DE1923256A1 - Water-insoluble monoazo dyes and a process for their preparation - Google Patents

Description

FARBWERKE HOECHST AG. formerly Master Lucius & Brüning

File number: Fw 6072

Date: April 22, 1969

Dr.B / Blt

Water-insoluble monoazo dyes and a process for their preparation

The present invention relates to new, valuable, water-insoluble Monoazo dyes that are free from water-solubilizing groups, such as, in particular, sulfonic acid and carboxylic acid groups are, and the general formula (1)

AT

ti

CCr

OH

(1) CO-NH

in which A is the residue of a diazotizable aromatic iso- or heterocyclic amine, R is an aryl group and X and X are hydrogen atoms, halogen atoms, preferably chlorine or bromine atoms, alkyl or alkoxy groups of 1-6 carbon atoms, and a process for their preparation, in which one diazotized amines of the general formula (2)

A-NH ₂ (2)

in which A has the meaning given above, with azo components of the general formula (3)

009847/1710

(3)

in which X-, X "and R have the meaning given above have coupled.

As amines of the general formula (2) mentioned, which are free from water-solubilizing groups, such as carboxylic acid and Sulfonic acid groups, compounds of the benzene, Naphthalene, anthraquinone or heterocyclic series, such as the carbostyril, quinazoline or benzthiazole series, be used. The radical A can have further substituents, such as halogen atoms, alkyl groups, Aralkyl groups, alkoxy groups, phenoxy groups, trifluoromethyl groups, Cyano groups, nitro groups, alkyl sulfone groups, aryl sulfone groups, Acyl groups, acyl amino groups, carboxamide groups, Sulfonic acid amide groups, carboxylic acid ester groups and / or sulfonic acid ester groups.

Examples of suitable amines of the formula (2) mentioned are:

Mono-, di- or trihaloanilines, such as 2-chloroaniline, 2,4-dichloroaniline, 2,5-dichloroaniline, 2,4-dibromaniline, 3,4-dichloroaniline, 2,6-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline or 2,4,6-trichloroaniline, also mono-, dioder Trichloro-amino-alkylbenzenes, such as, for example, 2-methyl-4-chloroaniline, 2-methyl-5-chloroaniline, 2,4-dichloro-5-ethylaniline, 2,5-dichloro-4-methylaniline or 2,4,6-trichloro-3-methylaniline, also alkoxyaminobenzenes, such as 2,5-dimethoxyaniline, 2,5-diethoxyaniline, 2-methoxy-4-chloroaniline, 2-methoxy-5-chloroaniline, 2-xthoxy-5-chloroaniline, (2-chloro-4-aminophenyl) benzyl ether. 2-Xthoxy-5-methylaniline

847/1 7 T0

or 2,4-dichloro-5-methoxyaniline, also nitroanilines, such as 2-nitro-4-methylaniline, 4-nitro-2-methylaniline, 2-methoxy-4-nitroaniline, 4-methoxy-2-nitroaniline, 2- Ethoxy-4-nitroaniline, 2-chloro-4-nitroaniline, 4-chloro-2-nitroaniline, 2-chloro-5-nitroaniline or 2,4-dinitroaniline, and also aminobenzonitriles such as 2-amino-5-nitrobenzonitrile Acylamino-aniline, such as 2-nitro-4-acetamino-aniline, 2-chloro-4-raethyl-5-acetamino-aniline, 2 ^ -Dichlor-ö-acetylamino-aniline or 2-chloro-5-benzoylaminoaniline, also trifluoromethyl anilines, such as, for example, 2-chloro-5-trifluoromethyl aniline or 3,5-bis-trifluoromethylaniline _r also nucleus acylated anilines, such as, for example, 3-amino-4-chloro-acetophenone, 3-amino-acetophenone or 3-amino -4-chloro-benzophenone, also aminosulfones, such as, for example, 3-Amino ^ 4-methoxyphenyl-ethylsulfone or 3-araino-4-methoxydiphenyl sulfone, and also aminobenzoic acid alkyl esters and aryl esters, such as, for example, 2-amino-benzoic acid methyl esters r, 2-aminobenzoic acid ethyl ester, 2-aminobenzoic acid isobutyl ester, 4- ⁱ chloro-2-aminobenzoic acid methyl ester, 4-methyl-3-aminobenzoic acid methyl ester, 1-amino-benzene-2,5-dicarboxylic acid dimethyl ester, l -Amino-3, 5-dicarboxylic acid dimethyl ester, also \ Äilobenzoic acid amides, such as 4-amino-benzoic acid amide, further aminobenzenesulfonic acid amides, alkylamides or -arylamides, such as, for example, 3-amino-4-methoxybenzenesulfonic acid methylamide, 2,5-dimethoxy 4-aminobenzene-sulfonic acid methylamide, 2-methyl-5-methoxy-4-aminobenzene-sulfonic acid methylamide, 3-amino-4-carboaethoxy-benzene-sulfonic acid amide, 3-amino-4-methylbenzene-sulfonic acid phenylamide, other isocyclic aromatic amines, such as l -Amino-2-methoxynaphthalene, l-amino-4-nitronaphthalene, 2-amino-5-nitronaphthalene, l-amino-2-chloroanthraquinone or 2-amino-3-chloroanthraquinone and heterocyclic amines, such as 4-methyl-7- amino-carboβtyril, 2 ^ -Dioxy-T-amino-quinazoline or 2-amino-benzothiazole.

