EP0107016A2 - Process for printing textile material - Google Patents

Abstract

By using water-repellent emulsions based on paraffin and/or polyorganosiloxanes in the preprinted resist it is possible to effect the preparation of white and coloured discharge resist effects on differently coloured grounds on synthetic fibre textile sheet materials with alkali-dischargeable disperse dyes by the energy-saving wet-on-wet technique. The novel process can also be used with advantage on polyester and cellulose or wool blend fabrics, in which case the diversity of design options can be increased still further by including reactive dyes. In addition, the crispness of the prints is significantly improved when, after the resists have been applied, the water-repellent emulsion is destroyed by adding sulphates or phosphates to the overprinting colour applied in the second phase.

Description

The present invention relates to an improved process for the etching reserve printing on textile goods made of purely synthetic fibers or fiber mixtures of these with those of natural origin; in particular, it is the creation of white or colored patterns on a different colored background of articles that have been treated according to the methods that are common in this field.

In accordance with conventional working practices, the production of etching reserves on hydrophobic fiber material, such as polyester fibers, or on mixtures thereof with other fibers, such as preferably polyester / cellulose fiber mixtures, has hitherto mainly been done by padding or, where appropriate, printing the etchable dyes on the web and, in a separate step, overprinting the pre-colored fund with an etching reserve paste, whereby the two application measures can also be carried out in reverse order. Subsequent heat treatment of the goods then, on the one hand, causes the unfixed base dye to be partially destroyed by the etching print, and on the other hand fixes the remaining, unaffected base dyeing and, if necessary, also the colored parts in the same work process. In this way, depending on the composition of the etching reserve paste on a colored background, white effects and - if the etching also contains an addition of etch-resistant dye - color effects in contrasting colors to the etching base can be achieved. In addition to reductive etching reserves, alkaline substances can be considered for the localized destruction of the dyes on polyester fibers. Such processes using the alkali sensitivity of certain disperse dyes are described, for example, in DE-PS 28 36 391, DE-OS 28 56 283, DE-OS 26 12 740, DE-OS 26 12 742, DE-OS 26 12 790, DE-OS 26 12 791 and DE-OS 26 12 792 are described; in the case of fiber blends with cotton - as is also shown in part in this literature - the inclusion of reactive dyes in such processes can further expand the range of coloring options.

All of the previously explained process variants of this type include drying the textile material between the two application measures, which, because of the time required for this and the additional costs caused by the additional energy consumption, must be perceived as disadvantageous for the economy of this patterning.

A certain further development of the alkaline etching reserve technology for polyester fibers in the direction of an energy-saving process is known from GB-OS 2 071 708, in addition to the chemical and the simultaneously occurring mechanical reserve effect of water glass with a specific composition corresponding to the molar ratio of Na ₂ 0: SiO ₂ or K ₂ 0: SiO ₂ is used and, when coloring the fund, not only avoids the comparatively cumbersome pre-padding of the goods on the foulard, but can also dispense with intermediate drying. This procedure has the advantage that the entire process can be carried out in one operation on the printing press. The usual alkaline etching reserves based on a purely chemical mode of action, such as NaOH, Na ₂ CO ₃ , NaHCO ₃ , K2C03 and the like, are unsuitable for such a project for wet-in-wet product application, since they occur in the course of bleed the final drying or fixing step out of the printed reserve paste and lead to blurred, washed out contours. The reasons why the water glass variant is not yet practiced on a large scale are difficult in choosing a suitable thickening. By adding water glass, the viscosity of the printing ink drops sharply. The stencils are also added more quickly. After all, it is difficult to meet the requirements of many assemblers for etched floors that are the same on both sides.

In a continuation of the efforts to remedy the difficulties in the production of etching reserves using the more cost-effective wet-on-wet technique on exclusively or predominantly synthetic fibers, where, due to their water-repellent nature, the problems with regard to slipping of the pattern outlines have become particularly serious, has now surprisingly been found that one can carry out pre-pressure reserves with much better contour sharpness in the form that, instead of water glass, an emulsion based on paraffin-zirconium salt and / or an emulsion based on polysiloxane is used as the reservation agent, to which one may also add highly disperse silicon dioxide.

