JPH09302254A - Azo lake pigment composition and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an azo lake pigment compsn. which, when used in a printing ink, can offer an ink possessing heat resistance, transparency, sharpness, tinting strength, fluidity and other properties by using a compound prepd. by substituting a part of a diazonium component in an azo lake pigment by a specific compd. SOLUTION: This azo lake pigment compsn. is prepd. by coupling a diazonium salt of an aniline deriv. having a water-soluble group with β-naphthol or β-oxynaphthoic acid and conducting laking after or simultaneously with the coupling. This azo lake pigment is one prepd. by substituting 0.1 to 30mol% of an aniline deriv. by a compd. represented by the formula (wherein X represents a sulfonic acid group; (m)>2; Y represents H, a halogen, or an alkyl, alkoxy, acetyl, hydroxyl, or aryl group; and (n) is 1 to 3) to prepare a mixed diazo component and then conducting coupling and laking.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an azo lake pigment composition which is useful for various coloring applications and a method for producing the same, and more specifically, it has heat resistance, transparency and vividness when used in a printing ink, for example. TECHNICAL FIELD The present invention relates to an azo lake pigment composition which gives an ink having excellent properties, coloring power and fluidity, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, an azo lake pigment obtained from a diazonium salt of an aniline derivative having a water-soluble group and β-naphthol or β-oxynaphthoic acid has good solvent resistance, light resistance and the like. ,plastic,
It is widely used for coloring paints and the like, and in particular, Pigment Red 57 (CI.15850) is widely used as a red pigment for process inks.

However, in this process printing method, a printing ink having excellent transparency is required for performing multicolor overprinting. Conventional Pigment Red 57
Is treated with rosin to improve transparency, and the treated pigment contains 10 to 30% by weight of rosin. Therefore, a decrease in the coloring power of the treated pigment cannot be avoided, and the fluidity of the ink is also poor. In offset printing, dampening water is used on the printing mechanism, so the rosin of the treated pigment is
The surface tension of the ink emulsified water was lowered, and printing problems such as plate stains were likely to occur, and the printability was not necessarily sufficient.

Therefore, studies have been conducted to reduce the treatment amount of rosin as much as possible (the treatment amount is set to 1 to 10% by weight), but only an opaque pigment having no tinting strength can be obtained. As a method of reducing the rosin treatment amount during pigment synthesis to make the pigment transparent, a method of adding an aniline derivative different from the original diazo component during the diazotization of the diazo component during pigment production has been proposed ( Japanese Patent Laid-Open No. 3-7
2574, etc.).

[0005]

However, in the case of the azo lake pigment obtained by the above-mentioned proposed method, when the pigment powder is made into an ink by a three-roll mill, the temperature rise during the inking process is not so serious and the problem is not solved. However, when ink is formed with a bead mill or the like, or when the pigment paste is made into ink by flushing, the temperature during the ink formation process rises to near 100 ° C., and thus crystal particles of the pigment grow and are obtained. It is inevitable that the pigment becomes opaque.
In addition, the pigment obtained by this proposed method has a drawback that the hue remarkably shifts to bluish and the waste water coloring during flushing is large. Therefore, it has been desired to develop an azo lake pigment that can withstand a temperature rise during ink formation and has little wastewater coloring during flushing.

Therefore, the object of the present invention is not only useful in various coloring applications, but when used in printing inks, for example, it provides inks excellent in heat resistance, transparency, coloring power, fluidity, etc. An object of the present invention is to provide an azo lake pigment composition having a clear yellow hue and less coloring of waste water during flushing.

[0007]

The above object can be achieved by the present invention described below. That is, the present invention relates to an azo lake pigment composition obtained by coupling a diazonium salt of an aniline derivative having a water-soluble group and β-naphthol or β-oxynaphthoic acid, and laked after coupling or simultaneously with coupling. The azo lake pigment composition is obtained by substituting a part of the aniline derivative with a compound represented by the following general formula (A), and a method for producing the same.

