JP2013139488A - Pigment composition, pigment dispersion, and ink-jet ink and electrophotographic toner using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a minute pigment composition consisting of a monoazo pigment and a monoazo pigment derivative that excels in tinting strength, dispersibility, and crystal stability; and to provide a pigment dispersion, an electrophotographic toner and an inkjet ink using the pigment derivative.SOLUTION: A pigment composition is used which comprises various monoazo pigments and a monoazo pigment derivative having various substituents.

Description

  The present invention relates to a monoazo pigment composition having high coloring power, excellent dispersion stability, and a small amount of impurities. More specifically, the present invention relates to an inkjet ink and electrophotographic toner using the same.

  Conventional yellow pigments for inkjet printing and electrophotography include C.I. I. Disazo pigments such as C.I. Pigment Yellow 12, 13, 13, 17; I. Monoazo pigments such as C.I. Pigment Yellow 1, 65 and 74; I. Condensed azo pigments such as CI Pigment Yellow 93, 95 and 128 have been mainly used.

  Among these, disazo pigments have good transparency and coloring power, but have low light resistance and are problematic. Furthermore, since dichlorobenzidine is used as a raw material, there is concern about the safety of its decomposition products. Condensed azo pigments are excellent in heat resistance and light resistance, but are inferior to disazo pigments and monoazo pigments in terms of coloring power, and are more expensive.

  On the other hand, monoazo pigments are excellent in terms of light resistance and safety compared to disazo pigments. Moreover, it is superior in terms of coloring power compared to condensed azo pigments, and can be produced at a relatively low cost. In particular, C.I. I. Since CI Pigment Yellow 74 is excellent in terms of hue and clarity, it has been widely used for inkjet printing and electrophotography in recent years.

  In recent years, in applications such as ink jet printing and electrophotography, it has been demanded to disperse fine pigments uniformly in ink or toner due to an increase in the required quality of printed matter. In general, however, fine pigments are often agglomerated between pigment particles and often have poor dispersion stability. Therefore, if the dispersion is stored for a long period of time, problems such as an increase in viscosity or precipitation may occur.

  Further, many monoazo pigments are inferior in crystal stability to heat and solvent, and the tendency is particularly remarkable in fine monoazo pigments. Depending on the use conditions, problems such as growth of primary particles may occur, and as a result, the coloring power and sharpness of the printed matter may be deteriorated. Various studies have been conducted to improve the crystal stability of such monoazo pigments, and the methods of Patent Document 1 and Patent Document 2 are disclosed.

  In Patent Documents 1 and 2, when a monoazo pigment is synthesized, coupling is performed in the state where an aromatic amine having a specific functional group is used as a diazo component or an acetoacetanilide compound having a specific functional group is used as a coupler component. C. I. Disclosed is a coloring composition for image recording, in which different pigments are produced simultaneously with Pigment Yellow 74, thereby improving heat resistance despite the fine primary particle size and imparting characteristics for inkjet and electrophotography. Has been. Although the colored composition obtained by these methods is excellent in heat resistance, the dispersion stability is insufficient. As described above, a pigment having both heat resistance and dispersion stability in a fine monoazo pigment has not been found.

JP-A-10-158555 JP-A-10-171165

  An object of the present invention is to provide a pigment composition containing a fine monoazo pigment, which has improved the heat resistance, which has been a problem with monoazo pigments, and has excellent dispersion stability. Furthermore, it aims at providing the pigment dispersion, inkjet ink, and electrophotographic toner using the same.

  That is, this invention relates to the pigment composition containing the compound represented by following General formula (1), and the compound represented by following General formula (2).

General formula (1)

General formula (2)

(In the formula, X _{1 to} X ₅ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, or a carboxyl group. A group, a nitro group, a sulfone group, a carbamoyl group, a sulfamoyl group, or a trifluoromethyl group, and X _{1 to} X ₅ are combined with adjacent groups to further contain a nitrogen atom, an oxygen atom, or a sulfur atom, A heterocyclic structure which may be substituted may be formed.
X _{6 to} X ₁₀ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an acetylamino group, a carboxyl group, or a sulfone group. Moreover, X < ₆ > -X < ₁₀ > may form the heterocyclic structure which an adjacent group unites and contains a further nitrogen atom, an oxygen atom, or a sulfur atom, and may be substituted.
X _{11 to} X ₁₅ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an acetylamino group, a carboxyl group, a sulfone group, the following general formula (3 ) Or a group represented by the following general formula (4). However, at least one of X _{11 to} X ₁₅ is either a group represented by the general formula (3) or a group represented by the general formula (4). )

General formula (3)

(In the formula, Y ₁ represents —SO ₂ NR′— or —CONR′—, wherein R ′ may have a hydrogen atom, a substituent and an alkyl group having 20 or less carbon atoms, It represents either an optionally substituted alkenyl group having 20 or less carbon atoms and an optionally substituted alkenyl group having 20 or less carbon atoms.
Y ₂ is a direct bond connecting Y ₁ and Y ₃ , an optionally substituted alkylene group having 20 or less carbon atoms, an optionally substituted alkenylene group having 20 or less carbon atoms, It may have a substituent and represents an arylene group having 20 or less carbon atoms, or —Y _2a —Y _2b —Y _2c —. Y _2a and Y _2c are each independently an optionally substituted alkylene group having 20 or less carbon atoms, an optionally substituted alkenylene group having 20 or less carbon atoms, or a substituted group. It may have a group and represents an arylene group having 20 or less carbon atoms. Y _2b represents a direct bond connecting Y _2a and Y _2c , —O—, —CO—, —NR′— or —SO ₂ —.
Y ₃ represents a hydrogen atom, —OR ₁ , —COOR ₁ , —NR ₁ R ₂ , —CONR ₁ R ₂ , or —SO ₂ NR ₁ R ₂ . Here, R ₁ and R ₂ each independently have a hydrogen atom, a substituent, may have a carbon number of 20 or less, may have a substituent, and have a carbon number of 20 or less. It represents either an alkenyl group or an aryl group which may have a substituent and has 20 or less carbon atoms. R ₁ and R ₂ may be combined to form a heterocyclic structure which may further contain a nitrogen atom, an oxygen atom or a sulfur atom and which may be substituted.
R ′, R ₁ , and R ₂ are each independently integrated with Y ₂ to form an optionally substituted heterocyclic structure which may contain further nitrogen, oxygen or sulfur atoms. May be. )

General formula (4)

(In the formula, Y ₄ represents —NR′— or —O—.
Y ₅ and Y ₆ each independently represent any of a group represented by the following general formula (5), —OR ′, —NR ′ ₂ , and a halogen atom. However, R 'is synonymous with what was defined by General formula (3). )

General formula (5)

(In the formula, Y ₂ , Y ₃ and Y ₄ have the same meanings as defined in the general formula (3) and the general formula (4).)

  In the present invention, the content of the compound represented by the general formula (2) is the sum of the number of moles of the compound represented by the general formula (1) and the number of moles of the compound represented by the general formula (2). It is related with the said pigment composition which is 0.1-40 mol% of the quantity made | formed.

  The present invention also relates to a method for producing the above pigment composition in which an aromatic amine is diazotized and then coupled with an acetoacetanilide compound, wherein the aromatic amine is a compound represented by the following general formula (6): Further, the present invention relates to a method for producing a pigment composition in which the acetoacetanilide compound is a mixture of a compound represented by the following general formula (7) and a compound represented by the following general formula (8).

General formula (6)

General formula (7)

General formula (8)

(The X ₁ to X ₁₀ in the formula have the same meanings as those defined in the general formula (1), X ₁₁ ~X ₁₅ has the same meaning as defined in the general formula (2).)

  The present invention is also a method for producing the above pigment composition, wherein the aromatic amine is diazotized and then coupled with an acetoacetanilide compound, wherein the aromatic amine is represented by the following general formula (6): A diazo of an aromatic amine represented by the general formula (6), which is an amine and the acetoacetanilide compound is a compound represented by the following general formula (7) and a compound represented by the following general formula (8): A pigment obtained by adding the acetoacetanilide compound represented by the general formula (8) to the aqueous solution of the compound and subjecting it to a coupling reaction, and then reacting the reaction mixture with the acetoacetanilide compound represented by the general formula (7) The present invention relates to a method for producing a composition.

General formula (6)

General formula (7)

General formula (8)

(The X ₁ to X ₁₀ in the formula have the same meanings as those defined in the general formula (1), X ₁₁ ~X ₁₅ has the same meaning as defined in the general formula (2).)

  The present invention is also a method for producing the above pigment composition, wherein the aromatic amine is diazotized and then coupled with an acetoacetanilide compound, wherein the aromatic amine is represented by the following general formula (6): It is an amine, and the acetoacetanilide compound is a compound represented by the following general formula (7) and a compound represented by the following general formula (8), and the general formula (6 And a basic aqueous solution in which the compound represented by the general formula (7) and the compound represented by the general formula (8) are dissolved at a constant flow rate at the same time. Relates to a method for producing a pigment composition obtained in (1).

General formula (6)

General formula (7)

General formula (8)

(The X ₁ to X ₁₀ in the formula have the same meanings as those defined in the general formula (1), X ₁₁ ~X ₁₅ has the same meaning as defined in the general formula (2).)

  The present invention is also a method for producing the above pigment composition, wherein the aromatic amine is diazotized and then coupled with an acetoacetanilide compound, wherein the aromatic amine is represented by the following general formula (6): It is an amine, and the acetoacetanilide compound is a compound represented by a compound represented by the following general formula (7), a compound represented by the general formula (2) and an aromatic represented by the general formula (6) The present invention relates to a method for producing a pigment composition obtained by reacting with an acetoacetanilide compound represented by the general formula (7) after mixing an amine diazotate.

General formula (6)

General formula (7)

(X _{1 to} X ₁₀ in the formula are synonymous with those defined in the general formula (1).)

  The present invention is also a method for producing the above pigment composition, wherein the aromatic amine is diazotized and then coupled with an acetoacetanilide compound, wherein the aromatic amine is represented by the following general formula (6): An amine and the acetoacetanilide compound is a compound represented by the following general formula (7), a compound represented by the general formula (2) and an acetoacetanilide represented by the general formula (7): It is related with the manufacturing method of the pigment composition obtained by making it react with the diazo compound of an aromatic amine represented by General formula (6), after mixing a compound.

General formula (6)

General formula (7)

(X _{1 to} X ₁₀ in the formula are synonymous with those defined in the general formula (1).)

  The present invention is also a method for producing the above pigment composition, wherein the aromatic amine is diazotized and then coupled with an acetoacetanilide compound, wherein the aromatic amine is represented by the following general formula (6): In a buffer aqueous solution having a pH of 3 to 6, which is an amine and the acetoacetanilide compound is a compound represented by the compound represented by the following general formula (7) and contains the compound represented by the general formula (2) A pigment composition obtained by simultaneously adding a diazotized aromatic amine represented by general formula (6) and a basic solution of an acetoacetanilide compound represented by general formula (7) at a constant flow rate. It relates to a manufacturing method.

General formula (6)

General formula (7)

(X _{1 to} X ₁₀ in the formula are synonymous with those defined in the general formula (1).)

  The present invention is also a method for producing the above pigment composition, wherein the aromatic amine is diazotized and then coupled with an acetoacetanilide compound, wherein the aromatic amine is represented by the following general formula (6): It is an amine, and the acetoacetanilide compound is a compound represented by the compound represented by the following general formula (7), and is a diazotized product of the aromatic amine represented by the general formula (6) and the general formula (7). The present invention relates to a method for producing a pigment composition obtained by mixing a pigment slurry obtained by reacting the represented acetoacetanilide compound with a compound represented by the general formula (2).

General formula (6)

General formula (7)

(X _{1 to} X ₁₀ in the formula are synonymous with those defined in the general formula (1).)

  The present invention also provides a method for producing the pigment composition, wherein the mixture of the compounds represented by the general formula (1) and the general formula (2) is added in the presence of a water-soluble inorganic salt and a water-soluble organic solvent. The present invention relates to a method for producing a pigment composition obtained by removing a water-soluble inorganic salt and a water-soluble organic solvent after wet-kneading.

  Moreover, this invention relates to the said pigment composition whose average primary particle diameter is 200 nm or less.

  Moreover, this invention relates to the said pigment composition whose specific conductivity of the aqueous solution which boiled and extracted the pigment composition with ion-exchange water is less than 200 microsiemens / cm.

  Moreover, this invention relates to the said pigment composition whose content of calcium, magnesium, and iron is each less than 150 ppm.

  Moreover, this invention relates to the said pigment composition whose sum total of content of calcium, magnesium, and iron is less than 300 ppm.

  Moreover, this invention relates to the pigment dispersion containing the said pigment composition.

  The present invention also relates to an ink-jet ink containing the pigment composition or the pigment dispersion according to claim 15.

  The present invention also relates to an electrophotographic toner containing the pigment composition.

  The pigment composition of the present invention includes various monoazo pigments and monoazo pigment derivatives having a specific functional group. A monoazo pigment derivative having a specific functional group has an effect of enhancing dispersibility of various monoazo pigments and further inhibiting crystal growth. Therefore, a fine pigment composition excellent in heat resistance and dispersibility stability can be produced as compared with these monoazo pigments not containing a monoazo pigment derivative. Furthermore, since these monoazo pigment derivatives can obtain the same effect by various methods of use, pigment compositions having the same effect can be produced by various methods.

  First, the compound represented by the general formula (1) and the compound represented by the general formula (2) of the present invention will be described.

As a halogen atom in X < ₁ > -X < ₁₅ > of General formula (1) and General formula (2), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

Examples of the alkyl group having 1 to 5 carbon atoms in X _{1 to} X ₁₅ in the general formula (1) and the general formula (2) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and sec-butyl. Group, tert-butyl group, pentyl group, isopentyl group, sec-pentyl group, neopentyl group and the like. However, it is not limited to these examples.

