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Publication numberUS3116278 A
Publication typeGrant
Publication dateDec 31, 1963
Filing dateApr 25, 1961
Priority dateApr 30, 1960
Publication numberUS 3116278 A, US 3116278A, US-A-3116278, US3116278 A, US3116278A
InventorsHasso Hcrtel, Reinhard Mohr, Richard Gross
Original AssigneeHoechst Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Water-insoluble azo-dyestuffs
US 3116278 A
Abstract  available in
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Description  (OCR text may contain errors)

United States Patent 3,116,278 WATER-lNSULUBLE AZO DYESTUFFS Richard Gross, Frankfurt am Main, and Hasso Her-tel and Reinhard Mohr, Ofienbach (Main), Germany, assignors to Farbwerke Hoechst Aktiengesellschait vormals Meister Lucius & Briining, Frankfurt am Main, Germany, a company of Germany No Drawing. Filed Apr. 25, 1% Ser. No, 105,296

Claims priority, application Germany Apr. 30, 1960 6 Claims. (Cl. 260-446) The present invention provides new water-insolube azo-dyestufis and a process for their manufacture; more particularly it provides new water-insoluble azo-dyestufis having the general formula N Ra wherein R and R represent hydrogen atoms or alkyl, aryl, aralkyl or cycloalkyl radicals which may be combined to an isocyclic ring, A stands for the radical of an arylamide of an aromatic or heterocyclic o-hydroxycarboxylic acid or of an acylacetic acid, It represents the integer 1 or 2 and the benzene nucleus a may be substituted by groups which do not impart solubility in water.

The invention is based on the observation that new Water-insoluble metalliferous azo-dyestulis are obtained by coupling in substance, on the fiber or on another substratum the diazonium compounds of amines having the general formula NHz wherein R and R stand for hydrogen atoms or for alkyl, aryl, aralkyl or cycloalkyl radicals which may be combined to an isocyolic ring, the benzene nucleus a may contain substituents which do not impart solubility in water, with arylamides of an aromatic or heterooyclic o-hydroxycarboxylic acid or of an acylacetic acid, the components being selected so that they do not contain groups imparting solubility in water, for example sulfonic acid or carboxylic acid groups, and treating the dyestuils so obtained with agents yielding metal.

The water-insoluble azo-dyestuils obtained according to the present invention may be treated in known manner with the agents yielding metal during or after the coupling in substance or on the fiber. When producing the dyestuiis on the fiber the metallization may be carried out by adding agents yielding metal to the developing bath or already to the impregnation bath. The treatmer of the dyestuffs with agents yielding metal may be carried out after the coupling in a second bath which is weakly acid, neutral or weakly alkaline and which may contain dispersing agents or detergents, for example a fatty alcohol polyglycol ether, an alkylphenol polyglycol ether, an alkylnaphthol poly'glycol ether, a fatty acid polyglycol ester or a fatty acid amide polyglycol ether.

As agents yielding metal, there are preferably used for the process of the present invention compounds yielding copper, cobalt, nickel, manganese, iron, zinc, chromium, aluminum or titanium, which may be used in the form of their mineral or organic salts, such for example as chlorides, bromides, sulfates, nitrates, formates, or as complex compounds of these metals, espe- 3,ll6,278 Patented Dec. 31, 1963 cially with hydroxyalkylamines, such for example as diethanolamine, triethanolamine or N-methylethanolamine or with aminocarboxylic acids, such as aminoacetic acid or mitrilotriacetic acid, with aliphatic hydroxycarboxyiic acids, such as citric acid, tartaric acid, gluconic acid or glycolic acid, with alkali metal phosphates, such as alkali metal pyrophosphates or alkali metal polyphosphates. When an agent yielding cobalt is used, the addition of compounds of hexavalent chromium or other oxidizing agents, for example alkali metal perborates, alkali metal persulfates or alkali metal percarbonates, has an advantageous effect on the metallization.

On vegetable fibers including fibers of regenerated cellulose there are obtained, according to the dyeing and printing methods known from the ice color industry, metal complex dyestuffs which possess in addition to good general properties of fastness a good fastness to light.

The dyestuffs may be prepared on vegetable fibers in long liquors. Piece goods, chains or ribbons can be dyed continuously or they can be printed according to the methods of base or naphtholate printing.

