RU2069678C1 - Pigment composition - Google Patents

Abstract

FIELD: organic chemistry, pigments. SUBSTANCE: product: pigment composition has 95.0-99.5 mole% 3,3-dichlorobenzidine pigment of the formula:

where: R¹=R² - H; R¹=R²=CH₃ and 0.5-5.0 mole% calcium or barium salt of bis-azodye of the general formula:

where R¹=R² - H; CH₃;

;

;

; M⁺⁺=Ca⁺⁺;Ba⁺⁺. Composition exhibits enhanced staining capability that is 110-120%, transparency (up to 10 points) and provides pigment resistance to crystallization in polygraphic dyes. Synthesized pigments were used in polygraphy. EFFECT: improved method of synthesis, enhanced quality of composition. 1 tbl

Description

 The invention relates to aniline-dye industry, in particular to a pigment composition used in process printing printing.

Known pigment composition, including 3,3'-dichlorobenzidine disazopigment acetoacetarylide series and a modifying additive drug OS-20 based on ethoxylated alcohols C ₁₄ C ₁₆ and the degree of hydroxyethylation 20.

 However, the known pigment composition does not have a sufficiently high coloring ability, transparency and resistance to crystallization in offset inks.

 The objective of the invention is the increase in coloring ability, transparency and resistance to crystallization of the pigment composition.

(I)
где R₁ H; R₂ H
R₁ CH₃; R₂ CH₃
а в качестве модифицирующей добавки соединение общей формулы

где R₁ H; R₂ H
R₁ CH₃; R₂ CH₃

Ме⁺⁺ Ca⁺⁺; Ba⁺⁺
при следующем соотношении компонентов, мол.The problem is solved in that the pigment composition as a 3,3'-dichlorobenzidine pigment contains compounds of the general formula

(I)
where R ₁ H; R ₂ H
R ₁ CH ₃ ; R ₂ CH ₃
and as a modifying additive, a compound of general formula

where R ₁ H; R ₂ H
R ₁ CH ₃ ; R ₂ CH ₃

Me ⁺⁺ Ca ⁺⁺ ; Ba ⁺⁺
in the following ratio of components, mol.

3.3 ¹ -dichlorobenzidine disazopigment of the acetoacetarylide series of the general formula I 95.0 99.5
Modifying additive 0.5 5.0
This pigment composition is not described in the literature.

 Example 1

1 a. Preparation of a solution of tetrazo-3,3 ^1- dichlorobenzidine.

17.7 g (0.07 mol) of 3.3 ^1- dichlorobenzidine is stirred in 210 ml of water and 29.5 ml (0.35 mol) of hydrochloric acid (d 1.184) and diazotized at 0 - +2 ^o C, adding 27 9 ml (0.148 mol) of a 30.2-sodium nitride solution.

 1 b Preparation of a solution of sodium salts of azo components.

 30.0 g (0.1467 mol) of acetoacetic acid M-Xylidide and 0.15 g (0.007 mol) of acetoacetic acid O-carboxyanilide are dissolved in 210 ml of water and 7.2 g (0.18 mol) of sodium hydroxide.

 1 century Getting pigment composition. 1070 ml of water, 11.5 ml (0.2 mol) of acetic acid are placed in a flask with a capacity of 3 l and a solution of a mixture of azo components is added while stirring.

 A solution of the tetrazo compound is added to the resulting suspension, avoiding its excess in the reaction mixture.

At the end of the combination, 0.11 g (0.001 mol) of calcium chloride is added, the reaction mass is heated to 93 95 ^° C, then filtered, washed and dried at 60 ^° C.

 Obtain 44 g of the pigment composition containing 99.5 mol of pigment and 0.5 mol of modifying additives (see table).

Model paint is prepared from the obtained sample (GOST 11279.1 83 p.2.6) and its coloristic and technological properties are determined. To determine the optical density (D ^c ), the intensity with respect to the European standard (J,) and the color difference (ΔE) on a laboratory printing device (GOST 11279.1-83 p. 2.6.), Printing prints are made with a variation in the thickness of the ink layers of 0.8 2.0 microns. To determine the transparency, prints are printed on a black substrate. D ^c , J, ΔE _min and transparency are determined according to GOST 11279.1-83 p. 2.6.3.2. and 2.6.3.3.