0 08847/1710

Particularly noteworthy are amines of the general formula (2), which are specifically of the general formula (2a) correspond

NH ₂

(2a) CONHR ₂

wherein Z is hydrogen, a low molecular weight alkyl or alkoxy group, a halogen atom, preferably chlorine, a carboxylic acid alkyl ester group or an aryloxy group and R _{2 is} a hydrogen atom, an alkyl group of 1-6 carbon atoms, an aralkyl group such as a benzyl group, a cycloalkyl group such as a Mean cyclohexyl group or an optionally substituted aryl group.

Suitable amines of this formula 2a are:

3-Amino-4-methylbenzoic acid amide, 3-Amino-4-methylbenzoic acid methylamide, 3-amino-4-ynethyl-benzoic acid isopropylamide, S-Araino ^ -methyl-benzoic acid-cyclohexylamide, 3-amino-4-methyl-benzoic acid-phenylamide, 3-Amino-4-methyl-benzoic acid- (2 ', 4'-dimethylphenyl) -amide, S-amino ^ -methyl-benzoic acid-benzylamide, 3-Amino-4-methyl-benzoic acid- (2'-methyl-4'-chlorophenyl} -amide, 3-Amino-4-methyl-benzoic acid (2 ', 5'-dichlorophenyl) amide, 3-amino-4-chloro-benzoic acid amide, 3-amino-4-chloro-benzoic acid methylamide, 3-Amino-4-chloro-benzoic acid-phenylamide, 3-Amino-4-methoxy-benzoic acid amide, 3-amino-4-methoxy-benzoic acid methylamide, 3-amino-4-methoxy-benzoic anilide, 3-amino-4-carbonethoxy-benzoic acid amide, 3-Amino-4-caΓbomethoxy-benzo € acid- (2 '-chloro-4'-methyl-phenyl) -amide, 3-amino-4-carbomethoxybenzoic acid- (2 ', 5-dichlorophenyl) amide, 2-amino-2' -chloro-diphenylether-4-carboxylic acid isopropylamide, 2-amino-2 ', 4'-dichloro-di-

0098A7 / 1710

phenylether ^ -carboxylic acid methylamide and 2-amino-4'-methyldiphenylether-4-carboxylic acid alkylaraid.

The compounds used as azo components can be prepared by known processes, for example by reacting 2,4-dinitrochlorobenzene with an amine of the formula R-NH «, in which R has the meaning given above, to give the corresponding 2,4-dinitro-diphenylamine , its partial reduction, for example with sulfhydrate, to the corresponding 2-amino-4-nitro-diphenylamine, reaction with urea or phosgene to give the corresponding nitrobenzimidazolone, reduction to the corresponding amino-benzimidazolone and condensation with 2-oxy-3-naphthoic acid to give the corresponding 5- (2 ^f , 3 ^f -oxynaphthoylamino) -benzimidazolone according to the following scheme:

₂ J ^ No _{2 0} Λ> νο _{2 N} 0

2 2 O ₂ N 2 V ^ 'NHg O ₂ N

^R R

N ^

_C0 _ _{NH N}

Instead of 2,4-dinitrochlorobenzene, 2,4-dinitrochlorobenzene can also be used as starting compounds, which _{carry further substituents X- and X 2} , where X- and X _{3 have} the meanings given above.