The alkoxyl group having 1 to 5 carbon atoms for X ₁ to X ₁₅ in formula (1) and general formula (2), a methoxy group, an ethoxy group, a propoxy group, a butoxy group, tert- butoxy group, pentyloxy group, And neopentyloxy group. However, it is not limited to these.

The alkoxycarbonyl group having 1 to 5 carbon atoms for X ₁ to X ₅ in the general formula (1) and general formula (2), a methoxycarbonyl group, an ethoxycarbonyl group, tert- butoxycarbonyl group, pentyloxycarbonyl group or the like Can be mentioned. However, it is not limited to these.

In X _{1 to} X ₅ and X _{6 to} X ₁₀ , the optionally substituted heterocyclic structure formed by including adjacent groups together and further containing a nitrogen atom, oxygen atom or sulfur atom includes an indole group, Examples thereof include a benzimidazolone group, a benzofuryl group, a benzothienyl group, a pyrrole group, and a quinoline group. However, it is not limited to these.

Examples of the alkyl group having 20 or less carbon atoms which may have a substituent in R ′, R ₁ and R ₂ in the general formula (3) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, sec-butyl, tert-butyl, sec-pentyl, tert-pentyl, A tert-octyl group, a neopentyl group, a cyclopropyl group, cyclobutyl, a cyclopentyl group and the like can be mentioned. However, it is not limited to these.

The alkenyl group having 20 or less carbon atoms which may have a substituent in R ′, R ₁ and R ₂ in the general formula (3) includes a vinyl group, a 1-propenyl group, an allyl group, and a 2-butenyl group. 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 1-octenyl group, 1-octadecenyl group, cyclopentenyl Group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group, trifluoroethenyl group, 1-chloroethenyl group, 2,2-dibromoethenyl group, 4-hydroxy-1-butenyl Groups and the like. However, it is not limited to these.

Examples of the aryl group having 20 or less carbon atoms which may have a substituent in R ′, R ₁ and R ₂ in the general formula (3) include a phenyl group, a biphenyl group, an indenyl group, a tolyl group, a xylyl group, Examples include a p-cyclohexylphenyl group, a p-cumenyl group, and an m-carboxyphenyl group. However, it is not limited to these.

As the alkylene group having 20 or less carbon atoms which may have a substituent in Y ₂ , Y _2a and Y _2c of the general formula (3), a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a propylene group Ethylmethylene group, chloromethylene group, dimethylmethylene group, bis (trifluoromethyl) methylene group and the like. However, it is not limited to these.

As the alkenylene group having 20 or less carbon atoms which may have a substituent in Y ₂ , Y _2a and Y _2c of the general formula (3), vinylene group, 1-methylvinylene group, propenylene group, 1-butenylene Group, 2-butenylene group, 1-pentenylene group, 2-pentenylene group and the like. However, it is not limited to these.

As an arylene group having 20 or less carbon atoms which may have a substituent in Y ₂ , Y _2a and Y _2c of the general formula (3), an o-phenylene group, an m-phenylene group, a p-phenylene group, 4-methyl-1,2-phenylene group, 4-chloro-1,2-phenylene group, 4-hydroxy-1,2-phenylene group, 2-methyl-1,4-phenylene group, p, p'-biphenylylene Groups and the like. However, it is not limited to these.

Examples of the optionally substituted heterocyclic structure formed by combining R ₁ and R ₂ with further nitrogen atom, oxygen atom or sulfur atom include indole group, benzimidazolone group, benzofuryl group, Examples thereof include a benzothienyl group, a pyrrole group, and a quinoline group. However, it is not limited to these.

As an optionally substituted heterocyclic structure in which R ′, R ₁ , and R ₂ are each independently formed with Y ₂ and further containing a nitrogen atom, an oxygen atom, or a sulfur atom, Include indole group, benzimidazolone group, benzofuryl group, benzothienyl group, pyrrole group, quinoline group and the like. However, it is not limited to these.

  The pigment composition of the present invention has a compound represented by the general formula (1) (hereinafter referred to as various monoazo pigments) and a compound represented by the general formula (2) (hereinafter referred to as various monoazo pigment derivatives). ).

  Various monoazo pigments used in the present invention are not particularly limited. I. Pigment Yellow 1, 2, 2, 3, 4, 6, 9, 49, 61, 62, 65, 73, 74, 75, 97, 98, 105, 111, 116, 120, 130, 133, 151, 154, 167, 168, 169, 175, 181, 194, 203, 213, C.I. I. Pigment Orange 1, 36, 60, 62, 64 and the like. Of these, C.I. is preferred in terms of hue, clarity and transparency. I. Pigment Yellow 74 is particularly preferable. These monoazo pigments may be used alone or in combination.

  The form of various monoazo pigments used in the present invention is not particularly limited. Commercially available pigments may be used as they are, or synthesized and used. Further, if necessary, it may be used after being refined to a desired particle size by a method such as acid pasting, solvent salt milling, or dry milling.

  Various monoazo pigments of the present invention can be synthesized by known methods. A typical synthesis method is illustrated below.

  As a first example, there is a method in which diazotized products of various aromatic amines are added to a slurry containing an acetoacetanilide compound. First, the acetoacetanilide compound represented by the general formula (7) is dissolved in an alkaline aqueous solution having a pH of 10 or more, and poured into a previously prepared acetic acid aqueous solution to prepare a pH 3-6 suspension. On the other hand, various aromatic amines represented by the above general formula (6) are added to a hydrochloric acid aqueous solution to prepare a suspension having a pH of 2 or less, and after cooling to 5 ° C. or less, sodium nitrite is added. In addition, diazotization is performed. After completion of diazotization, sulfamic acid is added to the reaction mixture to remove excess nitrous acid, and an aqueous solution of diazotized product is prepared. The aqueous solution of the diazotized compound prepared above is added to a slurry of an acetoacetanilide compound at 10 to 50 ° C. over 30 to 90 minutes to perform a coupling reaction, and the resulting slurry is filtered, washed with water, dried, The pigment composition can be obtained by grinding.

  As a second example, there is a method in which an alkaline aqueous solution of an acetoacetanilide compound is added to diazotized aqueous solutions of various aromatic amines. First, the acetoacetanilide compound represented by the general formula (7) is dissolved in an alkaline aqueous solution having a pH of 10 or more to prepare an aqueous solution. On the other hand, various aromatic amines represented by the above general formula (6) are added to a hydrochloric acid aqueous solution to prepare a suspension having a pH of 2 or less, and after cooling to 5 ° C. or less, sodium nitrite is added. In addition, diazotization is performed. After completion of diazotization, sulfamic acid is added to the reaction mixture to remove excess nitrous acid, and an aqueous solution containing acetic acid and sodium hydroxide is added to prepare a diazotized aqueous solution having a pH of 2 to 4. A coupling reaction is performed by adding the aqueous solution of the acetoacetanilide compound prepared above to a diazotized aqueous solution at 0 to 30 ° C. over 1 to 60 minutes, and the resulting slurry is filtered, washed with water, dried and pulverized. Thus, a pigment composition can be obtained.

  As a third example, an alkaline aqueous solution of an aromatic amine diazotate and an acetoacetanilide compound is gradually added at a constant flow rate simultaneously to an aqueous solution prepared by previously adding a base such as acetic acid and sodium hydroxide. A method is mentioned. First, the acetoacetanilide compound represented by the general formula (7) is dissolved in an alkaline aqueous solution having a pH of 10 or more to prepare an aqueous solution. On the other hand, various aromatic amines represented by the above general formula (6) are added to a hydrochloric acid aqueous solution to prepare a suspension having a pH of 2 or less, and after cooling to 5 ° C. or less, sodium nitrite is added. In addition, diazotization is performed. After completion of diazotization, sulfamic acid is added to the reaction mixture to remove excess nitrous acid, and an aqueous solution of diazotized product is prepared. Moreover, the buffer solution aqueous solution of pH 3-6 which melt | dissolved acetic acid and sodium hydroxide is prepared as a reaction tank. The aqueous solution of the diazotized compound and the aqueous solution of the acetoacetanilide compound prepared as described above were added to the aqueous buffer solution prepared as a reaction vessel, and the aqueous solution of the aqueous buffer solution was kept at a temperature of 10 to 50 ° C. and the pH was kept at 6 or less. By simultaneously adding them over a period of time, a coupling reaction is carried out, and the resulting slurry can be filtered, washed with water, dried and ground to obtain a pigment composition.

  Examples of the aromatic amine used in the present invention include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4 -(Trifluoromethyl) aniline, o-anisidine, m-anisidine, p-anisidine, 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-ni Roaniline, 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-2-methylaniline, 4-chloro-3-methylaniline, 5-chloro-2-methylaniline, 3 -Amino-4-chlorobenzamide, 4-amino-3-chlorobenzamide, 4-amino-3-methoxy-N-phenyl Zensulfonamide, 4-amino-N- (4-carbamoylphenyl) benzamide, dimethyl aminoterephthalate, dimethyl 5-aminoisophthalate, 6-amino-7-chloro-4-methylquinolin-2 (1H) -one, And 5-aminoisoindoline-1,3-dione. One of these may be used alone, or a plurality of these may be used in combination.

  Examples of the acetoacetanilide compound used in the present invention include acetoacetanilide, o-acetoacetanisidide, p-acetoacetanisidide, 2′-chloroacetoacetanilide, 4′-chloroacetoacetanilide, N-acetoacetyl-o. -Toluidine, N-acetoacetyl-p-toluidine, o-acetoacetaniside, p-acetoacetaniside, p-acetoacetophenidide, 4'-acetylaminoacetoacetanilide, 2 ', 4'-dimethylacetate Acetanilide, 4′-chloro-2′-methylacetoacetanilide, 5′-chloro-2′-methoxyacetoacetanilide, 4′-chloro-2 ′, 5′-dimethoxyacetoacetanilide, 5-acetoacetamide-2-benzimidazolinone , N- (7-Met Shi-2,3-dioxo-1,2,3,4-tetrahydroquinoxaline-6-yl) -3-oxo butanamide, and the like. One of these may be used alone, or a plurality of these may be used in combination.

  When the pigment is made finer by acid pasting, various monoazo pigments are dissolved in concentrated sulfuric acid and mixed with a large excess of water to precipitate fine pigment particles. Thereafter, filtration and washing with water are repeated and dried to obtain finer pigment particles.

  The method of acid pasting is not particularly limited. For example, there is a method in which various monoazo pigments are dissolved in 5 to 30 times by weight of 98% sulfuric acid, and the resulting sulfuric acid solution is mixed with 5 to 30 times by weight of water. Can be mentioned. In this case, the temperature at which various monoazo pigments are dissolved in sulfuric acid is not particularly limited as long as it does not cause a reaction such as decomposition of the raw materials or sulfonation, but it can be performed in the range of 3 to 40 ° C. Also, there are no particular limitations on the method of mixing the sulfuric acid solution of various monoazo pigments and water, and the conditions such as temperature, but in many cases, particles tend to become finer at low temperatures than when they are precipitated at high temperatures. It is preferable to carry out in the range of 0 to 60 ° C. Any water that can be used industrially, such as tap water, well water, and warm water, can be used as the water used at that time, but in order to reduce the temperature rise during precipitation, pre-cooled water is used. Is preferably used.

  The mixing method of the sulfuric acid solution and water is not particularly limited, and any method may be used as long as various monoazo pigments can be completely precipitated. For example, it can be precipitated by a method of injecting a sulfuric acid solution into ice water prepared in advance or a method of continuously injecting into running water using an apparatus such as an aspirator.

  The slurry obtained by the above method is filtered and washed to remove the acidic component, and then dried and pulverized to obtain the pigment composition of the present invention. When the slurry is filtered, the slurry obtained by mixing the sulfuric acid solution and water may be filtered as it is. However, if the slurry has poor filterability, the slurry may be heated and stirred before filtration. Moreover, you may filter, after neutralizing a slurry with various bases.

  When the pigment is refined by solvent salt milling, a mixture of at least three components of various monoazo pigments, a water-soluble inorganic salt and a water-soluble solvent is made into a clay and kneaded strongly using a kneader or the like. The kneaded mixture is put into water and stirred with various stirrers to form a slurry. By filtering this, the water-soluble inorganic salt and the water-soluble solvent are removed. The above-mentioned slurrying, filtration, and water washing are repeated to obtain a refined organic pigment.

  Sodium chloride, sodium sulfate, potassium chloride and the like can be used as the water-soluble inorganic salt. These inorganic salts are used in an amount of 1 times by weight or more, preferably 20 times by weight or less of the organic pigment. When the amount of the inorganic salt is less than 1 times by weight, it is difficult to sufficiently miniaturize the pigment. On the other hand, when the amount is more than 20 times by weight, a great amount of labor is required to remove the water-soluble inorganic salt and the water-soluble solvent after kneading, and at the same time, the amount of pigment that can be processed at one time is reduced. It is not preferable in terms.

  In the above-described method for refining the pigment, heat is often generated with kneading, and therefore, from the viewpoint of safety, it is preferable to use a water-soluble solvent having a boiling point of about 120 to 250 ° C. Examples include 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol. Monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Examples include low molecular weight polypropylene glycol.

  When the pigment is refined by dry milling, the various monoazo pigments are refined by dry pulverization with various pulverizers. In this method, the pulverization proceeds through collision and friction between the pulverizing media. An apparatus used for performing dry milling is not particularly limited, and examples thereof include a ball mill, an attritor, and a vibration mill which are dry pulverization apparatuses incorporating a pulverization medium such as beads. When dry pulverizing using these apparatuses, the inside of the pulverizing container may be decompressed or filled with an inert gas such as nitrogen gas as necessary. Further, after dry milling, the above-described solvent salt milling or stirring treatment in a solvent may be performed.