The present invention relates to the production of etching reserve effects on the colored background of textile fabrics, which consist of or contain hydrophobic synthetic fibers, by printing a printing paste, which contains an alkaline etching or reservation agent, in the desired pattern on the undyed web, then - without intermediate drying - overprinting or padding or spraying this pre-printed, not yet fixed pattern in a separate sequence, overlapping with one or more different, aqueous printing pastes or an aqueous dyeing liquor which, in addition to conventional printing or dyeing aids, also etches at least one alkali - or reserve disperse dye, followed by heat on the textile treated in this way material at temperatures of 100 ° to 230 ° C. and then washing out of unfixed dye and auxiliary residues, characterized in that an aqueous printing paste is used as the pre-pressure reserve, which, in addition to alkaline agents or alkali donors, as well as usual thickening and other printing aids, is also used contains water-repellent emulsion based on paraffin and / or polyorganosiloxanes, optionally in a mixture with highly disperse silicon dioxide.

Due to the mechanical reserve effect of the hydrophobizing substances present in the alkaline form paste, it is possible according to the invention to develop flawless etching reserve patterns using the wet-on-wet technique. For the functioning of the claimed patterning, it is irrelevant whether the background is produced by overprinting or by padding or spraying with the alkali-sensitive dyes. Under the conditions mentioned, the influence of dry or moist heat on the textile web leads to the formation of sharply delimited white effects in those areas of the goods where the alkali of the etching reserve is in contact with the etchable disperse dye and no coloring is provided.

If, on the other hand, you want to achieve colored effects within the basic tone, then one or more disperse dyes which are resistant to the action of the alkali are added to the otherwise dye-free form paste with the reservation agents mentioned for illumination. For the same purpose, disperse dyes with the same behavior can alternatively also be mixed with the etchable disperse dyes used for tinting the fund, but in such a way If the shade of the etched base is derived from a combination of both types of dye.

It is also quite conceivable within the scope of the inventive efforts for patterning to pre-print several reserve pastes of different composition with regard to the possible dye content in order to produce white and colored effects and / or colorful effects with different hues on the differently colored background.

The heat treatment to which the textile goods are subjected after the pre-printing of the reserve and the subsequent application of the background dyeing can be done by briefly applying dry heat at temperatures between 150 ° and 220 ° C. However, it is preferred to keep the goods exposed to steam, e.g. Submit saturated steam at about 100 ° C for a few minutes, followed by further treatment with hot air as a heat carrier at 160 ° to 220 ° C, or with superheated steam at 150 ° to 200 ° C, or with pressurized steam at 115 ° to 150 ° C.

After the heat exposure measures, which result in the destruction of the alkali-sensitive disperse dyes at the areas printed with the caustic reserve paste and a fixation of the disperse dyes applied as base dye, the textiles are first washed with cold water in the manner customary for polyester dyeings, then treated with an aqueous liquor with the addition of 0.2% of a nonionic detergent at 50 ° to 85 ° C, rinsed again with water at 60 ° C and again with cold water and finally dried.

According to the process, all textile fabrics, in particular woven or knitted fabrics, made of synthetic fibers with a hydrophobic character come from disperse dyes dyeable materials in question, especially from fibers of linear aromatic polyester such as polyethylene glycol terephthalate, furthermore from cellulose triacetate, cellulose-2 1/2 acetate and polyamide fibers. Textile based on mixtures of these synthetic fibers with fibers of natural origin, preferably native or regenerated cellulose, but also wool, in all mixing ratios customary in practice is also useful; primarily mixed. materials made of polyester fibers and cotton.

For the production of fund dyeings and colored etchings using the process of the present invention, the dispersions used are the compounds known under this term and suitable for application to the synthetic fibers described above, for example those described in the COLOR INDEX, 3rd edition 1971 and additions in 1975 be listed under the generic name "Disperse Dyes".

