JPH1088016A - Azo lake pigment composition, method for producing the same, and pigment dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an azo lake pigment composition which suppresses the amount of added components, simultaneously improves hue clarity, transparency, coloring power and bluish hue, and does not reduce water resistance. To do. SOLUTION: (1) A monoazo dye obtained by performing a coupling reaction between a diazotized product of 4-aminotoluene-3-sulfonic acid and 3-hydroxy-2-naphthoic acid or 2-hydroxynaphthalene is raked. Azo lake pigments (A) and (2) a diazotized product of 4-aminoacetanilide and 3-hydroxy-2-naphthoic acid or 2
-An azo lake pigment composition containing an azo lake pigment (B) obtained by laking a monoazo dye obtained by a coupling reaction with hydroxynaphthalene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an azo lake pigment useful for various uses, particularly for coloring printing inks, a method for producing the same, and a pigment dispersion using the pigment.

[0002]

2. Description of the Related Art 4-aminotoluene-3-sulfonic acid is used as a diazo component, and 3-hydroxy-2-naphthoic acid,
An azo pigment obtained by subjecting a hydroxy-naphthalene or the like to a coupling reaction as a coupler component and then forming a lake is known as a useful coloring agent, and is widely used in various applications. The particle size and particle shape of the pigment thus obtained affect various suitability of the dispersion using the pigment, for example, in a printing ink, sharpness, transparency, tinting strength, hue, and the like. , Liquidity, etc.

As a method of controlling the particle diameter, a method of replacing a part of the coupler component with another component has been widely studied. For example, Japanese Patent Application Laid-Open No. 61-181864,
JP-A-62-138560, JP-A-62-138
No. 561 discloses a method using bisnaphthylamines, Japanese Patent Application Laid-Open No. 61-203176 discloses a method using a 2-hydroxynaphthalene-3-carboylanilide derivative, and Japanese Patent Application Laid-Open No. 61-272271 discloses a method. A method using a 3-hydroxy-2-naphthamide-N-naphthalene derivative; a method using a 3-hydroxy-2-naphthamide-N-naphthalene derivative; a method using a 3-hydroxy-2-naphthamide-N-naphthalene derivative; 4-
No. 180969 discloses N-phenylalkylene-2.
A method using a -hydroxynaphthalene-3-carboxylic acid amide derivative is disclosed in JP-A-62-54663.
A method using a -hydroxy-3-naphthoic acid derivative is known. JP-A-1-193364 discloses a method in which part of a diazo component is replaced with an aniline derivative having a dialkylaminoalkyleneaminosulfonyl group.
JP-A-3-97762 discloses a method in which part of the diazo component is replaced with a benzene-based amine containing an electron-withdrawing group and having no soluble group.

[0004] Among these azo lake pigments,
Although 3-hydroxy-4-[(4-methyl-2-sulfophenyl) azo] -2-naphthalenecarboxylic acid calcium salt (Carmine 6B) is widely used as a red pigment for process colors of printing inks, In some cases, it is necessary to correct the hue by adding a bluish color to the application.

[0005] As the bluing method, a method using tobias acid as a part of the diazo component is known. In addition to this, JP-A-61-7367 and JP-A-61-12 are known.
Japanese Patent No. 3668 discloses a method using a diazo compound of a specific aniline derivative as a diazo component.

[0006]

The suitability for use of printing inks includes sharpness, transparency and tinting strength. The finer the pigment particle size, the more the suitability tends to be improved. For example, in the case of red pigment, generally, the hue becomes yellowish as the particle diameter becomes smaller, but when tobiasic acid or the like is used to correct this and make the hue bluish, even if a certain amount or more is used, the pigment particles become Since the effect of yellowing of the hue due to the miniaturization increases, a larger amount of tobias acid or the like must be used. Further, a desired hue may not be obtained depending on the degree of blue tint.

[0007] On the other hand, the method of replacing a part of the diazo component or the coupler component with another component generally causes lowering of water resistance and alcohol resistance as compared with pigments not using these methods, There is a problem that the cost is increased.

[0008] In particular, in the case of pigments for printing inks, it is desired to use a smaller amount of an additive component which is effective at the same time in improving sharpness, transparency, coloring power and bluish hue, and which does not reduce water resistance. I have.

An object of the present invention is to provide an azo lake pigment which suppresses the amount of added components, simultaneously improves hue clarity, transparency, tinting strength, and bluish hue, and does not reduce water resistance. It is to provide a composition.