  In the above-described method for refining a pigment, various monoazo pigments may be used alone or in combination. Moreover, you may use after drying and grind | pulverizing, and you may use it in the form of the water-containing cake before drying.

  Examples of various monoazo pigment derivatives used in the present invention include compounds having the structures shown below. However, the present invention is not limited to these examples. These various monoazo pigment derivatives may be used alone or in combination of two or more. The various monoazo pigment derivatives of the present invention can be synthesized by a known method, for example, in the same manner as the above-described various monoazo pigment synthesis methods.

  In preparing the pigment composition in the present invention, various monoazo pigments and various monoazo pigment derivatives can be mixed by any method. Examples of the mixing method include, for example, a method of mixing various monoazo pigments synthesized in advance and various monoazo pigment derivatives in powder form, a method of mixing water slurries with each other, a powdered or mixed water slurry of various monoazo pigments synthesized in advance. A method of adding various dissolved monoazo pigment derivatives, a method of simultaneously generating various monoazo pigment derivatives when synthesizing various monoazo pigments, a method of synthesizing various monoazo pigments in the presence of various monoazo pigment derivatives, various monoazo pigments and various Examples thereof include a method of kneading a pigment composition comprising a monoazo pigment derivative by a solvent salt milling method. By any of these methods, a pigment composition having good dispersibility and crystal stability can be obtained.

  In the pigment composition of the present invention, the content of various monoazo pigment derivatives is preferably in the range of 0.1 mol% to 40 mol% of the total amount of various monoazo pigments and various monoazo pigment derivatives. Preferably they are 0.3 mol%-30 mol%, More preferably, they are 0.5 mol%-20 mol%. When the content is less than 0.1 mol%, the dispersion stability and crystal stability of the obtained pigment composition become insufficient. On the other hand, when it exceeds 40 mol%, a remarkable dispersion stabilizing effect and crystal stabilizing effect accompanying an increase in the amount added cannot be obtained, and in addition, the content of various monoazo pigments decreases, so the coloring power decreases. It is not preferable.

  As a method for producing the pigment composition of the present invention, among the methods exemplified above, various monoazo pigment derivatives are produced simultaneously when synthesizing various monoazo pigments, or various monoazo pigment derivatives in the presence of various monoazo pigment derivatives. A method of synthesizing a pigment or a method of kneading a pigment composition composed of various monoazo pigments and various monoazo pigment derivatives by a solvent salt milling method is particularly preferable. When a pigment composition is produced by these methods, a pigment composition is obtained in which very fine and various monoazo pigment derivatives are uniformly treated. Therefore, when used for various applications, a pigment composition having excellent dispersibility and crystal stability and high coloring power and transparency can be obtained, which is particularly preferable.

  When a pigment composition is produced by simultaneously producing various monoazo pigment derivatives when synthesizing various monoazo pigments, the compound represented by the general formula (7) and the general formula (8) are represented as an acetoacetanilide compound. A pigment composition can be produced in the same manner as in the method of synthesizing various monoazo pigments and various monoazo pigment derivatives exemplified above by mixing the compounds. At that time, the amount of the compound represented by the general formula (8) is 0.1 mol% to the total amount of the compound represented by the general formula (7) and the compound represented by the general formula (8). The range is preferably 40 mol%. Preferably they are 0.3 mol%-30 mol%, More preferably, they are 0.5 mol%-20 mol%. When the amount used is less than 0.1 mol%, the dispersion stability and crystal stability of the obtained pigment composition become insufficient. On the other hand, when it exceeds 40 mol%, a remarkable dispersion stabilizing effect and crystal stabilizing effect accompanying an increase in the amount added cannot be obtained, and in addition, the coloring power decreases because the content of various monoazo pigments decreases. It is not preferable.

  When producing a pigment composition by a method of synthesizing various monoazo pigments in the presence of various monoazo pigment derivatives, any one of the various monoazo pigment derivatives synthesized in advance is either a base component, a coupler component, or a pH 3-6 aqueous buffer solution. Otherwise, the pigment composition can be produced in the same manner as the method for synthesizing the various monoazo pigments and various monoazo pigment derivatives exemplified above.

  The pigment composition obtained in the present invention may be produced by any one of the methods described above, or may be produced by combining a plurality of methods. Further, the pigment composition prepared by any one of the above methods may be used after being further refined to a desired particle size by a method such as acid pasting, solvent salt milling, or dry milling, if necessary. The method in that case can be performed similarly to the case of the various monoazo pigments.

  In any of the above methods, the pigment composition of the present invention can be produced by adding a resin, a surfactant or the like as necessary. These additives may be used at any stage of preparing the pigment composition. For example, it may be used together with an aromatic amine or an acetoacetamide compound in the step of synthesizing a pigment composition, and may be used when performing acid pasting, solvent salt milling, dry milling, or the like.

  The type of resin used at that time is not particularly limited. For example, rosin resin, acrylic resin, styrene-acrylic resin, polyester resin, polyamide resin, polyurethane resin, fluorine resin, vinylnaphthalene-acrylic Examples thereof include acid resins and styrene-maleic acid resins. These resins may be used alone or in combination of two or more. Moreover, these can be used in 0.1-30 weight% with respect to a pigment composition, Preferably it is 1-15 weight%.

  The type of surfactant used when using the pigment composition is not particularly limited. For example, fatty acid salts, alkyl sulfate esters, alkyl aryl sulfonates, alkyl naphthalene sulfonates, dialkyl sulfonates, dialkyl sulfosuccinates. Acid salt, alkyl diaryl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol Late fatty acid ester, polyoxyethylene glycerol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer Rimmer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene alkylamine, fluorine-based nonionic surfactant, silicon-based nonionic surfactant, alkylamine Salts, quaternary amine salts, alkylpyridinium salts, alkylimidazolium salts and the like. These surfactants may be used alone or in combination of two or more. Moreover, these can be used in 0.3-20 weight% with respect to a pigment composition, Preferably it is 1-10% of range.

  As described above, the pigment composition of the present invention prepared by any method preferably has an average primary particle size of 200 nm or less, more preferably 150 nm or less, and still more preferably 100 nm or less. When the average primary particle diameter exceeds 200 nm, the coloring power when used in various applications may be inferior, and a precipitate may be produced during storage of the dispersion or ink, which is not preferable.

  In the present invention, the average primary particle diameter of the pigment composition can be measured using a scanning electron microscope or a transmission electron microscope. For example, a photograph of pigment particles is taken with a scanning electron microscope or a transmission electron microscope, and the diameter of each primary particle constituting the aggregate is measured. At that time, the diameter of the maximum portion of each particle is defined as the primary particle diameter. This measurement is performed on 100 particles included in the same field of view, and the average of the obtained values is defined as the average primary particle size.

  In the pigment composition of the present invention, the specific conductivity of an aqueous solution obtained by boiling and extracting the pigment composition with ion-exchanged water is measured as an index of the ionic impurity content contained in the pigment composition. Generally, it is known that the ionic impurities contained in the pigment composition affect the dispersion stability when used in various applications, and it is preferable that the ionic impurities be as small as possible. In the present invention, the specific conductivity of the aqueous solution obtained by boiling and extracting the pigment composition with ion-exchanged water is preferably less than 200 μS / cm, more preferably less than 150 μS / cm, and still more preferably less than 100 μS / cm.

  The method for reducing the ionic impurities contained in the pigment composition is not particularly limited as long as the specific conductivity of the aqueous solution obtained by boiling and extracting the pigment composition with ion-exchanged water falls within the above range. The method of repeating filtration and washing | cleaning after preparing a composition is mentioned. Although the kind of water used in that case is not specifically limited, It is preferable that it does not contain ionic impurities, such as distilled water and ion-exchange water.

  In the pigment composition of the present invention, the total content of calcium, magnesium and iron is preferably less than 300 ppm, more preferably less than 200 ppm, still more preferably less than 150 ppm. Moreover, it is preferable that content of each said metal element is less than 150 ppm, respectively, More preferably, it is less than 100 ppm, More preferably, it is less than 80 ppm. When the total content of calcium, magnesium, and iron is 300 ppm or more, or 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 and the nozzle of the head This is not preferable because insoluble matters are generated in the portion, which may cause nozzle clogging.

  Various methods for measuring the content of calcium, magnesium, and iron are known. For example, a solution obtained by adding nitric acid to a pigment composition and decomposing it with a microwave is diluted to an appropriate concentration. And a method of measuring using inductively coupled plasma optical emission spectrometry (ICP).

  The method for reducing the content of calcium, magnesium, and iron contained in the pigment composition is not particularly limited. For example, there is a method in which the pigment composition is slurried in an acidic aqueous solution after preparation, and filtration and washing are repeated. It is done. Although the kind of acid used in that case is not specifically limited, For example, a sulfuric acid, hydrochloric acid, an acetic acid etc. can be mentioned. In addition, the type of water used for washing is not particularly limited, but is preferably one that does not contain ionic impurities such as distilled water or ion-exchanged water.

  The pigment dispersion of the present invention includes both an aqueous pigment dispersion in which the pigment composition of the present invention is dispersed in an aqueous medium and an oily pigment dispersion in which the pigment composition is dispersed in an organic solvent.

  The aqueous pigment dispersion of the present invention can be prepared by dispersing a mixture of the pigment composition of the present invention, an aqueous medium, a resin, a surfactant and the like with various dispersers. Moreover, you may add and disperse | distribute various additives other than said raw material as needed. There are no particular restrictions on the order of addition or the method of adding the raw materials when preparing the pigment dispersion.

  In the aqueous pigment dispersion of the present invention, the content of the pigment composition is not particularly limited, but it is preferably used in the range of 5 to 50% by weight. Particularly preferably, it is 10 to 40% by weight.

  The type and content of the aqueous medium used for the production of the aqueous pigment dispersion are not particularly limited, but it is preferable to use ion-exchanged water or distilled water from which metal ions and the like have been removed. The content of the aqueous medium is preferably 30 to 95% by weight in the aqueous pigment dispersion.

  Moreover, as an aqueous medium, water and a water-soluble solvent can be mixed and used as needed. The water-soluble solvent is not particularly limited. For example, ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, ketone alcohol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol mono Examples include ethyl ether, 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetrafuryl alcohol, 4-methoxy-4-methylpentanone. One of these may be used alone, or a plurality of these may be used in combination. When these water-soluble solvents are used, the content of the water-soluble solvent is preferably 1 to 50% by weight in the aqueous pigment dispersion.

  The resin used in the production of the aqueous pigment dispersion is not particularly limited as long as it can disperse the pigment composition in an aqueous medium. For example, those exemplified as resins that can be used in producing the pigment composition Can be used. One kind of those resins may be used alone, or a plurality of resins may be used in combination. Further, the amount of use thereof is not particularly limited, but is preferably 0.5 to 30% by weight in the pigment dispersion, and more preferably 1 to 20% by weight.

  The surfactant for use in the production of the aqueous pigment dispersion is not particularly limited as long as it can disperse the pigment composition in an aqueous medium, but can be used, for example, when producing a pigment composition. What was illustrated as a surface active agent can be used. Those surfactants may be used alone or in combination. Further, the amount of use thereof is not particularly limited, but is preferably 0.5 to 30% by weight in the pigment dispersion, and more preferably 1 to 20% by weight.

  Furthermore, when manufacturing an aqueous pigment dispersion, additives, such as an antifungal agent, a pH adjuster, and an antifoamer, can be used as needed.

  An antifungal agent is used to prevent generation of wrinkles in the aqueous pigment dispersion. The type of the antifungal agent is not particularly limited. For example, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazolin-3-one, 1- Examples include amine salts of benzisothiazolin-3-one. These are preferably used in the range of 0.05 to 2% by weight in the pigment dispersion.

  The pH adjuster is used to adjust the pH of the aqueous pigment dispersion to a desired value. Although the kind of pH adjuster is not specifically limited, For example, various amines, various inorganic alkalis, ammonia, various buffer solutions, etc. are mentioned.

  Antifoaming agents are used to prevent foaming in the production of aqueous pigment dispersions. The kind of antifoaming agent is not particularly limited, and any commercially available one can be used. For example, Surfinol 104A, Surfinol 104E, Surfinol 104H, Surfinol 104BC, Surfinol 104DPM, Surfinol 104PA, Surfinol 104PG-50, Surfinol 420, Surfinol 440, Surfinol 465, Surfinol 485, Surfinol PSA-336 (both manufactured by Air Products and Chemicals) and the like can be mentioned.

  The oily pigment dispersion of the present invention can be prepared by dispersing the mixture of the pigment composition of the present invention, an organic solvent, a dispersant and the like with various dispersers. Moreover, you may add and disperse | distribute various additives other than said raw material as needed. There are no particular restrictions on the order of addition or the method of adding the raw materials when preparing the pigment dispersion.

  In the oily pigment dispersion of the present invention, the content of the pigment composition is not particularly limited, but it is preferably used in the range of 5 to 50% by weight. Particularly preferably, it is 10 to 40% by weight.

  The type and content of the organic solvent used for the production of the oil pigment dispersion are not particularly limited, but alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, acetone, methyl ethyl ketone, Methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl isopropyl ketone, ethyl-n-butyl ketone , Ketones such as ethyl isobutyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, isophorone, methyl acetate, ethyl acetate, acetic acid-n-propyl, ethyl acetate Esters such as propyl, n-butyl acetate, isobutyl acetate, hexyl acetate, octyl acetate, methyl lactate, propyl lactate, butyl lactate, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol Ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dipropyl ether, tripropylene glycol monomethyl ether Glycol ethers such as, 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, Glycol acetates such as diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, n-hexane, isohexane, n-nonane, isononane, dodecane, Saturated hydrocarbons such as isododecane, unsaturated hydrocarbons such as 1-hexene, 1-heptene, 1-octene, cyclic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, cyclodecane, decalin, cyclohexene, cycloheptene, Cyclic unsaturated hydrocarbons such as cyclooctene, 1,3,5,7-cyclooctatetraene, cyclododecene, benzene, Ene, aromatic hydrocarbons such as xylene. The content of the organic solvent is preferably 30 to 95% by weight in the oil pigment dispersion. One of these may be used alone, or a plurality of these may be used in combination.

