stirred for 1 hour. Thereafter, it was filtered through a Buchner funnel having a diameter of 285 mm, and washed with ion-exchanged water of 25 liters. Then, it was dried and pulverized to obtain 147 g of the pigment composition P-21. The component of the pigment composition P-21 was a monoazo pigment A-01 (CI Pigment Yellow 74) and a compound D-12, and the content of the compound D-12 was 5.0 mol%.

Example 22 <Preparation of Pigment Composition P-22>
In Production Example 21, 63.9 g of 2-methoxy-4-nitroaniline used as a diazo component was changed to 57.8 g of 2-nitro 4-toluidine, and 8.1 g of the compound D-12 was changed. In the same manner as in Example 21 except that 7.9 g of the compound D-13 represented by the following formula was obtained, 141 g of the pigment composition P-22 was obtained. The component contained in the pigment composition P-22 was CI Pigment Yellow 203 and Compound D-13, and the content of the compound D-13 was 5.0 mol%.

Example 23 <Preparation of Pigment Composition P-23>
Using a 1 gallon kneader made of stainless steel (manufactured by Inoue Seisakusho Co., Ltd.), 273.9 g of monoazo pigment A-04 (CI Pigment Yellow 111) prepared in Production Example 4 and 27.5 g of Compound D represented by the following formula were added at 60 °C. 14. A mixture of 1500 g of sodium chloride and 250 g of diethylene glycol was mixed and stirred for 6 hours to obtain a clay-like mixed agitate. The kneaded material was placed in 15 liters of warm water, and heated to 70 ° C while stirring for 1 hour to obtain a slurry. The slurry was divided into three equal portions, and each was filtered with a Buchner funnel having a diameter of 285 mm, and 15 liters of warm water of 50 ° C was sprayed and washed, and dried and pulverized to obtain a pigment composition P-23. The content of the compound D-14 of the pigment composition P-23 was 7.0 mol%.

Example 24 <Preparation of Pigment Composition P-24>
In Production Example 23, 273.9 g of monoazo pigment A-04 (CI Pigment Yellow 111) was changed to 295.2 g of monoazo pigment A-05 (CI Pigment Yellow 120), and 27.5 g of Compound D-14 was changed. In the same manner as in Example 23 except that 20.6 g of the compound D-15 represented by the following formula was obtained, 262 g of the pigment composition P-24 was obtained. The content of the compound D-15 of the pigment composition P-24 was 7.0 mol%.




Example 25 <Preparation of Pigment Composition P-25>
61.8 g of the monoazo pigment A-01 (CI Pigment Yellow 74) prepared in Production Example 1 and 27.7 g of the powder of the compound D-16 represented by the following formula were uniformly mixed to obtain 81 g of the pigment composition P-25. The content of the compound D-16 of the pigment composition P-25 was 20.0 mol%.

Example 26 <Preparation of Pigment Composition P-26>
In Production Example 25, 61.8 g of the monoazo pigment A-01 was changed to 63.2 g of monoazo pigment A-02 (CI Pigment Yellow 3), and 15.8 g of the compound D-16 was changed to the following formula. In the same manner as in Example 25 except that 11.5 g of the compound D-17 was obtained, 67 g of the pigment composition P-26 was obtained. The content of the compound D-17 of the pigment composition P-26 was 20.0 mol%.




<Evaluation of monoazo pigments and pigment compositions>
The average primary particle diameters of the monoazo pigments prepared in Examples 1 to 5 and the pigment compositions prepared in Examples 1 to 26 were measured, and the results are summarized in Table 1. The average primary particle diameter was measured by the following method.
(average primary particle size)
The average primary particle size was determined from a photograph of the pigment particle size taken by a scanning electron microscope. A conductive double-sided tape was adhered to a metal sample stage to adhere a pigment or a pigment composition, and platinum was vapor-deposited on the surface of the sample by sputtering, and this was used as a sample by a scanning electron microscope (manufactured by JEOL DATUM Co., Ltd., JSM-6700F scanning electron microscope) photographed particles, and measured 100 primary particles of the pigments captured in the same field of view, and measured the maximum particle diameter, and calculated the averaged value, and used this value as the average primary particle diameter.