The new dyestuffs can also be produced on animal fibers, such as wool and silk or on synthetic fibers such, for example as polyamide, acetyl cellulose or polyvinyl alcohol fibers according to the methods used for dyeing these fibers whereby equally interesting dyeings of good fastness properties are obtained.

The dyestuifs can also be prepared in substance and converted into complex metal compounds by treatment with agents yielding metal. The metallization may be carried out in an aqueous solution or in organic solvents such, for example as acetone or dimethylformamide. The metal complex compounds thus obtained are suitable for dyeing animal and synthetic fibers as well as organic plastic masses of high molecular weight.

As coupling components there may be used for the process of the present invention arylamides of aromatic or heterocyclic o-hydroxycarboxylic acids or acylacetic acids, for example arylamides of 2.3-hydroxynaphthoic acid or its derivatives substituted in 6-position, furthermore arylamides of 2-hydroxyanthracene-3-carboxylic acid, 3-hydroxydiphenylene oxide2-carboxylic acid, 2- hydroxycarbaZole-3 carboxylic acid, 5-hydroxy-l.2.1.2'- benzocarbazole-4-carboxylic acid, acetoacetic acid, benzoylacetic acid or terephthaloyl-bis-acetic acid.

As diazo components there may be used compounds having the above general formula which, in the benzene nucleus a may contain substituents which do not impart solubility in water, for example halogen atoms, alkyl, alkoxy, tn'iiuoromethyl, nitro, alkylsulfonic, arylsulfonic and eventually substituted sulfonic acid amide or carboxylic acid amide, acylamino or acyl groups. Such compounds are obtained according to known methods, for example by reacting 3-nitro-l.2-diaminobenzenes with odiketones, such as glyoxal, diacetyl, benzil, phenanthrenequinone, acenaphthenequinone or 1.2-naphthoquinone and subsequently reducing the nitro group to the amino group. The amines thus obtained represent will crystallizing generally intensely yellow compounds.

The following examples serve to illustrate the invention but they are not intended to limit it thereto:

EXAMPLE 1 Cotton yarn was treated for 45 minutes at 35 C. at a goods-to-liquor ratio of 1:20 in an impregnation bath prepared as described below, then centrifuged, and while wet, developed first for some minutes at 20 C. and then, after being slowly heated to 95 C., for 20 to 30 minutes at C. to C. in a developing bath prepared as described below. The yarn was then rinsed with a solution containing, per liter of water, 3 cc. of hydrochloric 3 acid of 20 B., soaped first for 15 minutes at 60 C. and then for 15 minutes at 95 C. with a solution containing, per liter of water, 1 gram of a reaction product from about 10 mols of ethylene oxide and 1 mol of isododecylphenol, and 3 grams of sodium carbonate, rinsed and dried.

Impregnation Bath 1.75 grams of 2-(2'3'-hydroxynaphthoylamino)-naphthalene were dissolved in 3.5 cc. of denatured ethyl alcohol, 0.9 cc. of sodium hydroxide solution of 38 B., 2 cc. of warm water and 0.9 cc. of a formaldehyde solu tion of 30% strength. The solution so obtained was then made up to 1 liter with water at 45 C., 3 grams of a condensation product from fatty acids of high molecular weight and protein degradation products, and 10 cc. of sodium hydroxide solution of 38 B.

Developing Bath 1.9 grams of 5-amino-2.3.7-trimethyl-quinoxaline in the form of a diazonium compound prepared in the usual manner were dissolved in 1 liter of water containing 2 grams of a reaction product from about 20 mols of ethylene oxide and 1 mol of octadecyl alcohol, 1.5 cc. of acetic acid of 50% strength, 7 grams of sodium acetate and 2.5 grams of copper sulfate.

A garnet dyeing having good properties of fastness was obtained.

By using 2.4 grams of cobalt chloride or 2.8 grams of nickel sulfate instead of 2.5 grams of copper sulfate garnet dyeings equally having good properties of fastness were obtained.

EXAMPLE 2 Cotton yarn was treated for 45 minutes at 35 C. at a goods-to-liquor ratio of 1:20 in an impregnation bath prepared as described below, then centrifuged, and while wet, developed for 30 minutes at 20 C. in the developing bath prepared as described below. The yarn was then rinsed with a solution containing, per liter of water, 3 cc. of hydrochloric acid of 20 B., soaped for 20 minutes at 95 C. with a solution containing, per liter of water, 1 gram of a reaction product from about 10 mols of ethylene oxide and 1 mol of isododecylphenol, 1 gram of sodium carbonate, 2.5 grams of copper sulfate and 7.5 grams of triethanolamine, rinsed and dried.

