JPS584067B2 - Azore-Kiganriyou no Bunsanseikairiyouhouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for improving the dispersibility of azo lake pigments in color vehicles such as printing inks, paints, and synthetic resins.

Azo lake pigments are usually obtained by adding metal salts to an aqueous suspension of a sparingly soluble azo dye obtained by coupling a diazotized diazo component to an azo component to form a lake, followed by filtering, drying, and pulverizing. However, even though the resulting pigment particles are in a fine state immediately after their formation, they have the property of agglomerating extremely strongly after going through the drying process, and such agglomerated powder pigments can no longer be processed by simple mechanical crushing means. It cannot be dispersed to a fine state.

As a result of research to improve the dispersibility of azo lake pigments, the present inventors found that the general formula R-0(CH2CH20)nS03NH(C2H40H
]3 (wherein R is an alkyl group of 06 to C18, n is 1 to
Indicates 12 integers.

It has been discovered that the dispersibility of the azo lake pigment obtained can be improved by adding a compound represented by the following formula before lake formation, and the present invention has been achieved based on this discovery.

The azo lake pigments that are the object of the present invention include diazotized p-toluidine-m-sulfonic acid, 6-chloro-p-toluidine-m-sulfonic acid, 6-chloro-m-
Toluidine-p-sulfonic acid, 2-naphthylamine-
β-diazo components such as 1-sulfonic acid and acysulanilic acid
- A slightly soluble azo dye obtained by coupling to naphthol, β-oxynaphthoic acid, their derivatives, etc., is treated with a metal salt such as calcium, strontium, barium, magnesium, aluminum, zinc, cadmium, iron, etc. Azo lake pigments such as carmine 6
Examples include Ca lakes such as B, Ba lakes such as Resole Red, and other color index pigment reds such as 48 types and color index pigment reds 52 types.

General formula R-0(CH2CH20)nS03NH(C2H40H) used to improve the dispersibility of azo lake pigments
)3 (wherein R is a C6-C18 alkyl group, n is 1-
Indicates 12 integers.

) is a novel dispersion improver for azo lake pigments, and when R is an alkyl group of 06 to C18 and n is an integer of 1 to 12, the dispersibility can be improved. The most preferable effect is obtained when n is an integer of 4 to 8 in the C18 alkyl group.

The addition ratio is 3 to 10% by weight of the pigment, preferably 5 to 10% by weight of the pigment.

The method of treating azo lake pigment with a compound represented by the above general formula is: 1. Adding it to the raw materials in advance,
Synthesis is carried out in the presence of a dispersibility improver, and then lake formation is carried out. ① Directly in the aqueous slurry immediately after synthesis or once separated, the obtained wet cake is redispersed in water, and then the dispersion improver is added. Methods such as performing a rake ratio can also be adopted.

In the present invention, the azo lake pigment is treated with the compound represented by the above general formula to improve its dispersibility, but it is also possible to apply this compound to ordinary azo pigments.

Hereinafter, the present invention will be explained with reference to Examples, and unless otherwise specified, parts and % represent parts by weight and % by weight, respectively.

Example 1 10.0 parts of p-toluidine-m-sulfonic acid was suspended in 42.0 parts of 5% hydrochloric acid, cooled to below 5% with ice, and then
17.5 parts of a 0% sodium nitrite aqueous solution was slowly added dropwise and stirred at the same temperature for 1 hour to obtain a diazo solution.

On the other hand, 10.0 parts of β-oxynaphthoic acid was dissolved in 240 parts of a 2% caustic soda aqueous solution to prepare a coupling component solution,
The diazo solution is gradually added dropwise at 5° C. or below to perform coupling and synthesize the dye.
．． Neutralize to 0 and proceed to post-processing.

After adding 120 parts of 5% zinc alkali aqueous solution and stirring for 30 minutes, 10% C12H250(CH2CH20)6-
10 parts of 803NH(C2H40H)3 aqueous solution was added and stirred for an additional 30 minutes.

After setting the dye temperature to 20°C, 8.7 parts of calcium chloride dissolved in 40 parts of water was added to form a lake, and then 60 parts of calcium chloride was added.
It is heated to 70°C to 70°C, filtered, and dried at 60°C to form a powder.

Example 2 10.0 parts of p-toluidine-m-sulfonic acid was suspended in 42.0 parts of 5% hydrochloric acid, cooled to below 5°C with ice, and then
17.5 parts of a 0% sodium nitrite aqueous solution was slowly added dropwise and stirred at the same temperature for 1 hour to obtain a diazo solution.

Separately, 10.0 parts of β-oxidinaphthoic acid was dissolved in 240 parts of a 2% aqueous sodium hydroxide solution.

This was used as a coupling component solution, and the diazo solution was heated at 5°C.
The mixture is gradually added dropwise below to perform coupling and dye formation, thereby synthesizing the dye.

Neutralize to pH 8.0 to 9.0 with 5% hydrochloric acid and proceed to post-treatment.

10%c12H25O-(CH2CH20)4S03N
Add 30 parts of H(C2H40H)3 aqueous solution, and further add 60 parts of 5% gin alkaline aqueous solution, and stir for 30 minutes.

After setting the dye temperature to 15°C, add 72% calcium chloride 1
Add 2.5 parts of the solution to form a lake, then add 6NO°
Heat to 60°C, separate the powder, wash with water, and dry at 60°C to form a powder.

Example 3 6-chloro-m-toluidine-p-sulfonic acid 12.
0 part was suspended in 45.5 parts of 5% hydrochloric acid, cooled with ice to below 5°C, 19 parts of a 20% sodium nitrite aqueous solution was gradually added dropwise, and stirred at the same temperature for 1 hour to form a diazo solution. obtain.