<Preparation of Pigment Dispersion>
(Preparation of aqueous pigment dispersion)
Examples 27 to 40 and Comparative Examples 1 to 3
Mixed pigment composition or monoazo pigment 1000 g, JONCRYL HPD-96J (manufactured by BASF Corporation, styrene-acrylic resin, active ingredient 34.0%) 735 g, Surfynol 104E (Air Products and Chemicals, Inc., antifoaming agent, active ingredient 50) %) 50 g, Rebanax BX-150 (manufactured by Changrong Chemical Co., Ltd., preservative) 50 g, propylene glycol 250 g, and ion exchange water 415 g, and stirred until uniform by a high-speed mixer. The mixture was dispersed in a transverse wet disperser (DYNO-MILL TYPE KDL-PILOT) for 2 hours, and then 2500 g of ion-exchanged water was added thereto, and further dispersed for 1 hour to obtain aqueous pigment dispersions WD-01 to WD-17, respectively. The pigment composition or monoazo pigment used in each aqueous pigment dispersion is summarized in Table 2.
Comparative Example 4 (modulation of aqueous pigment dispersion WD-18)
An aqueous pigment dispersion WD was obtained in the same manner as in Examples 27 to 40 and Comparative Examples 1 to 3 except that the pigment composition or the monoazo pigment was changed to Hansa Brilliant Yellow 5GX (manufactured by Clariant Co., Ltd., CI Pigment Yellow 74). -18.
(modulation of oily pigment dispersion)
Examples 41 to 52 and Comparative Examples 5 and 6
Mixed pigment composition or 1000 g of monoazo pigment, 325 g of Disperbyk 130 (manufactured by BYK Chemie Co., Ltd., pigment dispersant), 250 g of JONCRYL 586 (manufactured by BASF Japan Co., Ltd.), and 925 g of ethylene glycol monobutyl ether acetate were mixed at a high speed. Stir the machine until it is even. The mixture was dispersed in a transverse wet disperser (DYNO-MILL TYPE KDL-PILOT) for 2 hours, and then 2500 g of ethylene glycol monobutyl ether acetate was added thereto, and further dispersed for 1 hour to obtain an oily pigment dispersion SD-01 to SD- 14. The pigment composition or monoazo pigment used for each oil pigment dispersion is summarized in Table 3.
Comparative Example 7 (modulation of oily pigment dispersion SD-15)
An oily pigment dispersion SD was obtained in the same manner as in Examples 41 to 52 and Comparative Examples 5 and 6 except that the pigment composition or the monoazo pigment was changed to Hansa Brilliant Yellow 5GX (manufactured by Clariant Co., Ltd., CI Pigment Yellow 74). -15.
<Evaluation of Pigment Dispersion>
For the pigment dispersion, the following methods were used to evaluate the dispersed particle size, viscosity, crystal stability, and dispersion stability. The results are summarized in Tables 2 and 3. For each evaluation item, the following method was used for measurement.
(dispersed particle size)
The D50 value measured by Microtrac UPA-150 (manufactured by Nikkiso Co., Ltd.) was used as the dispersed particle diameter.
(viscosity)
The viscosity was measured by a V-type viscometer VISCOMETER (manufactured by Toki Sangyo Co., Ltd.), and evaluated based on the value of 60 rpm.
(crystal stability)
As a parameter of crystal stability, a photograph of a pigment or a pigment composition particle in a pigment dispersion was taken by a transmission electron microscope.
The pigment dispersion was dropped on the mesh of the support film, and dried, and then used as a sample, and the particles were photographed by a transmission electron microscope (H-7650 penetrating electron microscope, manufactured by Hitachi High-Technologies Co., Ltd.) for the same 100 primary particles of the pigment dispersion or the pigment dispersion photographed in the field of view were measured, and the maximum particle diameter was measured, and the average value was calculated, and this value was made into the average primary particle diameter.
The pigment dispersion was sealed in a screw-top bottle and stored at 70 ° C for two weeks, and the same measurement was carried out. The crystal stability was evaluated based on the change in the average primary particle diameter before and after storage. Before and after the storage, the average primary particle diameter change rate is 0 to 15%, and it is judged as "○". If it exceeds 15% and is less than 30%, it is judged as "△", and if it exceeds 30%, it is judged as "X".
(dispersion stability)
The pigment dispersion was sealed in a screw-top bottle and stored at 70 ° C for two weeks, and then the dispersed particle diameter and viscosity were measured. The dispersion stability was evaluated based on the dispersion particle size and viscosity before and after storage, and whether or not there was a precipitate after storage.