Examples of suitable amines R-NH ₃ are aniline, the various anisidines, toluidines, chloroanilines, xylidines, chlorotoluidines, chloroanisidines or naphthylamines .

0098A7 / 1710

Suitable azo components of the formula (3) mentioned are named for example:

1-phenyl-5- (2 ', 3'-oxynaphthoylamino) -benzimidazolone, 1- Q4 "-methoxyphenyl] -5- (2', 3'-oxynaphthoylamino) -benzimidazolone _f 1- [_4" -Methyl- phenylJ -5- (2 ', 3 ^! -oxynaphthoylamino) -benzimidazolone, [1-4 "-chlorophenyF] -5- (2', 3'-oxynaphthoylamino) -benzimidazolone, 1- [4" -chloro-2 ^ll - methylphenyl_] -5- (2 ', 3' -oxynaphthoylamino) -benzimidazolone, 1- [2 "-chlorophenyl] -5- (2 ', 3'-oxynaphthoylamino) -benzimidazolone, 1- [2" -methoxyphenyl] -5 - (2 ^l , 3'-oxynaphthoylamino) -benziraidazolone, 1-naphthyl-5- (2 ', 3'-oxynaphthylamino) -benzimidazolone, 1-phenyl-6-chloro-5- (2', 3'-oxynaphthoylamino) benzimidazolone, 1-phenyl-7-chloro-5- (2 ', 3'-oxynaphthoylamino) -benzimidazolone and 1-phenyl-7-methoxy-5- (2', 3'-oxynaphthoylamino) -benzimidazolone.

The diazonium compounds are prepared from the amines of the general formula (2) in a known manner. In some In some cases, the diazonium salts are sparingly soluble in an aqueous medium and separate out. You can isolate them and Bring to the coupling as a moist paste. However, the diazotization can also be carried out in a suitable organic Carry out medium, for example in glacial acetic acid, alcohol, dioxane, tetrahydrofuran, formamide, or dimethylformamide Dimethyl sulfoxide, and the solution of the diazoniura compound thus obtained combine with the azo component.

The dyes can be in substance, on the fiber or on a substrate, for example barite.

The production of the dyes on vegetable fibers, especially cotton, takes place according to the known methods of the ice color technique.

009847/1710

The dyes are prepared in bulk by methods known per se, for example by combination of the diazonium compounds with the azo components in an aqueous medium, advantageously in the presence of an anion-active, cation-active or non-ionic dispersant or in the presence of an organic solvent.

The dyes obtained in this way are often of hard grain and must then in order to achieve the full color strength and the optimal fastness properties are subjected to an aftertreatment. For example, the dried ones are heated for this purpose and ground or wet dyes in pyridine, dimethylformamide or other organic solvents such as dimethyl sulfoside, alcohol or chlorobenzene under reflux for some time or to higher temperatures under pressure. In some cases, it can also be converted into a grain-soft form by heating with water under pressure, optionally with the addition of dispersants.

The dyes obtainable by the present process are water-insoluble pigments. They are suitable for ^s? Preparation of colored lacquers, lacquer formers, solutions and products made from acetyl cellulose, natural resins or synthetic resins such as polymerization or condensation resins such as aminoplasts or phenoplasts and from polystyrene, polyolefins such as polyethylene or polypropylene, polyacrylic compounds, polyvinyl compounds such as polyvinyl chloride or polyvinyl acetate, Polyesters, rubber, casein or silicone resins.

The new dyes are also suitable for pigment printing on a substrate, especially on a textile fiber as well also on other planar structures, such as on paper. They can also be used for other purposes ^ Kΐ. corner, e.g. in finely divided form for dyeing artificial silk sue Vickose or cellulose ethers or esters, polyamides or polyurethanes can be used in the spinning pulp or for dyeing paper.