Disperse dyes for producing the base coloring which can be etched in pure white with alkaline agents are, for example, in DE-OS 26 12 740, DE-OS 26 12 742, DE-OS 26 12 790, DE-OS 26 12 791, DE-OS 26 12 792, DE-OS 26 33 910, DE-PS 28 36 391, DE-OS 28 56 283, DE-OS 30 19 739, DE-OS 30 35 912, GB-OS 2 071 708 and in RESEARCH DISCLOSURE, October 1980 described under RD 198 026 and RD 198 027. These include azo and anthraquinone dyes, which can be converted into a water-soluble form when treated with alkaline agents, especially at elevated temperatures. The alkali solubility of these naturally water-insoluble dyes is caused by functional groups on the dye molecule, for example one or more carboxy groups, preferably esterified by alkyl, phenolic or enolic hydroxyl groups or a combination of such groups. Under the action of alkalis at the points printed with the reserve paste, for example, these ester groups are saponified during steaming and converted into the alkali salts of the underlying carboxylic acids. In their anionic form, the disperse dyes then no longer absorb and can no longer penetrate the hydrophobic fiber when thermosolated. This subheading also includes disperse azo dyes without carboxylic ester groups which have a heterocyclic ring system, such as nitro-thiazole or pyridone, which can be cleaved under alkaline conditions and whose cleavage products are easy to eliminate. In these two cases, such non-fixed, water-soluble dye residues can be removed from the textile material again by simple washing treatment, and the printed area remains colorless after washing.

Disperse dyes that are resistant to the alkaline etching reserve, which can be combined with the alkaline-etchable dispersion dyes of the base color or mixed with the form paste to produce multicolored designs, are the well-known commercial dyes from the class of azo or azomethine, anthraquinone, quinophthalone or nitro compounds, which are free from sulfonic acid, carboxylic acid or carboxylic ester groups. Some examples of alkali-stable disperse dyes are explained in DE-PS 28 38 391, DE-OS 28 56 283 and GB-OS 2 071 708.

The aforementioned etchable and etch-resistant dyes are in finely dispersed form in the liquors or printing inks to be used according to the process. The dye preparations are prepared in a manner known per se by mixing the liquor or printing paste components with the necessary amount of water and liquid finely dispersed or solid redispersible formulations of the disperse dyes listed above.

The pre-printing pastes to be used in carrying out the process according to the invention which, as mechanical reserve, contain a water-repellent emulsion based on paraffin and / or polyorganosiloxanes, for example wax-paraffin emulsions containing metal salts, especially zirconium salts or aluminum salts, or, for example, emulsions of chemically inactive silicones such as industrial silicone oils which are composed mostly of linear dimethylsiloxanes or methyl, and optionally comprise colloidal silicon dioxide is included as actual etch resist whose effectiveness is based on purely chemical function that bases on an inorganic or organic basis and having a _pH value in aqueous solution allow setting of at least 8 and have no reducing properties, such as aqueous solutions of fixed alkalis, for example alkali or alkaline earth metal hydroxides, preferably NaOH or KOH, and / or salts which have an alkaline reaction in water, for example alkali metal carbon ate or bicarbonates, primarily Na ₂ CO ₃ , K ₂ CO ₃ or NaHCO ₃ , as well as alkali donors that are effective in the heat or in steaming, such as sodium trichloroacetate. Finally, alkali sulfites or alkali bisulfites in combination with an alkali carbonate or alkali bicarbonate and optionally an aldehyde, expediently in the form of a prefabricated aldehyde-alkali bisulfite adduct, which themselves do not show any reducing properties compared to the alkali-sensitive dispersion dyes, are of particular interest for the claimed process as a chemical etching reserve and neither can reductively attack and destroy any azochromophore that may be present, nor can it reduce quinoid chromophores to colorless, alkali-soluble leuco form. In the case of white etching, the effect of the alkali or alkali donor can be enhanced with the new wet-on-wet method, however, if the reductin agents common in this field, such as zinc formaldehyde sulfoxylate, are present in the form paste.