As shown in Table 2, the aqueous pigment dispersion prepared by using the pigment composition obtained by the implementation of the present invention has a lower viscosity than other pigment dispersions and exhibits good dispersibility. It is understood that these aqueous pigment dispersion systems are relatively good in both crystal stability and dispersion stability.


As shown in Table 3, the oily pigment dispersion prepared by using the pigment composition obtained by the implementation of the present invention has a lower viscosity than other pigment dispersions and exhibits good dispersibility. It can be seen that these oily pigment dispersion systems are relatively good in both crystal stability and dispersion stability.
<Modulation of inkjet ink>
(Modulation of water-based inkjet ink)
Examples 53 to 66 and Comparative Examples 8 to 11
15.0 g of the aqueous pigment dispersion prepared in Examples 27 to 40 and Comparative Examples 1 to 4, 1.5 g of an acrylic resin emulsion W-215 (Japan Polymer Industry Co., Ltd., solid portion 30%), and 15.0 g of ethylene glycol were mixed. 68.5 g of ion-exchanged water was stirred for 1 hour, and then filtered through a PTFE membrane filter having a pore size of 1.0 μm to obtain aqueous inkjet inks WI-01 to WI-18.
(modulation of oily inkjet ink)
Examples 67 to 78 and Comparative Examples 12 to 14
25.0 g of the oily pigment dispersion prepared in Examples 41 to 52 and Comparative Examples 5 to 7, 55.0 g of propylene glycol monobutyl ether acetate, and 10.0 g of diethylene glycol monoethyl ether acetate were mixed, and after stirring for 1 hour, A PTFE membrane filter having a pore size of 1.0 μm was filtered to obtain oily inkjet inks SI-01 to SI-15.
<Evaluation of inkjet ink>
(Evaluation of water-based inkjet ink)
The ejectability of the aqueous inkjet ink by the printer and the coloring of the obtained print were evaluated. The results are summarized in Table 4. For the squirting and coloring power, the following methods were used for evaluation.
In the evaluation of the discharge property, the aqueous inkjet ink was filled in a cassette of an ink jet printer HG-5130 (manufactured by Seiko Epson Co., Ltd.), and printed on a photo paper ‧ gloss Gold (manufactured by Canon Co., Ltd.). The print point (unprinted portion) was visually observed for the presence or absence of the missing mark, and this was used as an ejection property index. When the nozzle of the printer head that has a missing print point is less than 1% of the total nozzle, it is judged as "○". If it is 1% or more and less than 5%, it is judged as "△". When it is more than 5%, it is judged as "×". .
In the coloring power evaluation, the reflection density of the portion where the printing dot was missing was measured by the reflection density meter D19C (manufactured by Gretag Machbeth Co., Ltd.) for each of the prints. With reference to the aqueous inkjet ink WI-18 prepared in Comparative Example 10, the reflection concentration ratio was greater than 95% and less than 105%, and it was judged as "△", and when the reflection density was 105% or more, it was judged as "○", and the reflection density ratio was determined. Less than 95% are judged as "X".
(Evaluation of oily inkjet ink)
Evaluate the squirting properties of the oil-based inkjet ink by the printer and the coloring of the obtained print. The results are summarized in Table 5. For the squirting and coloring power, the following methods were used for evaluation.
In the evaluation of the discharge property, the oil-based inkjet ink was filled in a cassette of an ink jet printer IP-6500 (manufactured by Seiko I Infotech Co., Ltd.), and printed on a glossy vinyl chloride sheet MD5 (manufactured by Metamark Co., Ltd.). The print point (unprinted portion) was visually observed for the presence or absence of the missing mark, and this was used as an ejection property index. When the nozzle of the printer head that has a missing print point is less than 1% of the total nozzle, it is judged as "○". If it is 1% or more and less than 5%, it is judged as "△". When it is more than 5%, it is judged as "×". .
In the coloring power evaluation, the reflection density of the portion where the printing dot was missing was measured by the reflection density meter D19C (manufactured by Gretag Machbeth Co., Ltd.) for each of the prints. With reference to the aqueous inkjet ink SI-15 prepared in Comparative Example 14, the reflection concentration ratio was greater than 95% and less than 105%, and it was judged as "△", and when the reflection density was 105% or more, it was judged as "○", and the reflection density ratio was determined. Less than 90% are judged as "X".