  The dispersant used for the production of the oil pigment dispersion is not particularly limited. For example, a hydroxyl group-containing carboxylic acid ester, a salt of a long-chain polyaminoamide and a high-molecular weight acid ester, a salt of a high-molecular-weight polycarboxylic acid, a long-chain polyaminoamide, Polar acid ester salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyacrylates, polyallylamine and polyesters having a free carboxylic acid, polyether ester type anionic surfactants, naphthalene Examples thereof include salts of sulfonic acid formalin condensate, aromatic sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl phenyl ether, stearylamine acetate and the like. One of these may be used alone, or a plurality of these may be used in combination. Although the usage-amount of these is not specifically limited, It is preferable that it is 0.5 to 30 weight% in a pigment dispersion, More preferably, it is 1 to 20 weight%.

  The disperser used for producing the pigment dispersion of the present invention is not particularly limited. For example, a horizontal sand mill, a vertical sand mill, an annular bead mill, an attritor, a microfluidizer, a high speed mixer, a homomixer, a homogenizer, and a ball mill. , Paint shakers, roll mills, stone mills, ultrasonic dispersers, and the like, and any disperser or mixer that is usually used to produce various dispersions can be used.

  Further, before dispersion with various dispersers, a pre-dispersion using a kneader mixer such as a kneader or a three roll mill, or a solid dispersion using a two roll mill or the like may be performed. In addition, after dispersing with various dispersers, a post-processing step of storing in a heated state at 30 to 80 ° C. for about several hours to one week or after using an ultrasonic disperser or a collision type beadless disperser The treatment step is effective for imparting dispersion stability to the pigment dispersion. Furthermore, after performing dispersion with various dispersers, treatment with a centrifuge may be performed. This treatment is effective for removing coarse particles contained in the pigment dispersion.

  The ink-jet ink of the present invention includes both a water-based ink using the water-based pigment dispersion and an oil-based ink using the oil-based pigment dispersion.

  The aqueous inkjet ink of the present invention can be produced by adding an aqueous medium, a resin, a surfactant, other additives and the like to the aqueous pigment dispersion of the present invention and mixing them uniformly.

  In the aqueous inkjet ink of the present invention, the content of the pigment composition is not particularly limited, but is preferably 1 to 10% by weight, more preferably 2 to 7% by weight in the aqueous inkjet ink.

  The type and content of the aqueous medium used for the production of the aqueous inkjet ink are not particularly limited, but it is preferable to use ion-exchanged water or distilled water from which metal ions have been removed. The content of the aqueous medium is preferably 60 to 99% by weight in the aqueous inkjet ink.

  As the aqueous medium, a water-soluble solvent can be used as necessary in order to prevent drying and solidification of the ink in the nozzle portion of the printer head and to perform stable ejection. Although the kind of water-soluble solvent is not specifically limited, For example, what was illustrated as a water-soluble solvent which can be used by manufacture of an aqueous pigment dispersion is mentioned. One of these may be used alone, or a plurality of these may be used in combination. When these water-soluble solvents are used, the content of the water-soluble solvent is preferably in the range of 1 to 50% by weight in the aqueous inkjet ink.

  In preparing the water-based inkjet ink of the present invention, a resin can be used for imparting fixability of the pigment composition to the printing material. Although the kind of resin is not specifically limited, For example, what was illustrated as resin which can be used when manufacturing an aqueous pigment dispersion, or those oil-in-water emulsions are mentioned. Of these, oil-in-water emulsions are preferred because they can provide a low-viscosity aqueous inkjet ink and a recorded product with excellent water resistance. These resins may be used alone or in combination of a plurality of resins. The content of these resins is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight in the aqueous inkjet ink. When the content is less than 0.5%, the effect of fixing the pigment composition becomes insufficient. When the content is more than 15%, the viscosity of the ink increases or the ejection stability decreases. It may occur and is not preferable. These resins can be used after neutralizing acidic functional groups with a pH adjuster such as ammonia, various amines, various inorganic alkalis, etc., if necessary.

  When preparing the water-based inkjet ink of the present invention, a surfactant can be used as necessary in order to impart dispersion stability of the pigment composition in the ink. Although the kind of surfactant is not specifically limited, For example, what was illustrated as surfactant which can be used when manufacturing an aqueous pigment dispersion is mentioned. These surfactants may be used alone or in combination of two or more. The content of these surfactants is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight in the aqueous inkjet ink.

  When manufacturing the water-based inkjet ink of this invention, a drying accelerator, a penetrating agent, an antifungal agent, a chelating agent, a pH adjuster etc. can be used as another additive.

  The drying accelerator can be used for speeding up drying when the aqueous inkjet ink is printed. Although the kind of drying accelerator is not specifically limited, For example, alcohols, such as methanol, ethanol, isopropyl alcohol, are mentioned. One of these may be used alone, or a plurality of these may be mixed and used. Moreover, it is preferable that these content is 1 to 50 weight% in water-based inkjet ink.

  Further, when the substrate to be printed is a permeable substrate such as paper, various penetrants can be used in order to promote ink permeation into the substrate and speed up apparent drying. Examples of penetrants include water-soluble solvents such as diethylene glycol monobutyl ether, alkylene glycol, alkylene diol, polyethylene glycol lauryl ether, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium oleate, di- (2-ethylhexyl) -Surfactants such as sodium sulfosuccinate. The amount of these used is less than 5% by weight in the water-based inkjet ink, and a sufficient effect is obtained. If the amount is higher than this, the viscosity of the ink increases, or the ink may bleed or lose paper, which is not preferable. .

  An antifungal agent can be used to prevent generation of wrinkles in an aqueous inkjet ink. Although the kind of antifungal agent is not specifically limited, What was illustrated as an antifungal agent which can be used when manufacturing an aqueous pigment dispersion can be used, for example. These are preferably used in the range of 0.05 to 1.0% by weight in the aqueous inkjet ink.

  The chelating agent can be used to capture metal ions contained in the water-based inkjet ink and prevent precipitation of insoluble matter in the nozzle portion of the printer head or the ink. The type of chelating agent is not particularly limited, and examples include ethylenediamine tetraacetic acid, sodium salt of ethylenediaminetetraacetic acid, diammonium salt of ethylenediaminetetraacetic acid, and tetraammonium salt of ethylenediaminetetraacetic acid. These are preferably used in the range of 0.005 to 0.5% by weight in the water-based inkjet ink.

  Moreover, in order to adjust pH of water-based inkjet ink to a desired value, various pH adjusters can be used. Although the kind of pH adjuster is not specifically limited, For example, the pH adjuster which can be used by manufacture of an aqueous pigment dispersion is mentioned.

  The oil-based inkjet ink of the present invention can be produced by adding an organic solvent, a resin, a dispersant, other additives and the like to the oil-based pigment dispersion of the present invention and mixing them uniformly.

  In the oil-based inkjet ink of the present invention, the content of the pigment composition is not particularly limited, but is preferably 1 to 10% by weight, more preferably 2 to 7% by weight in the oil-based inkjet ink.

  Although the kind of organic solvent used for manufacture of oil-based inkjet ink is not specifically limited, For example, what was illustrated as an organic solvent which can be used when manufacturing an oil-based pigment dispersion can be used. Although content of an organic solvent is not specifically limited, It is preferable that it is 80 to 97 weight% in oil-based inkjet ink. These organic solvents may be used alone or in combination of two or more.

In producing the oil-based ink jet ink of the present invention, a resin can be used in order to impart fixability of the pigment composition to the printing material. The type of resin is not particularly limited. For example, petroleum resin, casein, shellac, rosin resin, rosin ester resin, cellulose resin, natural rubber, synthetic rubber, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber, Phenol resin, terpene phenol resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, polyvinyl chloride, polyallylamine resin, vinyl chloride-vinyl acetate resin, ethylene-vinyl acetate resin , Vinylidene chloride resin, acrylic resin, methacrylic resin, urethane resin, silicone resin, fluorine resin, drying oil, synthetic drying oil, maleic acid resin, polyamide resin, polyimide resin, benzoguanamine resin, melamine resin, urea resin, butyral resin, Coumarone indene resin, Cyclohexylene resin, fumaric acid resin, polyolefin, polypropylene chloride, wax - latex resin, a styrene - acrylic resin, a styrene - maleic acid resins. One of these may be used alone, or a plurality of these may be used in combination. Although the usage-amount of these is not specifically limited, It is preferable that it is 1 to 15 weight% in oil-based inkjet ink, More preferably, it is 3 to 8 weight%.

  When preparing the oil-based inkjet ink of the present invention, a dispersant can be used as necessary in order to impart dispersion stability of the pigment composition in the ink. Although the kind of dispersing agent is not specifically limited, What was illustrated as a dispersing agent which can be used when manufacturing an oil-based pigment dispersion can be used, for example. One of these may be used alone, or a plurality of these may be used in combination. Although the usage-amount of these is not specifically limited, It is preferable that it is 0.1 to 15 weight% in oil-based inkjet ink, More preferably, it is 0.5 to 10 weight%.

  The oil-based inkjet ink of the present invention may contain further additives. Examples of the additive include a wetting agent, a degassing agent / defoaming agent, a preservative, and an antioxidant.

  When preparing the ink-jet ink by mixing the above raw materials, the method of mixing the raw materials is not particularly limited, and it can be performed using a high-speed disperser, an emulsifier, etc., in addition to a stirrer using a normal wing. it can. At that time, the order of adding the raw materials and the mixing method are not particularly limited.

  Moreover, the coarse particle contained in ink can be removed by mixing each raw material and filtering the prepared inkjet ink with various filters. The pore size of the filter used at that time is preferably 1 μm or less, and more preferably 0.65 μm or less.

  Hereinafter, although an example explains the details of the present invention, the present invention is not limited to this.

<Preparation of various monoazo pigments and various pigment compositions>
Production Example 1 <Preparation of Monoazo Pigment A (CI Pigment Yellow 74)>
As a diazo component, 67.3 g of 2-methoxy-4-nitroaniline was added to 500 g of water and stirred to prepare a suspension, and ice was added to adjust the temperature to 5 ° C. or lower. Thereto was added 105 g of 35% hydrochloric acid, and the mixture was stirred for 1 hour while maintaining at 5 ° C. or lower. Then, diazotization was performed by adding an aqueous solution in which 28.0 g of sodium nitrite was dissolved in 72.0 g of water and stirring for 1 hour. 0.5 g of sulfamic acid was added to the reaction mixture to eliminate nitrous acid, and a diazonium aqueous solution was prepared.

On the other hand, 84.5 g of o-acetoacetanisidide and 164 g of 25% aqueous sodium hydroxide solution were added to 140 g of water as a coupler component, and stirred to completely dissolve. It 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 coupler slurry.
The coupler slurry prepared above was heated to 40 ° C., and a diazonium aqueous solution was dropped therein over 1 hour. After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour to complete the reaction. After completion of the reaction, the slurry was heated to 90 ° C., stirred for 1 hour, and then filtered through a Buchner funnel having a diameter of 285 mm. The filter cake was washed with 25 liters of ion-exchanged water, dried, and pulverized to obtain 150 g of a monoazo pigment A (CI Pigment Yellow 74).

Production Example 2 <Preparation of Monoazo Pigment B (CI Pigment Yellow 1)>
In Production Example 1, 67.3 g of 2-methoxy-4-nitroaniline used as a diazo component was added to 60.9 g of 4-methyl-2-nitroaniline, and 84.5 g of o-acetoacetaniside used as a coupler component. In the same manner as in Production Example 1 except that the content was changed to 72.3 g of acetoacetanilide, and 132 g of monoazo pigment B (CI Pigment Yellow 1) was obtained.

Production Example 3 <Preparation of Monoazo Pigment C (CI Pigment Yellow 9)>
In Production Example 1, 67.3 g of 2-methoxy-4-nitroaniline used as a diazo component was added to 60.9 g of 4-methyl-2-nitroaniline, and 84.5 g of o-acetoacetaniside used as a coupler component. 137 g of monoazo pigment C (CI Pigment Yellow 9) was obtained in the same manner as in Production Example 1 except for changing to N-acetoacetyl-o-toluidine 78.0 g.

Production Example 4 <Preparation of Monoazo Pigment D (CI Pigment Yellow 73)>
In Production Example 1, 67.3 g of 2-methoxy-4-nitroaniline used as the diazo component was changed to 69.0 g of 4-chloro-2-nitroaniline, and the same procedure as in Production Example 1 was conducted, except that monoazo pigment was used. 151 g of D (C.I. Pigment Yellow 73) was obtained.

Production Example 5 <Preparation of Monoazo Pigment E (CI Pigment Yellow 105)>
In Production Example 1, 67.3 g of 2-methoxy-4-nitroaniline used as the diazo component was changed to 83.4 g of 6-amino-7-chloro-4-methylquinolin-2 (1H) -one, and the others Produced 165 g of monoazo pigment E (CI Pigment Yellow 105) in the same manner as in Production Example 1.

Production Example 6 <Preparation of Monoazo Pigment F (CI Pigment Yellow 213)>
In Production Example 1, 67.3 g of 2-methoxy-4-nitroaniline used as a diazo component was added to 83.7 g of dimethyl aminoterephthalate, and 84.5 g of o-acetoacetaniside used as a coupler component was N- (7 -Methoxy-2,3-dioxo-1,2,3,4-tetrahydroquinoxalin-6-yl) -3-oxobutanamide was changed to 119 g, respectively. (C.I. Pigment Yellow 213) 198 g was obtained.