In addition to the above-mentioned etching and preserving agents of both types (alkaline and reductive), the usual additives required for textile printing are present in the pre-printing pastes. Practically all thickeners that are resistant to the alkaline constituents of the etching reserve paste have proven themselves for the present task, in particular thickeners based on plants, such as e.g. highly viscous alginates, kernel meal derivatives, starch products, guar ethers etc. or mixtures thereof, and / or synthetic, polymeric thickeners, advantageously in combination with hydrotropic substances, for example urea or glycol. The presence of nonionic detergents is particularly favorable for the etching process. As such e.g. Glycerol and / or polyglycols, such as polyethylene glycol with an average molecular weight of 200 to 400, are used. While polyglycol acts as an etching enhancer (solubilizer) in this context, the use of a hygroscope, e.g. Glycerin, indispensable in the etching reserve paste, especially when fixing with hot air; A little glycerin is also generally added for fixation in the high-temperature damper.

In order to facilitate the washing out of thickeners based on natural products, as are common in practice in mineral oil-free printing pastes, it has proven to be advantageous to use a part of such difficult-to-wash out thickeners against polyoxalkylates, e.g. Alkyloxypropylates, advantageous to exchange reaction products from alkanols and propylene oxide without the pressure of the pressure thereby suffering. In addition, in such printing pastes, especially if the intention is to produce colored etchings, there should also be esterification products of higher molecular weight polyglycols with higher alkane or alkenecarboxylic acids, which has an advantageous effect on the quality of the product appearance.

According to the present invention, it is predominantly the rule to print the etched bottoms in the last hand after applying the etching reserve (possibly including the chromatic colors). Almost exclusively aqueous overprinting pastes are used for this purpose, which, in addition to the alkali-destructible disperse dyes (and possibly alkali-stable disperse dyes), have low-viscosity alginates, locust bean gum or guar derivatives as a thickening agent, because this means that the cover area is covered faster and more evenly than with highly viscous thickeners the design is guaranteed. It is generally not necessary to add oxidizing agents when using the alkaline etching reserve; it is sufficient if an optionally weak, fixed organic acid, such as e.g. Citric or tartaric acid, or acidic salts such as e.g. Monosodium phosphate are present in order to prevent the dyes from reacting prematurely with the etching reserve during the production process. In certain cases, however, it will be maintained to protect the etching trays against over-coating during the printing process or stains in the damper by adding oxidizing agents such as sodium chlorate, m-nitrobenzenesulfonate or a mixture of the latter two products, as well as to to eliminate a possible reduction in the color yield due to the thickening during the steaming process. In addition, the additives which are customary in textile printing on polyester fibers or mixtures thereof with other types of fibers, such as carriers, fixing accelerators, leveling agents, dispersants and / or defoamers, can be present in the overprint pastes.

The application of the pre- and overprint inks to the textile material can be carried out using all known printing processes, e.g. in rouleaux printing, film printing, rotatin film printing, etc.

However, if the fund colors are to be produced on the padder, then the acidic, aqueous medium is usually used in the padding liquors without the addition of oxidizing agents. Occasionally there may be cases where the presence of oxidizing agents may be required in addition to citric acid. ; Padding liquor in addition to the dye, small amounts of thickening agents and / or an anti-migration agent, as well as conventional, already mentioned in the enumeration of the components of overpressure paste aids ^- Finally, such contains in the treatment of knitted fabrics, a low-foaming wetting agent is advantageously added.

As has been found in the course of the procedure described above, a significant improvement in the etching effect can be achieved even with difficult to etch base dyes if water-soluble sulfates or phosphates are added to the base colors. Especially in the case of deep black tones, the often objectionable brownish runout of fine contours is reduced in this way.

The process-related addition of sulfates or phosphates to the base color primarily has the purpose of destroying the paraffin-zirconium salt emulsion of the white and colored reserves during the subsequent application of the background coloring by overprinting or padding. Depending on the product used, this process of destruction is manifested either in an increase or a decrease in the viscosity of the emulsion paints. This creates a layer of changed viscosity on the surface of the reserves, which during the short time section until the material web treated in this way enters the dry mansard prevents intensive mixing of the reserve and the base color. At temperatures above 110 ° C, the mansard then begins to develop the hydrophobic effect of the paraffin compound, and the base colors are destroyed by the alkali of the white and colored reserves. Eserven the concomitant use of silica in the _R most if unnecessary under the circumstances.