As shown in the results of Table 4, the aqueous inkjet ink prepared by the pigment composition obtained in the examples of the present invention was excellent in discharge property and coloring power as compared with other inkjet inks.


As shown in the results of Table 5, the oil-based inkjet ink prepared by using the pigment composition obtained in the examples of the present invention was excellent in discharge property and coloring power as compared with other inkjet inks.
<Preparation of Colored Resin Composition>
Examples 79 to 90 and Comparative Examples 15 to 17
In a pressure kneader, a pigment composition, 2500 g of a monoazo pigment, and 2500 g of a thermoplastic polyester resin were mixed, stirred, and taken out at a set temperature of 120 ° C for 15 minutes. Further, the mixture was stirred and stirred at 3 rolls having a roll temperature of 95 ° C, and after cooling, it was coarsely pulverized to 10 mm or less to obtain colored resin compositions M-01 to M-15.
<Modulation of toner>
4375 g of a thermoplastic polyester resin (500 rpm, 3 minutes), a colored resin composition of 500 g, and a calcium chloride compound of 3,5-di-tertiary butyl sulphate (Henschel mixer) having a volume of 20 L (manufactured by Henschel mixer) 50 g of a charge control agent, 75 g of an ethylene homopolymer (release agent, molecular weight 850, Mw/Mn=1.08, melting point 107 ° C), and melt-mixed and stirred at a discharge temperature of 120 ° C by a biaxial mixing and stirring extruder. Thereafter, the kneaded material was cooled and solidified, and then coarsely pulverized by a hammer mill, and then finely pulverized by a jet mill (IDS-2 type), and then classified to obtain carbon powder mother particles. Then, 2500 g of the carbon powder mother particles obtained above and 12.5 g of hydrophobic titanium oxide (STT-30A manufactured by Titanium Industries Co., Ltd.) were mixed with a 10 L Hansai mixer to obtain a negatively charged carbon powder.
Comparative Example 18
Comparative Example 4 (modulation of aqueous pigment dispersion WD-18)
The colored resin composition M16 was obtained in the same manner as in Examples 79 to 90 and Comparative Examples 15 to 17, except that the pigment composition or the monoazo pigment was changed to Hansa Brilliant Yellow 5GX (manufactured by Clariant Co., Ltd., CI Pigment Yellow 74). And toner.
<Evaluation of Colored Resin Composition and Carbon Powder>
The colored resin composition and the carbon powder were evaluated by the following methods. Further, regarding the toner, the image density, durability, and transparency were evaluated by the following methods. The results are summarized in Table 6.
(dispersion)
The obtained colored resin composition and carbon powder were cut into a thickness of 0.9 μm by a microtome, and the dispersed state of the pigment was observed by a transmission electron microscope. When the pigment is uniformly distributed in the colored resin composition, it is indicated as "○", and there is a pigment coagulum. If the uneven distribution is indicated as "△", there are many pigment coagulum, and the non-uniform distribution is indicated as "X".
(image density and durability)
As the carbon powder and the carrier, a ferrite carrier (DFC-350C, manufactured by Tosoh Corporation) coated with a silicone resin having an average particle diameter of 60 μm was used, and the toner concentration was set to 6% to prepare a color developing agent.
Color-application paper Ncolor 127 (A4 size, 127.9 g/m) manufactured by Fuji Xerox Co., Ltd., a full-color copier manufactured by Canon Inc. ² ), the output uses a monochrome image of each toner. The image density after the initial and 10,000 sheets of output was measured to evaluate the durability of the toner. The image density was measured by a reflection densitometer D19C (manufactured by Gretag Machbeth Co., Ltd.).
(transparency)
On the OHP transparencies, a Beta image was formed by using the above-obtained developer, and the sample was flattened by the fixing portion of the copying machine to visually confirm the penetrability. The visual judgment results were evaluated in three stages of "1", "2" and "3". The larger the number, the better the transparency.