0 0 9 8 A 7/1 7 1 0

BATH ORIGINAL

Let them because of their favorable theological properties the dyes process well in the media mentioned. They then have good light, weather and migration fastnesses on. They are also heat-resistant, strongly colored and in many cases show pure, brilliant shades. Against the influence chemicals, for example solvents, but especially against acidic and alkaline effects they persist.

example 1

15.0 parts by weight of 2-aminotoluene-4-carboxamide are stirred into 140 parts by volume of water and 60 parts by volume of 5N hydrochloric acid and diazotized with 20 parts by volume of 5N sodium nitrite solution at 0 ° to 5 ° C. The solution is then clarified.

200 parts by volume of 4N sodium acetate solution and 100 parts by volume of 2N acetic acid are placed in the coupling vessel. For this the diazo solution is added at 5 ° C. and a solution of 41.5 parts by weight of 1-phenyl-5- (2 *, 3'-oxynaphthoylamino) benzimidazolone is then left in 400 parts by volume of water, 160 parts by volume of 2N sodium hydroxide solution and 10 parts by volume of a 10% strength aqueous solution Run in solution of the reaction product from 1 mol of stearyl alcohol and 20 UoI of ethylene oxide. The mixture is then stirred for about 20 minutes, until the coupling reaction is over.

The dye is then filtered off with suction, washed and dried. The ground dye is heated in 500 parts by volume of dimethylformamide to 100.degree. C. for 2 hours to convert it into a grainy and strongly colored form. The dye is then filtered off with suction, washed and dried. The pigment dye of the formula obtained in this way

009847/1710

OH

CO-NH

When incorporated into polyvinyl chloride, a varnish, a printing ink or a spinning mass, it results in a very pure, bluish-red tint Dyeings with good heat resistance and very good light and solvent fastness.

If 67 g of polyvinyl chloride, 33 g of a plasticizer mixture (mixture of equal parts of dioctyl phthalate and dibutyl phthalate), 0.1 g of the dye and 0.5 g of titanium dioxide for 15 minutes at 150 ° C on a roller mill and mixed processed into a thin film, its red color is characterized by very good heat, migration and Lightfastness as well as high color strength and color purity.

If, instead of l-phenyl-5- (2 ', 3'-oxynaphthoylamino) -benzimidazolone, equivalent amounts of 1- [4 "-chloro-2" -methylphenyl] -5- (2', 3 '-oxynaphthoylamino) - benzimidazolone, 1- [j2 "-chlorophenylJ-5- (2 ', 3'-oxynaphthoylamino) -benzimidazolone, 1- [2" -methylphenyl -5- (2 ^f , 3'-oxynaphthoylamino) -benzimidazolone, 1- [3 "-ChlorophenylJ-5- (2 ', 3'-oxynaphthoylamino) -benzimidazolone, 1- [2" -methoxyphenyl] -5- (2', 3'-oxynaphthoylamino) -benzimidazolone, 1- [2 ^M , 4 "-dimethylphenyl ] -5- (2, 3'-oxynaphthoylamino) -benzimidazolone, l-naphthyl-5- (2, 3'-oxynaphthoylamino) -benzimidazolone or l-phenyl-7-chloro-5- (2 ', 3' -oxynaphthoylamino) -benzimidazolone, then one obtains red pigment dyes with similarly good fastness properties.

009847/1710

Example 2

35.3 parts by weight of 2-amino-2 ·, -! '- dlchloro-diphenylether-icarboxylic acid n-butylamide are dissolved hot in 120 parts by weight of glacial acetic acid, cooled and with 16.7 parts by volume of a 6n solution of sodium nitrite in concentrated sulfuric acid at 10 ° C diazotized. This solution is subsequently diluted with 200 parts by volume of water and clarified.

200 parts by volume of 4N sodium acetate solution and 100 parts by volume of 2N acetic acid are placed in the coupling vessel. at A solution of 41.5 parts by weight of 1-phenyl-5- (2 ', 3'-oxynaphthoylamino) benzimidazolone is then left at 20 to 25 ° C. at the same time in 400 parts by volume of water, 160 parts by volume of 2N sodium hydroxide solution and 10 parts by volume of a 10% strength aqueous solution Solution of the reaction product from 1 pint of stearyl alcohol and 20 mol of ethylene oxide and the diazo solution run in, 500 parts by volume to keep the pH constant at 5-6 2N sodium hydroxide solution are added dropwise. The mixture is stirred for a further 30 minutes until the coupling reaction has ended. The dye is then suctioned off, washed, dried and ground.

