DEN0005223MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: March 15, 1952. Advertised on December 29, 1955

GERMAN PATENT OFFICE

It is known that cellulose fiber !! through Application of aryl amides of 2,3-oxynaphthoic acid together with diazoamino compounds diazotized aromatic amines and primary or secondary aliphatic amines and subsequent Cleavage with acids insoluble azo dyes can be produced.

According to the process of German Patent 745 75 ^J , those diazoamino compounds are used for the production of azo dyes on cellulose ester fibers, which are obtained by reacting diazotized primary aromatic amines without water-solubilizing groups with secondary aliphatic amines or oxyamines which contain no sulfonic acid or carboxylic acid groups, with the exception of secondary aliphatic amines containing more than two ethenoxy groups can be obtained. From this patent it can be seen that diazoamino compounds from any substituted diazotized aromatic amines without water-soluble

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making groups and oxydialkylamines, such as. B. Diethanolamine, pull on the cellulose ester fiber, provided they do not include sulfonic acid or carboxylic acid groups.

However, such diazoamino compounds do not basically show the same thing on polyamide fibers Drawability as on cellulose ester fibers, proof that it is not possible to use known dyeing processes without further ado to the coloring entirely

ίο to transfer polyamide fibers that behave differently.

For example, the diazoamino compounds listed in the table below provide together with an azo component on polyamide fibers no or only very weak dyeing. Of these connec-

»5 fertilizers are those in Xr. ι to 3 of the table mentioned Diazoamino compounds in German Patent 7-15 751 as examples for dyeing cellulose esters listed:

Any azo component of the 2,3-oxynaphthoic acid arylanide series with 3/1000 mol / l of a diazoamino compound from diethanolamine and diazotized!

ι. ι -Ληηηο-5-nit ro-2-methoxybenzene,

2. i-Amiiio-2, 5-dichlorobenzene,

3. 1-Ami 110-2-nitro-.j-chlorobenzene,
.-]. ι-Ληιίηο-3-nitrobenzene,

5. j-Aniino-2-melhoxy -.} - nitrobenzene,

(). jA mi 110-2,5-dimet lioxy-.j-nitrilobenzene,

7. i-Ainino-5-methyl-2-clilor -.] - nitriloben / .ol,

8. i-Ainino-3, 5-ditrifluoromethylbenzene,

¹ ^ ⁰ (). i-Ainino-2-trilluonethyl-4-chl (irbenzene,

JO. 2-amino-dipheny] sulfone.

ICs has now been found that strong dyeings can be obtained on polyamide fibers if any A / .okomponenlen, ■ / .. B. Aryl amides of 'JL, 3-oxynaphthoic acid, 2-oxycarbazole-3-carboxylic acids and 5'- OxV-J ₁ 2, 1 ', 2'-beiizocarbazole-4'-carbonsäiire, also acylacetylaininoverbindungen of 2,5-Dielkoxybenzenes as well as the benzothiazole and diphenyl series, and diazoaniiiHn'erbindungen, which by reaction' of oxydialkylamines of the general formula

11 X

K.,

where K ₁ and i., alkyl esters 1) of which at least one is subsi ited by a hydroxyl group, such as diethanolamine or methylethanolamine, such diazotized primary aromatic amines are obtainable which are not nitro-, trilhiornietliyl- or cyano -, Plienylsulfonyl-, sulfonic acid or carboxylic acid groups or 2 halogen atoms

S5 (negative substituents) contain, together from alkaline solution or suspension applied to the polyamide fiber and the azo dye by treating developed in an acid bath.

Particularly strong colorations are obtained when the diazo component !! used aromatic Amines (the following groups are substituted: alkyl, aryl, alkoxy, phenoxy, amino, phenylazo, Acylamino (positive substituents).

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The depth of color of those with diazo components which have positive substituents of the type mentioned above 6; The presence of 1 halogen atom per aryl radical still makes the colors available reinforced.