The addition of. In addition, sulfates or phosphates for the base color pursue the purpose of starting gelation of the base colors and thereby bring about a better contour level of the prints. Depending on the pressure thickening used and the existing water hardness, the gelling can be so strong that the colors are no longer printable. These printing inks can be made usable again by adding small amounts of a polyphosphate.

Among the sulfates for use in the process according to the invention are: Zinc sulfate, sodium sulfate and ammonium sulfate, as the phosphates, calcium hydrogen phosphate and sodium phosphates. The amounts used of these substances are 5 to 50 g / kg of the overprinting ink or padding liquor. Here, the viscosity of the water-repellent emulsions is significantly reduced by zinc sulfate, likewise - if not to the same extent - by sodium sulfate, while a slight increase is caused by ammonium sulfate, and a greater increase in the viscosity of the emulsions mentioned in the form reserve by calcium hydrogen phosphate.

The new process is significantly enriched by the fact that, in the course of treating polyester / cellulose fiber mixtures, in addition to disperse dyes for coloring the polyester portion of the mixture, alkaline fixable reactive dyes for the cellulose component are also included in the patterning process according to the invention and in the Achieving the etching reserve effects - both as a white and as a colored pattern on a different colored background - can actively participate. Taking advantage of the different reactivity of reactive systems of such dyes reacting according to the addition and substitution mechanism with respect to cellulose, the generation of reserve effects on the cellulose portion with reactive dyes and reactive dyes can thus be seamlessly integrated into the process measures according to the present invention and thus combined.

In such a case, in addition to the alkali-etchable or reservable disperse dyes, those alkaline-fixable reactive dyes are also used for the base coloring which, due to the effect of the reserve, form a nucleophilic Binding with the cellulose fiber are prevented. Reactive dyes of this type possess the ß-haloethylsulfone group as a reactive radical one or more times, but preferably the ß-sulfatoethylsulfone or ß-sulfatoethylsulfonamide group, which, when normal dyeing conditions exist, under the influence of alkali with the fiber via the intermediate vinyl sulfone -Rest in the sense of an addition occurs in reaction. In this connection, sulfite compounds, such as stabilized sodium bisulfite, but especially the aldehyde-bisulfite addition products already mentioned above, can be used as chemical reserves, which result in perfect white reserves.

• - Der Reaktivfarbstoff wird an den mit der Reserve bedruckten Stellen durch das Alkali vollständig in die Vinylsulfon-Form umgesetzt;
• - Vom aufgedruckten Reservierungsmittel wird Sulfit freigesetzt und dieses lagert sich an die Doppelbindung des Vinylsulfon-Farbstoffes an;
• - Durch diese Sulfit-Anlagerung wird die Vinylsulfon-Gruppe für die Additionsreaktion mit der Cellulose blockiert.

If reactive dyes of the type defined above are now overprinted, padded or sprayed onto a form with such a reservation agent as a fund, the following reactions take place in the course of the subsequent heat or steam treatment:

• - The reactive dye is completely converted into the vinyl sulfone form at the points printed with the reserve by the alkali;
• - Sulfite is released from the printed reservation agent and this attaches to the double bond of the vinyl sulfone dye;
• - This sulfite attachment blocks the vinyl sulfone group for the addition reaction with the cellulose.

Simultaneously with the reactivity of the reactive anchor being prevented by the reservation agent just discussed, due to its alkalinity during the heat treatment, the etching of the disperse dye on the polyester component of the fiber mixture takes place at the points on the form.

• Am besten eignen sich hierfür die zweistufigen Arbeitsweisen; es bieten sich besonders das Zweiphasen-Blitzdämpf-Verfahren oder das Zweiphasen-Kaltverweil-Verfahren an, welche sich jeweils an den Thermosolierprozeß bzw. das HT-Dämpfen zur Fixierung der Dispersionsfarbstoffe anschließen. Dadurch werden ideale Bedingungen für die Fixierung der Dispersionsfarbstoffe erhalten: Man kann in schwach saurem Bereich arbeiten und muß keine vorzeitige Reaktionen mit dem Reaktivfarbstoff befürchten.