[0008]

Embedded image (However, X in the formula represents a sulfonic acid group, m represents an integer of 2 or more, and Y may be the same or different and each represents hydrogen, halogen, an alkyl group, an alkoxy group, an acetyl group, a hydroxyl group or an aryl group. Represents, and n represents an integer of 1 to 3.)

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to embodiments of the present invention. The azo lake pigment in the present invention is a dye having a water-soluble group such as a sulfonic acid group and a carboxylic acid group, which is water-insolubilized with barium, calcium, strontium, aluminum, manganese, nickel, and other polyvalent metal ions. Yes, for example,
Brilliant Carmine 6B, Permanent Red 2B,
Examples include Lake Red C, Resol Red, Brilliant Scarlet G, Lake Red D, Bordeaux 10B, Orange II, Carmine 3B, Pigment Rubin G, Bon Maroon Medium, and the like, and such azo lake pigments and their manufacturing methods themselves are well known. is there.

Examples of the diazo component of these pigments include 1-amino-4-methylbenzene-2-sulfonic acid and 1-amino-4-methyl-5-chlorobenzene-2.
-Sulfonic acid, 1-amino-4-chloro-5-methylbenzene-2-sulfonic acid, 1-aminonaphthalene-2-
Sulfonic acid or the like is used.

In the present invention, 0.1 of these diazo components is used.
To 30 mol% of the compound represented by the general formula (A) is substituted to form a mixed diazo component, which is diazotized by a conventional method to obtain the diazo compound and β-naphthol or β.
To obtain an azo lake pigment composition by coupling with oxynaphthoic acid to synthesize a dye, and lake the dye with a metal, or by adding the above metal to a diazotization solution in advance and then performing a lake at the same time as the coupling. Is characterized by.
The azo lake pigment composition of the present invention contains various aliphatic amines, water-soluble resins, surfactants, diazo solutions, dipping solutions, dyes or pigment slurries during the production thereof.
It is also possible to add other additives in an amount that does not interfere with the object of the present invention to further process the pigment composition.

In the compound represented by the general formula (A) of the present invention, X is a sulfonic acid group and m is an integer of 2 or more. Y may be the same or different and is 1 to 3 hydrogen; halogen such as chlorine, bromine or iodine; alkyl group such as methyl group, ethyl group, propyl group or butyl group; methoxy group, ethoxy group or butoxy group. And other alkoxy groups; acetyl groups; hydroxyl groups; aryl groups which may have a substituent. Examples of the compound represented by the general formula (A) include aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, 2-amino-5-hydroxy-m-benzenedisulfonic acid, 5-amino. -4-Hydroxy-m-benzenedisulfonic acid and the like can be mentioned.
All of these are industrially easily available and practical. Of course, the compound represented by formula (A) may be used in combination.

When the amount of the compound represented by the general formula (A) is less than 0.1 mol%, the effect of the present invention is low, while when it exceeds 30 mol%. However, the original excellent properties of the azo lake pigment are deteriorated, which is not preferable. A particularly effective range of the amount used is that which accounts for 0.1 to 10 mol% of the total amount of the diazo component.

[0014]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples below. In the text, “part” or “%” is based on weight unless otherwise specified. Example 1 1-Amino-4-methylbenzene-2-sulfonic acid 1
7.8 parts and sodium hydroxide 3.8 parts are added to water 360 parts, and it melt | dissolves with stirring at normal temperature. 25% hydrochloric acid in this solution 25
Parts of water, and then 0.4 parts of sodium hydroxide in 30 parts of water.
Parts and 1.38 parts of aniline-2,4-disulfonic acid (5 mol% of all diazo components) were added and dissolved by heating, and then ice was added to bring the temperature to 5 ° C. Next, a solution prepared by dissolving 6 parts of sodium sulfite in 20 parts of water is added all at once to the above solution to be diazotized, and stirred at 5 to 8 ° C. for 30 minutes to obtain a diazo solution. On the other hand, 18 parts of β-oxynaphthoic acid was added to 800 parts of water.
8 parts and 10.0 parts of sodium hydroxide are added and dissolved by stirring, and the amount of water is adjusted to 1000 parts and the temperature is adjusted to 10 ° C. to prepare a dipping solution.