[0010]

In order to solve the above-mentioned problems, the present invention provides (1) a diazotized product of 4-aminotoluene-3-sulfonic acid, 3-hydroxy-2-naphthoic acid or 2-hydroxynaphthalene. Azo lake pigments (A) obtained by lacking a monoazo dye obtained by a coupling reaction with (A) and (2) a diazotized product of 4-aminoacetanilide, and 3-hydroxy-2-naphthoic acid or 2-
An azo lake pigment composition characterized by containing an azo lake pigment (B) obtained by lacking a monoazo dye obtained by coupling reaction with hydroxynaphthalene.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The azo lake pigment composition of the present invention is prepared by diazotizing a mixture comprising (1) 4-aminotoluene-3-sulfonic acid and (2) 4-aminoacetanilide, and then diazotizing the mixture. Of the monoazo dye composition obtained by the coupling reaction of the compounded mixture with 3-hydroxy-2-naphthoic acid or 2-hydroxynaphthalene.

The ratio of the azo lake pigment (A) to the azo lake pigment (B) in the azo lake pigment composition of the present invention is preferably in the range of 99.9: 0.1 to 80:20 in molar ratio.

The azo lake pigment composition of the present invention having such a ratio can be obtained by the method described above, wherein (1) 4-aminotoluene-3-sulfonic acid and (2) 4-aminoacetanilide in the diazotized mixture are used. In a molar ratio of 9
9.9: 0.1 to 80:20.

The diazotized mixture contains 15 parts of the diazo component.
If it is within mol%, it may contain isomers or derivatives of the above components, for example, 1-amino-4-methylbenzene-3-sulfonic acid.

The coupler component is 3-hydroxy-2-
It is naphthoic acid or 2-hydroxynaphthalene or a mixture thereof, but may contain an isomer or derivative of the above component as long as it is within 15 mol% of the coupler component.

According to the method for producing an azo lake pigment composition of the present invention, the diazo component is diazotized according to a conventional method according to a conventionally known method for producing an azo lake pigment, while the coupler component is coupled according to a conventional method. Rake simultaneously with or after the ring. At this time, as the metal for pigment lake, for example, barium, calcium,
Examples include strontium and aluminum. Also,
During the production of the azo lake pigment, a resin acid such as rosin may be added in order to prevent aggregation of the pigment particles, and the amount and timing of the addition are not limited. Further, the pigment slurry or the wet cake can be treated with an anionic surfactant such as a fatty acid or a dialkyl sulfosuccinate or various commercially available nonionic surfactants, if necessary.

The pigment composition of the present invention provides a pigment dispersion by dispersing it in a vehicle for printing ink, a vehicle for paint, and the like. These pigment dispersions are produced by known methods using vehicles such as rosin-modified phenol, petroleum resins, alkyd resins, extenders, solvents and other auxiliaries.

[0018]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples, and Test Examples. In the following examples, “parts” and “%” are based on weight unless otherwise specified.

<Example 1> 99 parts of 4-aminotoluene-3-sulfonic acid and 4-aminoacetoanilide 0.1 part.
After dispersing 80 parts in 1500 parts of water, 35% hydrochloric acid 65
Then, while keeping the temperature at 5 ° C. or lower, 95 parts of 40% sodium nitrite was added dropwise to prepare a diazo component (A).

Next, 3-hydroxy-2-naphthoic acid 1
After dispersing 03 parts in 3000 parts of water, 201 parts of a 25% aqueous sodium hydroxide solution was added and dissolved, and then cooled to 5 ° C. or lower to obtain a coupler component (B).

While the coupler component (B) was being stirred, the diazo component (A) was added dropwise to cause a coupling reaction. After adding 316 parts of a 10% aqueous solution of gum rosin to the reaction mixture, a 35% aqueous solution of calcium chloride 22 was added.
3 parts were added and the mixture was stirred for 60 minutes or more to terminate the lake formation reaction. Hydrochloric acid was added dropwise to the reaction mixture to adjust the pH to 7.0.
After adjusting to between 8.0 and 8.0, the temperature was raised to 60 ° C., and the mixture was stirred at the same temperature for 60 minutes. Then, the product was filtered, and the residue obtained by filtration was washed with water to obtain a pigment content of 20 to 30% water content. A pigment was obtained.

Comparative Example 1 After 100 parts of 4-aminotoluene-3-sulfonic acid was dispersed in 1500 parts of water, 35 parts of
65 parts of hydrochloric acid was added thereto, and 95 parts of 40% sodium nitrite was added dropwise while keeping the temperature at 5 ° C. or lower to prepare a diazo component (C).

Example 1 was repeated except that the disazo component (C) was used in place of the disazo component (A).
In the same manner as in the above, a water-containing pigment was obtained.

COMPARATIVE EXAMPLE 2 97 parts of 4-aminotoluene-3-sulfonic acid and 3.6 parts of tobias acid were mixed with 1500 parts of water.
Then, 65 parts of 35% hydrochloric acid was added, and 95 parts of 40% sodium nitrite was added dropwise while keeping the temperature at 5 ° C. or lower to prepare a diazo component (D).

