CH624977A5 - Process for the preparation of azo pigments - Google Patents

Description

624 977

2nd

PATENT CLAIMS 1. Process for the production of azo pigments with increased color strength and purity by condensation of an azo dye carboxylic acid halide of the formula

N-A-Y

Chlorine atom, a methyl or a nitro group and Zi denotes an H or chlorine atom or an alkoxycarbonyl group or chloroalkoxycarbonyl group with 2-6 C atoms, where Yi and Zi are in the m or p position to the azo group.

3. Process according to claims 1 and 2, characterized in that a carboxylic acid chloride of the formula is used as the additional component

10th

(I)

COHal

15

in which B denotes an arylene radical which may contain non-solubilizing substituents, in a molar ratio of 2: 1, characterized in that, in addition to the carboxylic acid chloride of the formula I (main component), an additional component of the formula

• A Y 1

(II)

COHal

(VI)

where Xi is a chlorine atom, a methyl or nitro group, an alkoxy group with 1-4 C atoms or an alkoxycarbonyl group with 2-6 C atoms, Yi is an H or where A is a carbocyclic or heterocyclic aromatic radical, Q, X , Y and Z represent H atoms or non-solubilizing substituents and shark represents a halogen atom, 20 with a diamine of the formula

H2N-B-NHz

25th

30th

where Qi is an H or halogen atom, an alkoxy group with 1-4 C atoms, a nitro or cyano group, X2 is a -COOR group, wherein R is alkyl with 3-30 C atoms, haloalkyl with 2-6 C atoms, a phenyl group optionally substituted by halogen, alkyl or alkoxy having 1 to 30 C atoms or alkoxycarbonyl having 1 to 30 C atoms, a carbamoyl group, an alkylcarbamoyl group having 2 to 30 C atoms, one optionally chlorine -, nitro-, trifluoromethyl, alkyl or alkoxy with 1-30 C atoms or alkoxycarbonyl with 2-6 C atoms substituted phenyl group, Y2 and Z2 chlorine atoms, methyl or nitro groups or alkoxycarbonyl groups with 2-6 C atoms.

4. Process according to claims 1-3, characterized in that the main component is a carbon

35

40

used, in which A has the meaning given, Q, X ', Y' and Z 'are non-water-solubilizing substituents, at least one of the substituents X', Y 'and Z' having at least 45 atoms from the series C, O, S, N or Si has more than X, Y or Z or at least 2 of the substituents X ', Y' or Z 'have at least one atom from the series C, O, S, N or Si have more than X, Y or Z.

2. The method according to claim 1, characterized in that the main component is a carboxylic acid chloride of the formula

55

C0C1

used, wherein X3 is chlorine or methyl, Y3 is chlorine or alkoxycarbonyl with 1-4 C atoms.

5. Process according to claims 1-4, characterized in that a carbon is added as an additional component

«0

used, wherein Yi and Qi have the meaning given in claim 3, X4, H, chlorine, methyl or alkoxycarbonyl having 2-6 C atoms and RI alkyl having 3-6 C atoms, chloroalkyl having 2-4 C- Atoms or the rest of the formula

65

3rd

624 977

where V is H, chlorine or methyl and W is H, chlorine, methyl, phenyl or alkoxycarbonyl having 2-6 C atoms.

6. The method according to claims 1-5, characterized in that the proportion of the main component 70-

98 fl / o and the proportion of the additional component is 30-2%, based on the stated amount of the components.

7. The method according to claim 6, characterized in that the proportion of the main component is 95-98% and the proportion of the additional component is 5-2%.

8. The method according to claim 1, characterized in that a phenylene or naphthylene diamine is used as the diamine.

9. The method according to claim 8, characterized in that a phenylenediamine of the formula is used in which X3 and Y3 are H or halogen atoms, alkyl or alkoxy groups having 1-4 C atoms.

10. A method for pigmenting high molecular weight organic material, characterized by the use of the azo pigments according to claim 1.

represent groups with 1 to 30 C atoms, aryloxycarbonyl, aroyl, arylsulfonyl, arylsulfamoyl, aroylamino, arylureido, arylcarbamoyl or arylazo groups.

The new mixed condensates are valuable pigments that can be used to pigment high-molecular organic material. In the following examples, the parts mean parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

example 1

A. 7-2? 2 'parts of the azo dye, which is obtained by coupling diazotized l-amino-2,5-dichlorobenzene with 2,3-hydroxynaphthoic acid, are finely divided in a mixture with 520 parts of o-dichlorobenzene Stirring heated to 85 °. Then, at 80-90 °, 32.7 parts of thionyl chloride are added dropwise in the course of 10 minutes. The reaction mixture is heated further and held at 115-120 ° for 60 minutes. After cooling to 20 °, the crystalline azo dye carboxylic acid chloride is isolated by filtration, washed with a little cold o-dichlorobenzene, then washed with petroleum ether and dried in a vacuum cabinet at 70 °.