The above diazo solution is added dropwise to this underpickling solution for 20 minutes to cause a coupling reaction to prepare a dye, which is then stirred for 1 hour. Then, the pH was adjusted to 10 to 11 and rosin soap (a solution of 3.2 parts of gum rosin (7% based on the pigment) and 0.4 parts of sodium hydroxide dissolved in 60 parts of water) was added, followed by calcium chloride (2 Aqueous salt) (19 parts) (1.3 mol per mol of dye) is added to form a lake. After stirring for 1 hour, the temperature was raised to 80 ° C., filtration and washing with water to give a press cake, and a portion of the cake was dried and ground to give a powder. The azo lake pigment composition of the present invention (dry yield 45.6 parts) Got

Comparative Example 1 In Example 1, using 18.7 parts of 1-amino-4-methylbenzene-2-sulfonic acid alone, aniline-2,4
A conventional azo lake pigment composition was obtained in the same manner as in Example 1 except that disulfonic acid was not used.

Comparative Example 2 In Example 1, 17.8 parts of 1-amino-4-methylbenzene-2-sulfonic acid and aniline-2,4-disulfonic acid were used instead of JP-A-3-72574. 1,
An azo lake pigment composition was obtained using 1.5 parts of 5-disulfonic acid-2-naphthylamine (5 mol% of all diazo components).

Example 2 Example 1 was repeated except that 1.38 parts (5 mol% of all diazo components) of aniline-2,5-disulfonic acid was used in place of the aniline-2,4-disulfonic acid of Example 1. An azo lake pigment composition was obtained in the same manner as in.

Example 3 In place of the aniline-2,4-disulfonic acid of Example 1, 1.46 parts of 2-amino-5-hydroxy-m-benzenedisulfonic acid (5 mol% of all diazo components) was used. A soloke pigment composition was obtained in the same manner as in Example 1 except for the above.

Example 4 1-Amino-4-methylbenzene-2-sulfonic acid 1
7.8 parts and sodium hydroxide 3.8 parts are added to water 360 parts, and it melt | dissolves with stirring at normal temperature. Add 25 parts of 35% hydrochloric acid,
1.38 parts of aniline-2,4-disulfonic acid (5 mol% of all diazo components) were dissolved in the same manner as in Example 1 and added,
Furthermore, 19 parts of calcium chloride (dihydrate) (1.3 mol per 1 mol of dye) is added to bring the temperature to 5 ° C. Then, to this solution, a solution prepared by dissolving 6 parts of sodium sulfite in 20 parts of water is added all at once to diazotize, and the mixture is stirred at 5 to 8 ° C for 30 minutes to obtain a diazo solution.

On the other hand, 18.8 parts of β-oxynaphthoic acid and 10.0 parts of sodium hydroxide were added to 800 parts of water and dissolved by stirring to obtain rosin soap (3.2 parts of gum rosin (7% based on the pigment) and hydroxylated). After adding 0.4 parts of sodium in 60 parts of water), the amount of water was increased to 1000 parts and the temperature was adjusted to 10
Adjust the temperature to ℃ and use it as a soaking solution. The diazo solution is added dropwise to this under-pickling solution for 20 minutes, and a lake reaction is carried out simultaneously with the coupling. After stirring for 1 hour, the temperature was raised to 80 ° C., filtration and washing with water to give a press cake, and a part of the cake was dried and pulverized to give a powder. The azo lake pigment composition of the present invention (dry yield 45.6 parts) Got

Comparative Example 3 In Example 4, using 18.7 parts of 1-amino-4-methylbenzene-2-sulfonic acid alone, aniline-2,4
A conventional azo lake pigment composition was obtained in the same manner as in Example 4, except that disulfonic acid was not used.

