JP3236804B2 - Azo lake pigment composition, method for producing the same, and pigment dispersion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-treated azo lake pigment useful for various coloring applications, a method for producing the same, and a pigment dispersion. The present invention relates to a surface-treated azo lake pigment that provides an ink such as a gravure ink having excellent gloss, hot water bleeding property, and soiring suitability, a method for producing the same, and a dispersion of the pigment.

[0002]

2. Description of the Related Art Hitherto, azo lake pigments have been widely used as colorants for synthetic resins and rubbers and paints because of their good physical properties such as solvent resistance and water resistance.
Further, it is also used as a colorant for printing inks, for example, as a colorant for various gravure inks.

[0003]

However, when an azo lake pigment is used for various gravure inks, the viscosity of the ink may increase to lower the fluidity, making it impossible to use the azo lake pigment.

[0004] For the purpose of modifying azo lake pigments, azo lake pigments using different metals at the time of lake are disclosed in
As proposed in JP-A-10142, when this pigment is used as a gravure ink, the effect of improving the viscosity is small. Further, as a pigment having improved fluidity, an azo lake pigment coated with a water-soluble acrylic resin has been proposed in JP-A-7-292274. However, when this pigment is used as a gravure ink, it is increased. The effect of suppressing viscosity is insufficient. An azo lake pigment surface-treated with an aluminum salt has been proposed in JP-A-3-43462 as a pigment having improved soiring resistance among the viscosity characteristics. However, this pigment is used as a colorant for gravure ink. In such a case, the hot water bleeding property, which is a required property of the gravure ink, becomes extremely poor.

Accordingly, an object of the present invention is to suppress the increase in the viscosity of various dispersions, which are important as ink properties, when a pigment is used as a colorant for various gravure inks, for example. It is an object of the present invention to provide an azo lake pigment which is excellent in hot water bleeding property and the like which are required characteristics. The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the object can be achieved by using an azo lake pigment whose surface has been treated with a water-soluble iron salt and / or nickel salt. Was.

[0006]

The above object is achieved by the present invention described below. That is, the present invention provides an azo lake pigment composition comprising an azo lake pigment and an iron salt and / or a nickel salt, and adding a water-soluble iron salt and / or a nickel salt to a slurry of the azo lake pigment. And a dispersion of the azo lake pigment composition described above.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to embodiments of the invention. The azo lake pigment in the present invention is a azo dye having a hydrophilic group such as a sulfonic acid group and a carboxylic acid group, sodium, barium, calcium, strontium, manganese, aluminum, and water insolubilized by other metal ions. For example,
C. I. Pigment Red 57, also 53, 52, 4
9, 64, 50, 63, 60, 58, 151, 243
Et al., C.I. I. Pigment Orange 17, C.I. I. Pigment Yellow 168, etc. are azonaphthoic acid-based, naphthol-based, acetoacetic anilide-based azo lake pigments, and the production method of such azo lake pigment itself is known. There is no restriction.

In the present invention, the azo lake pigment used as a starting material is obtained by rake after coupling in water, or azo lake pigment obtained by rake simultaneously with coupling. The azo lake pigment is used in a slurry state in the following processing,
The slurry may be any of a slurry after producing an azo lake pigment, a slurry obtained by pulverizing a pigment paste obtained by filtering the slurry, and a slurry obtained by dispersing a dried pigment in water. The azo lake pigment slurry can be heated and cooled, ripened, and adjusted for the pH of the slurry, if necessary. In addition, the azo lake pigment which is a starting material of the present invention is a diazo solution, a submerged solution,
At an appropriate stage of the dye or pigment slurry, use is made by treating the pigment by adding various aliphatic amines, water-soluble resins, surfactants, and other additives within a range that does not impair the gist of the present invention. You can also.

The azo lake pigment composition of the present invention comprising an azo lake pigment and an iron salt and / or a nickel salt is produced by adding a water-soluble iron salt and / or a nickel salt to the above-mentioned slurry of the azo lake pigment and stirring the mixture. can do. These salts can be dissolved in the form of a solid by adding the slurry, but are usually added as a solution.
After the addition, if necessary, heating, cooling, aging, pH adjustment of the slurry, and the like can be performed.

The iron salt and nickel salt used in the present invention are not particularly limited as long as they are both water-soluble.
Ferrous chloride, ferric chloride, nickel chloride, ferrous sulfate,
Inorganic salts such as ferric sulfate, nickel sulfate, ferric nitrate, nickel nitrate, and ferric phosphate; and organic salts such as ferrous oxalate and nickel acetate. These salts may include water.