B. 82.5 parts of the azo dye, which is obtained by coupling diazotized 4-methyl-3-amino-benzoic acid 2'-chloroethyl ester with 2,3-hydroxynaphthoic acid, are converted into carboxylic acid chloride as described under A.

30th

It has been found that pigments with increased color strength and purity are obtained if a mixture of a carboxylic acid halide of the formula I (main component) specified in claim 1 with an additional component of the formula II specified in claim 1 with a diamine of the formula

H2N-B-NH2

in which B denotes an arylene radical which may contain non-solubilizing substituents, condensed in a molar ratio of 2: 1.

The main and additional components differ in that they have different bulk.

Non-solubilizing substituents are understood to mean 45 those which do not dissolve the pigment in water or in organic solvents, for example halogen atoms, alkyl or alkoxy groups with 1-6 C atoms, nitro, trifluoromethyl, carbamoyl, ureido , Sulfamoyl or cyano groups, alkoxycarbonyl, alkanyol, 50 alkylcarbamoyl, alkylureido or alkanyolamino groups with 2-6 C atoms, alkylsulfonyl or alkylsulfamoyl groups with 1-6 C atoms, aryloxycarbonyl, aroyl, aroyl amino, arylsulfonyl, arylcarbamoyl, arylsulfamoyl, aryl, arylcarbamoyl, arylureido or arylazo groups. 5y

Q preferably represents an H or bromine atom, a methoxy, nitro or cyano group.

It is sufficient for the substituents X ', Y' and Z 'of the additional component that they are not water-solubilizing. Since the proportion of the additional component is generally low, X ', Y' and Z 'can also represent groups which bring about a certain solution of the dye in organic solvents. X ', Y' and Z 'can thus be, for example, halogen atoms, alkyl or alkoxy groups having 1-30 C atoms, nitro, trifluoromethyl, carbamoyl, sulfamoyl, 65 ureido or cyano groups, alkoxycarbonyl, alkylcarbamoyl, alkanoyl -, alkylureido or alkanoylamino groups with 2-30 C atoms, alkylsulfonyl or alkylsulfamoyl

Mixed condensation

14.42 parts of chloride A (= 95% by weight / »of the total amount of acid chloride) and 0.86 part of acid chloride B (= 5% by weight /» of the total amount) are mixed with 260 parts of o-di-chlorobenzene Stirring heated to 110-120 °. A 120 ° warm solution containing 2.16 parts of 1,4-phenylenediamine in 65 parts of o-dichlorobenzene is then added over the course of 2-3 minutes. The precipitated pigment mixture is stirred at 140-145 ° for 16 hours. The disazo pigment mixture obtained is filtered off at 100 °, first washed with 100 ° warm o-dichlorobenzene, then with 20 ° warm methanol and finally with warm water. Drying in a vacuum cabinet at 100 ° gave 14.7 parts of a red disazo pigment mixture which is practically insoluble in the customary solvents. It colors PVC and varnishes in brilliant, strong, pure red tones with excellent light, migration and overpainting fastness.

Example 2

A. 68.2 parts of the azo dye, which is obtained by coupling diazotized l-amino-2-methyl-5-chlorobenzene with 2,3-hydroxynaphthoic acid, are converted into carboxylic acid chloride as described in Example 1A.

B. 78.4 parts of the azo dye, which is obtained by coupling of diazotized 4-methyl-3-aminobenzoic acid isopropyl with 2,3-hydroxynaphthoic acid, are converted into carboxylic acid chloride as described in Example 1A.

Mixed condensation 12.92 parts of acid chloride A (= 90%> the total amount) and 1.64 parts of acid chloride B (= 10% of the total amount) are prepared analogously to Example 1 with 3.13 parts of 2-methyl-5-chloro-l, 4-phenylenediamine condensed and worked up. 14.8 parts of a carmine-red disazo pigment mixture are obtained with. the same fastness properties as the product obtained according to Example 1.

624 977

4th

Example 3

17.2 parts of the azo dye obtained by coupling diazotized 1-amino-2,5-dichlorobenzene with 2,3-hydroxynaphthoic acid (= 95 ° / o of the total amount) and 1.14 parts of the azo dye obtained by coupling obtained from diazotized 4-methyl-3-amino-benzoic acid 3 ', 5'-dimethyl-phenyl ester with 2,3-hydroxynaphthoic acid are heated in a finely divided mixture with 325 parts of o-dichlorobenzene to 85 ° with stirring. Then, at 80-90 °, 10, 8.2 parts of thionyl chloride are added dropwise in the course of 10 minutes. The reaction mixture is heated further and held at 115-120 ° for 60 minutes. Now the excess of thionyl chloride is distilled off together with 65 parts of o-dichlorobenzene at 100 ° under a weak vacuum. At 110-120 °, a 120 ° warm solution containing 2.7 parts of 1,4-phenylenediamine and 130 parts of o-dichlorobenzene is added to the resulting solution, which contains the mixture of azo dye carboxylic acid chlorides, over the course of 2-3 minutes. The condensation mixture 20 formed is stirred for 16 hours at 140-145 °, worked up at 100 ° as described in Example 1. 18.4 parts of a scarlet disazo pigment mixture are obtained, with the same fastness properties as that obtained according to Example 1.

