DE2256179A1 - HYDRO-INSOLUBLE AZO DYES - Google Patents

Description

Dr.-lng. E. BERKENFELD · Dipl.-Ing. H. BERKENFELD, patent attorneys, Cologne Attachment file number

for entry dated November 13, 1972 vA / Name d. Note Yorkshire Chemicals

Limited

Water-insoluble azo dyes

The invention relates to water-insoluble azo dyes in general Formula:

- Ν »Ν

in which each

R chlorine or bromine,.

R is hydrogen, chlorine or bromine or an alkyl, alkoxyl

or acylamino group,
R * hydrogen or an alkyl or alkoxyl group,

R is an alkylene group and

5
Br is hydrogen or an aryl, hydroxy, alkoxy, carboalkoxy, cyano or β-cyanoethoxy group.

The preferred dyes are those whose alkyl and alkylene groups Contain 1 to 4 carbon atoms; preferably contains each alkoxy group 1 to 4 carbon atoms

The invention also relates to a process for the preparation of the dyes of the general formula: (I), in which one mole the diazo compound of a heterocyclic amine of the general formula:

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- 2 -N (ID

with one mole of a tertiary amine of the general formula:

(III)

1 2 3 U 5

couples, in which R, R, R, R and R are as defined above to have"

Examples of heterocyclic amines of the general formula (II) which can be used for the preparation of the diazo compounds, are 2-amino-5,6-dichlorobenzothiazole and 2-amino-5,6-dibromobenzothiazole.

Examples of tertiary amines of the general formula (III) which can be used as coupling components are N, N-dimethylaniline, N-butyl-N-methylaniline, 1- (N, N-dimethyl) -3-methylaniline, 1- (N, N-dimethyl) -3-chloroaniline, 1- (N, N-dimethyl) -3-acetaminoaniline, 1- (N, N-dimethyl) -3-acetamino-6-ethoxyaniline, N-benzyl-N-methylaniline, 1- (N-Benzyl-N-methyl) -3-methalaniline, 1- (N-Benzyl-N-methyl) -3-methoxyaniline, N-ß-hydroxyethyl-N-methylaniline, 1- (N-ß-hydroxyethyl-N-methyl) -3-methylaniline, N-ß-methoxyethyl-N-methylaniline, N-ß-ethoxyethyl-N-methylaniline, 1- (N-ß-methoxyethyl-N-methyl) -3-chloroaniline, N-ß-carbomethoxyethyl-N-methylaniline, N-ß ~ carboethoxyethyl-N-methylaniline, N-ß-cyanoethyl-N-

309821/1069

methylaniline, N-Y-cyanopropyl-N-methylaniline, 1- (N-ß-cyanoethyl-N-methyl) -3-methylaniline, 1 - (N-ß-cyanoethyl-N-methyl) -3-bromaniline, 1- (N, β-cyanoethyl-N-methyl) -3,6-dimethylaniline, 1 - (N-β-cyanoethyl-N-methyl) -3-acetamino-6-methoxyaniline and Ν-ω-cyanoethoxyethyl-N-methylaniline.

The invention also relates to the use of the dyes according to of the general formula (I) for dyeing and printing hydrophobic fibers, for example fibers made of cellulose acetate, such as secondary cellulose acetate or cellulose triacetate; other examples are polyamide fibers, polyester fibers such as "TERYLENE", and polyacrylonitrile fibers such as "COURTELLE".

The dyes are preferably by milling with water and a suitable dispersant, such as a formaldehyde / cresol sulphonic acid condensation product, like "Dyapol PT", dispersed. The dyeing of polyester fibers can, for example, from a boiling Water bath take place, which as a carrier for example a

eth if-t

decapitates

Emulsion of 2-phenylphenol, such as ⁿ Optinol B '^ carried baths in a pressure vessel at 125 to 140 ° C or by padding an aqueous dispersion onto the fabric, dried and thirty seconds, heated to 200 ° C · The dyes may also for Printing of a fabric made of a polyester, polyamide, polyacrylonitrile, secondary cellulose acetate or cellulose triacetate can be used, for example by means of a roller or in a known manner by a SJä> by means of a dispersion of a dye, which, as known for printing textiles, by a thickening agent such as sodium alginate is thickened. After the fabric has dried, the dye is fixed, for example, by steaming at a pressure of 1.05 kg / cm or by heating the fabric to 90 to 200 ° C. The colorations obtained in this way are red to purple; the dyeings have excellent resistance to light, wet treatments, sublimation, heat setting, rubbing, dry cleaning, as well as gas and vapors.

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The invention is described in more detail in the following examples.

EXAMPLE

There were 6.9 parts of sodium nitrite with stirring 150 parts of 100 # - iger sulfuric acid was added, the temperature being reduced by external cooling was kept at 30 ° C. The temperature was then increased to 70 ° C before cooling to 0 ° C. Then one was prepared A solution of 21.9 parts of 2-amino-5,6-dichlorobenzothiazole in 250 parts of 5Obiger sulfuric acid was added. The diazotization was

guided by stirring the mixture at 0.

