DE3841482A1 - A PHASE PROCESS FOR PREPARING PRINTINGS WITH REACTIVE PURPOSES IN ADDITION TO AZO DEVELOPING DYES ON ALKALIALLY PRESCRIBED TEXTILES - Google Patents

Description

The present invention relates to a single-phase Process for making prints on previously Coupling components under alkaline conditions primed, cellulosic or exclusively from Cellulose fibers existing textiles by separate Overprinting with reactive dyes in addition to primary aromatic amines with addition of sodium nitrite and in Presence of acid or acid-supplying substances Diazotieren generated, directly coupling capable Diazonium compounds with simultaneous development of water-insoluble azo dyes due to spontaneous Coupling, as well as following the drying of these prints taking place fixation of the reactive dyes by Vapors.

For the dyeing of textiles come to the generic Production of developing dyes usual, in the color Index, 3rd edition 1971 as "C.I. Azoic Coupling Component" (Coupling component) and from "C.I. Azoic Diazo Component" (Diazo component listed chemical compounds in Question.

Printing on with coupling components - below briefly referred to as "Naphtole" - primed textiles with the diazo components, eg. B. so-called Echtfärbesalzen or Diazotized Echtfärbebasen, has long been known and becomes common in practice according to this principle For this purpose, the textiles are in the form of Webs with an alkaline solution of naphthol paddled and dried. Printing on this Pre-priming is done either by means of Commercially available, stabilized diazonium compounds such  Antidiazotaten or Diazoaminoverbindungen, which by itself from in alkaline medium with the coupling components do not react and only by acidity in the couplable diazonium salt must be converted or by means of primary aromatic amines produced directly by a diazotization process free diazonium compounds. In both cases arises the printed areas of the textile goods Dye coupling on the fiber of - as well Development dye familiar - azo dye.

The diazotization of the primary aromatic amines takes place conventionally in strongly acidic medium, usually with Help of hydrochloric acid. To the prospected Dye coupling rapidly and as completely as possible ensure that the strongly acidic diazonium salt solution on pH values are buffered by 3 to 4. At the same time must be sure that there is still sufficient Acid capacity remains present to that along with the Naphtol neutralized alkali. The way adjusted diazonium salt solution is then used for printing thickened. The dye formation itself is close to Neutral point instead.

In DE-PS 28 50 901 now a simplified method for preparing printing pastes with couplable Echtfärbebasen described in which the diazotization of Amines are not in solution, as usual, but instead directly in the thickening is made, namely by Merging two thickened approaches, one with the Diazotate needed acid, the other with the too diazotizing amine and sodium nitrite in the for the Diazotization necessary amounts.

It is also known that one on such with a Coupling component pretreated textiles next to or  the diazo component (s) beyond that still separately Reactive dyes can print, it being in this case theoretically possible, the existing in excess Alkali the Naphtol primer at the same time to fix the Use reactive dyes.

Such a project fails when using the previously usual Diazotierungsmethoden however, because both during the drying process of the printed goods as also during the subsequent damping in the course of Dye fixation volatile acids are released and escape, that for fixing the Reativfarbstoffe neutralize necessary alkali uncontrolled partially. The fixation of the reactive dyes then proceeds uneven and in some areas not at all or only incomplete.

The presence or origin of this volatile Acids stir in the known printing methods of blunting (Buffering) of the diazonium salt solutions forth, usually with a mixture of Na acetate / acetic acid, which in the Pressure thickening is stirred.

Also, the use of increased amounts of alkali in the form of Na bicarbonate or soda, directly the reactive printing paste added, often helps no further. In addition occurs here the problem of often only low stability of already alkaline reactive printing pastes.

It is therefore from this single-phase operation to Fixation of the reactive dyes by steaming off and fixed for such occasion, the reactive dyes in In this case, two - phase, by the printed goods in the Connection to the coupling process for the development of Azo dyes once again through an alkaline bath leads and only then dampens, or that one another, two-phase fixing method for reactive dyes selects.

The invention defined below is now the Task based, a single-phase printing process of Reactive dyes besides azo developing dyes (i.e. the relevant diazo components) to previously with Coupling components alkaline primed goods too create the disadvantages of being in this field of work does not have known techniques.

This object is achieved in that one in the diazotization of the printed amines as the sole acidic agent neither in the drying process nor in the Water vapor in the fixation operation volatile acids and optionally for buffering the printing pastes with the Diazonium compounds only water-soluble salts of such Acids used.