The preferred amount of the water-soluble iron salt and / or nickel salt is from 0.3 to 100 parts by weight per 100 parts by weight of the azo lake pigment, and the most effective amount is from 0.5 to 30 parts by weight. Range. After the above treatment, the azo pigment is separated from the slurry according to a conventional method such as filtration, and the intended azo lake pigment composition is obtained by pigmentation.
That is, an azo lake pigment having been subjected to a surface treatment is obtained. It is presumed that iron salts and / or nickel salts exist in the azo lake pigment composition (hereinafter sometimes referred to as surface-treated azo lake pigment) as respective hydroxides or the like.

By using the water-soluble iron salt and / or nickel salt in the above amount, the treated azo lake pigment composition contains iron and / or nickel per 100 parts by weight of the pigment by atomic absorption spectrometry. 0.1 to 50 parts by weight, most preferably 0.3 to 20 parts by weight, as an atomic weight analysis value. If the amount is less than the above-mentioned amount or the lower limit of the content in the pigment, the effect of suppressing the thickening when the surface-treated azo lake pigment is used for a gravure ink or the like becomes insufficient. ) Cannot be expected to further increase the thickening suppression effect or the hot water bleeding property, and is uneconomical.

When the surface-treated azo lake pigment of the present invention obtained as described above is used as a coloring agent such as ink, for example, it can be used alone or of the same type without the surface treatment. It can also be used as a mixture with a pigment. When used as a mixture, the content of iron and / or nickel in the mixture is controlled by the azo lake pigment 10
It is preferred that the above amount be used per 0 parts by weight.

The surface-treated azo lake pigment of the present invention can be used in a solid state or as a dispersion. When used as a dispersion, it is used as a pigment dispersion containing a surface-treated azo lake pigment and a dispersion resin vehicle. As the dispersion resin vehicle, any of the conventionally known vehicles can be used, and there is no particular limitation. For example, nitrocellulose resin, maleic acid resin, urethane resin, polyamide resin, lime rosin resin, rosin modified phenol resin, acrylic resin, alkyd resin, melamine resin, epoxy resin, polyolefin resin, And vinyl chloride resins.

The method for producing the pigment dispersion may be in accordance with a conventional method and is not particularly limited. For example, there may be mentioned a method in which the above-mentioned dispersion resin vehicle is dissolved in a varnish in which an oil component is dissolved, if necessary, with a diluting solvent to disperse the surface-treated azo lake pigment.

[0016]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the description, parts and% are based on weight unless otherwise specified.

Example 1, Comparative Example 1 A sodium dye is prepared by coupling 2-chloro-4-aminotoluene-5-sulfonic acid diazotized by a conventional method with β-oxynaphthoic acid. The temperature of the solution containing the dye is raised to 50 ° C., and a strontium chloride solution is added (1.4 mol of strontium chloride is used per 1 mol of the dye) for lake formation. Thereafter, the temperature is raised to 100 ° C. and ripened for 30 minutes. After aging, an aqueous solution of ferric chloride hexahydrate (4 parts dissolved in 50 parts of water with respect to 100 parts of the obtained azo lake pigment) was added, and the mixture was stirred for 20 minutes. Was dried at 90 ° C. to obtain 100 parts of the surface-treated azo lake pigment of the present invention. The azo lake pigment of Comparative Example 1 without surface treatment was obtained in the same manner as described above.

Example 2, Comparative Example 2 A sodium dye is prepared by coupling 2-chloro-4-aminotoluene-5-sulfonic acid diazotized by a conventional method with β-oxynaphthoic acid. The temperature of the liquid containing the dye is raised to 95 ° C., and a barium chloride solution is added (1.4 mol of barium chloride is used per 1 mol of the dye) to form a lake. Thereafter, the temperature is raised to 100 ° C. and ripened for 30 minutes. After aging, an aqueous solution of nickel chloride (the resulting azo lake pigment 1
Of 10 parts in 50 parts of water).
Stir for a minute. Further, the pH of the obtained slurry is adjusted to 9.0.
And stir for 20 minutes. This slurry is filtered,
The coagulated product was dried at 90 ° C. to obtain 100 parts of the surface-treated azo lake pigment of the present invention. The azo lake pigment of Comparative Example 2 without surface treatment was obtained in the same manner as described above.