To convert the dyestuff into a grainy and strongly colored form in 500 parts by volume of dimethylformamide for 2 hours heated to 120 ° C with stirring, suction filtered while hot, washed and dried.

The pigment of the formula obtained in this way

009847/17 1.0

- li -

^C1 "U

Cl N

Il

C-O H

When incorporated in polyvinyl chloride, in a lacquer, a printing ink or in a spinning mass, it produces bluish-tinged red colorations with very good light and migration fastness properties,

0.8 parts by weight of this pigment, 2.4 parts by weight of alumina hydrate and 4.8 parts by weight of a letterpress varnish mixed and rubbed on a three-roll mill, the result is a letterpress ink with a pigment content of 10 Percentage by weight, which results in red prints, high color strength and purity with good lightfastness »

Example 3

19.4 parts by weight of methyl 2-amino-1-terephthalate-4-carboxamide are stirred into 80 parts by volume of 5N hydrochloric acid, diluted with 240 parts by volume of ice water and diazotized at 5 ° to 10 ° C. with 20 parts by volume of 5N sodium nitrite solution. The solution is then clarified.

In the coupling vessel, 200 parts by volume of 4N sodium acetate, 100 volumes Telle 2N acetic acid and 10 parts by volume of a 10% aqueous solution of the action product of 1 mol of stearyl alcohol and 20 mole Xthylenoxyd vt diazo solution added "At 10 runs to 20 ° C EISU .a 44.6 weight splitter l -. (4 ^M -methoxyphenyl) -5- (2, 3 '-oxy-

009847/1710 BATH ORIGINAL.

Water naphthoylamino) benziraidazolone in 400 parts by volume / and 160 Parts by volume of 2N sodium hydroxide solution in the course of 45 minutes. After the coupling reaction has ended, the dye is filtered off with suction and washed.

The moist press cake is converted into a strongly colored and grainy form in 400 parts by volume of dimethylformamide Heated to 100 ° C. for 120 minutes while stirring. The dye is then filtered off with suction, washed, dried and ground.

The pigment dye of the formula obtained in this way

When incorporated into polyvinyl chloride, a varnish, a printing ink or a spinning mass, it produces pure, yellow-tinged red Dyeings of very good light and solvent fastness.

Example 4

21.3 parts by weight of 2-chloro-4-methyl-5-n-propionylaminoaniline are stirred with 80 volumes / BN hydrochloric acid, then diluted with 100 parts by volume of ice water and ^{diazotized at 5 to 10 °} C. with 20 parts by volume of 5N sodium nitrite solution. 43.3 parts by weight of 1- [4 "-methylphenyl] -5- (2 ', 3'-oxynaphthoylamino) benzimidazolone are suspended in 650 parts by volume of pyridine in the coupling vessel. For this purpose, the diazolÖBunp is allowed to run in over 45 minutes. The coupling reaction is complete soon

0 C 9 8 u 7 / "'1 0

BAD ORiQfNAt.

completed. The coupling mixture is then heated to 140 ° C. for 2 hours in a closed vessel. The dye is then suctioned off, washed, dried and ground.

The pigment of the formula obtained in this way

NH-CO-CH ₂ -C

CCX

When incorporated into polyvinyl chloride, a varnish, a printing ink or a spinning mass, it produces pure, yellowish tones red dyeings with very good light and solvent fastness properties.

Example 5

23.2 parts by weight of 2-amino-toluene-4-carboxylic acid-cyclohexylamide are stirred in 80 parts by volume of 5N hydrochloric acid and diazotized at 5 to 10 ° C. with 50 parts by volume of 2N sodium nitrite solution. The solution is then clarified. 45.2 parts by weight of 1- [4 ^{lf -chlorophenyl} ] 5- (2 ', 3'-oxynaphthoylamino) -benzimidazolone and 40 parts by weight of anhydrous sodium acetate are suspended in 600 parts by volume of dimethylformamide in the coupling vessel. For this purpose, the diazo solution is allowed to run in at 60 ° C. within 30 minutes. The mixture is stirred for a further 15 minutes and the coupling mixture is then heated in a closed vessel at 140 ° C. for 3 hours. The dye is then filtered off with suction, washed and dried. The pigment of the formula obtained in this way

009847/1710 ORIGINAL BATHROOM -. ,,, -

HN-OC

When incorporated into polyvinyl chloride, varnish, printing ink or spinning material, it gives a pure, yellowish tinge red colorations of very good light and solvent fastness.

