DE1265894B - Process for the production of metal-containing, water-insoluble azo dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C09b

German class: 22a-l

Number: 1 265 894

File number: F 31125IV c / 22 a

Filing date: April 30, 1960

Open date: April 11, 1968

French patent 981 432 describes a process for the preparation of azo dyes, using substantive azo components, for example arylides of / I- oxynaphthoic acid, 2,3-oxyanthracenecarboxylic acid or acetoacetic acid, with a diazo compound of an amine of the general formulas

H, N

H, N

N-Y

in which X is a hydrogen or halogen atom and Y is a hydrogen atom or an alkyl, aralkyl or cycloalkyl group, and the benzene nucleus denotes non-water-solubilizing substituents may contain, coupled and the azo dyes thus obtained are optionally metallized.

It has been found that new, metal-containing, water-insoluble azo dyes are obtained, if you take the diazonium compounds from amines of the general formula

NH

CR ₁
CR ₂

where R is a non-water-solubilizing substituent and Ri and R _{2 are} hydrogen atoms, alkyl, aryl, aralkyl or cycloalkyl radicals, which can also be linked to one another to form an isoeyclic ring, with arylamides of aromatic or heterocyclic o-oxycarboxylic acids or of acyl acetic acids, which are free of sulfonic acid and carboxylic acid groups, in substance, on the fiber or on another substrate, and the dyes thus obtained are treated with metal donating agents.

Process for the production of metal-containing,
water-insoluble azo dyes

Applicant:

Farbwerke Hoechst Aktiengesellschaft
formerly Master Lucius & Brüning,
6230 Frankfurt-Höchst

Named as inventor:

Dr. Richard Gross, 6230 Frankfurt-Sossenheim; Dr. Hasso Hertel,

Dr. Reinhard Mohr, 6050 Offenbach

The treatment of the water-insoluble azo dyes obtainable according to the process with the metal donating Agents can be known during or after the coupling in bulk or on the fiber Way. When producing the dyes on the fiber, one can proceed as follows: that the metallization is carried out by adding the metal donating compounds to the development bath, or these compounds already to the primer bath. Treatment of dyes with metal donors after the coupling can be done in a second bath, which is weakly acidic, neutral or weakly alkaline is held and the optionally dispersing or detergent, for example fatty alcohol polyglycol ether, Alkylphenol polyglycol ether, alkyl naphthol polyglycol ether, Fatty acid polyglycol esters or fatty acid amide polyglycol ethers.

As metal donors in the method according to the invention are preferably copper, cobalt, nickel, manganese, iron, zinc, chrome, aluminum or titanium releasing compounds in Consider that in the form of their inorganic or organic salts, for example as chlorides, bromides, Sulfates, nitrates, formates or as complex compounds, in particular with oxyalkylamines, for example diethanolamine, triethanolamine or N-methylethanolamine, or with aminocarboxylic acids, for example aminoacetic acid or nitrilotriacetic acid, or with aliphatic oxycarboxylic acids, z. B. citric acid, tartaric acid, gluconic acid or glycolic acid, or with alkali phosphates, for example Alkali pyrophosphates or alkali polyphosphates, can be used. In the

809 538/476

Use of a cobalt-releasing agent affects an addition of compounds of the hexavalent Chromium or other oxidizing agents, for example alkali perborates, alkali persulfates or Alkali percarbonates, favorably on the metallization.

On vegetable fibers, including those made from regenerated cellulose, according to the Dyeing and printing processes known from the ice color technique, metal complex dyes, which in addition to have good general fastness properties, in particular good lightfastness.

The production of the dyes on vegetable fibers can take place in long liquors. Piece goods, Chains or ribbons can also be colored in a continuous manner or by the methods of Basenoder Naphtholataufdruckes can be printed.

The new dyes can also be used on animal fibers, such as wool or silk, as well as on synthetic ones Fibers, e.g. B. polyamide, acetyl cellulose or polyvinyl alcohol fibers, are produced by the dyeing processes customary for these fibers, valuable dyeings with good fastness properties also being obtained.