Impregnation Bath 0 cc. of warm water and 0.9 cc. of a formaldehyde solution of 30% strength. The solution so obtained was then made up to 1 liter with water at C., 3 grams of a condensation product from fatty acids of high molecular weight and protein degradation products, and 10 cc. of sodium hydroxide solution of 38 B.

Developing Bath 1.6 grams of 5-amino-7-methyl-quinoxaline in the form of a diazonium compound prepared in the usual manner were dissolved in 1 liter of water containing 2 grams of a reaction product from about 20 mols of ethylene oxide and 1 mol of octadecyl alcohol, 1.5 cc. of acetic acid of strength and 10 grams of sodium acetate.

A violet dyeing having good properties of fastness was obtained.

By using in the above example 2.5 grams of cobalt chloride and 11 grams of the sodium salt of nitrilotriacetic acid instead of 2.5 grams of copper sulfate and 7.5 grams of triethanolamine a currant dyeing was obtained and by using 2.8 grams of nickel sulfate and 3 grams of aminoacetic acid a garnet dyeing was obtained.

EXAMPLE 3 18.7 grams of 5-amino-2.3.7-trimethyl-quinoxaline were dissolved in 500 cc. of ice water and cc. of 5 N-hydrochlorie acid. To the deep red solution 20 cc. of a 5 N-sodium nitrite solution were added dropwise at 0 C. to 5 C. After the diazotization the eventually clarified diazo solution was introduced, at 20 C. to 25 C., into a fine suspension prepared from 27.1 grams of 2.3-hydroxynaphthoylaminobenzene of 96.8% strength 'n a mixture of 1000 cc. of water, 500 cc. of a 2 N-sodium acetate solution and 0.5 grams of a reaction product from about 20 mols of ethylene oxide and 1 mol of oleyl alcohol. After the coupling was terminated the bluish-red dyestuff had precipitated. In order to convert the dyestufi suspension into the complex copper compound a solution containing 25 grams of crystallized copper sulfate in 200 cc. of water and 25 grams of triethanolarnine was added and the whole was stirred for some hours at C. to C. until the complex metal compound had completely formed. In the course of this reaction the initially bluish-red suspension became dark red. After the metallization the metal complex compound formed was filtered olf with suction at an elevated temperature, washed with hot water and dried. The complex copper compound so obtained was a garnet powder.

in the following table further components are listed which can be used in the process of the invention, and the tints produced by forming the metalliferous azo-dye-stufis from these components on the fibers which tints equally possess good fastness properties.

Tint Diazo component Coupling component copper cobalt nickel complex complex complex 5-amino-7-methylquinoxaline 2.3-hydroxynephthoylaminobenzene garnet currant violet.

D 1-(2,3-hydroxynaphthoylamino)-3-nitrobluish gard0 reddish benzene. net. violet. l g2.3-hydroxynaphthoylamino)-napl1thablue garnet do garnet.

ene. 1-(2.3-hydroxy11aphthoylamino)-4-methoxbluish gardo reddish ybenzene. net. violet. 1-(2.3-11ydroxynaphthoylamino)-2-methdo do bluish oxy-l-chloro-S-Inethylbenzene. garnet. l-(2.3-hydroxynaphthoylamino)-2-methblue garnet" ..d0 Do.

oxybenzene. 1-(2.3-hydroxynaphthoylamino)-2-methyldo Do.

benzene bluish garnet.

benzene. l-(2.3-hydroxy'naphthoylamino)-2-methyldo 4-chlorobenzene. 1-(2.3-hydroxynaphthoylamino)-2-methyld0 methoxybenzene.

Do l-(2.3-hydr0xynaphthoylamino)-2,4- reddish dimethoxy-5-ch]orobenzene. violet.

Do l-(2.3-hydroxynaphthoylamino)-2-5- bluish gardo garnet,

dimethoxy-4-chlorobenzene. net.

Do l-(2f.3-hydrorrynaphthoylamino)-2.5- blue garnet do Violet.

dlrnethoxybenzene.