The diazotization of the free amine can be both in the Solution or dispersion as well as according to the method take place according to DE-PS 28 50 901 in the thickening.

Be beneficial because of the lighter and faster Diazotization course, the primary aromatic amines used in the form of finely divided dispersions, as in DE-PS 23 46 612 or DE-PS 24 49 782 are explained.

As diazotizable amines (also Aminoazofarbstoffe) come in principle, all that for the usual Ice color technique are suitable. Preferred amines are in the DE-PS 23 46 612 and 24 49 782 called. There is also described how these amines in suitable finely divided Dispersions can be transferred.

Thickeners are used to prepare the printing inks suitably modified or degraded Locust bean gum or guar products, if appropriate also cellulose or starch ethers or mucilages used.  

As under the process conditions are not steam-volatile, acidic chemicals are used for the implementation of diazotization medium to weak, inorganic or organic acids into consideration. Prefers are low molecular weight aliphatic carboxylic acids such Glycolic acid, citric acid, tartaric acid or oxalic acid, but preferably also phosphoric acid, in amounts of from 20 to 80 g / kg of parent color used.

It may in the claimed process in certain cases but also with strong acids such as sulfuric acid or hydrochloric acid are diazotized, provided that the amine requires such a diazotization. The blunting then has with neutral or alkaline salts of in water vapor non-volatile acids to happen, for example with tertiary or secondary sodium salts of phosphoric acid, such as tri- or disodium phosphate or with corresponding Buffer mixtures.

As coupling components for the primer of cellulosic materials are suitable alkaline solutions Such compounds, which are adjacent to a Couple hydroxyl group. Such compounds are in the DE-PS 28 50 901 listed.

In addition to the diazo components are in the speech neutral, thickened solutions of Reactive dyes printed. In principle, all are in the Color Index, 3rd edition 1971 and supplements 1975, 1982 and 1987 under the name "C.I. Reactive Dyes" said organic colorant without limitation used.

These reactive dyes are according to the method with the for these classes of dyes commercial low-body as well as  alkali-insensitive thickeners, such as. B. Thickened alginate thickening.

The two variants of the method will be according to this Invention thus carried out as follows:

a) Diazotization in the solution

The tissue to be colored is first with the after standard procedure for alkaline solutions Coupling component padded and dried. As Diazo components provided amines are also after Regulation diazotized, instead of the otherwise normally used hydrochloric acid here, however equivalent amounts of a moderate to weak, not steam-volatile organic or inorganic acid be used. Should be in one only in a narrow pH range well coupling primer a precise Adjustment to the pH value for the coupling be necessary, so for the Dye development used solutions of Diazonium compounds in such a case with a alkaline or neutral salt of a weaker, not steam-volatile acid. The on this The resulting diazonium salt solutions are then thickened and printed.

The reactive dyes used for printing are in Dissolved water neutral, this solution is thickened and then in the same operation next to the diazo components printed.

The pressure of the diazonium compounds on the naphtol-primed Goods immediately gives the developing dye.

To fix the reactive dyes, the goods must after the Pressure to be steamed for 6 to 8 minutes at 100 ° to 105 ° C.  

The aftertreatment of the prints is done as usual.

b) Diazotization in the thickening

The priming of the printed matter with the coupling component takes place as in variant a). The diazotization of as Diazo component provided amines found according to the Regulation in DE-PS 28 50 901 by stirring together two thickenings instead, with one not steam-volatile acid, the other the amine and Contains sodium nitrite. The reactive dyes are separated as in variant a) dissolved in water neutral and thickened.

After printing both printing pastes side by side on the Primed goods, the textile material for fixing the Reactive dyes as under variant a) steamed and treated.

In practice, the following procedure has been found:

Prepare the thickened nitrite solution and apply first the corresponding, finely divided amine, the stirred Mixture and then sets directly needed for diazotizing Acid, usually diluted phosphoric acid, is added and finally stirs up the simplified in this way prepared printing ink with the diazonium compound thoroughly.

The following examples are intended to be claimed Explain the procedure without changing it in the indicated ways limit.

The dyes or dye precursors are in commercial presentation used so that Quantities refer to such commercial products.