To determine the stability and crystallization, the finished model ink is placed in a thermostat and incubated for 1 h at 70 ^o C. Then, printing prints (GOST 11279.1-83 p. 2.6) with a thickness of the ink layer of 1.5 microns from the original ink and ink that has been kept in the thermostat . The intensity, hue, optical density and transparency of the samples are determined. A sample is considered resistant to crystallization if there is no deterioration in the optical properties of the samples after heating in a thermostat compared to the original ones. Testing the coloristic properties of the paint prepared from the pigment composition obtained in Example 1 gave the following results: D $\genfrac{}{}{0ex}{}{\text{from}}{\text{1.5 μm}}$ 1.55, J 120 Δ less than 2.3; strength 10 points; shade N. redder than the prototype; the sample is resistant to crystallization (see table).

 The table shows the coloristic properties of various pigment compositions obtained in the conditions of examples 1 to 15, the structure and number of components included in the pigment compositions.

 Example 2

2a. The preparation of a solution of tetrazo-3,3 ^1- dichlorobenzidine is carried out in accordance with 1A.

 2b. Preparation of a solution of sodium salts of azo components.

 29.64 g (0.1446 mol) of m-Xylidide acetoacetic acid and 0.77 g (0.003 mol) of n-sulfanilide acetoacetic acid are dissolved in 210 ml of water and 7.2 g (0.18 mol) of sodium hydroxide.

 2c. Getting pigment composition.

 Azo coupling is carried out similarly to 1c.

At the end of the combination, 0.44 g (0.004 mol) of calcium chloride is added, the reaction mass is heated to 93 95 ^° C, then filtered, washed and dried at 60 ^° C. 45.7 g of a pigment composition containing 98 mol of the disazo compound I and 2 are obtained. , 0 mol of the disazo compound II (table, item 2).

 Example 3

3a. The preparation of a solution of tetrazo-3,3 ^1- dichlorobenzidine is carried out in accordance with 1A.

 3b. The preparation of a solution of sodium salts of azo components is carried out in accordance with 2b.

 3c. Getting pigment composition.

 Azo coupling is carried out similarly to 1c.

At the end of the combination add 0.83 g (0.04 mol) of barium chloride, heat the reaction mass to 93 95 ^o C, filter, rinse and dry at 60 ^o C.

 45.6 g of a pigment composition containing 98 mol of a disazo compound I and 2 mol of a disazo compound II are obtained (table, p. 3).

 Example 4

4a. The preparation of a solution of tetrazo-3,3 ^1- dichlorobenzidine is carried out in accordance with 1A.

 4b. Preparation of a solution of sodium salts of azo components 29.34 g (0.1431 mol) of m-Xylidide acetoacetic acid and 1.12 g (0.0044 mol) of n-sulfophenylmethylpyrazolone are dissolved in 210 ml of water and 7.2 g (0.18 mol) caustic soda.

 4c. Getting pigment composition.

 Azo coupling is carried out similarly to 1c.

At the end of the combination, add 0.56 g (0.005 mol) of calcium chloride, heat the reaction mass to 93 95 ^o C, then filter, wash the precipitate and dry at 60 ^o C.

 45.5 g of a pigment composition containing 97 mol of a disazo compound I and 3 mol of a disazo compound II are obtained (table, p. 4).

 Example 5

5a. The preparation of a solution of tetrazo-3,3 ^1- dichlorobenzidine is carried out in accordance with 1a.

 5 B. Preparation of a sodium salt solution of azo component.

 30.24 g (0.1475 mol) of acetoacetic acid m-Xylidide are dissolved in 210 ml of water and 7.2 g (0.18 mol) of sodium hydroxide.

 5c. Getting pigment.

 Azo coupling is carried out similarly to 1c.

At the end of the combination, the reaction mass is heated to 93 95 ^o C, then the pigment is filtered off, washed and dried at 60 ^o C.

 45.4 g of pigment containing 100 disazo compounds I are obtained (table, p. 5).

 Example 6

6a. The preparation of a solution of tetrazo-3,3 ^1- dichlorobenzidine is carried out in accordance with 1A.

 6b. Preparation of a solution of sodium salts of azo components.