Example 1 was repeated except that the disazo component (D) was used in place of the disazo component (A).
In the same manner as in the above, a water-containing pigment was obtained.

<Example 2> 97 parts of 4-aminotoluene-3-sulfonic acid and 4-aminoacetanilide
After 4 parts were dispersed in 1500 parts of water, 65 parts of 35% hydrochloric acid was added, and 95 parts of 40% sodium nitrite was added dropwise while keeping the temperature at 5 ° C. or lower to prepare a diazo component (E).

A water-containing pigment was obtained in the same manner as in Example 1, except that the diazo component (E) was used instead of the diazo component (A).

Comparative Example 3 97 parts of 4-aminotoluene-3-sulfonic acid and 10.7 parts of tobias acid were mixed with 150 parts of water.
After dispersing in 0 parts, 65 parts of 35% hydrochloric acid was added, and 95 parts of 40% sodium nitrite was added dropwise while keeping the temperature at 5 ° C. or lower to prepare a diazo component (F).

A water-containing pigment was obtained in the same manner as in Example 1, except that the diazo component (F) was used instead of the diazo component (A).

<< Test Example >><Preparation of Offset Ink> Each of the hydrous pigments obtained in Examples and Comparative Examples, "KM-51" (Dainippon Ink and Chemicals, Ltd.)
After mixing lithographic ink varnish) and light oil,
After preparing a base ink having a pigment content of 25% by a flushing method, an offset ink having a pigment content of 17% and a tack value of 8.5 to 9.5 was prepared using a three-roll mill. The final ink composition is shown below. Pigment 17 parts "KM-51" Varnish 65 parts Light oil 18 parts

<Preparation of White Ink> As a white ink for evaluation, "New Champion AT 179 white ink" manufactured by Dainippon Ink and Chemicals, Inc. was used.

<< Evaluation Method >> In terms of ink transparency, the offset ink is applied to an art paper (drawdown).
The light-colored ink mixed at a ratio of 20 and kneaded with three rolls was spread on art paper and evaluated. Table 1 summarizes the evaluation results obtained by relative evaluation using a colored plate using the pigment obtained in Comparative Example 1 as a standard. In addition, the transparency was determined by five levels of visual determination [1 (small transparency) >> 5 (large transparency)].

In order to test the water resistance of the pigment, the following test was conducted. A hydrated pigment equivalent to 5 g by dry weight was weighed, and thereafter, the pigment was boiled in ion-exchanged water and filtered according to JIS K-5101-22 pigment water content test method to obtain 100 ml of an aqueous solution. The degree of coloring of the aqueous solution was determined by five levels of visual determination [1 (large coloring) >> 5 (small coloring)], and the water resistance of the pigment was evaluated. The results are shown in Table 1.

[0034]

[Table 1]

[0035]

As described above, the pigment composition of the present invention can simultaneously achieve bluish hue, transparency, improved tinting strength and water resistance.
In particular, when used for a lithographic ink, the effect on the blackening of the thick part of the ink is great.

Claims (5)

[Claims] (1) A monoazo dye obtained by subjecting a diazotized product of 4-aminotoluene-3-sulfonic acid to a coupling reaction with 3-hydroxy-2-naphthoic acid or 2-hydroxynaphthalene is laked. Azo lake pigments (A) and (2) a diazotized product of 4-aminoacetanilide, and 3-hydroxy-2-naphthoic acid or 2
-An azo lake pigment composition comprising an azo lake pigment (B) obtained by laking a monoazo dye obtained by a coupling reaction with hydroxynaphthalene. 2. A molar ratio of the azo lake pigment (A) and the azo lake pigment (B) is 99.9: 0.1 to 80: 2.
The azo lake pigment composition according to claim 1, which is in the range of 0. 3. After diazotizing a mixture comprising (1) 4-aminotoluene-3-sulfonic acid and (2) 4-aminoacetanilide, the diazotized mixture and 3-hydroxy-2-naphthoic acid or 2 The azo lake pigment (A) and the azo lake pigment composition containing the azo lake pigment (B) according to claim 1, wherein the monoazo dye composition obtained by a coupling reaction with -hydroxynaphthalene is laked. Method. 4. The use ratio of (1) 4-aminotoluene-3-sulfonic acid and (2) 4-aminoacetanilide in a molar ratio of 99.9: 0.1 to 80:20. Item 4. A method for producing the azo lake pigment composition according to Item 3. 5. A pigment dispersion comprising the azo lake pigment composition according to claim 1 or 2 and a pigment dispersing resin.