Example 1

A cotton fabric is treated with an aqueous solution containing 20 g of Azoic Coupling Component 2 with C.I. 37505 (2-hydroxy-3-naphthoylamino-benzene) and 25 g sodium hydroxide solution (32.5%) in liters, primed and dried. Then a printing paste is printed on the goods so treated, the production of which is as follows:

Master batch I In 500 g a 5% aqueous solution of a carob bean gum as a thickener 16-18 g Incorporated sodium nitrite. By filling with 484-482 g Water is going up 1000 g completed.

Master batch II In 500 g the same thickening as in stock batch I. 60 g Phosphoric acid (85%) stirred and filled with 440 g Water is going up 1000 g completed.

To make the printing ink

300 g of the master batch I submitted, 15 g a 60% aqueous dispersion of Azoic Diazo Component 11 with the C.I. 37085 (4-chloro-o-toluidine) and 300 g of the master batch II and stirred 385 g Water for completion on 1000 g added.

In addition to this print paste is another print paste off

30 g of the dye Reactive Blue 19 with the C.I. 61200, 500 g a neutral, 4% alginate thickening, 50 g Urea and 420 g water 1000 g printed on the pre-primer.

After printing, the fabric is dried to give the dye Fixation steamed at 102 ° C for 8 minutes, rinsed with water, soaped hot and finally rinsed with water again.

You get on the goods a deep red print with good Fastnesses based on the development dye next to a true, clear blue based on the reactive dye.

example 2

A cotton fabric is primed with the alkaline solution from

16 g / l of Azoic Coupling Component 2 with C.I. 37505 (2-hydroxy-3-naphthoylaminobenzene),

manufactured according to the regulation from the company brochure "Naphtol AS application instructions" Hoe 4026 inking Hoechst Aktiengesellschaft, Frankfurt / Main and dry it so treated textile.

Also according to the above instructions one diazotiert one

12 g / kg of Azoic Diazo Component 34 with the C.I. 37100 (o-chloroaniline hydrochloride)

using sodium nitrite and hydrochloric acid. Blunting of the diazonium salt solution, however, does not take place in this case with sodium acetate, but here with
30 g / kg disodium phosphate.

This solution is now mixed with

600 g a carob kernel meal thickening and x g Water too 1000 g Printing paste thickened.

Furthermore, you make a second printing paste ago

40 g of the dye Reactive Yellow 17 with the C.I. 18852, 50 g Urea, 700 g a neutral, 6% alginate thickening and 210 g water 1000 g.

The two printing pastes are side by side on the primed tissue is printed and this is then at 100 ° C dried.

Now, the fabric for dye fixation for 6 minutes Steamed at 105 ° C, then rinsed with water, neutralized and neutral soaped. You get a golden yellow on the goods Reactive pressure, next to a red pressure of the Development dye.

If one leads in the above example with otherwise the same Operation dulling the diazonium salt solution against it with sodium acetate, so you get an incomplete and uneven fixation of the reactive dye, before especially in the vicinity of simultaneously printed printing paste with the diazotized amine to form the Development dye.

example 3

A cotton fabric is primed as in Example 2 described and dried it. For the coupling of Primer with a diazonium compound is sold separately of which a printing ink is prepared as follows:

In 814 g a carob kernel flour thickening (medium viscosity adjusted), containing 6 g Sodium nitrite, be 20 g of Azoic Diazo Component 34 with the C.I. 37100 (4-nitro-o-toluidine) are stirred in finely divided, liquid commercial form and then still 160 g Phosphoric acid (diluted 1: 8 with water) 1000 g

added. After 5 minutes, the diazotization is without Evolution of nitrous gases terminated and the resulting Print paste can be printed.  

As printing ink with the reactive dye is used here the second printing paste from Example 2.

Both printing pastes are side by side on the primed Fabric printed, this is dried and then for dye fixation at 103 ° C for 6 minutes.

On the goods one receives the example 2 corresponding Print. A tear strength test did not reveal any damage of the tissue.

example 4

A cotton fabric is primed as in Example 1 and dried. In addition, a printing ink is the following Composition stated:

Furthermore, imagine a second ink ago

These two printing pastes are side by side on the primed tissue is printed and this is then at 100 ° C dried.

Thereafter, the goods for dye fixation for 8 minutes Steamed at 105 ° C, rinsed with water cold and hot and soaped neutral at 90 ° C.