 30.58 g (0.1446 mol) of acetoacetic acid o-chloroaniline and 0.66 g (0.003 mol) of acetoacetic acid o-carboxyanilide are dissolved in 210 ml of water and 7.2 g (0.18 mol) of sodium hydroxide.

 6c. Getting pigment composition.

 Azo coupling is carried out similarly to 1c.

At the end of the combination, 0.44 g (0.004 mol) of calcium chloride is added, the reaction mass is heated to 93 95 ^o C, the pigment is filtered off, washed and dried at 60 ^o C.

 45.6 g of a pigment composition containing 98.0 mol of a disazo compound I and 2.0 mol of a disazo compound II are obtained (table, p. 6).

 Example 7

7a. The preparation of a solution of tetrazo-3,3 ^1- dichlorobenzidine is carried out as described in 1a.

7b. Preparation of a solution of sodium salts of azo compounds
30.09 g (0.1423 mol) of o-Chloranilin acetoacetic acid and 1.28 g (0.005 mol) of n-sulfoanilide acetoacetic acid are dissolved in 210 ml of water and 7.2 g (0.18 mol) of sodium hydroxide.

 7c. Getting pigment composition.

 Azo coupling is carried out similarly to 1c.

At the end of the combination add 0.78 g (0.007 mol) of calcium chloride, heat the reaction mass to 93 95 ^o C, then filter, wash the precipitate and dry at 60 ^o C.

 45.2 g of a pigment composition are obtained containing 96.5 mol of a disazo compound I and 3.5 mol of a disazo compound II (table, clause 7).

 Example 8

8a. The preparation of a solution of tetrazo-3,3 ^1- dichlorobenzidine is carried out as described in 1a.

 8b. Preparation of a solution of sodium salts of azo components.

 30.09 g (0.1423 mol) of o-Chloraniline acetoacetic acid and 1.27 g (0.005 mol) of n-sulfophenylmethylpyrazolone are dissolved in 210 ml of water and 7.2 g (0.18 mol) of sodium hydroxide.

 8c. Getting pigment composition.

 Azo coupling is carried out similarly to 1c.

At the end of the azo coupling, 0.78 (0.007 mol) of calcium chloride is added, the reaction mass is heated to 93 95 ^o C, then filtered, the precipitate is washed and dried at 60 ^o C.

 45.2 g of a pigment composition containing 96.5 mol of a disazo compound I and 3.5 mol of a disazo compound II are obtained (table, p. 8).

 Example 9

9a. The preparation of a solution of tetrazo-3,3 ^1- dichlorobenzidine is carried out as described in 1a.

9b. Preparation of a solution of sodium salts of azo compounds
29.63 g (0.1401 mol) of acetoacetic acid o-Chloranilide and 1.88 g (0.0074 mol) of n-sulfophenylmethylpyrazolone are dissolved in 210 ml of water and 7.2 g (0.18 mol) of sodium hydroxide.

 9th century Getting pigment composition.

 Azo coupling is carried out similarly to 1c.

At the end of the combination, 2.08 g (0.01 mol) of barium chloride is added, the reaction mass is heated to 93 95 ^° C, then filtered, the precipitate is washed and dried at 60 ^° C.

 45.8 g of a pigment composition are obtained containing 95.0 mol of a disazo compound I and 5.0 mol of a disazo compound II (table, clause 9).

 Example 10

10a. The preparation of a solution of tetrazo-3,3 ^1- dichlorobenzidine is carried out as described in 1a.

 10b. Preparation of a sodium salt solution of azo component.

 31.20 g (0.1475 mol) of o-Chloranilin acetoacetic acid is dissolved in 210 ml of water and 7.2 g (0.18 mol) of sodium hydroxide.

 10th century Getting pigment.

 Azo coupling is carried out similarly to 1c.

At the end of the combination, the reaction mass is heated to 93 95 ^o C, then the pigment is filtered off, washed and dried at 60 ^o C.

 45.4 g of pigment are obtained containing 100 disazo compounds I (table, claim 10).

 Example 11

11a. The preparation of a solution of tetrazo-3,3 ^1- dichlorobenzidine is carried out as described in 1a.

 11b. Preparation of a solution of sodium salts of azo components.

 25.84 g (0.1460 mol) of acetoacetic acid anilide and 0.33 g (0.0015 mol) of acetoacetic acid o-carboxyanilide are dissolved in 210 ml of water and 7.2 g (0.18 mol) of sodium hydroxide.