If, instead of 1- | 4 ^(I -chlorophenylj -5- (2 ', 3' -oxynaphthoylamino) - · benzimidazolone, equivalent amounts of 1- [4 "-chloro-2" -methylphenyl] -5- (2 ', 3 '-oxynaphthoylamino) -benzimidazolone, l - {_ 2 "-Chlorphenylj -5 ~ (2', 3 '-oxynaphthoylamino) -benzimidazolone., 1-j_2 ^H -MethylphenylJ-5- (2 ^r , 3' -oxynaphthoylamino) - benziraidazolon, l - [_ 3 "-Chlorphenylj-5-f 2 ', 3' -ox * naphthoylamino) -benzimidazolone, l-r2" -Hethoxyphenyl] -5- (2 ', 3' -oxynaphthoylamino) -benzimidazolone, 1- [2 ^U , 4 "-DimethylphenylΙ-5-Γ2 ', 3'-oxynaphthoylamino) -benzimidazolone, l-naphthyl-5-f2', 3 -oxynaphthoylamino) -benzimidazolone or l-phenyl-T-chloro-S- ^ ' , 3 ^f -oxynaphthoylamino) benzimidazolone, red pigment dyes of similarly good fastness properties are obtained.

The following table contains a number of additional procedural methods usable components and the color tones of the dyes prepared with the dyes obtained in substance graphic prints.

009047/1710 BAD

Diazo component

l-Amino-2-methoxybenzene ~ 5-carboxylic acid anilide

Anthranilic acid methyl ester 2,5-dichloroaniline

2,4-dichlorane i1in 4-Amino-benzoesiiurearaid

l-amino-2-methoxy-lchlorobenzene

1-amino-2-methoxy-4-nitrobenzene

2-Amino-1-terephthaisäurείπε thy lester-4-carboxamide

l-aaino-2,5-dinethoxybenzene-4-sulf onsäuremethylamid

3-Amino-4-chloro-benzene acid amide

1-amino ^ -methoxy-S-chlorobenzene

2-Amino-toluene-4-carboxylic acid ethylamide

4-Am in O-3-nitro-toluene

l-aminobenzene-3 _f 5-di- (carboxylic acid methylamide)

l-aminobenzene-3,5-dicarboxamide

2-aminotoluene-4-carboxylic acid butylamide

2-aminotoluene-4-carbonic acid isopropylamide

Azo component

hue

l-phenyl-5- (2 ', 3' -oxy-

naphthoylamino) -benz-

imidazolone

bluish red

yellowish red

bluish red

Red

bordo

yellow ichigot

bordo

Red

bluish red

bordo

yellowish-red

Red Red

Red

0098 ^ 7/1710 BAÖ

_ ir. _

Diazo component

2-aminotoluene-4-carboxylic acid p-chloroanilide

2-aminotoluene-4-carboxylic acid-5-chloro-2-toluidide

2-aminotoluene-4-carboxylic acid benzylamide

Azo component e-

hue

l-phenyl-5- (2 ', 3' -

oxynaphthoylamino) -

benzimidazolone

Red

bluish red

yellowish red

2-aminotoluene-4-carboxylic acid-2 ', 4'-dimethylanilide

2, 4-dichloro-2'-amino-4'-diphenyl ether-carbonsäureraethylamid

4-methyl-2'-aminodiphenyl ether-4'-carboxylic acid propylamide

4-chloro-2'-amino-diphenylether-4'-carboxylic acid propylamide

2-Anino-1-terephthalic acid methyl 1-ester-4-carboxylic acid [2 ' , 5'-dichloroanilide:

bluish red

l-Amino-2-methoxyphenyl-5-carboxylic acid anilide

2,5-dichloroanilide

p-Amino-benzoic acid araid

l-Amino-2-chlorophenyl-5-carboxylic acid amici

2-aminotoluene-4-carboxamide

2- Amino-1-terephthalic acid methyl ester-4-carboxylic acid- (2 ', ö'-rdichloroanilide) 1- ^ 4 "-methoxyphenyl) -5- (2', 3 '-oxynaphthoylamino) -benzimidazolone