The reactive dyes of the vinyl sulfone type present in the base color can be fixed in a manner known per se in various ways:

• The two-stage working methods are best suited for this; the two-phase flash damping method or the two-phase cold residence method are particularly suitable, each of which follows the thermal insulation process or HT steaming for fixing the disperse dyes. This results in ideal conditions for fixing the disperse dyes: one can work in a weakly acidic range and there is no need to fear premature reactions with the reactive dye.

Likewise, the vinyl sulfone dyes can also be fixed by the single-phase process, by using neutral fixing aids, such as alkali or alkaline earth metal salts of low molecular weight, aliphatic or aromatic mono- or polycarboxylic acids, especially polyhalogenated aliphatic carboxylic acids, e.g. an alkali metal formate are added, which has the effect that the chemical bonding of the reactive reactive dye with the cellulose already occurs in the course of the heat treatment for fixing the disperse dyes as a result of the successive release of alkali from these substances.

Color effects, on the other hand, are achieved with reactive dyes that are largely insensitive to the sulfite compounds mentioned; they can either be pre-printed together with these as a color reserve or can also be added to the background color of the overprint. For color reserves with good printing paste stability, reactive dyes come into consideration, which as the reactive group have the chloraminotriazine, dichloropyrimidine, trichloropyrimidine, dichlorotriazine, monochlorotriazine, quaternized chlorotriazine or dichloropyridazine group and which have a nucleophile with substitution with the cellulose.

Reactive dyes of the two types of different behavior are listed in COLOR INDEX, 3rd edition 1971 and additions in 1975 under the generic name "Reactive Dyes".

The claimed method therefore also extends to the fashionable design and colorful coloring of polyester / cellulose fiber mixtures with the production of white and / or colored etching and / or reserve effects on a differently colored background, which is more targeted when using disperse and reactive dyes Utilization of the substance-specific behavior of both types of dye, the fiber components and the etching reserve succeed. If one now uses sulfite ion-forming compounds as a chemical reserve in the context of the other measures according to the invention for patterning, then the heat treatment provided after the wet-on-wet application of reserve and base color effects

a) at the points printed with the reserve paste, an inhibition of the reservable disperse and reactive dyes and a fixation of the possibly non-reservable dispersion and reactive dyes, b) at the points not printed with the reserve paste, a fixation of the dispersion dyes and - if the printing ink or Padding liquor for the bottom coloring has contained an alkali metal formate - also at the same time the reactive dyes. Inhibition of the dye is understood here to mean the change in the dye molecule caused by the reservation agent, which leads to the dye in question no longer staining the substrate. In the two-phase process, ie if the printing ink or pad liquor for the fund did not contain any alkali formate
the fixation of the reactive dyes in the fund coloring, ie at the areas not printed with reserve paste, then.

The amounts of the dyes contained in the printing inks or padding liquors to be used for the fund according to the invention are, as usual, matched to the depth of color of the desired color and intensity of the reserve effect. In addition, the amount of dyes suitable for one of the fiber types involved also corresponds to the mass fraction of this fiber type in the total fiber mass of the mixture. For example, a printing ink or pad liquor, which is prepared for a base color of a certain shade, contains a high proportion of etchable and possibly non-etchable reactive dyes and a low proportion of etchable and possibly non-etchable disperse dyes in the case that the substrate predominantly contains cellulose fibers, and im If the substrate contains predominantly polyester fibers, a high proportion of the disperse dyes and a low proportion of the reactive dyes.

The method according to the invention is primarily intended for the finishing of textiles made of cellulose polyester fibers. However, the quantity ratio of the two types of fibers is not subject to any restrictions when taking into account the criteria given above for the composition of the padding liquor, and in the limit case, the process can also be used to produce reserve effects on pure cellulose textiles or pure polyester textiles, in which case the padding liquors are exclusively etchable and optionally contain non-etchable reactive dyes or exclusively etchable and optionally non-etchable disperse dyes.

It is particularly advantageous to carry out the measures according to the invention using sulfates or phosphates for the base color for the design of sensitive fabric qualities, such as are present in the case of mixed materials made of polyester fibers and wool; these are optionally carried out with the addition of a commercially available fixing accelerator. The additional use of a commercially available reducing agent based on sulfoxylate in the etching reserve paste and / or the additional use of a reactive dye in the base color has also proven to be advantageous.