25th

Example 4

18.15 parts of a mixture of the azo dye carboxylic acids obtained by coupling a mixture consisting of 98% of diazotized 2,5-dichloroaniline and 2 ° / 30% of diazotized l-amino-2-methyl-5-benzoic acid - (3 ', 5'-dimethylphenyl) ester with 2,3-hydroxynaphthoic acid, are condensed with 2.7 parts of 1,4-phenylenediamine according to the information in Example 3 after conversion into the azo dye carboxylic acid chlorides. This gives 18.2 parts of a scarlet-35 red disazo pigment mixture which is largely identical to the mixed pigment prepared according to Example 3.

Example 5

A. 72.8 parts of the azo dye obtained by Kupp40

tion of diazotized methyl 4-methyl-3-aminobenzoate with 2,3-hydroxynaphthoic acid are converted into carboxylic acid chloride as described in Example 1A.

B. 102.4 parts of the azo dye obtained by coupling diazotized 4-methyl-3-aminobenzoic acid 4'-propoxycarbonyl-phenyl ester with 2,3 hydroxynaphthoic acid are converted into carboxylic acid chloride as described in Example 1A.

Mixed condensation

14.52 parts of acid chloride A (= 95% of the total amount of acid chloride) and 1.06 parts of acid chloride B (= 57% of the total amount of acid chloride) are condensed with 2.72 parts of 2,5-dimethyl-1,4-phenylenediamine and worked up according to the instructions in Example 1. 15.4 parts of a red disazo pigment mixture are obtained which have the same fastness properties as the product obtained according to Example 1.

Example 6

A mixture consisting of 16.98 parts (= 80% of the total amount of acid chloride) from the azo dye chloride obtained according to Example 5B and 3.04 parts (= 20 * / o of the total amount of acid chloride) from the azo dye chloride obtained according to Example 1A is described of Example 1 condensed with 2.16 parts of 1,4-phenylenediamine. 18.6 parts of a red disazo pigment mixture having the same fastness properties as that obtained in Example 1 are obtained.

Examples 7-16

The following table lists further disazo pigment mixtures which are obtained if the amines given in columns III and V are diazotized by the process given in Example 1, coupled with 2,3-hydroxynaphthoic acid and the azo dye carboxylic acids obtained in the acid chlorides transferred, the latter mixes and condensed in a molar ratio of 2: 1 with the diamine indicated in column VI. Columns II and IV indicate the percentages of the azo dye carboxylic acid chlorides used.

I II

example

III

IV

VI

VII

7

95

2,5-dichloroaniline

5

Isopropoxycarbonyl-phenyl l-amino-2-methoxy-5-benzoate p-phenylenediamine scarlet

8th

90

2,5-dichloro-aniline

10th

l-Amino-2-methyl-5-benzoic acid / 8-chloroethyl ester p-phenylenediamine

Scarlet fever

9

95

2,5-dichloro-aniline

5

l-Amino-2-methyl-benzoic acid-l ', 3'-dichloroisopropyl ester p-phenylenediamine red

10th

95

2,5-dichloroaniline

5

Aminoterephthalic acid diisopropyl ester p-phenylenediamine red

11

90

2,5-dichloro-aniline

10th

Amino-terephthalic acid dimethyl ester p-phenylenediamine red

12

95

2,5-dichloro-aniline

5

1-Amino-2-methyl-5-benzoic acid 1 ', 3'-dichloroisopropyl ester

2-chloro-1,4-phenylenediamine red

13

90

2,5-dichloroaniline

10th

l-Amino-2-methyl-5-benzoic acid - /? - chloroethyl ester

2-chloro-l, 4-phenylenediamine red

14

97

2,5-dichloroaniline

3rd

l-Amino-2-methyl-5-benzoic acid isopropyl ester

2-chloro-1,4-phenylenediamine red

15

95

2,5-dichloro-aniline

5

Methyl l-amino-2-methyl-5-benzoate

2-chloro-l, 4-phenylenediamine red

16

98

2-methyl-5-chloroaniline

2nd

1-Amino-2-methyl-5-benzoic acid isopropyl ester

2-methyl-5-chloro-1,4-phenylenediamine carmine red

M