Red

yellowish red

bluish red

yellowish red

bluish red

yellowish red

Red

Red

1-Amino-2-raethoxy-benzene-5-carboxylic acid an i1 id

0098 ^ 7/1710

bluish red

BATH

Diazo component

Azo component

hue

2-chloro ~ 4-methyl-5-acetylaminoaniline

2-Amino-1-terephthalic acid methyl ester-4-carboxamide

2-aminotoluene-4-carboxamide

4-Amino-benzoic acid amide

l-Amino-2-methoxybenzene-5-carboxylic acid amide

2-aminotoluene-4-carboxylic acid anilide

2-aminotoluene-4-carboxylic acid cyclohexylamide

l-C4 "-methoxyphenyl) -5- (2 ', 3' -oxynaphthoylamino) ·
benzimidazolone

1- (4 "-chlorophenyl) -5- (2nd
3'-oxynaphthoylamino> benzimidazolone

1-Amino-2-methoxybenzene-4-carboxylic acid anilide

3-Amino-4-chloro-benzoic acid amide

2-EraLnotoluene-4-carboxylic acid mes thylamide

2-aminot, oluene-4-carboxylic acid en-butylamide

4-chloro-3-amino-acetophenone

4-methyl-6-amina-7-chlorocarbostyril

2 , 4-dichloroaniline 2,4,5-trichloroaniline 1- (4 "-chlorophenyl) -5- (2
'-oxynaphthoylamino) benzimidasolone

2-methyl-5-trifluoromethyl- _{n Q o} / τ / 1 ^M 7 1

₃ niHn 0098A / / I / I

Red

Red

I blush igrot

Red

Red

blue-

pithy

Red

Red

b laust igrot

red red

ti

It

BATH

Diazo component

Azo components

hue

2-Amino-1-terephthalic acid methyl ester-4-carboxamide

1- [4 "-Chlor-2" ~ methylphenyl] -5- (2 ', 3' -oxy-, yellowish naphthoylamirio) ~ benz- red imidazo! on ^s

2-aminotoluene-i-carboxamide

l-Amino-2-methoxy-benzene-5-carboxamide

2-Alninotoluene-4-carboxylic acid- l-Naphthyl-5 (2 ', 3' cylohexylaraid oxynaphthoylamino) -

benz imidazolone

Red

bluish red

Red

3-Amino-4-chlorobenzoic acid amide

2-amino toluene-4-carboxylic acid (2 ', 4'-diroethylanilide)

2-aminotoluene-4-carboxylic acid p-chloroanilide

2,4-dichloro-2'-aminodiphenyl ether carboxylic acid »aethylamict

2-aminotoluene-4-carboxylic acid-hexy1-araid

benzoic acid methylamide

yellowish red

1-L2 "-ChI orphenylj 5- (2 ', 3'-oxynaphthoylamino) -benziraidazolone Red

1- [2 ", 4" -DimethylphenylJ-5- (2 ' , 3'-oxynaphthoylamino) benzimidazolone

Red

bluish red

Red

Red

l-r3 ' ^f -chlorophenylJ-5- (2', 3 '-oxynaphthoylaminoi-benzimidazolone red

Red

eäure-eethylester-4- c ar bonsäur eamid

(2 ^f , 3 '-oxynaphthoyla * ino) -benziaidazolon red

3 8

Red

BAD LOCAL

50 g cotton yarn are treated for 45 minutes at 35 ° C in the primer bath described below, spun off, dried and colored in the below-mentioned developing bath at 20 ° C. Then it is squeezed off and after a minute of air passage for 5 seconds with water at 70-80 ° C and 5 seconds in a bath containing 3 ecm of hydrochloric acid Contains 20 ° Be per liter. The so obtained Dyeings are soaped and rinsed in the usual way.

Primer bath

17.8 g of 1-phenyl-5- (2 ', 3'-oxynaphthylamino) benzimidazolone are made into a paste with 50 g of denatured ethyl alcohol and after adding 15.5 ecm of sodium hydroxide solution of 38 ° Be approximately 800 ecm of boiling water dissolved and adjusted to 1 liter.