The effect of the negative substituents given above can be enhanced by the introduction of a positive 7 < Substituents, e.g. B. an amino group, are canceled.

The weak dyeing on polyamide fibers when using diazoamino compounds, which are in the Diazo component the negative 7 given above; Containing substituents are characterized by low drawability and more difficult to cleave compared to diazoamino compounds with positive substituents conditional.

8e lying method weaker dyeings obtained ^- polyurethane fibers after VOi -.

The new process offers particular advantages in the production of dyeings on mixtures of polyamide fibers and animal or vegetable fibers, such as wool, silk, cotton or fibers of 8; regenerated cellulose. So far, one was to produce insoluble azo dyes, ζ. Β. on mixes of wool and polyamide fibers, relying on the fiber mixture with the amino compound and to prime the azo component, the g <azo component on both fibers and the amino compound pulled mainly on the polyamide portion while soiling the wool. According to the usual Development of the azo dye on wool with a solution of a diazotized base had to be 9: Amino compound are diazotized on the polyamide portion and then coupled. The diazotization means an additional work step and fiber damage for the wool content; therefore a do not introduce such a procedure in practice. According to the present process, the fiber mixture, the azo component and the diazoamino compound are applied, first treated with the solution of a diazotized amine and then the coloring on the polyamide part by simple treatment in an acid bath without fiber damage developed.

example 1

0.5 g of i- (2 ', 3'-oxynaphthoylamino) -2-methyl-4-methoxybenzene are in 0.15 cm sodium hydroxide solution, 32%, ι ecm of an organic solvent, such as diglycol, ι ecm an organic base, such as monoethanolamine, and ι ecm of water and dissolved in a bath of 1 1 75 ° given warm water that contains 3 g of a protective colloid that is effective and 1 ecm of ammonia, 25%. The dye bath can also be kept soda or caustic alkaline.

1 g of the diazoamino compound from diethanolamine and the diazo compound are added to this bath i-Amino-a-methyl- ^ chlorobenzene, dissolved in water and Alcohol, added.

The well-wetted Polyamidwarc is treated in a liquor ratio ι: 30 ι to τ ¹ / .. hours at 75 ⁰ in the specified bath, rinsed and in a bath of So °, the 5 g of sulfuric acid, ₆ ° / 0 ig, or

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20 cc of formic acid, _o ig containing 85 ° /, per liter of water, develops ίο minutes.

A full red dyeing with very good fastness properties is obtained.

The following table describes a number of
further colorations which can be obtained by the same process 65 using 3/1000 mol of diazoamino compound.