 11th century Getting pigment composition.

 Azo coupling is carried out similarly to 1c.

At the end of the combination add 0.22 g (0.002 mol) of calcium chloride, heat the reaction mass to 93 95 ^o C, then filter, wash the precipitate and dry at 60 ^o C.

 Get 41.6 g of a pigment composition containing 99.0 mol of a disazo compound I and 1.0 mol of a disazo compound II (table, clause 11).

 Example 12

12a. The preparation of a solution of tetrazo-3,3 ^1- dichlorobenzidine is carried out as described in 1a.

 12b. The preparation of a solution of sodium salts of azo components is carried out as described in 11b.

 12th century Getting pigment composition.

Azo coupling is carried out similarly to 1c. At the end of the azo coupling, 0.41 g (0.002 mol) of barium chloride is added, the reaction mass is heated to 93 - 95 ^° C, then filtered, the precipitate is washed and dried at 60 ^° C.

 41.3 g of a pigment composition are obtained containing 99.0 mol of a disazo compound I and 1.0 mol of a disazo compound II (table, clause 12).

 Example 13

13a. The preparation of a solution of tetrazo-3,3 ^1- dichlobenzidine is carried out as described in 1a.

13b. Preparation of a solution of sodium salts of azo compounds
25.33 g (0.1431 mol) of acetoacetic acid anilide and 1.13 g (0.0044 mol) of acetoacetic acid n-sulfoanilide are dissolved in 210 ml of water and 7.2 g (0.18 mol) of sodium hydroxide.

 13th century Getting pigment composition.

 Azo coupling is carried out similarly to 1c.

At the end of the combination, add 0.56 g (0.005 mol) of calcium chloride, heat the reaction mass to 93 95 ^o C, then filter, wash the precipitate and dry at 60 ^o C.

 41.3 g of a pigment composition containing 97.0 mol of a disazo compound I and 3.0 mol of a disazo compound II are obtained (table 1, clause 13).

 Example 14

 14a. The preparation of a solution of tetrazo-3,3'-dichlorobenzidine is carried out as described in 1a.

14b. Preparation of a solution of sodium salts of azo compounds
25.06 g (0.1416 mol) of acetoacetic acid anilide and 1.50 g (0.0059 mol) of n-sulfophenylmethylpyrazolone are dissolved in 210 ml of water and 7.2 g (0.18 mol) of sodium hydroxide.

 14th century Getting pigment composition.

 Azo coupling is carried out similarly to 1c.

At the end of the azo coupling, 0.89 g (0.008 mol) of calcium chloride are added, the reaction mass is heated to 93 95 ^° C, then filtered, the precipitate is washed and dried at 60 ^° C.

Obtain 41.2 g of the pigment composition containing 96.0 mol of the disazo compound I and 4.0 mol of the disazo compound II (table, p. 14)
Example 15

15a. The preparation of a solution of tetrazo-3,3 ^1- dichlorobenzidine is carried out as described in 1a.

 15b. Preparation of a sodium salt solution of azo component.

 26.11 g (0.1475 mol) of acetoacetic acid anilide are dissolved in 210 ml of water and 7.2 g (0.18 mol) of sodium hydroxide.

 15th century Getting pigment.

 Azo coupling is carried out similarly to 1c.

At the end of the combination, the reaction mass is heated to 93 95 ^o C, filtered, the precipitate is washed and dried at 60 ^o C.

 Obtain 41.0 g of pigment containing 100 disazo compounds I (table 1, p. 15).

Claims (1)

A pigment composition based on a 3,3'-dichlorobenzidine disazopigment of the acetoacetarylide series, characterized in that it contains a compound of the general formula I as a 3,3'-dichlorobenzidine pigment

where R ¹ H, R ² H;
R ¹ CH ₃ , R ² CH ₃ ,
and optionally calcium or barium salt of a disazo dye of general formula II

where R ¹ H, R ² H;
R ¹ CH ₃ , R ² CH ₃ ;

in the following ratio of components, mol. 3,3'-Dichlorobenzidine disazopigment of the formula I 95.0 99.5
Calcium or barium salt of a disazo dye of the general formula II 0.5 - 5.0

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