Developing bath

12.1 g of l-amino-2methoxybenzene-5-carboxamide are in as is known, diazotized in the cold with 20.5 ecm of hydrochloric acid of 20 Be and 4 g of sodium nitrite dissolved in water. When the diaotation has ended, 15 g of dissolved sodium acetate and 2 g of a commercially available 20% condensation product are made up from 1 mole of dodecyl alcohol and 30 moles of ethylene oxide per 1 liter.

In this way, a pure, bluish-red color is obtained Dyeing with good fastness properties. Is used in the present example instead of l-phenyl-5 (2 ', 3'-oxynaphthoylamino) -beneniraidazolone the equivalent Amount of 1-Ql "-methoxyphenyl] -5- (2 ', 3'-r-oxynaphthoylamine O-benziniidazolone or 1- [4 "-chlorophenyl] -5- {2 ', 3' -oxynaphthoyla» ino) -benzimidazolone or l-naphthyl-5- (2 ', 3'-oxynaphthoylamino) benzimidazolone, this also gives red dyeings with similarly good fastness properties.

0098 ^^ / 1710

BATH ORIGINAL

The following table contains a number of additional offices according to the procedure usable components, such as the color tones of the dyes produced on the fiber:

Diazo component

Azocora component

hue

2,5-dichloroaniline 2-liter ethoxy-4-nitroaniline

I-phenyl-5- (2 *, 3'-oxy-yellow-colored & phthoylamino) -benz ~ red imidazolone

bluish red

l-araino-2,5-dimethoxy-

benzene-4-sulfonic acid-methyl- "

amide

4-Araino-3-nitro-toluene 1- | [4 "-Methoxyphenyl | -5-

(2 ', 3'-oxynaphthoylamino) benzimidazolone

2-methyl-5-trifluoromethyl-aniline

" Red

1_ U "-chlorophenyl] -5- (2 ', 3'-oxynaphthoylamino) -

benzimidazolone red

0098A7 / 1710

Claims (5)

- 21 - Claims 1) Water-insoluble monoazo dyes that are free from water-solubilizing groups are and the general formula TO _R N ^X l '" C = ON ^ X ₂ H correspond, in which A is the radical of a diazotizable aromatic iso- or heterocyclic amine, R is an aryl group and X ₁ and X _{0 are} hydrogen atoms, halogen atoms, alkyl or alkoxy groups of 1 to 6 carbon atoms. 2) Dyes according to claim 1, wherein the radical A is a group of the formula CO-NHR ₂ is, in which Z is a hydrogen or halogen atom, preferably a chlorine or bromine atom, an alkyl group, a Alkoxy group, a carboxylic acid ester group, preferably a carbomethoxy group or an optionally substituted one Phenoxy group and R "a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an aralkyl group, preferably a benzyl group, a cycloalkyl group, preferably mean a cyclohexyl group or an aryl group. 0098A7 / 1710 3) Process for the production of water-insoluble monoazo dyes, which are free from water-solubilizing groups and the general formula AT Il ^N OH Ooc Λ Jl ' CO - NH correspond, in which A is the radical of a diazotizable aromatic isc- or heterocyclic amine, R is an aryl group and X- and X _{0 are} hydrogen atoms, halogen atoms, alkyl or alkoxy groups of 1-6 carbon atoms, characterized in that diazotized amines are the general formula A-NH ₂ in which A has the abovementioned meaning, it azo components of the general formula CXi Y ^R X ₁ ι oh ^w CO-NH S X ₂ H in which Χχ, χ and R have the meanings given above have coupled. 4) Lacquers, solutions and products made from acetyl cellulose, natural resins or synthetic resins, polystyrene, polyolefins, polyacrylic compounds, polyvinyl compounds, polyesters, gumai, casein or silicone resins, as well as paper or textile fibers made from cellulose, cellulose ethers, cellulose tea esters, polyamides or polyurethanes that are mixed with the dyes mentioned in claim 1 have been colored or printed. 009847/1710 BATH ORIGINAL 5) Use of dyes of the general formula mentioned in claim 1 for dyeing or printing paints, Solutions and products made from acetyl cellulose, natural or synthetic resins, polystyrene, polyolefins, polyacrylic compounds, polyvinyl compounds, polyesters, rubber? Casein or silicone resins, as well as paper or textile fibers made from cellulose, cellulose ethers, cellulose esters, polyamides or polyurethanes. 009847/1710