The percentages given in the examples below mean percentages by weight.

example 1

• 400 Gewichtsteilen einer 15%igen,wäßrigen Lösung einer Verdickermischung aus einem nichtionischen Guarderivat und Carboxymethylstärke,
• 20 Gewichtsteilen einer 10%igen, wäßrigen Lösung eines Veresterungsproduktes aus Polyethylenglykol mit einem Molgewicht von etwa 2000 und 1 Mol Stearinsäure,
• 60 Gewichtsteilen eines Umsetzungsproduktes von 1 Mol n-Butanol mit' 35 Mol 1,2-Propylenoxid,
• 120 Gewichtsteilen einer 50%igen, wäßrigen Lösung von trichloressigsaurem Natrium,
• 30 Gewichtsteilen Glyoxalbisulfit-monohydrat,
• 40 Gewichtsteilen Polyethylenglykol mit einem Molgewicht von etwa 400,
• 100 Gewichtsteilen einer 50%igen,wäßrigen Emulsion eines flüssigen Polyorganosiloxans,
• 10 Gewichtsteilen hochdispersem Siliciumdioxid,
• 25 Gewichtsteilen der Handelsform des Farbstoffes Disperse Yellow 199 (ätzbeständig),
• 30 Gewichtsteilen der Handelsform des Farbstoffes Reactive Yellow 95 (reservebeständig),
• 10 Gewichtsteilen m-nitrobenzolsulfonsaurem Natrium,
• 80 Gewichtsteilen Harnstoff und
• 75 Gewichtsteilen Wasser
• 1000 Gewichtsteile, wird auf der Rotationsfilmdruckmaschine mittels einer mustergemäßen Schablone ein Mischgewebe aus Polyesterfaser und Baumwolle im Verhältnis 65:35 bedruckt.

With an etching reserve paste consisting of

• 400 parts by weight of a 15% strength aqueous solution of a thickener mixture composed of a nonionic guar derivative and carboxymethyl starch,
• 20 parts by weight of a 10% strength aqueous solution of an esterification product made of polyethylene glycol with a molecular weight of about 2000 and 1 mole of stearic acid,
• 60 parts by weight of a reaction product of 1 mol of n-butanol with '35 mol of 1,2-propylene oxide,
• 120 parts by weight of a 50% strength aqueous solution of trichloroacetic acid sodium,
• 30 parts by weight of glyoxal bisulfite monohydrate,
• 40 parts by weight of polyethylene glycol with a molecular weight of about 400,
• 100 parts by weight of a 50% aqueous emulsion of a liquid polyorganosiloxane,
• 10 parts by weight of highly disperse silicon dioxide,
• 25 parts by weight of the commercial form of the dye Disperse Yellow 199 (resistant to etching),
• 30 parts by weight of the commercial form of the dye Reactive Yellow 95 (reserve-resistant),
• 10 parts by weight of sodium m-nitrobenzenesulfonate,
• 80 parts by weight of urea and
• 75 parts by weight of water
• 1000 parts by weight, a mixed fabric of polyester fiber and cotton is printed in a ratio of 65:35 on the rotary film printing machine using a sample template.

• 60 Gewichtsteile der Handelsform des Farbstoffes Disperse Blue 96 (ätzbar),
• 60 Gewichtsteile der Handelsform des Farbstoffes Reactive Blue 122 (reservierbar),
• 417 Gewichtsteile Wasser,
• 450 Gewichtsteile einer 10%igen, wäßrigen Lösung eines Natriumalginats,
• 10 Gewichtsteile m-nitrobenzolsulfonsaures Natrium und 3 Gewichtsteile Zitronensäure

1000 Gewichtsteile.Immediately afterwards, the pre-printed etching reserve is overprinted without any intermediate drying using a blind stencil with a base color that has the following composition:

• 60 parts by weight of the commercial form of the dye Disperse Blue 96 (etchable),
• 60 parts by weight of the commercial form of the reactive blue 122 dye (can be reserved),
• 417 parts by weight of water,
• 450 parts by weight of a 10% aqueous solution of sodium alginate,
• 10 parts by weight of sodium m-nitrobenzenesulfonate and 3 parts by weight of citric acid

1000 parts by weight.