Azo component Hue on
Polyamide fiber Diazoamino compound
from diethanolamine and diazotized ι. i-amino-2-methoxy-5-chlorobenzene i- (2 ', 3'-oxynaphthoylamino) -
2-methyl-4-methoxybenzene full red 2. i-Amino-2-methyl-5-chlorobenzene -4-chlorobenzene full scarlet fever 3. i-Amino-2-methyl-3-chlorobenzene 2, 2'-dimethyl "4, 4'-di- (acetoacetyl-
amino) diphenyl full yellow 4. i-Amino-2-methoxy-5-chlorobenzene i- (2'-Oxycarbazole-3'-carboylamino) -
4-chlorobenzene full red-brown 5. 2-Amino-4-chlorodiphenyl ether
) i- (2 ', 3'-oxynaphthoylamino) -
2-methyl-4-chlorobenzene full red 6. 4-Amino-2 ', 3-dimethyl-i, i'-azobenzene the same full bordo 7. i-Amino-2,5-dimethoxy-4-chlorobenzene the same full bordo 8. i-Amino-2,5-diethoxy-4-benzoylamino
'benzene . the same full blue 9. 4,4'-diamino-3, 3'-dimethoxydiphenyl i- (2 ', 3'-oxynaphthoylamino) -
2-methyl-4-methoxybenzene full blue 10. i-aminonaphthalene i- (2 ', 3'-oxynaphthoylamino) -
benzene full bordo 11. i, 4-Diamino-2,6-dichlorobenzene
(monodiazotized) "4-chloro-2,5-dimethoxybenzene full red-tinged
Bordo 12. i-Amino-2-methoxy-5-chlorobenzene
5 i-acetoacetylamino-4-chloro-
2,5-dimethoxybenzene full yellow 13. i-Amino-2-methyl-4-chlorobenzene i-Benzoylacetylamino-4-benzoyl-
amino-2,5-diethoxybenzene full golden yellow 14. i-Aminoanthraquinone i- (2 ', 3'-oxynaphthoylamino) -
3-chloro-4,6-dimethoxybenzene full brownish tinge
Red 15. i-Amino-2-methyl-4-chlorobenzene 2-acetoacetylamino-6-ethoxy-
benzothiazole yellow 16. the same
5 i- (5 "-0xy-i ', 2', 1", 2 "-benzocarba-
zol-4 "-carboylamino) -4-methoxy-
benzene Corinth 17. i-Amino-2, 5-diethoxy-4-cyclohexylcarboyl-
aminobenzene i- (2 ', 3'-oxynaphthoylamino) -
2-methyl-4-methoxybenzene blue 18. 4,4'-diaminodiphenyl
Diazoamino compound from methyl ethanol
amine and diazotized i- (5 "-0xy-i ', 2', 1", 2 "-benzocarba-
Z0I-4 "-carboylamino) -4-methoxy-
benzene black 5 19. i-Amino-2-methyl-4-chlorobenzene i- (2 ', 3'-oxynaphthoylamino) -
2-methyl-4-chlorobenzene full red

Example 2

20 g of i- (2 ', 3'-oxynaphthoylamino) -2-methyl-4-me-0 thoxybenzene with 32 g of the diazoamino compound from diazotized i-Arm'no-2-methyl-4-chlorobenzene and diethanolamine in a mixture consisting of equal parts of diglycol and diethanolamine

is, with the addition of 6 cc of sodium hydroxide solution, 32 ° / _o ig,
and 2 ecm of water and stirred into 700 g of tragacanth thickener 60/1000.

The printing paste obtained is in the machine or
Film printing applied to polyamide ware. After drying, steaming is carried out for 5 to 10 minutes and neutral

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then the dye developed in a bath at 90 °, which contained 5 g of sulfuric acid, 9%> K. ^{Contains per} liter of water. Soap up in a weakly alkaline or non-ioniacal bath and get a full blue-tinged red print of good real healing properties.

The dye can also be developed by acidic steaming; the prints 6 thus obtained; are, however, somewhat behind in terms of their fastness to rubbing.

The following table describes a number of additional shades that can be obtained using the same procedure are available.

10 Diazoamino compound
from diethanolamine and diazotized Azo component Hue on
Polyamide fiber 2-amijio- / | -chloro-diphenyl ether '5 . <| -Amino-2,3-dimethyl-i, i'-azobeiizole i- (2 ', 3'-oxynaphthoylamino) -
2-methyl-4-methoxybenzene full red i-A) nino-2-niethoxy-5-chlorobenzene i- (2 ', 3'-oxynaphthoylamino) -
2-methyl-4-chlorobenzene full bordo 20th i-Amino - '.;,. ■ j-dimethyl-3-benzoylaminobenzene i- (2 ', 3'-oxynaphthoylamino) -
2-methoxybenzene bluish red i-Aniino-a-ynethyl-.j-chlorobenzene i- (2 ', 3'-oxynaphthoylamino) -
2-methylbenzene full red 25th i-Amino-c'-inelhyl-.i-chlorobenzene i- (2'-oxycarbazole-3'-carboyl-
amino) -4-chlorobenzene full brown i-Amino-2, ^ -diethoxy-.j-acetylaminobenzene i-acetoacetylamino-2, 5-dimethoxy-
4-chlorobenzene full yellow ok i-Ajnino-2-methoxybenzene-5-silfonic acid
n-butylamide I- (2 ', 3'-0xynaphthoylamino) -
2-methyl-4-chlorobenzene blue i-amino-2-methyl-4-chlorobenzene i- (2 ', 3'-oxynaphthoylamino) -
2,4-dimethoxy-5-chlorobenzene full red i- (2 ', 3'-0xynaphthoylamino) -
benzene full red