Example 1 <Preparation of Pigment Composition A>
93.5 g of monoazo pigment A (CI Pigment Yellow 74) prepared in Production Example 1 and 6.5 g of powder of monoazo pigment derivative A represented by the following formula were uniformly mixed to obtain 100 g of pigment composition A. . The content of the monoazo pigment derivative A in the pigment composition A was 5.0 mol%.

Monoazo pigment derivative A

Example 2 <Preparation of Pigment Composition B>
93.1 g of monoazo pigment A (CI Pigment Yellow 74) prepared in Production Example 1 and 6.9 g of powder of monoazo pigment derivative B represented by the following formula were uniformly mixed to obtain 100 g of pigment composition B. . The content of the monoazo pigment derivative B in the pigment composition B was 5.0 mol%.

Monoazo pigment derivative B

Example 3 <Preparation of Pigment Composition C>
89.3 g of monoazo pigment B (CI Pigment Yellow 1) prepared in Production Example 2 and 10.7 g of monoazo pigment derivative C powder represented by the following formula were uniformly mixed to obtain 100 g of pigment composition C. . The content of the monoazo pigment derivative C in the pigment composition C was 5.0 mol%.

Monoazo pigment derivative C

Example 4 <Preparation of Pigment Composition D>
93.2 g of monoazo pigment C (CI Pigment Yellow 9) prepared in Production Example 3 and 6.8 g of powder of monoazo pigment derivative D represented by the following formula were uniformly mixed to obtain 100 g of pigment composition D. . The content of the monoazo pigment derivative D in the pigment composition D was 5.0 mol%.

Monoazo pigment derivative D

Example 5 <Preparation of Pigment Composition E>
93.4 g of monoazo pigment D (CI Pigment Yellow 73) prepared in Production Example 4 and 6.6 g of powder of monoazo pigment derivative E represented by the following formula were uniformly mixed to obtain 100 g of pigment composition E. . The content of the monoazo pigment derivative E in the pigment composition E was 5.0 mol%.

Monoazo pigment derivative E

Example 6 <Preparation of Pigment Composition F>
92.1 g of monoazo pigment E (CI Pigment Yellow 105) prepared in Production Example 5 and 7.9 g of powder of monoazo pigment derivative F represented by the following formula were uniformly mixed to obtain 100 g of pigment composition F. . The content of the monoazo pigment derivative F in the pigment composition F was 5.0 mol%.

Monoazo pigment derivative F

Example 7 <Preparation of Pigment Composition G>
94.6 g of monoazo pigment F (CI Pigment Yellow 213) prepared in Production Example 6 and 5.4 g of powder of monoazo pigment derivative G represented by the following formula were uniformly mixed to obtain 100 g of pigment composition G. . The content of the monoazo pigment derivative G in the pigment composition G was 5.0 mol%.

Monoazo pigment derivative G

Example 8 <Preparation of Pigment Composition H>
A mixture of 280.4 g of monoazo pigment A (CI Pigment Yellow 74) prepared in Production Example 1, 19.6 g of monoazo pigment derivative A, 1500 g of sodium chloride, and 250 g of diethylene glycol was used as a stainless gallon kneader (manufactured by Inoue Seisakusho). And kneaded at 60 ° C. for 6 hours to obtain a clay-like kneaded product. This kneaded product was put into 15 liters of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry. The slurry was divided into three equal parts and each was filtered through a Buchner funnel with a diameter of 285 mm. The filter was washed by sprinkling 15 liters of warm water at 50 ° C. The filter cake was taken out and added to an aqueous solution in which 250 g of 35% hydrochloric acid and 15 liters of tap water were mixed and stirred to form a slurry. After stirring for 1 hour, the slurry was divided into three equal parts, and each was filtered through a Buchner funnel having a diameter of 285 mm. Each filter was washed with 15 liters of tap water. The filter cake was taken out, added to 15 liters of ion exchange water, and stirred to form a slurry. After stirring for 1 hour, the slurry was divided into three equal parts, and each was filtered through a Buchner funnel having a diameter of 285 mm. The filter cake was washed with 15 liters of deionized water, dried and pulverized to obtain 230 g of a pigment composition. The content of the monoazo pigment derivative A in the pigment composition H was 5.0 mol%.

Example 9 <Preparation of Pigment Composition I>
A mixture of 280.4 g of monoazo pigment A (CI Pigment Yellow 74) prepared in Production Example 1, 19.6 g of monoazo pigment derivative A, 1500 g of sodium chloride, and 250 g of diethylene glycol was used as a stainless gallon kneader (manufactured by Inoue Seisakusho). And kneaded at 60 ° C. for 6 hours to obtain a clay-like kneaded product. This kneaded product was put into 15 liters of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry. The slurry was divided into three equal parts and each was filtered through a Buchner funnel with a diameter of 285 mm. The filter cake was washed with 15 liters of warm water at 50 ° C., dried and pulverized to obtain 235 g of a pigment composition I. The content of the monoazo pigment derivative A in the pigment composition I was 5.0 mol%.

Example 10 <Preparation of Pigment Composition J>
In Example 8, the monoazo pigment A (CI Pigment Yellow 74) 280.4 g used in Example 8 was changed to 279.4 g, the monoazo pigment derivative A 19.6 g was changed to monoazo pigment derivative B 20.6 g, and the others were changed to Example 8. In the same manner, 230 g of a pigment composition J was obtained. The content of the monoazo pigment derivative B in the pigment composition J was 5.0 mol%.

Example 11 <Preparation of Pigment Composition K>
The monoazo pigment A (CI Pigment Yellow 74) 280.4 g used in Example 9 was changed to 279.4 g, the monoazo pigment derivative A 19.6 g was changed to monoazo pigment derivative B 20.6 g, and the rest of the examples In the same manner as in No. 9, pigment composition K234g was obtained. The content of the monoazo pigment derivative B in the pigment composition K was 5.0 mol%.

Example 12 <Preparation of Pigment Composition L>
In Production Example 1, 84.5 g of o-acetoacetaniside used as the coupler component was changed to a mixture of 80.3 g of o-acetoacetaniside and 6.8 g of acetoacetanilide compound A represented by the following formula, Otherwise, the same procedure as in Production Example 1 was carried out to obtain a pigment composition L152g. The components contained in the pigment composition L were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative A, and the content of the monoazo pigment derivative A was 5.0 mol%.

Acetoacetanilide compound A

Example 13 <Preparation of Pigment Composition M>
In Production Example 1, 84.5 g of o-acetoacetaniside used as the coupler component was changed to a mixture of 84.4 g of o-acetoacetaniside and 0.068 g of acetoacetanilide compound A. Otherwise, Production Example 1 Similarly, 150 g of pigment composition M was obtained. The components contained in the pigment composition M were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative A, and the content of the monoazo pigment derivative A was 0.05 mol%.

Example 14 <Preparation of Pigment Composition N>
In Production Example 1, 84.5 g of o-acetoacetaniside used as a coupler component was changed to a mixture of 84.1 g of o-acetoacetaniside and 0.68 g of acetoacetanilide compound A. Otherwise, Production Example 1 Similarly, 150 g of pigment composition N was obtained. The components contained in pigment composition N were monoazo pigment A (CI Pigment Yellow 74) and monoazo pigment derivative A, and the content of monoazo pigment derivative A was 0.50 mol%.

Example 15 <Preparation of Pigment Composition O>
In Production Example 1, 84.5 g of o-acetoacetaniside used as the coupler component was changed to a mixture of 71.9 g of o-acetoacetaniside and 20.4 g of acetoacetanilide compound A. Otherwise, Production Example 1 Similarly, a pigment composition O157g was obtained. The components contained in the pigment composition O were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative A, and the content of the monoazo pigment derivative A was 15.0 mol%.

Example 16 <Preparation of Pigment Composition P>
In Production Example 1, 84.5 g of o-acetoacetaniside used as a coupler component was changed to a mixture of 59.2 g of o-acetoacetaniside and 40.8 g of acetoacetanilide compound A. Similarly, 165 g of pigment composition P was obtained. The components contained in the pigment composition P were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative A, and the content of the monoazo pigment derivative A was 30.0 mol%.

Example 17 <Preparation of Pigment Composition Q>
In Production Example 1, 84.5 g of o-acetoacetaniside used as the coupler component was changed to a mixture of 42.2 g of o-acetoacetaniside and 68.0 g of acetoacetanilide compound A represented by the general formula 16, Other than that was carried out similarly to manufacture example 1, and obtained pigment composition Q174g. The components contained in the pigment composition Q are a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative A represented by the general formula 9, and the content of the monoazo pigment derivative A is 50.0 mol%. there were.

Example 18 <Preparation of Pigment Composition R>
In Production Example 1, 84.5 g of o-acetoacetaniside used as a coupler component was changed to a mixture of 80.3 g of o-acetoacetaniside and 7.4 g of acetoacetanilide compound B represented by the following formula, Except that, Pigment composition R152g was obtained in the same manner as in Production Example 1. The components contained in the pigment composition R were a monoazo pigment A (CI Pigment Yellow 74) and a pigment derivative B, and the content of the monoazo pigment derivative B was 5.0 mol%.

Acetoacetanilide compound B

Example 19 <Preparation of Pigment Composition S>
In Production Example 1, 84.5 g of o-acetoacetaniside used as a coupler component was changed to a mixture of 84.4 g of o-acetoacetaniside and 0.074 g of acetoacetanilide compound B. Similarly, 150 g of pigment composition S was obtained. The components contained in the pigment composition S were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative B, and the content of the monoazo pigment derivative B was 0.05 mol%.

Example 20 <Preparation of Pigment Composition T>
In Production Example 1, 84.5 g of o-acetoacetaniside used as the coupler component was changed to a mixture of 84.1 g of o-acetoacetaniside and 0.74 g of acetoacetanilide compound B. Similarly, 150 g of pigment composition T was obtained. The components contained in the pigment composition T were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative B, and the content of the monoazo pigment derivative B was 0.5 mol%.

Example 21 <Preparation of Pigment Composition U>
In Production Example 1, 84.5 g of o-acetoacetaniside used as a coupler component was changed to a mixture of 71.8 g of o-acetoacetaniside and 22.2 g of acetoacetanilide compound B. Similarly, pigment composition U157g was obtained. The components contained in the pigment composition U were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative B, and the content of the monoazo pigment derivative B was 15.0 mol%.

Example 22 <Preparation of Pigment Composition V>
In Production Example 1, 84.5 g of o-acetoacetaniside used as the coupler component was changed to a mixture of 59.1 g of o-acetoacetaniside and 44.3 g of acetoacetanilide compound B. Other than that, Production Example 1 Similarly, 166 g of pigment composition V was obtained. The components contained in the pigment composition V were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative B, and the content of the monoazo pigment derivative B was 30.0 mol%.

Example 23 <Preparation of Pigment Composition W>
In Production Example 1, 84.5 g of o-acetoacetaniside used as the coupler component was changed to a mixture of 42.3 g of o-acetoacetaniside and 73.9 g of acetoacetanilide compound B. Similarly, 175 g of pigment composition W was obtained. The components contained in the pigment composition W were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative B, and the content of the monoazo pigment derivative B was 50.0 mol%.

Example 24 <Preparation of Pigment Composition X>
In Production Example 1, 67.3 g of 2-methoxy-4-nitroaniline used as a diazo component was converted to 56.6 g of 4-chloro-2-methylaniline, and 84.5 g of o-acetoacetaniside used as a coupler component. Is changed to a mixture of 105.3 g of 4′-chloro-2 ′, 5′-dimethoxyacetoacetanilide and 7.0 g of an acetoacetanilide compound represented by the following formula, and otherwise the same as in Production Example 1, 166 g of pigment composition X was obtained. Components contained in the pigment composition X are C.I. I. Pigment Yellow 49 and the monoazo pigment derivative H represented by the following formula, and the content of the monoazo pigment derivative H was 5.0 mol%.

Acetoacetanilide compound H

Monoazo pigment derivative H

Example 25 <Preparation of Pigment Composition Y>
In Production Example 1, 67.3 g of 2-methoxy-4-nitroaniline used as a diazo component was converted to 111.3 g of 4-amino-3-methoxy-N-phenylbenzenesulfonamide as o-acetate used as a coupler component. 84.5 g of acetanisidide was changed to a mixture of 105.3 g of 4′-chloro-2 ′, 5′-dimethoxyacetoacetanilide and 8.4 g of an acetoacetanilide compound I represented by the following formula. Similarly, 220 g of pigment composition Y was obtained. Components contained in the pigment composition Y are C.I. I. Pigment Yellow 97 and a monoazo pigment derivative I represented by the following formula, and the content of the monoazo pigment derivative I was 5.0 mol%.

Acetoacetanilide Compound I

Monoazo pigment derivative I

Example 26 <Preparation of Pigment Composition Z>
In Production Example 1, 84.5 g of o-acetoacetaniside used as a coupler component was mixed with 93.7 g of 5′-chloro-2′-methoxyacetoacetanilide and 10.7 g of acetoacetanilide compound J represented by the following formula. Other than that was carried out similarly to manufacture example 1, and obtained pigment composition Z169g. Components contained in the pigment composition Z are C.I. I. Pigment Yellow 111 and the monoazo pigment derivative J represented by the following formula, and the content of the monoazo pigment derivative J was 5.0 mol%.

Acetoacetanilide compound J

Monoazo pigment derivative J

Example 27 <Preparation of Pigment Composition a>
In Production Example 1, 67.3 g of 2-methoxy-4-nitroaniline used as a diazo component was converted to 64.8 g of 5-aminoisoindoline-1,3-dione, and o-acetoacetaniside used as a coupler component 84.5 g was changed to a mixture of 29.5 g of 2 ′, 4′-dimethylacetanilide and 6.8 g of acetoacetanilide compound A, and 149 g of pigment composition a was obtained in the same manner as in Production Example 1. Components contained in the pigment composition a are C.I. I. Pigment Yellow 167 and a monoazo pigment derivative K represented by the following formula, and the content of the monoazo pigment derivative K was 5.0 mol%.