As shown by the results of Table 6, the pigment composition obtained by the examples of the present invention was used to prepare a colored resin composition to exhibit good dispersibility as compared with other colored resin compositions. Further, the carbon powder obtained in the embodiment of the present invention exhibited good dispersibility as compared with other carbon powders, and the image density and transparency were also good. In other words, in terms of durability, the carbon powder of this aspect is superior to other carbon powders, so that it is possible to obtain a toner which simultaneously achieves crystal stability and dispersion stability.
By obtaining the pigment composition containing the azo pigment according to the embodiment of the present invention, the problem of the monoazo pigment has hitherto improved, that is, the crystal stability is improved, and a fine pigment composition having dispersion stability can be provided.
For the peers, further benefits and distortions are easy. Therefore, the invention in its broader aspects is not limited to the specific description or representative aspects described herein. Therefore, various modifications may be made without departing from the true scope and scope of the inventions of the invention.

Claims (7)

A pigment composition comprising: at least one monoazo pigment represented by the following general formula (1); and each represented by one of the following general formulas (2) to (5) At least one compound;
General formula (1):

(wherein X ¹ to X ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, a carboxyl group, One of a nitro group, a sulfonic acid group, a carbamic acid group, an amine sulfonyl group, and a trifluoromethyl group. The adjacent two of X ¹ to X ⁵ are bonded to each other, and two of the benzene rings are bonded thereto. The carbon atom may form a heterocyclic moiety together, or a hydrogen atom bonded to a ring atom of the heterocyclic moiety may be substituted.
X ⁶ to X ¹⁰ each independently represent one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an acetamino group, a carboxyl group and a sulfonic acid group. The adjacent two of X ⁶ to X ¹⁰ are bonded to each other, and the two carbon atoms of the benzene ring bonded thereto may form a hetero ring moiety, or the hydrogen atom of the ring atom bonded to the hetero ring moiety may be substituted. )
General formula (2):

(In the formula, A represents one of -CO- and -SO ₂ -. R ¹ represents one of the following: a hydrogen atom; an alkyl group having a carbon number of 20 or less having a substituent; or a substitution An alkenyl group having a carbon number of 20 or less; and an aryl group having a carbon number of 20 or less which may have a substituent.
Y ¹ represents -SO ₂ NH-R ² -NR ³ R ⁴ -, -CONH-R ⁵ -NR ⁶ R ⁷ -, -SO ₂ NH-R ⁸ -SO ₃ H, -CONH-R ⁹ -SO ₃ H, -SO ₂ NH-R ¹⁰ -COOH, -CONH-R ¹¹ -COOH, and one of the groups represented by the following general formula (3). Wherein R ² , R ⁵ and R ⁸ to R ¹¹ each independently represent one of the following: an alkylene group having a carbon number of 20 or less having a substituent group; and an alkylene group having a carbon number of 20 or less having a substituent group And an arylene group having a carbon number of 20 or less which may have a substituent group. R ³ , R ⁴ , R ⁶ and R ⁷ each independently represent one of the following: a hydrogen atom; an alkyl group having a carbon number of 20 or less having a substituent; or an alkenyl group having a carbon number of 20 or less having a substituent. And an aryl group having a carbon number of 20 or less having a substituent. R ³ and R ⁴ or R ⁶ and R ⁷ are bonded to each other, and the nitrogen atom bonded thereto or the like forms a heterocyclic moiety together, or a part of a carbon atom which is a ring atom of the heterocyclic moiety is subjected to another nitrogen atom, an oxygen atom or The sulfur atom may be substituted or the hydrogen atom of the ring atom bonded to the heterocyclic moiety may be substituted. )
General formula (3):