The dyes can also be prepared in bulk and by treatment with the metal donating Transfer agents into the complex metal compounds. The metallization can be in aqueous solution or in organic solvents, such as acetone or dimethylformamide. The metal complex compounds obtainable in this way are suitable for dyeing animal and synthetic fibers as well as high molecular weight organic plastic masses.

Arylamides of aromatic compounds can be used as azo components in the process according to the invention or heterocyclic o-oxycarboxylic acids or acyl acetic acids, for example 2,3-oxynaphthoic acid or their derivatives substituted in the 6-position, also 2-oxyanthracene-3-carboxylic acid, 3-oxydiphenylene oxide-2-carboxylic acid, of 2-oxycarbazole-3-carboxylic acid, of 5-oxy-1,2,1 \ 2'-benzocarbazole-4-carboxylic acid, acetoacetic acid, benzoylacetic acid or terephthaloyl-bis-acetic acid. used will.

Suitable diazo components are compounds of the formula given above, in which R means a non-water-solubilizing substituent, for example a halogen atom, an alkyl, Alkoxy, trifluoromethyl, nitro, alkylsulfone, arylsulfone, optionally substituted sulfonamide or carboxamide, acylamino or. Acyl group. Such compounds can be obtained by known methods, for example by Implementation of 3-nitro-1,2-diaminobenzoIen. those in the 5-position do not have a water-solubilizing substituent wear, with o-diketones, for example glyoxal, diacetyl, benzil, phenanthrenequinone, acenaphthenquinone or 1,2-naphthoquinone, and subsequent reduction of the nitro group to the amino group. The amines which can be obtained in this way are compounds which crystallize well and are usually intensely yellow in color represent.

Compared to the known from the French patent 981432 copper complex compound des Azo dyes from diazotized 7-aminoindazole and 1 - (2 ', 3' - oxynaphthoylamino) - 4 - methoxybenzene the metal-containing azo dyes of a similar structure obtainable according to the process are characterized by a better etchability of the cotton colors.

example 1

Cotton yarn is a liquor ratio of 1: 20 for 45 minutes at 35 ° C in the below described surrounded Grundierungsbad treated, centrifuged and wet first few minutes at 20 "C and then slowly warmed to 95 ⁰ C for 20 to 30 minutes at 90 to 95 ° C developed in the below-described developing bath. Dana is flushed with 3 cc of hydrochloric acid of 20 ° be in liters of water, first 15 minutes at 60 ⁰ C, then 15 minutes at 95 "C with 1 g of the action product of about 10 moles of ethylene oxide to 1 mole of Isododecylphenol and 3 g soda per liter of water soaped, rinsed and dried.

Primer bath

1.75 g of 2- (2 ', 3'-oxynaphthoylamino) naphthalene are in 3.5 ecm denatured ethyl alcohol, 0.9 ecm sodium hydroxide solution of 38Be, 2 ecm warrrAi Dissolved water and 0.9 ecm 30% formaldehyde solution. The solution thus obtained is with Wasäer of 45 C, 3 g of a condensation product of higher molecular weight fatty acids and protein degradation products and 10 ecm sodium hydroxide solution of 38 Be adjusted to 1 l.

Developing bath

1.9 g of 5-amino-2,3,7-trimethylquinoxaline in the form

- A diazonium compound prepared in the usual way are dissolved in 1 1 of water, the 2 g an action product of about 20 moles of ethylene oxide to 1 mole of octadecyl alcohol, 1.5 ecm 50% Contains acetic acid, 7 g sodium acetate and 2.5 g copper sulfate.

A garnet dyeing with good fastness properties is obtained.

If 2.4 g of cobalt chloride or 2.8 g of nickel sulphate are used instead of 2.5 g of copper sulphate, the result is garnet tones with good fastness properties are also obtained.

Example 2

Cotton yarn is in the liquor ratio 1:20 45 minutes at 35 C in the one described below Treated primer bath, spun off and wet for 30 minutes at 20 C in the following Developed development bath described. Then with 3 ecm hydrochloric acid of 20 Be per liter Rinsed with water, then 20 minutes at 95 C with 1 g of an action product of about 10 moles of ethylene oxide to 1 mole of isododecylphenol, 1 g of soda. 2.5 g copper sulfate and 7.5 g triethanolamine Soaped, rinsed and dried in a liter of water.