Monoazo pigment derivative K

Example 28 <Preparation of Pigment Composition b>
As a diazo component, 67.3 g of 2-methoxy-4-nitroaniline was added to 500 g of water and stirred to prepare a suspension, and ice was added to adjust the temperature to 5 ° C. or lower. Thereto was added 105 g of 35% hydrochloric acid, and the mixture was stirred for 1 hour while maintaining at 5 ° C. or lower. Then, diazotization was performed by adding an aqueous solution prepared by adding 28.0 g of sodium nitrite to 72.0 g of water and stirring for 1 hour. 0.5 g of sulfamic acid was added to the reaction mixture to eliminate nitrous acid, and a diazonium aqueous solution was prepared. To this diazonium aqueous solution, 6.8 g of acetoacetanilide compound A was added and stirred for 10 minutes to react a part of the diazonium compound with acetoacetanilide compound A to obtain a diazonium aqueous solution containing monoazo pigment derivative A.

  On the other hand, 80.3 g of o-acetoacetanisidide and 164 g of 25% aqueous sodium hydroxide solution were added to 140 g of water as a coupler component, and the mixture was stirred and completely dissolved. It 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 coupler slurry.

  The coupler slurry prepared above was heated to 40 ° C., and a diazonium aqueous solution containing the monoazo pigment derivative A was dropped therein over 1 hour. After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour to complete the reaction. After completion of the reaction, the slurry was heated to 90 ° C., stirred for 1 hour, and then filtered through a Buchner funnel having a diameter of 285 mm. The filter cake was washed with 25 liters of ion-exchanged water, dried and pulverized to obtain 150 g of a pigment composition b. The components contained in the pigment composition b were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative A, and the content of the monoazo pigment derivative A was 5.0 mol%.

Example 29 <Preparation of Pigment Composition c>
In Example 28, acetoacetanilide compound A (6.8 g) was changed to acetoacetanilide compound B (7.4 g). Otherwise, pigment composition c (150 g) was obtained in the same manner as in Example 28. The components contained in the pigment composition c were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative B, and the content of the monoazo pigment derivative B was 5.0 mol%.

Example 30 <Preparation of Pigment Composition d>
As a diazo component, 63.9 g of 2-methoxy-4-nitroaniline was added to 500 g of water and stirred to prepare a suspension, and ice was added to adjust the temperature to 5 ° C. or lower. Thereto was added 105 g of 35% hydrochloric acid, and the mixture was stirred for 1 hour while maintaining at 5 ° C. or lower. Then, diazotization was performed by adding an aqueous solution prepared by adding 28.0 g of sodium nitrite to 72.0 g of water and stirring for 1 hour. 0.5 g of sulfamic acid was added to the reaction mixture to eliminate nitrous acid, and a diazonium aqueous solution was prepared. To this diazonium aqueous solution, 10.3 g of the monoazo pigment derivative A was added and stirred uniformly to obtain a suspension, whereby a diazonium aqueous solution containing the monoazo pigment derivative A was obtained.

  On the other hand, 80.3 g of o-acetoacetanisidide and 164 g of 25% aqueous sodium hydroxide solution were added to 140 g of water as a coupler component, and the mixture was stirred and completely dissolved. It 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 coupler slurry.

  The coupler slurry prepared above was heated to 40 ° C., and a diazonium aqueous solution containing the monoazo pigment derivative A was dropped therein over 1 hour. After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour to complete the reaction. After completion of the reaction, the slurry was heated to 90 ° C., stirred for 1 hour, and then filtered through a Buchner funnel having a diameter of 285 mm. The filter cake was washed with 25 liters of ion-exchanged water, dried and pulverized to obtain 150 g of a pigment composition. The components contained in the pigment composition d were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative A, and the content of the monoazo pigment derivative A was 5.0 mol%.

Example 31 <Preparation of Pigment Composition e>
In Example 30, 10.3 g of the monoazo pigment derivative A was changed to 10.8 g of the monoazo pigment derivative B. Otherwise, 150 g of a pigment composition e was obtained in the same manner as in Example 30. The components contained in the pigment composition e were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative B, and the content of the monoazo pigment derivative B was 5.0 mol%.

Example 32 <Preparation of Pigment Composition f>
In Example 30, 63.9 g of 2-methoxy-4-nitroaniline used as a diazo component was added to 65.6 g of 4-chloro-2-nitroaniline, and 80.3 g of o-acetoacetaniside used as a coupler component. The pigment was changed to 82.0 g of 2′-chloroacetoacetanilide, and 10.3 g of the monoazo pigment derivative A was changed to 12.2 g of the monoazo pigment derivative L1 represented by the following formula. The composition f157g was obtained. The components contained in the pigment composition f are C.I. I. Pigment Yellow 3 and monoazo pigment derivative L, and the content of monoazo pigment derivative L was 5.0 mol%.

Monoazo pigment derivative L

Example 33 <Preparation of Pigment Composition g>
In Example 30, 63.9 g of 2-methoxy-4-nitroaniline used as a diazo component was added to 65.6 g of 4-chloro-2-nitroaniline, and 80.3 g of o-acetoacetaniside used as a coupler component was added. In the same manner as in Example 30 except that 68.7 g of acetoacetanilide and 10.3 g of monoazo pigment derivative A were changed to 8.2 g of monoazo pigment derivative M represented by the following formula, 140 g of pigment composition were prepared. Obtained. Components contained in the pigment composition g are C.I. I. Pigment Yellow 6 and monoazo pigment derivative M, and the content of monoazo pigment derivative M was 5.0 mol%.

Monoazo pigment derivative M

Example 34 <Preparation of Pigment Composition h>
In Example 30, 10.3 g of the monoazo pigment derivative A was changed to 14.1 g of the monoazo pigment derivative N represented by the following formula, and a pigment composition h156 g was obtained in the same manner as in Example 30 except that. Components contained in the pigment composition h are C.I. I. Pigment Yellow 74 and monoazo pigment derivative N, and the content of monoazo pigment derivative N was 5.0 mol%.

Monoazo pigment derivative N

Example 35 <Preparation of Pigment Composition i>
In Example 30, 63.9 g of 2-methoxy-4-nitroaniline used as a diazo component was added to 79.5 g of dimethyl aminoretephthalate, and 80.3 g of o-acetoacetaniside used as a coupler component was 5-acetoacetamide. 2-Benzimidazolinone was changed to 90.4 g, and the monoazo pigment derivative A10.3 g was changed to a monoazo pigment derivative O12.2 g represented by the following formula. 179 g of composition i was obtained. The components contained in the pigment composition i are C.I. I. Pigment Yellow 175 and monoazo pigment derivative O, and the content of monoazo pigment derivative O was 5.0 mol%.

Monoazo pigment derivative O

Example 36 <Preparation of Pigment Composition j>
As a diazo component, 63.9 g of 2-methoxy-4-nitroaniline was added to 500 g of water and stirred to prepare a suspension, and ice was added to adjust the temperature to 5 ° C. or lower. Thereto was added 105 g of 35% hydrochloric acid, and the mixture was stirred for 1 hour while maintaining at 5 ° C. or lower. Then, diazotization was performed by adding an aqueous solution prepared by adding 28.0 g of sodium nitrite to 72.0 g of water and stirring for 1 hour. 0.5 g of sulfamic acid was added to the reaction mixture to eliminate nitrous acid, and a diazonium aqueous solution was prepared.

  On the other hand, 80.3 g of o-acetoacetanisidide and 164 g of 25% aqueous sodium hydroxide solution were added to 140 g of water as a coupler component, and the mixture was stirred and completely dissolved. Further, an aqueous solution in which 82.0 g of 80% acetic acid and 420 g of water were mixed was prepared, and 10.3 g of monoazo pigment derivative A was added to this aqueous solution to obtain a suspension containing monoazo pigment derivative A. Into that, the coupler solution prepared above was injected to prepare a coupler slurry containing the monoazo pigment derivative A.

  The coupler slurry containing the monoazo pigment derivative A was heated to 40 ° C., and the diazonium aqueous solution prepared above was dropped therein over 1 hour. After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour to complete the reaction. After completion of the reaction, the slurry was heated to 90 ° C., stirred for 1 hour, and then filtered through a Buchner funnel having a diameter of 285 mm. The filter cake was washed by sprinkling 25 liters of ion exchange water, dried and pulverized to obtain 152 g of a pigment composition. The components contained in pigment composition j were monoazo pigment A (CI Pigment Yellow 74) and monoazo pigment derivative A, and the content of monoazo pigment derivative A was 5.0 mol%.

Example 37 <Preparation of Pigment Composition k>
In Example 36, 10.3 g of the monoazo pigment derivative A was changed to 10.8 g of the monoazo pigment derivative B, and a pigment composition k150 g was obtained in the same manner as in Example 36 except that. Components contained in the pigment composition k were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative B, and the content of the monoazo pigment derivative B was 5.0 mol%.

Example 38 <Preparation of Pigment Composition l>
In Example 36, 63.9 g of 2-methoxy-4-nitroaniline used as the diazo component was added to 52.5 g of 4-nitroaniline, and 80.3 g of o-acetoacetaniside used as the coupler component was acetoacetanilide 68. In addition, the monoazo pigment derivative A10.3 g was changed to 7 g, and the monoazo pigment derivative P9.0 g represented by the following formula was changed, respectively, and a pigment composition l129 g was obtained in the same manner as in Example 36. The components contained in the pigment composition l are C.I. I. Pigment Yellow 4 and monoazo pigment derivative P, and the content of monoazo pigment derivative P was 5.0 mol%.

Monoazo pigment derivative P

Example 39 <Preparation of Pigment Composition m>
In Example 36, 63.9 g of 2-methoxy-4-nitroaniline used as the diazo component was added to 79.5 g of dimethyl 5-aminoisophthalate, and 80.3 g of o-acetoacetaniside used as the coupler component was 5- In the same manner as in Example 36, except that 90.4 g of acetoacetamide-2-benzimidazolinone and 10.3 g of monoazo pigment derivative A were changed to 11.0 g of monoazo pigment derivative Q 11.0 represented by the following formula, respectively. As a result, 177 g of a pigment composition was obtained. Components contained in the pigment composition m are C.I. I. Pigment Yellow 120 and monoazo pigment derivative Q, and the content of monoazo pigment derivative Q was 5.0 mol%.

Monoazo pigment derivative Q

Example 40 <Preparation of Pigment Composition n>
In Example 36, 63.9 g of 2-methoxy-4-nitroaniline used as a diazo component was added to 61.2 g of 2- (trifluoromethyl) aniline, and 80.3 g of o-acetoacetaniside used as a coupler component. The same procedure as in Example 36 was conducted, except that 9-acetoacetamide-2-benzimidazolinone of 5-acetoacetamide-2-benzimidazolinone and 10.3 g of monoazo pigment derivative A were changed to 12.8 g of monoazo pigment derivative R represented by the following formula. Thus, 161 g of pigment composition was obtained. Components contained in the pigment composition n are C.I. I. Pigment Yellow 154 and monoazo pigment derivative R, and the content of monoazo pigment derivative R was 5.0 mol%.

Monoazo pigment derivative R

Example 41 <Preparation of Pigment Composition o>
In Example 36, 63.9 g of 2-methoxy-4-nitroaniline used as a diazo component was added to 46.8 g of o-anisidine, and 80.3 g of o-acetoacetaniside used as a coupler component was 5-acetoacetamide-2. -Pigment composition in the same manner as in Example 36, except that 90.4 g of benzimidazolinone and 10.3 g of monoazo pigment derivative A were changed to 9.8 g of monoazo pigment derivative S represented by the following formula. o145 g was obtained. Components contained in the pigment composition o are C.I. I. Pigment Yellow 194 and monoazo pigment derivative S, and the content of monoazo pigment derivative S was 5.0 mol%.

Monoazo pigment derivative S

Example 42 <Preparation of Pigment Composition p>
As a diazo component, 67.3 g of 2-methoxy-4-nitroaniline was added to 500 g of water and stirred to prepare a suspension, and ice was added to adjust the temperature to 5 ° C. or lower. Thereto was added 105 g of 35% hydrochloric acid, and the mixture was stirred for 1 hour while maintaining at 5 ° C. or lower. Then, diazotization was performed by adding an aqueous solution prepared by adding 28.0 g of sodium nitrite to 72.0 g of water and stirring for 1 hour. To the reaction mixture, 0.5 g of sulfamic acid was added to eliminate nitrous acid, and water was further added to adjust the liquid volume to 1000 g to prepare a diazonium aqueous solution.

  On the other hand, 80.3 g of o-acetoacetaniside, 6.8 g of acetoacetanilide compound A, and 164 g of 25% aqueous sodium hydroxide solution were added to 140 g of water as a coupler component and stirred to completely dissolve, and then water was added. The amount of liquid was adjusted to 400 g to prepare a coupler aqueous solution.

  A reaction tank aqueous solution was prepared by uniformly mixing 365 g of water, 64.0 g of 80% acetic acid, and 71.2 g of 25% sodium hydroxide aqueous solution. The mixture was heated to 40 ° C., and the diazonium aqueous solution and the coupler aqueous solution were simultaneously added dropwise over 1 hour while maintaining the temperature while maintaining the pH of the reaction vessel at 6.0 or lower. After completion of dropping, the mixture was stirred at 40 ° C. for 1 hour to complete the reaction. After completion of the reaction, the slurry was heated to 90 ° C., stirred for 1 hour, and then filtered through a Buchner funnel having a diameter of 285 mm. The filter cake was washed with 25 liters of ion-exchanged water, dried and pulverized to obtain 151 g of a pigment composition. The components contained in the pigment composition p were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative A, and the content of the monoazo pigment derivative A was 5.0 mol%.