One receives on the thus treated tissue a yellow one Reactive pressure next to a black print of the Development dye.

example 5

A cellulosic tissue is treated with an aqueous solution containing 20 g of Azoic Coupling Component 5 with C.I. 37610 (3,3'-dimethyl-4,4'-bis-acetoacetylamino-diphenyl) and 15 g Contains caustic soda (32.5%) in liters, padded and dried. For the following overpressure two Prepared inks. The printing paste with the Diazonium compound consists of:

300 g of the stock batch I from Example 1, 12 g a 50% aqueous solution Azoic Diazo Component 44 with the C.I. 37000 (o-chloroaniline hydrochloride), 300 g of the stock solution II from Example 1, but here instead of phosphoric acid contains citric acid, and 388 g water 1000 g.

The printing paste with the reactive dye settles like follows together:

40 g of the dye Reactive Orange 16 with the C.I. 17757, 6 g Formaldehyde solution (35%), 44 g Urea, 700 g a neutral, 6% alginate thickening and 210 g water 1000 g.

These two printing pastes are side by side on the primed fabrics printed and dried at 100 ° C. After that is used for dye fixation and completion of Pattern proceed as in Example 4.

Obtained on the thus treated tissue a brilliant red reactive pressure, without being affected by in the Steam escaping acid, next to a yellow from the Development dye.

example 6

A cotton fabric is padded with an aqueous solution, the 20 g of Azoic Coupling Component 44 with the C.I. 37613 (5-chloro-2-acetoacetylamino-1,4-dimethoxybenzene), 32 g of ethanol, 40 g of water and 20 g of sodium hydroxide solution (32.5%) in Contains liters. The dried tissue comes with a Printed ink of the following composition:

300 g of the stock batch I from Example 1 are with 20 g the 45% aqueous dispersion of Azoic Diazo Component 13 with the C.I. 37130 (5-nitro-o-anisidine) and 300 g of the stock II from Example 1 mixed. 380 g Water is added to the completion 1000 g added.

In addition, the reactive printing paste of Example 1 is printed containing the dye Reactive Blue 19 with the C.I. 61200. The further processing of the pressure in order to Dye fixation and completion takes place as in the previous examples.

You get on the goods a yellow print with good Fastness next to one of blue color.

In all examples, besides the cited Reactive printing paste even more reactive pastes than Illustration colors are printed.

Likewise it is possible, also still further C. I. Diazo Components to print when the preparation of the according to the invention measures are observed.

Claims (8)

1. Single-phase process for the preparation of prints on previously primed with coupling components under alkaline conditions, cellulosic or consisting solely of cellulose fibers textiles by separate overprinting with reactive dyes in addition to primary aromatic amines with the addition of sodium nitrite and in the presence of acid or acid-supplying substances produced by diazotizing, directly coupling diazonium compounds with simultaneous development of water-insoluble azo dyes due to spontaneous coupling, and subsequent to the drying of these prints held fixation of the reactive dyes by steaming, characterized in that in the diazotization of the printed amines as the sole acid-acting agent either during the drying process in the water vapor at the fixing operation volatile acids and optionally for buffering the printing pastes with the diazonium compounds only water-soluble Sal ze of such acids. 2. The method according to claim 1, characterized in that the diazotization of the amine and the buffering of the Diazonium compound is carried out in aqueous solution and that this solution is thickened directly for printing. 3. The method according to claim 1, characterized in that the diazotization by union of a first Thickening containing sodium nitrite, with a further thickening takes place, which does not contains steam-volatile acid, wherein the amine of a the two thickenings, preferably with the Nitrite, is mixed.   4. The method according to claim 1, characterized in that into a thickened solution of sodium nitrite first stirred in finely divided primary aromatic amine and then the non-steam-volatile acid, the latter then possibly still buffered. 5. The method according to one or more of claims 1 to 4, characterized in that one as not steam-volatile acid for diazotizing glycolic acid, Citric acid, tartaric acid, oxalic acid, sulfuric acid, but preferably used phosphoric acid. 6. The method according to one or more of claims 1 to 4, characterized in that as acid for Diazotize hydrochloric acid and then use this tertiary or secondary sodium salts of Phosphoric acid buffered. 7. The method according to one or more of claims 1 to 6, characterized in that the reactive dye having printing pastes on neutral reaction are set. 8. The method according to one or more of claims 1 to 7, characterized in that after printing and Drying the prints the goods to fix the Reactive dyes for 6 to 8 minutes at 100 ° to 105 ° C. dampens, wherein the excess alkali of the Naphthol primer for fixing the reactive dyes is being used.