DE1795052C3 - Water-insoluble monoazo compounds, process for their preparation and their use as pigments - Google Patents

Description

CONHR

NH-

CONHR

N = N-CH-CO-NH

COCH ₃

wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and X is Is hydrogen or halogen atom or a methyl, methoxy or ethoxy group.

2. Process for the preparation of the monoazo compounds mentioned in claim I, characterized in that that the diazonium compounds of 5-amino-isophthalic acid diamides of the general formula

CONHR

with 5-acetoacetylamino-benzimidazoloneR the general formula

X NH

CH, CO -CH ₂ -CO-NH

CO

NH

H ₂ N

CONHR

CONHR

wherein R is a hydrogen atom or an alkyl group with 5-acetoacetylaminobenzimidazolones of general formula

NH

CHjCO-CH ₂ CO-NH

v \

CO

NH

wherein X is a hydrogen or halogen atom or is a methyl, methoxy or ethoxy group, couples.

3. Use of the monoazo compounds according to Claim 1 as pigments.

The invention relates to valuable, water-insoluble monoazo compounds of the general formula

CONMR

CONHK

N N-CH-CO-NH- ';

C (XH, X

NH ^
-NH

; co

worm R is a hydrogen atom or an alkyl group ! to 4 carbon atoms and X is a hydrogen or halogen atom or a methyl, methoxy or Ethoxy group is a process for their preparation,

where R and X have the meanings given above, coupling and the use of these monoazo -'- compounds as pigments.

From DT-AS 12 27 585 pigments are known which in '' he diazo component also has a carbonamide substituent and whose coupling component is an acetoacetylaminobenzimidazolone. These well-known Pigments, however, do not have the resistance to hydrogenation required for polyethylene injection molding processing on.

The diazo components can be prepared by known methods by z. B. 5-nitroisophthalic acid dichloride with ammonia or alkylamines with 1 to 4 carbon atoms or esters of 5-nitro-isophthalic acid with the compounds mentioned brings to reaction at elevated temperature. The 5-nitro-isophthalic acid diamides thus obtained can be converted into the 5-amino-isophthalic acid diamides by catalytic reduction.

The coupling reaction can be carried out in a known manner; be carried out, especially in an aqueous medium, advantageously in the presence of nonionic, anionic or cationic dispersants.

To achieve a particularly favorable crystal structure, it is expedient to use the coupling mixture to heat for some time, for example to boil or bring it to temperatures above 100 ° C under pressure, optionally in the presence of organic solvents such as dichlorobenzene or dimethylformamide or of resin soap. Particularly pure and genuine dyeings are obtained with the dyes according to the invention, if the dyes are used after coupling as a moist press cake or as a dried powder for an aftertreatment with organic solvents such as pyridine, dimethylformamide, alcohol, glycol, glycol monomethyl ether, Glacial acetic acid, chlorobenzene, dichlorobenzene or nitrobenzene at reflux temperature or under pressure at elevated temperature subjects or a grinding of the dyes with the addition of grinding aids connects.

The dyes can also be used in the presence of carrier substances which are suitable for the production of colored varnishes are to be coupled.

The pigment dyes of the invention are suitable for the production of printing inks, color lakes and Dispersion paints for coloring rubber, plastics and natural or synthetic Resins. The new dyes are also suitable for pigment printing on substrates, especially textile

fiber materials or other flat structures such as paper. The dyes can also be used for other purposes, e.g. B. in fine distributed form for dyeing rayon or cellulose ethers or esters, polyamides, polyurethanes, PolyglycoJterephthalaten or polyacrylonitrile in the spinning pulp or for dyeing paper be used.

The dyes can be used in the media mentioned

process well. The dyeings have good light, weather and migration fastness properties and are against

Exposure to heat and chemicals all solvents, resistant.

example 1

18 parts by weight of 5-amino-isophthalsäurediamid are stirred with 50 parts by volume glacial acetic acid 15 minutes is then diazotized at 20 ⁰ C with the equivalent amount NitrosyJschwefelsäure, stirred for 30 minutes, poured into 400 parts by volume of water, clarified with diatomaceous earth and destroy a possible excess of nitrous acid with sulfamic acid.

24 parts by weight of 5-acetoacetylamino-benzimidazolone are dissolved at 20 to 25 ° C. in a mixture of 200 parts by volume of water and 30 parts by volume of 10 η sodium hydroxide solution. The solution is clarified with activated charcoal and the coupling component is precipitated in the filtrate with stirring at 10 ^° C. by adding dropwise 18 parts by volume of glacial acetic acid. Another 20 parts by volume of a 10% aqueous solution of an action product of about 20 mol ethylene oxide on stearyl alcohol are added.

In this suspension of the coupling component is allowed while keeping constant the adjusted pH of about 5.5, the diazo solution at about 20 ⁰ C while stirring well incorporated. The clutch is immediately terminated Heat the coupling mixture to a boil, filtered hot, washed thoroughly with water and dried at 65 ° C. The yellow pigment obtained is pulverized and with 600 parts by volume of glacial acetic acid, 1.5 hours to 90 ⁰ C heated. It is then filtered off with suction, the glacial acetic acid is washed out with methanol and water and the dye is dried. Nfan receives a yellow pigment of soft grain and pure shade. Incorporated into polyvinyl chloride, a varnish, a printing ink or a dispersion paint, the dye gives yellow colorations of high lightfastness, very good fastness to overcoating and perfect resistance to bleeding in polyvinyl chloride with very good heat resistance at the same time.

