US1934789A - Production of fast color reserves under ground dyeings - Google Patents

Description

Patented Nov. 14,1933

PRODUCTION OF FAST COLOR RESERVES UNDER GROUND DYEINGS Philippe Brandt, Mulhouse, Haut-Rhin, France, and Emil Gubler and Ernst Tschan, Basel, Switzerland, assignors to 'firm Durand & Huguenin S. A., Basel, Switzerland No Drawing. Application October 10, 1931, gggal No. 568,202, and in Germany October 10,

Claims.

In the U. S. patent application Ser. No. 554,945, filed August 3, 1931, a process for producing fast color reserves under ground dyeings is described in which a steaming operation for developing the 5 dyestuff is avoided. According to the .said process it is possible to produce such color reserves under ground dyeings with the aid of ester-salts oi. leuco-vat-dyestuffs (see U. S. Patent No. 1,448,251) by printing on a material impregnated with an arylide of -2z3-hydroxy-naphthoic acid a reserve color containing an ester-salt of a leucovat-dyestufi and, besides the usual additions, an acid reacting salt, drying and afterwards padding the material in a solution of a diazotized 4-aminodiphenylamine compound in order to produce the ground dyeing. Finally the ester-salt is developed by passing the material through an acid bath containing a mild oxidizing agent.

Surprisingly it has now been found, that such vat dyestuiis can be produced in a still simpler way, without anysteaming operation and without an acid developing bath, by means of a drying operation only. According to the invention 35 aluminium chlorate is printed on the naphtholated material simultaneously with the ester salt and an acid reacting salt. The material is then subjected to a drying operation, whereby the 'color reserves are developed. Finally theground dyeing is produced by padding the material in a solution of a diazo compound.

As a number of ester-saltsrequire some time for their development, as the case may be, the goods/are left lying for a certain time after drying.

The developing time can be shortened, that is to say, the developing power of the aluminium chlorate may be increased by the presence of an oxidizing catalyst, such as for instance ammonium vanadate, osmium tetroxide, potassium ferricyanide, a copper-salt, brought on to the fibre previously or simultaneously with the naphthol or in any other step of the process. The above mentioned catalysts may also be used in combination with each other.

In the German'Patent No. 525,302 the use of color reserves with the aid of ester salts of leuco flcation but also a considerable improvement over the prior art inasmuch as the useot aluminium chlorate does not act as developing agent-only, but it helps to improve the reserve-efliciency of the acid reacting salt. It is therefore possible to economize on this product.

Furthermore in the earlier process, wherein the development of the ester-salt-reserves followed the development ofthe ground dyeing, the latter was more or less affected by the oxidizing agents, so that it was necessary to choose a mild one. But as certain ester-salts require more powerful oxidizing agents for their development, it is clear, that hitherto the choice of these dyestuffs for color reserve purposes has been limited. This disadvantage has been overcome, since,

'contrarily to the prior process, it has been found. 7

that the developer, in this case aluminium chlorate, acts only locally and not on the whole material'and is capable of developing practically the whole of the ester-salts of leuco-vat-dyestufis. As the color reserves aredeveloped before the ground dyeing, there is no more danger for the latter to be damaged.

Besides ester-salt-reserves other color-reserves, for instance when printing a preparation of a diazotized para-nitraniline compound on the material, red reserves may be obtained. The variety of the efiects which can be produced may still be increased, when using other suitable dyestuffs.

The new process is illustrated by the following examples.

. v Emample 1 On the material padded with the anilide of 2:3-hydroxy-naphthoic 'acid in the usual way, there is printed, after drying, a color of the following composition:

Parts Sodium salt of the disulphuric acid ester of leuco-tetra-bromindigo 2 Thio-methylene-glycol 6 Water I Neutral-starch and gum tragacanth thickening. I 50 Solution of aluminium sulphate (1:1) l 4 Solution of aluminium chlorate (25 B.) 8

The material is dried at 60 to '10" c. in a drying chamber or on the drum,- left lying for 24 106 hours, whereby the light blue reserve effect, originating in the ester of leuco-tetra-bromindigo is developed. After drying, the material is padded in a solution containing the diazo compound of 4-amino-4'-methoxy-diphenylamine. Then an air passage for 30 to seconds is applied, whereby the development of the ground dyeing takes place. To destroy any excess of the diazo compound, the material is treated for 5 minutes in a bath of 60 C. containing 5 com. of muriatic acid per litre of water, thoroughly rinsed and dried. A fast light blue on a navy ground is obtained.

Example 2 Parts Sodium salt of the disulphuric acid ester of leueo-dibenzpyrenequinone Thio-diethylene-glycol -e 6 Water Neutral-starch and gum tragacanth thickening Solution of aluminium sulphate (1:1) 6

Solution of aluminium chlorate (25 B.) 6 Oxalic acid 0, 2

The material is dried at a temperature of 60 to C. in a drying chamber or on the drum. During this drying operation the ester-salt is developed completely. The ground dyeing is produced and the goods are finally treated as in Example 1. Thus yellow reserves on a new ground are obtained.