Example 43 <Preparation of Pigment Composition q>
A pigment composition q 152 g was obtained in the same manner as in Example 42 except that 6.8 g of the acetoacetanilide compound A used in Example 42 was changed to 7.4 g of the acetoacetanilide compound B represented by the general formula 17. The components contained in the pigment composition q were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative B, and the content of the monoazo pigment derivative B was 5.0 mol%.

Example 44 <Preparation of Pigment Composition r>
In Example 42, 67.3 g of 2-methoxy-4-nitroaniline used as a diazo component was added to 69.0 g of 4-chloro-2-nitroaniline, and 80.3 g of o-acetoacetaniside used as a coupler component was added. Pigment composition r153g was obtained like Example 42 except having changed into 79.6g of 2 ', 4'-dimethylacetoacetanilide. Components contained in the pigment composition r are C.I. I. Pigment Yellow 2 and a monoazo pigment derivative T represented by the following formula, and the content of the monoazo pigment derivative T was 5.0 mol%.

Monoazo pigment derivative T

Example 45 <Preparation of Pigment Composition s>
In Example 42, 6.8 g of acetoacetanilide compound A was changed to 6.9 g of acetoacetanilide compound U represented by the following formula, and other than that was performed in the same manner as in Example 42, to obtain 152 g of a pigment composition s. Components contained in the pigment composition s are C.I. I. Pigment Yellow 74 and a monoazo pigment derivative U represented by the following formula, and the content of the monoazo pigment derivative U was 5.0 mol%.

Acetoacetanilide compound U

Monoazo pigment derivative U

Example 46 <Preparation of Pigment Composition t>
In Example 42, 67.3 g of 2-methoxy-4-nitroaniline used as a diazo component was added to 69.0 g of 4-chloro-2-nitroaniline, and 80.3 g of o-acetoacetaniside used as a coupler component was added. The same procedure as in Example 42 was conducted, except that 87.5 g of 4′-chloro-2′-methylacetoacetanilide and 6.8 g of acetoacetanilide compound A were further changed to 8.8 g of acetoacetanilide compound V 8 represented by the following formula. As a result, 162 g of a pigment composition was obtained. Components contained in the pigment composition t are C.I. I. Pigment Yellow 98 and a monoazo pigment derivative V represented by the following formula, and the content of the monoazo pigment derivative V was 5.0 mol%.

Acetoacetate compound V

Monoazo pigment derivative V

Example 47 <Preparation of Pigment Composition u>
In Example 42, 67.3 g of 2-methoxy-4-nitroaniline used as the diazo component was changed to 60.9 g of 4-methyl-2-nitroaniline, and 6.8 g of acetoacetanilide compound A was added to an acetoacetate represented by the following formula. Pigment composition u149g was obtained like Example 42 except having changed to acetanilide compound W10.7g. Components contained in the pigment composition u are C.I. I. Pigment Yellow 203 and a monoazo pigment derivative W represented by the following formula, and the content of the monoazo pigment derivative W was 5.0 mol%.

Acetoacetanilide compound W

Monoazo pigment derivative W

Example 48 <Preparation of Pigment Composition v>
As a diazo component, 63.9 g of 2-methoxy-4-nitroaniline was added to 500 g of water and stirred to prepare a suspension, and ice was added to adjust the temperature to 5 ° C. or lower. Thereto was added 105 g of 35% hydrochloric acid, and the mixture was stirred for 1 hour while maintaining at 5 ° C. or lower. Then, diazotization was performed by adding an aqueous solution prepared by adding 28.0 g of sodium nitrite to 72.0 g of water and stirring for 1 hour. To the reaction mixture, 0.5 g of sulfamic acid was added to eliminate nitrous acid, and water was further added to adjust the liquid volume to 1000 g to prepare a diazonium aqueous solution.

  On the other hand, 80.3 g of o-acetoacetanisidide and 164 g of 25% aqueous sodium hydroxide solution were added to 140 g of water as a coupler component, stirred to dissolve completely, and further water was added to adjust the liquid volume to 400 g. A coupler aqueous solution was prepared.

  A reaction tank aqueous solution was prepared by uniformly mixing 365 g of water, 64.0 g of 80% acetic acid, and 71.2 g of 25% sodium hydroxide aqueous solution. The monoazo pigment derivative A10.2g was added in it, and it stirred uniformly, and was set as the suspension. The mixture was heated to 40 ° C., and the diazonium aqueous solution and the coupler aqueous solution were simultaneously added dropwise over 1 hour while maintaining the temperature while maintaining the pH of the reaction vessel at 6.0 or lower. After completion of dropping, the mixture was stirred at 40 ° C. for 1 hour to complete the reaction. After completion of the reaction, the slurry was heated to 90 ° C., stirred for 1 hour, and then filtered through a Buchner funnel having a diameter of 285 mm. The filter cake was washed with 25 liters of ion-exchanged water, dried and pulverized to obtain 152 g of a pigment composition. The components contained in the pigment composition v were monoazo pigment A (CI Pigment Yellow 74) and monoazo pigment derivative A, and the content of monoazo pigment derivative A was 5.0 mol%.

Example 49 <Preparation of Pigment Composition w>
Monoazo pigment derivative A10.2g used in Example 48 was changed to monoazo pigment derivative B10.8g, and other than that was carried out similarly to Example 48, and obtained pigment composition w152g. The components contained in the pigment composition w were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative B, and the content of the monoazo pigment derivative B was 5.0 mol%.

Example 50 <Preparation of Pigment Composition x>
As a diazo component, 63.9 g of 2-methoxy-4-nitroaniline was added to 500 g of water and stirred to prepare a suspension, and ice was added to adjust the temperature to 5 ° C. or lower. Thereto was added 105 g of 35% hydrochloric acid, and the mixture was stirred for 1 hour while maintaining at 5 ° C. or lower. Then, diazotization was performed by adding an aqueous solution in which 28.0 g of sodium nitrite was dissolved in 72.0 g of water and stirring for 1 hour. 0.5 g of sulfamic acid was added to the reaction mixture to eliminate nitrous acid, and a diazonium aqueous solution was prepared.
On the other hand, 80.3 g of o-acetoacetanisidide and 164 g of 25% aqueous sodium hydroxide solution were added to 140 g of water as a coupler component, and the mixture was stirred and completely dissolved. It 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 coupler slurry.

  The coupler slurry prepared above was heated to 40 ° C., and a diazonium aqueous solution was dropped therein over 1 hour. After completion of the dropwise addition, 10.2 g of the monoazo pigment derivative A represented by the general formula 9 was added and stirred at the same temperature for 1 hour. Thereafter, the slurry was heated to 90 ° C., stirred for 1 hour, and then filtered through a Buchner funnel having a diameter of 285 mm. The filter cake was washed with 25 liters of ion-exchanged water, dried and pulverized to obtain 152 g of a pigment composition. The components contained in the pigment composition x were monoazo pigment A (CI Pigment Yellow 74) and monoazo pigment derivative A, and the content of monoazo pigment derivative A was 5.0 mol%.

Example 51 <Preparation of Pigment Composition y>
In the same manner as in Example 50 except that 10.2 g of the monoazo pigment derivative A used in Example 50 was changed to 10.8 g of the monoazo pigment derivative B, 150 g of a pigment composition was obtained. The components contained in the pigment composition y were a monoazo pigment A (CI Pigment Yellow 74) and a monoazo pigment derivative B, and the content of the monoazo pigment derivative B was 5.0 mol%.

<Evaluation of various monoazo pigments and various pigment compositions>
For the monoazo pigments and pigment compositions prepared in Production Examples 1 to 6 and Examples 1 to 51, the average primary particle size, the specific conductivity of the extracted water, and the metal content were measured. The results are summarized in Table 3. Each item was measured by the following method.

(Average primary particle size)
The average primary particle size was measured from a photograph of pigment particle size taken with a scanning electron microscope. A scanning electron microscope (manufactured by JEOL Datum Co., Ltd., JSM) was prepared by applying a conductive double-sided tape to a metal sample stage, depositing a pigment or pigment composition, and depositing platinum on the sample surface by sputtering. Particles were photographed with a −6700F scanning electron microscope), and the maximum diameter was measured for each of the 100 primary particles of the pigment photographed in the same field of view. A value obtained by averaging them was calculated, and the value was defined as an average primary particle size.

(Specific conductivity of extracted water)
Various monoazo pigments or pigment compositions (5.0 g) were moistened with 10.0 g of ethanol, and 90.0 g of ion-exchanged water was further added to form a slurry. The mixture was heated while stirring with a magnetic stirrer, and after boiling, the mixture was stirred for 5 minutes. After completion of the stirring, the mixture was cooled to room temperature, and ion-exchanged water was added so that the total amount of slurry was 105.0 g. The slurry was stirred uniformly and filtered through 5 C filter paper defined by JIS P 3801. The container for receiving the filtrate was rinsed with the filtrate, filled with the filtrate, and the specific conductivity was measured with an electric conductivity meter (CM-40V, manufactured by Toa DKK Corporation).

(Metal content)
About 2 g of various monoazo pigments or pigment compositions were added to 8 ml of nitric acid, and treated with a microwave sample pretreatment device (ETHOS1 manufactured by Milestone General Co., Ltd.) according to the temperature program shown in Table 1.

Table 1

  After the treatment solution was cooled to room temperature, 2 ml of nitric acid was added, and the treatment was further carried out according to the temperature program shown in Table 2.

Table 2

  The treatment liquid was filtered through 5 types C filter paper defined by JIS P 3801, and the filtrate was measured in a 50 ml volumetric flask to obtain a measurement sample.

  The measurement sample was measured with a multi-ICP emission spectroscopic analyzer (manufactured by Varian Technologies Japan Limited, 720-ES type), and each metal element was quantified.

Table 3

<Preparation of various pigment dispersions>
(Preparation of various oil pigment dispersions)
Examples 52-76 and Comparative Examples 1-3
1000 g of various pigment compositions or various monoazo pigments, 325 g of Disperbyk130 (manufactured by BYK Chemie, pigment dispersant), 250 g of John Cryl 586 (manufactured by BASF Japan, styrene-acrylic resin), 925 g of ethylene glycol monobutyl ether acetate are mixed, The mixture was stirred with a high speed mixer until uniform. Disperse it with a horizontal wet disperser (DYNO-MILL TYPE KDL-PILOT) for 2 hours, then add 2500 g of ethylene glycol monobutyl ether acetate and disperse for another 1 hour, and disperse the oil pigment dispersions A to Z and a to b. Obtained. Table 4 summarizes the pigment composition or monoazo pigment used in each oil pigment dispersion.

Comparative Example 4 (Preparation of oil pigment dispersion c)
Various pigment compositions or various monoazo pigments were changed to Hansa Brilliant Yellow 5GX (manufactured by Clariant, CI Pigment Yellow 74), and the rest was the same as in Examples 52 to 76 and Comparative Examples 1 to 3. Dispersion c was obtained.

(Preparation of various aqueous pigment dispersions)
Examples 77-102 and Comparative Examples 5-7
1000 g of various pigment compositions or various monoazo pigments, 735 g of Joncryl HPD-96J (manufactured by BASF, styrene-acrylic resin, active ingredient 34.0%), Surfynol 104E (manufactured by Air Products and Chemicals, defoaming agent) , 50 g of active ingredient), 50 g of Revanax BX-150 (manufactured by Shoei Chemical Co., Ltd., preservative), 250 g of propylene glycol and 415 g of ion-exchanged water were mixed and stirred with a high speed mixer until uniform. It was dispersed with a horizontal wet disperser (DYNO-MILL TYPE KDL-PILOT) for 2 hours, and then 2500 g of ion-exchanged water was added and further dispersed for 1 hour to obtain aqueous pigment dispersions A to Z and a to c. . The pigment compositions or monoazo pigments used for each aqueous pigment dispersion are summarized in Table 5.

Comparative Example 8 (Preparation of aqueous pigment dispersion d)
Various pigment compositions or various monoazo pigments were changed to Hansa Brilliant Yellow 5GX (manufactured by Clariant, CI Pigment Yellow 74). Otherwise, aqueous pigments were obtained in the same manner as in Examples 77-102 and Comparative Examples 5-7. Dispersion d was obtained.

<Evaluation of various pigment dispersions>
With respect to various pigment dispersions, the dispersion particle size, viscosity, crystal stability and storage stability were evaluated by the following methods. The results are summarized in Tables 4 and 5.

(Dispersed particle size)
The dispersed particle size was evaluated based on the D50 value measured with Microtrac UPA-150 (manufactured by Nikkiso Co., Ltd.).

(viscosity)
The viscosity was measured with a B-type viscometer VISCOMETER (manufactured by Toki Sangyo Co., Ltd.) and evaluated based on a value of 60 rpm.

(Crystal stability)
As an index of crystal stability, photographs of pigments or pigment composition particles in various pigment dispersions were taken with a transmission electron microscope.

  Particles were photographed with a transmission electron microscope (H-7650 type transmission electron microscope, manufactured by Hitachi High-Technologies Corporation) using a sample obtained by dripping and drying various pigment dispersions on a mesh with a support film. The maximum diameter was measured for 100 primary particles of the pigment or pigment composition taken in the field of view. A value obtained by averaging them was calculated, and the value was defined as an average primary particle size.

  Various pigment dispersions were sealed in a screw cap bottle and stored at 70 ° C. for 4 weeks, and the same measurement was performed. Crystal stability was evaluated by the change in average primary particle size before and after storage. Before and after storage, the change rate of the average primary particle size was determined as 0, 15% exceeding 30% and 30% or less, and exceeding 30% as X.

(Storage stability)
Various pigment dispersions were sealed in a screw-mouth bottle and stored at 70 ° C. for 4 weeks, and then the dispersed particle size and viscosity were measured. Storage stability was evaluated based on changes in the dispersed particle size and viscosity before and after storage, and the presence or absence of sediment after storage.