Example 2

23.5 parts by weight of 5-amino-isophthalic acid-bis-N, N'-ethylamide are stirred with 60 parts by volume of 5N hydrochloric acid and 60 parts by volume of water for about 1 hour. It is then diluted with 150 parts by volume of water and diazotized at 0 to 5 ° C. with 20 Parts by volume of 5 N sodium nitrite solution. You clarify with kieselguhr and remove any existing Excess of nitrous acid with sulfamic acid.

This diazo solution is allowed at about 20 ⁰ C with good stirring to an acetic acid suspension of the coupling component flow that is prepared as follows:

24 parts by weight of 5-acetoacetylamino-benzimidazolone are stirred at 20 to 25 ° C with 200 parts by volume of water and by adding 30 parts by volume 10 η sodium hydroxide solution dissolved. This solution is left in about 30 minutes after clearing with activated charcoal with thorough stirring into a solution of 300 parts by volume Water, 41 parts by volume of glacial acetic acid and 40 parts by volume of 10 η-sodium hydroxide solution, of the 20 parts by volume a 35% aqueous solution of an action product of about 30 mol of ethylene oxide on oleyl alcohol have been added.

The clutch is finished very quickly. You bring that Coupling mixture to boiling, sucks off, washes

ίο thoroughly with water and dry at 65 ° C

The deep reddish-tinged yellow pigment obtained in this way gives colorations of the same very good fastness properties like the dye described in Example 1.

Example 3

The coupling is carried out in the manner described in Example 2 and the dry dye powder is then heated with 300 parts by volume of glacial acetic acid at 70 ^° C. for 75 minutes. The glacial acetic acid is filtered off with suction, displaced by washing with methanol and water and dried.

In this way, a pigment is obtained which gives yellow colorations with a significantly greener cast however, have the same very good fastness properties as that produced according to Example 2 Dye.

Example 4

26.3 parts by weight of 5-amino-isophthalic acid-bis-N, N'-isopropylamide are described in Example 2 Way diazotized. The preparation of the suspension of the azo component and the coupling take place in the in example 1 indicated manner.

The dry powder dye thus obtained 1.5 hours 470 parts by volume of glacial acetic acid at 10O ⁰ C is heated, suction filtered then washed with methanol and water, is displaced to the glacial acetic acid. and dried.

The pigment obtained in this way gives reddish-yellow colorations. It corresponds in its authenticity properties practically the dye prepared according to Example 1.

Example 5

The coupling is carried out as described in Example 4 and the dry dye powder is then heated for 2 hours with 280 parts by volume of o-dichlorobenzene to 110 ^° C. It is filtered off with suction and the o-dichlorobenzene is washed out with methanol. Finally, wash with water and dry

The pigment obtained gives colorations which have practically the same fastness properties like the dye obtained according to Example 4, but which have a significantly greener shade.

Example 6

20.8 parts by weight of 5-amino-isophthalic acid-bis-N, N'-methylamide are diazotized in the manner indicated in Example 2.

The suspension of the coupling component is prepared as follows:

25 parts by weight of Z-methyl-S-acetoacetylaminobenzimidazolone are dissolved in the mixture of 200 parts by volume of water and 60 parts by volume of 10 η sodium hydroxide solution at 20 to 25 ° C. After clarification with activated charcoal, the azo component at 10 ⁰ C is precipitated with stirring by adding 18 parts by volume of glacial acetic acid in the filtrate.

The coupling takes place according to the information in Example 1.

^{The dry dye powder is then heated to 100 to 110 °} C. for 4 hours with 360 parts by volume of glacial acetic acid. After suctioning off, washing with methanol and water and drying, a yellow pigment is obtained which has the same very good fastness properties as the dye described in Example 1

The following table contains a number of other dyes which are obtained in an analogous manner as well as the color tones of these dyes in print:

CONHR

CONHR

N = N-CH-CO-NH
COCH ₃

-NH

NH '

, CO Ri

hue

H H Cl greenish yellow

H CI H yellow

H H Br greenish yellow

H H CH3 yellow

H CH3 H greenish yellow

H OCH3 H yellow

CH3 H H yellow

CH3 H Cl yellow

CH3 CI H greenish yellow

CH ₃ H Br yellow

CH3 H CH3 yellow

CH3 CH3 H reddish yellow

C2H5 H H greenish yellow

n-CjH? H H yellow

i-C3H7 H CH3 reddish yellow

1-C3H7 CH3 H reddish yellow

n-GtH9 H H greenish yellow

1-C4H9 H H yellow

Claims (1)

Patent claims: 1. Water-insoluble monoazo compounds of the general formula in which the diazonium compounds of 5-aminoisophthalic acid diamides the general formula CONHR