Example 3 The following printing color is prepared:

Parts Sodium salt of the disulphuric acid ester of leuco dimethoxydibenzanthrone Th10-d1 thy1 y 5 reserve is developed, and afterwards padding the Wate 24 same in a solution of a diazotized 4-amino-di- Neutral starch and gum tragacanth thickphenylamine compound in order t prgduce t ening 0 ground dyeing. Solution of aluminium ph r. 4 2. A process for producing fast color reserves s01utin f alumlmumchlorate B.) 8 under dyemgs by means of ester salts of leuco vat dyestuffs without steaming, consisting 125 This color is printed on cotton material, previously padded with the anilide of 2:3-hydroxynaphthoic acid. The material is afterwards dried at 60 to 70 C. in a drying chamber or on the drum. whereby the green color 'reserv is developed.

The ground dyeing is produced by means of a solution of diazo-4-amino-4-methoxy-diphenylamine as stated inExample l. on a navy ground results.

Example 4 Thus a fast green following composition:

. Parts Anilide of the 2 3-hydroxy-naph ,thoic acid 11,5 f i i Caustic soda lye (34 B.) 20 water;

Ricino-sulphonic acid 16 the whole diluted with water to 1 litre.

The material is first padded in a bath of the After drying there is printed on a color composed as follows: I

. Parts Sodium salt of the disulphuric acid ester of 2:1-naphthioindigo 2 Thio-diethylene-glycol 5 Sodium salt of benzyl-aniline sulph nic acid- 5 Diethyl ether of diethylene-glycol 5 Warm water 17 Neutral-starch and gum tragacanth thickening' Solution of aluminium sulphate (1:1) 4

' Solution of aluminium chlorate (25-B. 12

The material is dried at 60 to 70 C. in a drying chamber or on the drum and left lying for 2'4. hours. whereby the ester salt is developed. Afterwardsthe ground dyeing is produced and the goods are finally treated as stated in Example 1. A fast brown reserve on navy ground is obtained.

In a similar manner color reserves'on navy ground may be obtained by printing on the following ester-salts of leuco-vat-dyestuifs:

' Sodium salt of the disulphuric acid ester of isatin anilide and l-methyl-7z8-oxybenzocarbazol:-giving grey to black efiects.

-Sodium salt of the disulphuric acid ester of leuco-6:5 :'7'-trichlorindigo:'giving violet effects.

In the aforesaid examples instead of aluminium sulphate another acid reacting salt, for instance zinc sulphate, may be used with a similar eflect.

What 'we claim is:

1. A process for producing under ground dyeings by means of ester salts of leuco vat dyestuffs without steaming, consisting in taking a fabric impregnated with an arylide of 2:3-hydroxy-naphthoic acid, printing fast color reserves 11 thereon a reserve color containing an ester salt of a leuco vat dyestuif, aluminium chlorate as oxidizing agent and an acid reacting salt, therein taking a fabric impregnated with an arylide of 2:3-hydroxy-naphthoic acid, printing thereon a reserve color containing an ester salt of a leuco vat dyestuil, aluminium chlorate as oxidizing agent and aluminium salt, thereupon drying the material, whereby the color reserve is developed, and afterwards padding the same in a solution of a diazotized 4-am- "ino-diphenylaminecompound in order to produce the ground dyeing.

,3. A process for producing fast color reserves underground dyeings by means of ester salts of leuco vat dyestuifswithout steaming, consisting in taking a fabric impregnated with an arylide of 2:3-hydroxy-naphthoic acid, printing thereon a reserve color containing an ester salt of a leuco vat dyestufl, aluminium chlorate as oxidizing agent, a catalyst and an acid reacting salt, thereupon drying the material, whereby the color reserve is developed, and afterwards padding the same in a solution ,of a diazotized e-amino-diphenylamine compound in order to produce the ground dyeing. p 1 k 4. A process for producing fast color reserves under ground dyeings by means of ester sulphate as acid reacting saltsof same in a solution of a diazotized l-amino-diphenylamine compound in order to produce the ground dyeing.

6. A process for producing last color reserves undergrounddy ingsbymeansotestersaltsot leuco vat dyestuirs without steaming,

in taking a fabric impregnated with an-ary ld or 2:8-hydroxy-naphthoic acid, printing thereon a reserve color, containing an ester salt 01' a leuco vat dyestufl aluminium chlorate as oxidizing agent and an acid reacting salt, thereupon drying the material, whereby the color reserve isdeveloped, and afterwards'padding the same in] solution of diazotized 4-amino-4'-methoxy-di-v phenylamine in order to produce the ground dyeing.

' PHILIPPE BRANDT.

v EIHLGUBLER.