Example 5 21.0 parts of 1-amino-4-chloro-5-methylbenzene-2-sulfonic acid and 3.8 parts of sodium hydroxide were added to 400 parts of water and dissolved by heating at 80 ° C. 35% hydrochloric acid 25
And added ice to bring the temperature to 5 ° C., and then aniline-2,4-
1.38 parts of disulfonic acid (5 mol% of all diazo components) are dissolved and added in the same manner as in Example 2. Next, a solution prepared by dissolving 6 parts of sodium sulfite in 20 parts of water is added all at once to the above solution to be diazotized, and stirred at 5 to 8 ° C. for 30 minutes to prepare a diazo solution. On the other hand, 1 part of β-naphthol in 800 parts of water
4.4 parts and 8.0 parts of sodium hydroxide were added and dissolved by heating, and the amount of water was adjusted to 1000 parts and the temperature was adjusted to 10 ° C. to obtain a dipping solution.

The above diazo solution is added dropwise to this underpickling solution for 20 minutes to cause a coupling reaction to prepare a dye, which is then stirred for 1 hour. Next, the pH was adjusted to 7 to 8 and rosin soap (a solution of 2.3 parts of gum rosin (5% based on the pigment) and 0.3 part of sodium hydroxide dissolved in 46 parts of water) was added, and the temperature was raised to 90 ° C. Warm up and add 16 parts barium chloride (dihydrate) to lake. After stirring for 30 minutes, the mixture was filtered and washed with water to give a press cake, and a part of the cake was dried and pulverized to give a powder, whereby the azo lake pigment composition of the present invention (dry yield 46.7 parts) was obtained.

Comparative Example 4 In Example 5, 22.1 parts of 1-amino-4-chloro-5-methylbenzene-2-sulfonic acid was used alone, and aniline-2,4-disulfonic acid was not used. Is Example 5
A conventional azo lake pigment was obtained in the same manner as in.

Example 6 21.0 parts of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid and 3.8 parts of sodium hydroxide were placed in 400 parts of water and dissolved by heating at 80 ° C. 35% hydrochloric acid 25
And added ice to bring the temperature to 5 ° C., and then aniline-2,4-
1.38 parts of disulfonic acid (5 mol% of all diazo components) are dissolved and added in the same manner as in Example 2. Next, a solution prepared by dissolving 6 parts of sodium sulfite in 20 parts of water is added all at once to the above solution to be diazotized, and stirred at 5 to 8 ° C. for 30 minutes to prepare a diazo solution. On the other hand, 18.8 parts of β-oxynaphthoic acid and 10.0 parts of sodium hydroxide were added to 800 parts of water and dissolved by stirring at room temperature to adjust the amount of water to 1000 parts and the temperature to 10 ° C. to obtain a dipping solution. .

The above diazo solution is added dropwise to this under-pickling solution for 20 minutes to cause a coupling reaction to prepare a dye, which is then stirred for 1 hour. Then, adjust the pH to 10 to 11, add rosin soap (a solution of gum rosin 1.0 part (2% based on the pigment) and sodium hydroxide 0.2 part in water 20 parts), and then raise the temperature to 50 ° C. And strontium chloride (dihydrate) 3
Add 4 parts to rake. Further, the temperature was raised to 90 ° C., filtration and washing with water to give a press cake, and a part of the cake was dried and pulverized to give a powder, whereby an azo lake pigment composition of the present invention (dry yield 51.6 parts) was obtained.

Comparative Example 5 In Example 6, 22.1 parts of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid was used alone, and aniline-2,4-disulfonic acid was not used. Is Example 6
A conventional azo lake pigment composition was obtained in the same manner as in. The press cakes and powder pigments of the above Examples and Comparative Examples were used as planographic inks according to the following ink preparation method, and various tests were conducted.

Preparation of base ink 1. Inking of press cake 300 parts of the planographic ink varnish is put into a test flasher, 100 parts of the press cake obtained in Examples 1 to 6 is added by pigment weight, and the mixture is kneaded at a temperature of 70 ° C. to remove primary separated water. Furthermore, after removing the secondary separated water at 110 ° C. under reduced pressure,
100 parts of varnish is added and taken out from the test flasher to prepare a base ink through a three-roll mill.

2. Making powder pigment into ink After premixing 100 parts of powder pigment and 400 parts of planographic ink varnish, a base ink is prepared at 85 ° C. through a bead mill. 100 parts powder pigment and 40 lithographic ink varnish
After premixing 0 part, a base ink is prepared by passing through a three-roll mill.