Tint

Diazo component Coupling component copper cobalt nickel complex complex complex 5-arnino-Y-metliylquinoxaline 1g2.3hyd.r0xynaphth0ylamlno)-2-eth0xybluisth garcurraat garnet.

enzene. ne Do 2-(2.3-hydr0xynaphthoylemiuo)-3-methred violet do D0.

oxy-diphenylene oxide. Do 1-( -b 0 0-2.3-l1ydroxynaplithoylamino)- blue garnet do violet.

2-methoxybenzene. Do l-(2.3-hydr0xynaphthoylamino)-2-methylclo "don-.." bluish 5-chloi-obenzene. garnet. Do 1-(2-hydr0xyanthracene-3-carboylamino)- greenish bl Q-methylbcnzene. blue green Do -(2- l1y r0xynephth0ylariiino)-4-etlioxybluish garourrant blue garnet.

benzene. net Do 1-(2-hydroxy0arbazole-3-carboy1amino)-4- reddish reddish chlorobenzene. violet. violet. 5-amin0-2.3-diphenyl-7-methyl- 2.3-hydroxynaphthoyl-aminobenzene current claret quinoxal'ine.

D 1-(2- -hy lroxynaphthoylamiiioy do d bluish red.

naphthalene. D 2-(2.3-hydroXy-naphthoylamino)- do do Do.

naphthalene. D0 1-(2.3-hy(lroxy-naphthoylamino)-2- r do (1o Do.

metlioxy-i-ehloro-5-methylbenzene. D 1-(2.3-l1ydroxy-naphtlioylaiiiino)-4- d0 d0 bluish red.

clilorobenzene. 5-amino-23-naplitlio-(1.8) 7- 1-(2.3-hydroxy-naphtlioylaniino)- d0 brownish bluish inethylquinoxaline. naphthalene. garnet. eogllererl re Do 1-(2.3-liydroxy naplithoylainino)-2- do do Do.

methoxy--chloro-5-methy1benzene. D0 l-(Z'B'-liyclr0xy-1iaphth0ylamino)-2- do (lo covered ethoxybenzcne. bllllsll I8 Do 1-(6-bromo-2.3-liydroxynaplithoyldo do covered amino)-2-methoxy-benzene. claret. 5-amino-2.3.7-trimethylquinoxaline 2.3-l1ydroxynaphthoylerninobenzene garnet blue t covered red.

garne D 1-(2.3-hydroxy-naphtlioylaiiiino)-3- blue d Do.

nitrobenzene. garnet. D0 1-(2.3-hyclroXy-naplitlioylamino)-4- garnet 1 claret.

rnetlioxybenzene. D0 1-(2.3-liydroXy-naplitlioylamino)-2 blue (lo covered ted.

methoxyA-chloro-5-iiiethylbenzene. garnet. Do 1-(2. hydroxymaphthoylainino)-2- garnet garnet D0.

metlioxybenzene. D 1-(2.3-hydroXy-naphthoylamino)-2- bluish d D0.

niethylbenzene. garnet D 1-(2.3-liydroXy-naphthoylamino)-4- do blue elei-et.

ehlorobenzene. garnet D 1 (2.3-hydroxy-naphthoylamino)-2- d garnet methyl-4 chloro-benzene. 1- (2 .3-hydr0Xy-nap hthoylamino) -2- blue bluish methyll-methoxy-benzene. garnet garnet 1-(2-3-hyclroxy-naphtlioylamino)-2.4- do do dimethoxy-5-cliloro-benzene. 1-(2.3-hydroxy-naphthoylaintno)-2.5- (1o dimethoxyl-chloro-benzene. 2-(2.3-hydroxy-naphthoylamino)-3- (lo garnet covered methoxycliphenylene oxide. red. 1(2.3-hyclroxy-naphthoylan1in0)-2 bluish D0.

n1ethyl-5-clil0ro-benzeiie. garnet 1-(2.3-hyclroxy-naphthoylainino)-2-meth- -ido garnet a- D0.

oxy-fiehloro-bcnzene. terephtheloyl-bis-(1-actylamino-2.4-diyellow methoxy-S-ohloro-benzene) brown. 1-(5-hydroxy-1.2.1".2-benzoearbaz0le4- blue black blue black currant.

cerboyleinino)-4-methoxybenzene. l-(2-hydr0xyanthraccne-3-carboylamino)- current 2-rnethylbenzene. 1-(2-hydroxyoarbazole-3-carboylamino)-4- garnet brownish brownish ehlorobenzene. garnet garnet 5. i g 2 3-naphtho-(l.8)-7-methyl 1-(5-liy lroxy-1.2.1".2-benzocarbazole-4- black quinoxaline. oarboylaniino)A-methoxybcnzene.