On the other hand, 7.9 parts of β-naphthol is dissolved in 156 parts of a 2% aqueous sodium hydroxide solution to prepare a coupling component solution, and the diazo solution is gradually added dropwise at 5° C. or below to perform coupling and synthesize a dye.

Neutralize to pH 7.0 to 8.0 with 5% hydrochloric acid and proceed to post-treatment.

Add 72 parts of 5% gin alkali aqueous solution and stir for 30 minutes.
Add 15 parts of an aqueous H(C2H40H)3 solution.

After adding 7.5 parts of barium chloride dihydrate, the dye temperature is gradually raised to 80° C., resulting in crystal conversion and formation of a lake.

The mixture is further heated to 90°C to 95°C, filtered, and dried at 60°C to form a powder.

Example 4 6-chloro-p-toluidine-m-sulfonic acid 13.
6 parts were suspended in 105 parts of 5% hydrochloric acid, dispersed and stirred for 1 hour, cooled to below 5°C with ice, and then added with 20% sodium nitrite aqueous solution 2.
2 parts were gradually added dropwise and stirred at the same rate for 1 hour to obtain a diazo liquid.

Separately, 12.3 parts of β-oxynaphthoic acid was dissolved in 350 parts of a 2% aqueous sodium hydroxide solution to prepare a coupling component solution, and the diazo solution was gradually added dropwise at 5° C. or below to perform coupling and synthesize a dye.

Neutralize to pH 7.0-8.5 with 10% acetic acid and proceed to post-treatment.

Add 58 parts of 5% aqueous zinc alkali solution and stir for 30 minutes to obtain 10% C14H2oO(CH2CH20)8SO3N
Add 15 parts of an aqueous H(C2H40H)3 solution.

After adding 24 parts of a 36% calcium/um chloride aqueous solution, the mixture was stirred for 30 minutes to perform Regi formation, then the temperature was raised to 90°C, P filtered,
Dry at 60°C to form a powder.

Example 5 11.0 parts of 2-naphthylamine-1-sulfonic acid was added to 2
% caustic soda aqueous solution, cooled with ice to below 5°C, and precipitated with 64.5 parts of 5% hydrochloric acid to form a suspension.

18 parts of a 20% sodium nitrite aqueous solution was gradually added dropwise, and the mixture was heated to 5°C.
The mixture is stirred for 1 hour to obtain a diazotized solution.

On the other hand, 8.1 parts of β-naphthol is dissolved in 281 parts of a 2% aqueous sodium hydroxide solution to prepare a coupling component solution, and the diazo solution is gradually added dropwise at 5° C. or below to perform coupling and synthesize a dye.

Neutralize to pH 7.5-8.5 with 10% acetic acid and proceed to post-treatment.

10%C12H250(CH2CH20)8SO3NH
−? Add 20 parts of C2H40H)8 aqueous solution and stir for 30 minutes, then add 7.3 parts of barium chloride dihydrate, gradually increase the dye temperature to 90°C, and dry at 60°C to form a powder. .

Examples 6-8 10%C1H250(CH2CH20)6SO3NH(
A pigment powder was prepared in exactly the same manner as in Example 1, except that the following aqueous solution was used instead of 10 parts of the C2N{4-OH)3 aqueous solution.

In Example 6, 10% CsH. 70(CH2CH20)toSOsNH
(20 parts of C2H4(I{)3 aqueous solution In Example 7, 10% C18H350(CH2CH20)2SO3NH
(C2f{40H)3 aqueous solution 20 parts In Example 8, 10% C16H330(CH2CH20)6803NH
(C2}{10H)3 aqueous solution 10 parts Comparative example 1 10%C12H2,0(CH2CH20)6SO3NH
A pigment powder is prepared in the same manner as in Example 1 except that the addition of the (02I{lOH)3 aqueous solution is omitted.

Comparative example 2 10% C12H250 (CH2CH20) 4803NH
10% C instead of 15 parts of (C2}{40H)3 aqueous solution
12H250S03NH-(C2H40H)3 aqueous solution 1
Pigment powder was prepared in exactly the same manner as in Example 3 except that 5 parts were used.

Comparative example 3 10% C14H290 (CH2CH20) 6803NH
(Pigment powder was prepared in exactly the same manner as in Example 4 except that the addition of the 02N{40H aqueous solution was omitted.)

Comparative example 4 10% C12H250 (CH2CH20) 8803NH
A pigment powder is prepared in exactly the same manner as in Example 5, except that the addition of the (C2H40H)3 aqueous solution is omitted.

Red facial sting 1 obtained in Examples 1 to 8 and Comparative Examples 1 to 3
and 1.6 parts of No. 4 fess on an automatic Hoover muller with a load of 100 to 150 pounds.
Make a paste by kneading it 2 to 3 times at a time, and use a 25μ grind meter to grind each paste according to JISK-51.
When a dispersion test was conducted using a grindmeter according to No. 01-7, the dispersibility of the pigments obtained in Examples 1 to 8 was extremely good compared to the pigments obtained in Comparative Examples 1 to 3.

The results are shown in Table 1.

Claims (1)

[Claims] 1 General formula R-0(CH2CH20)nS03NH(C2H40H
) A method for improving the dispersibility of an azo lake pigment, which comprises adding the compound represented by 3 before forming a lake. (In the formula, R is a C6-C18 alkyl group, n is 1-12
indicates an integer. )