(wherein Y ² and Y ³ each independently represent one of -OH-, -NH-R ¹² -NR ¹³ R ¹⁴ -, -NH-R ¹⁵ -SO ₃ H and -NH-R ¹⁶ -COOH Wherein R ¹² , R ¹⁵ and R ¹⁶ each independently represent one of the following: an alkylene group having a carbon number of 20 or less having a substituent; or an alkenyl group having a carbon number of 20 or less having a substituent; And an arylene group having a carbon number of 20 or less of the substituent group. R ¹³ and R ¹⁴ each independently represent one of the following: a hydrogen atom; or an alkyl group having a carbon number of 20 or less having a substituent; An alkenyl group having a carbon number of 20 or less; and an aryl group having a carbon number of 20 or less having a substituent group. R ¹³ and R ¹⁴ are bonded to each other, and a nitrogen atom bonded thereto or the like forms a heterocyclic moiety together, or A part of the carbon atom of the ring atom of the heterocyclic moiety may be replaced by another nitrogen atom, an oxygen atom or a sulfur atom, or the hydrogen atom of the ring atom bonded to the heterocyclic moiety may be substituted.
General formula (4):

(In the formula, Y ⁴ represents a single bond, -CONH-R ¹⁷ -, -SO ₂ NH-R ¹⁸ -. R ¹⁷ and R ¹⁸ each independently represent one of the following: may also have a substituent An alkylene group having a carbon number of 20 or less; an alkenyl group having a carbon number of 20 or less having a substituent; and an arylene group having a carbon number of 20 or less having a substituent.
Y ⁵ represents one of -SO ₃ H and -COOH. )
General formula (5):

(wherein R ¹⁹ and R ²⁰ each independently represent one of the following: a hydrogen atom; an alkyl group having a carbon number of 20 or less having a substituent; and an alkenyl group having a carbon number of 20 or less; It may also have one of the aryl groups having a carbon number of 20 or less of the substituent group.
Y ⁶ represents -SO ₂ NH-R ²¹ -NR ²² R ²³ -, -CONH-R ²⁴ -NR ²⁵ R ²⁶ -, -SO ₂ NH-R ²⁷ -SO ₃ H, -CONH-R ²⁸ -SO ₃ H, -SO ₂ NHR ²⁹ -COOH and -CONH-R ³⁰ -COOH. R ²¹ , R ²⁴ and R ²⁷ to R ³⁰ each independently represent one of the following: an alkylene group having a carbon number of 20 or less having a substituent; or an alkenyl group having a carbon number of 20 or less having a substituent; And an arylene group having a carbon number of 20 or less of a substituent group. , R ²³ , R ²⁵ and R ²⁶ each independently represent one of the following: a hydrogen atom; an alkyl group having a carbon number of 20 or less having a substituent; or an alkenyl group having a carbon number of 20 or less; It may also have an aryl group having a carbon number of 20 or less. R ²² and R ²³ or R ²⁵ and R ²⁶ are bonded to each other, and a nitrogen atom bonded thereto or the like forms a heterocyclic moiety together, or a part of a carbon atom which is a ring atom of the heterocyclic moiety is subjected to another nitrogen atom, an oxygen atom or The sulfur atom may be substituted or the hydrogen atom of the ring atom bonded to the heterocyclic moiety may be substituted. ) The pigment composition according to the first aspect of the invention, wherein the total content of the at least one compound represented by any one of the general formulas (2) to (5) is each a general formula ( 1) The content of the at least one monoazo pigment represented by the total amount of each of the at least one compound represented by one of the general formulas (2) to (5) The ratio is from 0.1 to 40 mol%. The pigment composition of claim 1 or 2, wherein the average primary particle diameter is 200 nm or less. A pigment dispersion containing the pigment composition and the liquid medium according to any one of claims 1 to 3. An inkjet ink comprising a pigment dispersion as in item 4 of the patent application. A colored resin composition comprising the pigment composition according to any one of claims 1 to 3, and a binder resin. A toner for electronic photographs comprising the colored resin composition as claimed in claim 6 of the patent application.