Preparation of ink The tack values (incometer, 30 ° C., 1,200) of the base inks of the above 1 and 2 were applied with a planographic varnish and a solvent.
(rpm, 20 seconds) was adjusted to 10 to 10.5 to prepare an ink.

Ink test A black belt art paper was proof-printed with an RI tester, and hue and transparency were visually evaluated with a comparative example (conventional pigment without partial replacement of diazo component) as a standard, and the consistency (fluidity) Property), density and gloss were evaluated by the following methods. (1) Consistency: Spread meter (JIS standard) 100
Second value (2) Concentration: Measured with a reaction densitometer (Gretag densitometer) (3) Gloss (%): Measured with a photometer (60 degrees)

The results of evaluation of the pigment press cake made into an ink by the flushing method are shown in Table 1, the results of the evaluation of the pigment powder made into an ink by the bead mill method are shown in Table 2, and the results of the pigment powder made by the bead mill method and the three-roll mill method are used. Table 3 shows the results of the evaluation of transparency in the case of conversion (transparency was evaluated as 5 and opacity was evaluated as 1).

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3]

As is clear from the results of Tables 1 to 3, the pigments of Comparative Examples are opaque and change greatly with temperature, but the azo lake pigment composition of the present invention is transparent and changes little with temperature. The product of the present invention is Pigment Red 5
7 The hue is similar to the original hue, or slightly yellowish, and the amount of wastewater coloring during flushing is small.

[0038]

The azo lake pigment composition obtained by the present invention is transparent and excellent in heat resistance as compared with the conventional azo lake pigments, and even when the pigment paste is flushed at a high temperature,
Further, even if the pigment powder is dispersed at a high temperature with a bead mill or the like, the thermal change of the pigment is extremely small. Therefore, the ink is transparent, has coloring power, and is excellent in fluidity and gloss. As the amount of rosin was reduced, plate stains were less likely to occur, and printability was improved. In addition, the pigment composition of the present invention has a hue which is equal to or slightly clear to the original hue of Pigment Red 57, and has a small amount of waste water coloring during flushing. Further, when used in a gravure ink, the azo lake pigment composition of the present invention has good viscosity stability over time, excellent fluidity, and good swirling resistance. It is also useful for applications such as plastics, and the application of the azo lake pigment composition of the present invention is not limited to planographic ink.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masahiro Takayama 1-7-6 Bakurocho, Nihonbashi, Chuo-ku, Tokyo Inside Dainichiseika Kogyo Co., Ltd.

Claims (4)

[Claims] 1. An azo lake pigment composition obtained by coupling a diazonium salt of an aniline derivative having a water-soluble group with β-naphthol or β-oxynaphthoic acid, and forming a lake after coupling or simultaneously with coupling, An azo lake pigment composition, wherein the azo lake pigment is obtained by substituting a part of the aniline derivative with a compound represented by the following general formula (A). Embedded image (However, X in the formula represents a sulfonic acid group, m represents an integer of 2 or more, and Y may be the same or different and each represents hydrogen, halogen, an alkyl group, an alkoxy group, an acetyl group, a hydroxyl group or an aryl group. Represents, and n represents an integer of 1 to 3.) 2. The azo lake pigment composition according to claim 1, wherein 0.1 to 30 mol% of all diazo components is a compound represented by the general formula (A). 3. A method for producing an azo lake pigment composition, which comprises coupling a diazonium salt of an aniline derivative having a water-soluble group with β-naphthol or β-oxynaphthoic acid and forming a lake after or simultaneously with the coupling. A method for producing an azo lake pigment composition, which comprises substituting a part of the aniline derivative with a compound represented by the following general formula (A). Embedded image (However, X in the formula represents a sulfonic acid group, m represents an integer of 2 or more, and Y may be the same or different and each represents hydrogen, halogen, an alkyl group, an alkoxy group, an acetyl group, a hydroxyl group or an aryl group. Represents, and n represents an integer of 1 to 3.) 4. The method for producing an azo lake pigment composition according to claim 3, wherein 0.1 to 30 mol% of all diazo components is a compound represented by formula (A).