C ended for two hours

The diazo solution obtained in this way was a solution of 16.0 parts of N-β-cyanoethyl-N-methylaniline in 40 parts of acetic acid and 60 parts of ice water were added at 0 ° C. and the mixture was stirred for one hour at 0 ° C., followed by neutralization with ice cold 25 # sodium hydroxide solution was carried out. The precipitated dye of the formula:

. Eq

was filtered off, washed and dried.

One part of the dye was mixed with one part of the product "Dyapol PT" dissolved in ten parts of water and the mixture was ground in a ball mill to reduce the particle size of the dye to 1 to 5 μ. The dispersion was diluted with a further 990 parts of water and 50 parts of "TERYLENE ¹¹ " were added to the dispersion and the whole thing was done for 45 minutes at a temperature

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temperature of 130 ° C in a pressurized molding machine given. The dyed yarn was yellowish red and the dyeing was excellent lightfast, washfast and sublimation fast.

Further monoazo dyes according to the invention are shown in the table below of the general formula (I) listed, prepared according to Example 1 and as above in the example 1 specified can be used for dyeing.

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«5
Oil example
number R ¹ R ² r3 R ⁴ R ⁵ Hue on
Polyester fibers 2 Cl H H CH ₂ H Red 3 Cl H H ^C 4 ^H 8 H Red 4th Cl CH ₃ H CH ₂ H Red 5
6th
7th
θ Cl
Cl
Cl
Cl Cl
NHC0CfcH ₃
NHC0efeH ₃
H H
H
OC ₂ H ₅
H CH ₂
CH ₂
CH ₂
CH ₂ H
H
H Red
Red
violet
Red

Cl CH,

10 Cl OC 11 Cl H 12th Cl CH 13th Cl H 14th Cl H 15th Cl Cl 16 Cl H 17th Cl H 18th Cl H 19th Cl CH 20th Cl Br 21st Cl CH

H H H H H H H H H H H CH,

Red

CH ₂ OH Red Q Red C ₂ H ₄ OH Red C ₂ H ₄ OCH ₃ bluish-red C ₂ H ₄ OC ₂ H ₅ Red C ₂ H ₄ OCH ₃ Red C ₂ H ₄ COOCH ₃ Red C ₂ H ₄ COOC ₂ H ₅ Red C ₂ H ₄ CN Red ^C 3% CN yellowish red C ₂ H ₄ CN Red C ₂ H ₄ CN C «H ,.

3/14 example
number R ¹ R ² r3 ^R 4 CN Hue on
Polyester fibers 22nd Cl NHCOCH, OCH ₃ C ₂ H ₄ OC ₂ H ₄ CN violet 23 Cl H H C ₂ H ₄ COOCH ₃ yellowish red 24 Br H H C ₂ H ₄ CN Red 25th Br H H ^C 2 ^H 4 OC ₂ H ₄ CN yellowish red 309821 / 26th Br H H C ₂ H ₄ yellowish red M069

Claims (9)

Dr.-1 ng. E. BERKENFELD · Dipl.-Ing. H. BERKENFELD, patent attorney, Cologne Attachment file number for the entry dated November 13, 1972 vA / Name d. Yorkshire Chemicals Limited CLAIMS 1. Water-insoluble azo dyes of the general formula: N =? N - in the each R chlorine or bromine, R is hydrogen, chlorine or bromine or an alkyl, alkoxyl or acylamino group, R ^ hydrogen or an alkyl or alkoxyl group, R is an alkylene group and Hydrogen or an aryl, hydroxy, alkoxy, carboalk mean oxy, cyano (o) or ß-cyanoethoxy group. 2. Dye according to claim 1, characterized in that each alkyl and alkylene group contains 1 to 4 carbon atoms. 3. Dye according to claim 1 or 2, characterized in that each alkoxy group 1 to Contains 4 carbon atoms. 4o Process for the preparation of a dye of the general Formula (I), characterized in that one mole of the diazo compound of a heterocyclic amine of the general formula: Y 3/14 309821/1069 with one mole of a tertiary amine of the general formula: • (in) 1 P ^ U B couples, in which R, R, R, R and R ^ have the meaning given above to have. 5. Use of a dye of the general formula (I) for
Dyeing or printing of hydrophobic fibers. 6. Use of a dye according to claim 5, characterized in that that the hydrophobic fibers are made of cellulose acetate, polyamide, polyesters or polyacrylonitrile. 7. Use of a dye according to claims 5 or 6,
characterized in that the dye is dispersed by means of a dispersing agent by grinding with water. 8.Use of a dye according to claims 5 to 7, characterized characterized in that the polyester fibers are taken from a boiling water bath containing a carrier or in pressure vessels at 125 to 140 ° C or by padding an aqueous dispersion on the fabric and then dried and heated 9. Use according to one of claims 5 to 7, characterized in that that one made of polyester, polyamide, polyaerylonitrile 309821/1069 _ 10 - secondary cellulose acetate or cellulose triacetate existing fabric by means of a roller or through a sieve with a thickened Disperse dye dyes, the fabric dries and the dye sets. Y 3/14 309821/1089