Primer bath

1.75 g of 2- (2 ', 3'-oxynaphthoylamino) naphthalene are in 3.5 ecm denatured ethyl alcohol, 0.9 ecm sodium hydroxide solution of 38 Be. 2 ecm warm Water and 0.9 ecm 30% formaldehyde solution solved. The solution obtained in this way is mixed with water at 45 ° C. 3 g of a condensation product higher molecular weight fatty acids and protein degradation products and 10 ecm sodium hydroxide solution of 38 Be set to 11.

Developing bath

1.6 g of S-amino ^ -methyl-quinoxaline in the form of a in the usual way prepared diazonium compound are dissolved in 11 water, which is 2 g an action product of about 20 moles of ethylene oxide on 1 mole of octadecyl alcohol, 1.5 ecm 50% Contains acetic acid and 10 g sodium acetate.

A violet dyeing with good fastness properties is obtained.

Is used in the above example instead of 2.5 g of copper sulfate and 7.5 g of triethanolamine 2.5 g of cobalt chloride and 11 g of sodium nitrilotriacetate give a color of Corinth and when using 2.8 g of nickel sulfate and 3 g of aminoacetic acid, a garnet color.

Example 3

18.7 g of S-amino ^^ J-trimethyl-quinoxaline become in 500 ecm ice water and 60 ecm 5N hydrochloric acid solved. 20 ecm of 5N sodium nitrite solution is allowed to drip into the deep red colored solution at 0 to 5 ° C. After the end of the diazotization, the optionally clarified diazo solution is combined at 20 to

25 ⁰ C with a fine suspension of 27.1 g of 2,3-Oxynaphthoylaminobenzol (96.8 ° / oig) in a mixture of 1000 cc of water, 500 cc of 2 N sodium acetate solution and 0.5 g of a product by exposure to about 20 mole Ethylene oxide to 1 mole of oleyl alcohol. After the coupling has ended, the bluish-red dye has separated out. To convert it into the copper complex compound, the dye suspension is mixed with a solution of 25 g of crystallized copper sulfate in 200 ecm of water and 25 g of triethanolamine and stirred for several hours at 90 to 95 ° C. until the metal complex is completely formed. The initially bluish red suspension turns dark red. After the metallization has ended, the metal complex compound is filtered off while hot, washed with hot water and dried. The copper complex compound obtained in this way is a garnet-colored powder.
The table below also contains a number of further components that can be used according to the invention and the color shades of the metal-containing azo dyes which can be obtained therefrom on the fiber and which also have good fastness properties:

Diazo component

5-amino-7-methylquinoxaline

the same
the same
the same
the same

the same
the same
the same
the same
the same
the same
the same
the same
the same
the same
the same
the same