DO 1-(2-hydroxyanthracene-3-carboylamino)- covered 2-rnethylbenzene. olive. Do 1-(2-hyclroxycarbza0le-3-carboylami110)-4- luish brown reddish elilorobenzene brown brown. DO l-(3-hydroxycliphenylene oxide-2-carboylbrown reddish brown.

amino)-2.5-dimethoxybenzene brown Do tereplitlialoyl-bis-ll-acetylamino-2A- red brownm yellow yellow diinethoxy-fi chlorobenzene) brown bro vn. 5.ami 2,3- limethyl-7-chlor0quin0xa- 2.3-hydr0xynaphthoyl-amm0benzenc current fiat violet.

line.

D0 2-(2.3-hydroxynaplith0ylamino)-naphtha- (lo Do.

lene. Do 1-(2,3-hydroxy-naphthoylamino)2- "do garnet.

mothoxybenzene. D0 1-(2.3-hy lroxynaphth0ylamino)-2.4- do Do.

dimethoxy-S-chlorobenzone. 5-amin0-2.3(limethyl-F-rncthoxy- 2-(2.3-hydroxynaphthoylamino)naphtha garnet garnet quinoxaline. leiie.

Diazo component 5-amin0-2.3.7- Tint:

trimethylquin- Aluminum complex Bluish red. oxalirie. 70 Chromium complex Covered red.

Iron complex Covered bluish I I Coupling component 2( -3 -hyred.

droxynaphtho- Manganese complex Covered red. ylarnino)-na- Zinc complex Covered red. plithalene. 75 Titanium complex Covered red.

We claim:

1. A complex metal compound containing a metal selected from the group consisting of copper, cobalt and nickel, of a water-insoluble azo-dyestuif having the formula 3-hydroxydiphenylene oxide 2 carbonylamino-, 2-hydroxycarbazole 3 carbonylamino-, 5-hydroxy-1.2.1'.2 benzocarbazole 4 carbonylaminoand terephthaloylbis-acetylamino-, and n represents one of the integers 1 and 2.

2. The complex nickel compound of the water-insolun ble azo-dyestuff having the formula 3. The complex nickel compound of the water-insoluble azo-dyestuff having the formula S 4. The complex nickel compound of the Water-insoluble azo-dyestuff having the formula 5. The complex nickel compound of the Water-insoluble azo-dyestuif having the formula IINO(|] |OH l N cm 0/ 6. The complex nickel compound of the water-insoluble azo-dyestutf having the formula N CH3 l C IIaC- y N CH References Cited in the file of this patent UNITED STATES PATENTS 2,432,419 Heimbach Dec. 9, 1947 FOREIGN PATENTS 458,843 Great Britain Dec. 28, 1936

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2432419 *Apr 19, 1944Dec 9, 1947Gen Aniline & Film CorpAzo hydroxy aza indolizines
GB458843A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3492287 *Sep 8, 1966Jan 27, 1970Bayer AgMonoazo heterocyclic dyestuffs
US3607358 *Dec 18, 1968Sep 21, 1971Glanzstoff AgMethod of dyeing a polyurethane surface layer coated on a substrate and resultant product
US3897411 *Aug 3, 1973Jul 29, 1975Ciba Geigy CorpMonoazo pigments containing a phenylamino-quinazoline radical
US4028322 *Sep 12, 1975Jun 7, 1977Ciba-Geigy Corporation6-Methylbenzimidazolonylazobarbituric acid pigment
US4171301 *Apr 26, 1977Oct 16, 1979Ciba-Geigy CorporationMonoazo pigments containing barbituric acid derivatives
Classifications
U.S. Classification534/705, 534/779, 8/670, 8/623, 534/658, 8/686, 534/740, 8/624, 534/765
International ClassificationC09B33/00, C09B33/153
Cooperative ClassificationC09B33/153
European ClassificationC09B33/153