Example 3
In a bath of 60 ° which contains 1.2 g of i- (2 ', 3'-oxynaphthoylamino) -2-methyl-4-chlorobenzene per liter, dissolved in the amount of caustic soda, alcohol and formaldehyde theoretically necessary to form the sodium salt, 3 0.8 g of the diazoamino compound from diethanolamine and diazotized i-amino-2-ine (hyl-4-elilorbonzo) are added to g of a condensation product of higher molecular weight fatty acids and protein building products, 3 g of soda and ίο g of table salt.

The washed mixture of polyamide fiber and wool (or you with rayon) is in Flottcnverhältnis 1:.. 30 at Γιο "treated 1 hour in this Bede The diazoamino compound pulls this case substantially only to the polyamide fiber Because k; ilt rinsed in a Bede , which contains 40 g of table salt and 3 g of dehydrated sodium carbonate per liter.

Subsequently, the coloring is developed on the wool fiber by entering into a cold bath, des per liter contains the diazo compound obtained by diazotizing 1 g of i-amino-2-methyl-4-chlorobenzene is obtained. To establish a Ρι, range that is favorable for the coupling, the bath per liter 2.5 g of monosodium phosphite and 2 g of disodium phosphite crystallize, also as a dispersant

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ι g of a condensation product of an alkylphenol and ethylene oxide added.

After 15 minutes of treatment in the specified bath, the fiber mixture is in a second bath containing 5 g of concentrated sulfur io per liter; acid and 1 g of a dispersant, treated at 70 to 80 ° for 10 minutes. The color is developed on the polyamide fiber. It is then washed at 45 ° with 1 g of a condensation product of an alkylphenol and ethylene oxide n <and ι ecm ammonia, then aftertreated at 80 ° with a fatty acid condensation product and 0.5 ecm acetic acid, 50 ° / ₍₁ ig).

A strong, thread-like red dyeing with good fastness properties is obtained. Obtains similar results when using polyamide fibers in a mixture with z. B. Cotton or in a mixture with Rayon and wool, rayon and acetate silk, cotton and acetate silk. Of course they can Azo components and diazoamino compounds which can be used according to the invention are also largely varied here will.

Claims (3)

PATENT CLAIMS: i. Process for the production of insoluble azo dyes !! on polyamide fibers or their N5223IVb / 8m Mixtures with other fibers, characterized in that any azo components are used and diazoamino compounds obtained by reacting oxydialkylamines from the general formula HN: , R ₁ ¹ R, wherein R ₁ and R ₂ denote alkyl radicals, of which at least one is substituted by a hydroxyl group, are obtainable with those diazotized primary aromatic amines which contain no nitro, trifloromethyl, cyano, phenylsulfonyl, sulfonic acid or carboxylic acid groups or 2 halogen atoms , applied together from an alkaline solution or suspension on the polyamide fiber and developed the azo dye by treatment in an acidic bath. 2. The method according to claim i, characterized in that that aromatic amines are used as diazo components that are replaced by alkyl, Aryl, alkoxy, phenoxy, amino, phenylazo or acylamino groups are substituted. 3. Process according to Claims 1 and 2, characterized in that one is used to produce insoluble Azo dyes on mixtures of polyamide fibers with other fibers the fiber mixture, to which the azo component and the diazoamino compound are applied, initially with the Treated solution of a diazotized amine and then the coloring on the polyamide part developed by treatment in an acid bath. Referred publications: German Patent No. 745751; U.S. Patent No. 2,078,388; Diserens »Latest Advances and Processes in the Chemical Technology of Textile Fibers ^, 1949, Part I, Vol. 2, pp. 360 and 375 ff.