Azo component

2,3-oxynaphthoylaminobenzene

1 - (2 ', 3'-oxynaphthoylamino) -3-nitrobenzene

1 - (2 ', 3'-oxynaphthoylamino) naphthalene

1- (2 ', 3'-oxynaphthoylamino) -4-methoxybenzene

1- (2 ', 3'-oxynaphthoylamino) -2-methoxy-4-chloro-5-methylbenzene

1- (2 ', 3'-oxynaphthoylamino) -2-methoxybenzene

1- (2 ', 3'-oxynaphthoylamino) -2-methylbenzene

1- (2 ', 3'-oxynaphthoylamino) -4-chlorobenzene

1 - (2 \ 3'-Oxynaphthoylamino) -2-methyl-4-chlorobenzene

1- (2 \ 3'-Oxynaphthoylamino) -2-methyl-4-methoxybenzene

1- (2'.3'-Oxynaphthoylamino) -2,4-dimethoxy-5-chlorobenzene

1 - (2 ', 3' -oxynaphthoylamino) -2,5-dimethoxy-4-chlorobenzene

1- (2 ', 3'-oxynaphthoylamino) -2,5-dimethoxybenzene

1- (2 ', 3'-oxynaphthoylamino) -2-ethoxybenzene

2- (2 ', 3'-oxynaphthoylamino) -3-methoxy-diphenylene oxide

1- (6'-Bromo-2 \ 3'-oxynaphthoylamino) -2-methoxybenzene

1- (2 ', 3'-oxynaphthoylamino) -2-methyl-5-chlorobenzene

Copper complex

garnet

bluish
garnet

blue
garnet

bluish tint
garnet

bluish tint
garnet

hue

Cobalt complex

- [- - -

¹ Koriiuh
Corinth
Corinth
Korimli
Corinth

Nickel complex

'Violet

¹ reddish

■ purple

garnet

reddish
; violet

j bluish
ι garnet

blue
garnet Corinth bluish
garnet bluish tint
garnet Corinth bluish
garnet ^: bluish tint
^; garnet Corinth bluish
garnet bluish tint
garnet Corinth garnet bluish tint
garnet Corinth violet reddish
violet Corinth violet bluish
garnet Corinth garnet blue
garnet Corinth violet bluish tint
garnet Corinth garnet red
violet Corinth garnet 'blue
'Garnet Corinth violet blue
garnet Corinth bluish tint
garnet

continuation

Azo component Copper complex Color peat Nickel complex Diazo component l- (2'-oxyanthracene-3'-carboyl- greenish Cobalt complex _ 5-amino-7-methyl- amino) -2-methylbenzene blue Blue green quinoxaline l - ^ '^' - Oxynaphthoylamino) - bluish tint blue the same 4-ethoxybenzene garnet Corinth garnet l- (2'-oxycarbazole-3'-carboyl- reddish - the same amino) -4-chlorobenzene violet reddish 2,3-oxynaphthoylaminobenzene Corinth violet - 5-amino-2,3-diphenyl- Bordo 7-methylquinoxaline l- (2 ', 3'-oxynaphthoylamino) - Corinth bluish tint the same naphthalene Bordo Red 2- (2 ', 3'-oxynaphthoylamino) - Corinth bluish tint the same naphthalene Bordo Red 1 - {! ', 3'-Oxynaphthoylamino) - Corinth - the same 2-methoxy-4-chloro-5-methyl- Bordo benzene 1 - (2 ', 3'-oxynaphthoylamino) - Corinth bluish ÖS the same 4-chlorobenzene Bordo Red l- (2 ', 3'-oxynaphthoylamino) - Corinth bluish tint 5-amino naphthalene brownish covered 2,3-naphtho- (l ', 8') - garnet Red 7-methylquinoxaline l- (2 ', 3'-oxynaphthoylamino) - Corinth bluish tint the same 2-methoxy-4-chloro-5-methyl- brownish covered benzene garnet Red l- (2 ', 3'-oxynaphthoylamino) - Corinth covered the same 2-ethoxybenzene brownish bluish garnet Red l- (6'-bromo-2 ', 3'-oxynaphthoyl- Corinth covered the same amino) -2-methoxybenzene brownish Bordo 2,3-oxynaphthoylaminobenzene garnet garnet covered S-amino ^ SJ-trimethyl- blue Red quinoxaline l- (2 ', 3'-oxynaphthoylamino) - blue garnet covered the same 3-nitrobenzene garnet blue Red l- (2 ', 3'-oxynaphthoylamino) - garnet garnet Bordo the same 4-methoxybenzene blue l- (2 ', 3'-oxynaphthoylamino) - blue garnet covered the same 2-methoxy-4-chloro-5-methyl- garnet blue Red benzene garnet l- (2 ', 3'-oxynaphthoylamino) - garnet covered the same 2-methoxybenzene garnet Red l- (2 ', 3'-oxynaphthoylamino) - bluish covered the same 2-methylbenzene garnet garnet Red l- (2 ', 3'-oxynaphthoylamino) - bluish Bordo the same 4-chlorobenzene garnet blue l- (2 ', 3'-oxynaphthoylamino) - bluish tint garnet - the same 2-methyl-4-chlorobenzene garnet garnet l- (2 ', 3'-oxynaphthoylamino) - blue the same 2-methyl-4-methoxybenzene garnet bluish tint l- (2 ', 3'-oxynaphthoylamino) - blue garnet - the same 2,4-din ¹ ^ thoxy-S-chlorobenzene garnet bluish tint l- (2 ', 3'-oxynaphthoylamino) - blue garnet - the same 2,5-dimethoxy-4-chlorobenzene garnet - 2- (2 ', 3'-oxynaphthoylamino) - blue covered the same 3-methoxydiphenylene oxide garnet garnet Red l- (2 ', 3'-oxynaphthoylamino) - bluish tint covered the same 2-methyl-5-chlorobenzene garnet - Red