Example 3 and Comparative Example 3 A sodium dye is prepared by coupling 2-chloro-4-aminotoluene-5-sulfonic acid diazotized by a conventional method with β-oxynaphthoic acid. The temperature of the solution containing the dye is raised to 55 ° C., and a strontium chloride solution is added (1.4 mol of strontium chloride is used per 1 mol of the dye) for lake formation. Thereafter, the temperature is raised to 100 ° C. and ripened for 30 minutes. After aging, an aqueous solution of ferric sulfate (5 parts in 100 parts of the obtained azo lake pigment is dissolved in 50 parts of water) and a solution of nickel sulfate (7 parts in 100 parts of the obtained azo lake pigment are 50 parts of water) ) And stirred for 20 minutes, the resulting slurry was filtered off, and the solidified product was dried at 90 ° C to obtain 100 parts of the surface-treated azo lake pigment of the present invention.
The azo lake pigment of Comparative Example 3 without surface treatment was obtained in the same manner as described above.

Example 4, Comparative Example 4 Surface-treated azo lake pigment 50 obtained in the same manner as in Example 1.
Were mixed with 50 parts of the untreated azo lake pigment of Comparative Example 1 to obtain 100 parts of the surface-treated pigment of the present invention. The untreated azo lake pigment of Comparative Example 1 is referred to as the pigment of Comparative Example 4.

Example 5 Using the surface-treated azo lake pigment obtained above, urethane-based and polyamide-based gravure inks were prepared as follows. Also, a gravure ink using the azo lake pigment of the comparative example instead of the surface-treated azo lake pigment was prepared. Using these obtained inks, the physical properties of the inks were examined. Table 1 shows the results.

1. Urethane-based gravure ink surface-treated azo lake pigment 10 parts Urethane varnish 50 parts Solvent 40 parts Steel ball 200 parts The above components are placed in a tin can having an inner diameter of 60 mm and a height of 120 mm, and subjected to a dispersion treatment with a paint shaker for 30 minutes. The obtained ink was put in a glass container, water (2 parts per 100 parts of ink) was added, and the mixture was stirred.
Was placed in a constant temperature bath and the change with time of the viscosity was measured.

[0023] 2. Polyazo gravure ink surface-treated azo lake pigment 10 parts Polyamide varnish 58 parts Nitrified cotton varnish 17 parts Solvent 15 parts Steel ball 200 parts The above components are placed in a tin can having an inner diameter of 60 mm and a height of 120 mm, and dispersed with a paint shaker for 30 minutes. To process. The gloss of the printed surface printed using the obtained ink is visually observed, and ◎, ○, △,
It evaluated by x. Further, the viscosity over time of the obtained ink was measured in the same manner as described above.

[0024]

[Table 1]

[0025]

The azo lake pigment composition (surface-treated azo lake pigment) of the present invention and the pigment dispersion using the same are, for example, when used as a colorant for ink, as compared with conventional azo lake pigments. For example, the color is clear, the gloss (gloss) is large, and the hot water bleeding property and the fluidity show good suitability. In particular, in the case of conventional pigments of the same type, various inks using the same thicken during storage and become unusable, whereas the surface-treated azo lake pigment of the present invention solves such disadvantages. The surface-treated azo lake pigment of the present invention, when used in a lithographic ink, has coloring power and is excellent in dispersibility and gloss. Therefore, the surface-treated azo lake pigment of the present invention and its dispersion are suitable for producing various inks such as gravure inks. Furthermore,
The surface-treated azo lake pigment of the present invention is also useful for applications such as plastic paints, and is suitable as a colorant for various uses.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-43462 (JP, A) JP-A-3-43464 (JP, A) JP-A-3-163169 (JP, A) JP-A-63-63 120764 (JP, A) JP-A-55-69657 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09B 67/46 C09B 67/20 C09B 67/08 C09B 63/00

Claims (7)

(57) [Claims] 1. An azo lake pigment composition comprising an azo lake pigment and an iron salt and / or a nickel salt. 2. The azo lake pigment composition according to claim 1, wherein the azo lake pigment is surface-treated with a water-soluble iron salt and / or nickel salt. 3. The azo lake pigment composition according to claim 1, which contains 0.1 to 50 parts by weight of iron and / or nickel by atomic weight per 100 parts by weight of the azo lake pigment. 4. The azo lake pigment composition according to claim 1, wherein the azo lake pigment is an oxynaphthoic acid pigment and a naphthol pigment. 5. A method for producing an azo lake pigment composition, comprising adding a water-soluble iron salt and / or nickel salt to an azo lake pigment slurry. 6. The method for producing an azo lake pigment composition according to claim 5, wherein 0.3 to 100 parts by weight of a water-soluble iron salt and / or nickel salt is used per 100 parts by weight of the azo lake pigment. 7. A pigment dispersion comprising the azo lake pigment composition according to claim 1 and a dispersion resin vehicle.