Table 4

  As shown in Table 4, various oil-based pigment dispersions prepared using the pigment composition obtained in the present invention had a lower viscosity and a smaller dispersed particle size than the others, and showed good dispersibility. . These oil pigment dispersions were good in both storage stability and crystal stability.

Table 5

  As shown in Table 5, various aqueous pigment dispersions prepared using the pigment composition obtained in the present invention had a lower viscosity and a smaller dispersed particle size than the others, and showed good dispersibility. . These aqueous pigment dispersions were good in both storage stability and crystal stability.

<Preparation of various ink-jet inks>
(Preparation of various oil-based inkjet inks)
Examples 103-127 and Comparative Examples 9-12
25.0 g of various oil pigment dispersions prepared in Examples 57 to 76 and Comparative Examples 1 to 4, 10.0 g of propylene glycol monomethyl ether acetate, 55.0 g of ethylene glycol monobutyl ether acetate, and 10.0 g of diethylene glycol monoethyl ether acetate After mixing and stirring for 1 hour, oil-based inkjet inks A to Z and a to c were obtained by filtering with a PTFE membrane filter having a pore size of 1.0 μm.

(Preparation of water-based inkjet ink)
Examples 128-153 and Comparative Examples 13-16
15.0 g of the aqueous pigment dispersion prepared in Examples 77 to 102 and Comparative Examples 5 to 8, acrylic resin emulsion W-215 (manufactured by Nippon Polymer Kogyo Co., Ltd., solid content 30%) 1.5 g, ethylene glycol 15.0 g Then, 68.5 g of ion-exchanged water was mixed and 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 A to Z and a to d.

<Evaluation of various ink-jet inks>
(Evaluation of oil-based inkjet ink)
The dischargeability of various oil-based inkjet inks by a printer and the coloring power of the obtained printed matter were evaluated. The results are summarized in Table 6.

  In the evaluation of ejection properties, various oil-based ink-jet inks were filled in a cartridge of an ink-jet printer IP-6500 (manufactured by Seiko Eye Infotech Co., Ltd.) and printed on a glossy PVC sheet MD5 (manufactured by Metamark). The printed matter was visually observed for the presence of missing dots (portions where printing was not performed), and used as an index of ejection properties. When the nozzle of the printer head in which the dot missing occurred was less than 1% of all the nozzles, it was judged as ○, when it was 1% or more and less than 5%, Δ when it exceeded 5%, and ×.

  In the evaluation of coloring power, for each printed matter, the reflection density of a portion where no dot omission occurred was measured with a reflection densitometer D19C (manufactured by Gretag Machbeth). Based on the oil-based ink-jet ink c prepared in Comparative Example 12, the ratio of reflection density was greater than 90% and less than 105%, Δ, the ratio of reflection density was 105% or more, Those having a ratio of less than 90% were judged as x.

(Evaluation of water-based inkjet ink)
The dischargeability of various water-based inkjet inks by a printer and the coloring power of the obtained printed matter were evaluated. The results are summarized in Table 7.

  In the evaluation of ejection performance, various aqueous inkjet inks were filled in a cartridge of an inkjet printer HG-5130 (manufactured by Seiko Epson Corporation) and printed on photographic paper / glossy gold (manufactured by Canon Inc.). The printed matter was visually observed for the presence or absence of missing dots (portions where printing was not performed), and used as an index of ejection properties. When the nozzle of the printer head in which the dot missing occurred was less than 1% of all the nozzles, it was judged as ○, when it was 1% or more and less than 5%, Δ when it exceeded 5%, and ×.

  In the evaluation of the coloring power, the reflection density of a portion where no missing dot was generated for each printed matter was measured with a reflection densitometer D19C (manufactured by Gretag Machbeth). Based on the water-based inkjet ink d prepared in Comparative Example 16, the ratio of reflection density was greater than 95% and less than 105%, Δ, the ratio of reflection density was 105% or more, and the reflection density Those having a ratio of less than 95% were judged as x.

Table 6

  As shown in the results of Table 6, various oil-based ink-jet inks prepared using the various pigment compositions obtained in the present invention were superior in dischargeability and coloring power as compared with the others.

Table 7

  As shown in the results of Table 7, various water-based inkjet inks prepared using the various pigment compositions obtained in the present invention were superior in dischargeability and coloring power as compared with the others.

  The pigment composition containing the monoazo pigment obtained according to the present invention has improved the heat resistance, which has been a problem with conventional monoazo pigments, and has made it possible to provide a fine pigment composition with excellent dispersion stability.

Claims (17)

A pigment composition comprising a compound represented by the following general formula (1) and a compound represented by the following general formula (2).
General formula (1)

General formula (2)

(In the formula, X _{1 to} X ₅ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, or a carboxyl group. A group, a nitro group, a sulfone group, a carbamoyl group, a sulfamoyl group, or a trifluoromethyl group, and X _{1 to} X ₅ are combined with adjacent groups to further contain a nitrogen atom, an oxygen atom, or a sulfur atom, A heterocyclic structure which may be substituted may be formed.
X _{6 to} X ₁₀ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an acetylamino group, a carboxyl group, or a sulfone group. Moreover, X < ₆ > -X < ₁₀ > may form the heterocyclic structure which an adjacent group unites and contains a further nitrogen atom, an oxygen atom, or a sulfur atom, and may be substituted.
X _{11 to} X ₁₅ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an acetylamino group, a carboxyl group, a sulfone group, the following general formula (3 ) Or a group represented by the following general formula (4). However, at least one of X _{11 to} X ₁₅ is either a group represented by the general formula (3) or a group represented by the general formula (4). )
General formula (3)

(In the formula, Y ₁ represents —SO ₂ NR′— or —CONR′—, wherein R ′ may have a hydrogen atom, a substituent and an alkyl group having 20 or less carbon atoms, It represents either an optionally substituted alkenyl group having 20 or less carbon atoms and an optionally substituted alkenyl group having 20 or less carbon atoms.
Y ₂ is a direct bond connecting Y ₁ and Y ₃ , an optionally substituted alkylene group having 20 or less carbon atoms, an optionally substituted alkenylene group having 20 or less carbon atoms, It may have a substituent and represents an arylene group having 20 or less carbon atoms, or —Y _2a —Y _2b —Y _2c —. Y _2a and Y _2c are each independently an optionally substituted alkylene group having 20 or less carbon atoms, an optionally substituted alkenylene group having 20 or less carbon atoms, or a substituted group. It may have a group and represents an arylene group having 20 or less carbon atoms. Y _2b represents a direct bond connecting Y _2a and Y _2c , —O—, —CO—, —NR′— or —SO ₂ —.
Y ₃ represents a hydrogen atom, —OR ₁ , —COOR ₁ , —NR ₁ R ₂ , —CONR ₁ R ₂ , or —SO ₂ NR ₁ R ₂ . Here, R ₁ and R ₂ each independently have a hydrogen atom, a substituent, may have a carbon number of 20 or less, may have a substituent, and have a carbon number of 20 or less. It represents either an alkenyl group or an aryl group which may have a substituent and has 20 or less carbon atoms. R ₁ and R ₂ may be combined to form a heterocyclic structure which may further contain a nitrogen atom, an oxygen atom or a sulfur atom and which may be substituted.
R ′, R ₁ , and R ₂ are each independently integrated with Y ₂ to form an optionally substituted heterocyclic structure which may contain further nitrogen, oxygen or sulfur atoms. May be. )
General formula (4)

(In the formula, Y ₄ represents —NR′— or —O—.
Y ₅ and Y ₆ each independently represent any of a group represented by the following general formula (5), —OR ′, —NR ′ ₂ , and a halogen atom. However, R 'is synonymous with what was defined by General formula (3). )
General formula (5)

(In the formula, Y ₂ , Y ₃ and Y ₄ have the same meanings as defined in the general formula (3) and the general formula (4).)   The content of the compound represented by the general formula (2) is 0.1, which is the sum of the number of moles of the compound represented by the general formula (1) and the number of moles of the compound represented by the general formula (2). The pigment composition according to claim 1, which is ˜40 mol%. The method for producing a pigment composition according to claim 1, wherein the aromatic amine is diazotized and then coupled with an acetoacetanilide compound, wherein the aromatic amine is a compound represented by the following general formula (6): A method for producing a pigment composition, wherein the acetoacetanilide compound is a mixture of a compound represented by the following general formula (7) and a compound represented by the following general formula (8).
General formula (6)

General formula (7)

General formula (8)

(The X ₁ to X ₁₀ in the formula have the same meanings as those defined in the general formula (1), X ₁₁ ~X ₁₅ has the same meaning as defined in the general formula (2).) The method for producing a pigment composition according to claim 1 or 2, wherein the aromatic amine is diazotized and then coupled with an acetoacetanilide compound, wherein the aromatic amine is represented by the following general formula (6). A diazo of an aromatic amine represented by the general formula (6), which is an amine and the acetoacetanilide compound is a compound represented by the following general formula (7) and a compound represented by the following general formula (8): A pigment obtained by adding the acetoacetanilide compound represented by the general formula (8) to the aqueous solution of the compound and subjecting it to a coupling reaction, and then reacting the reaction mixture with the acetoacetanilide compound represented by the general formula (7) A method for producing the composition.
General formula (6)

General formula (7)

General formula (8)

(The X ₁ to X ₁₀ in the formula have the same meanings as those defined in the general formula (1), X ₁₁ ~X ₁₅ has the same meaning as defined in the general formula (2).) The method for producing a pigment composition according to claim 1 or 2, wherein the aromatic amine is diazotized and then coupled with an acetoacetanilide compound, wherein the aromatic amine is represented by the following general formula (6). It is an amine, and the acetoacetanilide compound is a compound represented by the following general formula (7) and a compound represented by the following general formula (8), and the general formula (6 And a basic aqueous solution in which the compound represented by the general formula (7) and the compound represented by the general formula (8) are dissolved at a constant flow rate at the same time. The manufacturing method of the pigment composition obtained by this.
General formula (6)

General formula (7)

General formula (8)

(The X ₁ to X ₁₀ in the formula have the same meanings as those defined in the general formula (1), X ₁₁ ~X ₁₅ has the same meaning as defined in the general formula (2).) The method for producing a pigment composition according to claim 1 or 2, wherein the aromatic amine is diazotized and then coupled with an acetoacetanilide compound, wherein the aromatic amine is represented by the following general formula (6). It is an amine, and the acetoacetanilide compound is a compound represented by a compound represented by the following general formula (7), a compound represented by the general formula (2) and an aromatic represented by the general formula (6) A method for producing a pigment composition obtained by reacting an acetoacetanilide compound represented by the general formula (7) after mixing an amine diazotized product.
General formula (6)

General formula (7)

(X _{1 to} X ₁₀ in the formula are synonymous with those defined in the general formula (1).) The method for producing a pigment composition according to claim 1 or 2, wherein the aromatic amine is diazotized and then coupled with an acetoacetanilide compound, wherein the aromatic amine is represented by the following general formula (6). An amine and the acetoacetanilide compound is a compound represented by the following general formula (7), a compound represented by the general formula (2) and an acetoacetanilide represented by the general formula (7): A method for producing a pigment composition obtained by mixing a compound and then reacting with a diazotized aromatic amine represented by the general formula (6).
General formula (6)

General formula (7)

(X _{1 to} X ₁₀ in the formula are synonymous with those defined in the general formula (1).) The method for producing a pigment composition according to claim 1 or 2, wherein the aromatic amine is diazotized and then coupled with an acetoacetanilide compound, wherein the aromatic amine is represented by the following general formula (6). In a buffer aqueous solution having a pH of 3 to 6, which is an amine and the acetoacetanilide compound is a compound represented by the compound represented by the following general formula (7) and contains the compound represented by the general formula (2) A pigment composition obtained by simultaneously adding a diazotized aromatic amine represented by general formula (6) and a basic solution of an acetoacetanilide compound represented by general formula (7) at a constant flow rate. Production method.
General formula (6)

General formula (7)

(X _{1 to} X ₁₀ in the formula are synonymous with those defined in the general formula (1).) The method for producing a pigment composition according to claim 1 or 2, wherein the aromatic amine is diazotized and then coupled with an acetoacetanilide compound, wherein the aromatic amine is represented by the following general formula (6). It is an amine, and the acetoacetanilide compound is a compound represented by the compound represented by the following general formula (7), and is a diazotized product of the aromatic amine represented by the general formula (6) and the general formula (7). The manufacturing method of the pigment composition obtained by mixing the pigment slurry obtained by making the acetoacetanilide compound represented and the compound represented by General formula (2) mix.
General formula (6)

General formula (7)

(X _{1 to} X ₁₀ in the formula are synonymous with those defined in the general formula (1).)   It is a manufacturing method of the pigment composition of Claim 1 or 2, Comprising: The mixture of the compound represented by General formula (1) and General formula (2) is in presence of a water-soluble inorganic salt and a water-soluble organic solvent. A method for producing a pigment composition obtained by wet-kneading and then removing a water-soluble inorganic salt and a water-soluble organic solvent.   The pigment composition according to claim 1 or 2, wherein the average primary particle diameter is 200 nm or less.   The pigment composition according to any one of claims 1, 2, and 11, wherein a specific conductivity of an aqueous solution obtained by boiling and extracting the pigment composition with ion-exchanged water is less than 200 µS / cm.   The pigment composition according to any one of claims 1, 2, 11, and 12, wherein the contents of calcium, magnesium, and iron are each less than 150 ppm.   The pigment composition according to any one of claims 1, 2, 11, 12, and 13, wherein the total content of calcium, magnesium, and iron is less than 300 ppm.   The pigment dispersion containing the pigment composition in any one of Claims 1, 2, 11-14.   An ink-jet ink containing the pigment composition according to claim 1, or the pigment dispersion according to claim 15. An electrophotographic toner containing the pigment composition according to claim 1.