continuation

10

Azo component Copper complex hue Nickel complex Diazo component l- (2 ', 3'-oxynaphthoylamino) - bluish tint Cobalt complex covered 5-amino-2,3,7-trimethyl 2-methoxy-5-chlorobenzene garnet garnet Red quinoxaline Terephthaloyl-bis- (1 -acetyl- Yellow-brown .— the same amino-2,4-dimethoxy- 5-chlorobenzene) l- (5'-oxy-l ', 2', 1 ", 2" -benzo- Blue black Corinth the same carbazole-4-carboylamino) - Blue black 4-methoxybenzene 1 - (2'-oxyanthracene-3'-carboyl- - - the same amino) 2-methylbenzene Corinth 1 - (2'-oxycarbazole-3 '-carboyl- garnet Brown- the same amino) -4-chlorobenzene Brown- prickly prickly garnet l- (5'-oxy-l ', 2'4 ", 2" -benzo- black garnet 5-amino carbazole-4'-carboylamino) - 2,3-naphtho- (l ', 8') - 4-methoxybenzene 7-methylquinoxaline l- (2'-oxyanthracene-3'-carboyl- covered the same amino) -2-methylbenzene Olive l- (2'-oxycarbazole-3'-carboyl- bluish tint reddish the same amino) -4-chlorobenzene Brown Brown Brown l- (3'-oxydiphenylene oxide Brown Brown the same 2'-carboylamino) - reddish 2,5-dimethoxybenzene Brown TerephthaIoyl-bis- (1 -acetyl- Red-brown yellow brown the same amino-2,4-dimethoxy- yellow brown 5-chlorobenzene) 2,3-oxynaphthoylaminobenzene - blunt 5-amino-2,3-dimethyl- Corinth violet 7-chloroquinoxaline 2- (2 ', 3'-oxynaphthoylamino) - - blunt the same naphthalene Corinth violet l- (2 ', 3'-oxynaphthoylamino) - - garnet the same 2-methoxybenzene Corinth l- (2 ', 3'-oxynaphthoylamino) - - garnet the same 2,4-dimethoxy-5-chlorobenzene Corinth 2- (2 ', 3'-oxynaphthoylamino) - garnet • - 5-amino-2,3-dimethyl- naphthalene garnet 7-methoxyquinoxaline

Diazo component Azo component aluminum
complex chrome
complex Far
iron
complex )volume_
manganese
complex zinc
complex titanium
complex 5-amino
2,3,7-trimethyl-
quinoxaline 2- (2 ', 3'-oxynaph-
thoylamino) -naph-
thalin bluish
Red covered
Red covered
blue
prickly
Red covered
Red covered
Red covered
Red

Claims (5)

Patent claims: 1. A process for the preparation of metal-containing, water-insoluble azo dyes, characterized in that the 6o Diazonium compounds from amines · of the general formula NH CR ₁ CR, where R is a non-water-solubilizing substituent and Ri and R _{2 are} hydrogen atoms, alkyl, aryl, aralkyl or cycloalkyl radicals, which can also be linked to one another to form an isocyclic ring, with arylamides of aromatic or heterocyclic o-oxycarboxylic acids or of acyl acetic acids, which are free of sulfonic acid and carboxylic acid groups, in substance, on the fiber or on another substrate, and the resulting coupling 809 5S8M76 11 12 Dyes with metal-releasing agents - nickel, manganese, iron, zinc, titanium, aluminum, miniums or chromes are used. 2. The method according to claim 1, characterized in that '' indicates that one is a metal donor Means inorganic or organic salts or 5. Publications considered:, Complex compounds of copper and cobalt, French patent specification No. 981432. \ \ When the application was announced, a coloring table with explanations was laid out. i * - ^t: / fly- ■■ ■ Xi S09 53i / 476 +.68 θ Bundesdruckerei Berlin ^!