The goods treated in this way are then dried immediately and first steamed in a high-temperature steamer at 175 ° C. for 7 minutes; the disperse dyes of the etching reserve and the base color as well as the reactive dye of the colored reserve are fixed. The fabric is then padded with water glass at 48 - 50 ° Bé and left to stand at room temperature for 6 hours; During this dwell time, the reactive dye portion of the base color is fixed, except at the points on the pre-printed sample where there is no fixation due to the reserve effect.

To complete the design, the mixed fabric is rinsed cold with water, then treated in succession with aqueous baths with the addition of 2 g / 1 of an aid based on fatty acid polyglycol ester in the compartments of a wide-area washing machine at temperatures of 40 °, 60 ° and 80 ° C, again with water rinsed and finally dried.

You get a yellow print on a blue fund.

Example 2

• 400 Gewichtsteile einer 15%igen,wäßrigen Lösung einer Verdickermischung aus einem nichtionischen Guarderivat und Carboxymethylstärke,
• 20 Gewichtsteile einer 10%igen, wäßrigen Lösung eines Veresterungsproduktes aus Polyethylenglykol mit einem Molgewicht von etwa 2000 und 1 Mol Stearinsäure,
• 60 Gewichtsteile des Umsetzungsproduktes aus n-Butanol und Propylenoxid aus Beispiel 1,
• 120 Gewichtsteile einer 50%igen, wäßrigen Lösung von trichloressigsaurem Natrium,
• 30 Gewichtsteile Glyoxalbisulfit-monohydrat,
• 40 Gewichtsteile Polyethylenglykol mit einem Molgewicht von etwa 400,
• 100 Gewichtsteile einer 50%igen,wäßrigen Paraffin-Zirkonsalz-Emulsion,
• 10 Gewichtsteile hochdisperses Siliciumdioxid,
• 25 Gewichtsteile der Handelsform des Farbstoffes Disperse Red 132 (ätzbeständig),
• 30 Gewichtsteile der Handelsform des Farbstoffes Reactive Red 58 (reservebeständig),
• 10 Gewichtsteile m-nitrobenzolsulfonsaures Natrium,
• 80 Gewichtsteile Harnstoff und
• 75 Gewichtsteile Wasser 1000 Gewichtsteile.

A knitted fabric made from a mixture (70:30) of polyester fibers and leached cellulose is printed in rouleaux by means of a printing roller engraved according to the pattern printed with an etching reserve paste, which contains the following components per kg:

• 400 parts by weight of a 15% strength aqueous solution of a thickener mixture composed of a nonionic guar derivative and carboxymethyl starch,
• 20 parts by weight of a 10% strength aqueous solution of an esterification product made of polyethylene glycol with a molecular weight of about 2000 and 1 mole of stearic acid,
• 60 parts by weight of the reaction product of n-butanol and propylene oxide from Example 1,
• 120 parts by weight of a 50% strength aqueous solution of trichloroacetic acid sodium,
• 30 parts by weight of glyoxal bisulfite monohydrate,
• 40 parts by weight of polyethylene glycol with a molecular weight of about 400,
• 100 parts by weight of a 50% aqueous paraffin-zirconium salt emulsion,
• 10 parts by weight of highly disperse silicon dioxide,
• 25 parts by weight of the commercial form of the dye Disperse Red 132 (corrosion-resistant),
• 30 parts by weight of the commercial form of the reactive red 58 dye (reserve-resistant),
• 10 parts by weight of sodium m-nitrobenzenesulfonate,
• 80 parts by weight of urea and
• 75 parts by weight of water 1000 parts by weight.

A base ink corresponding to the composition of Example 1 is overprinted wet-on-wet by means of a decker roller, and the printing effects thus produced are fixed and washed as indicated there.

After drying you get a red print on a blue background.

Example 3

• 400 Gewichtsteile einer 15%igen, wäßrigen Lösung einer Verdickermischung aus einem nichtionischen Guarderivat und Carboxymethylstärke,
• 20 Gewichtsteile einer 10%igen, wäßrigen Lösung eines Veresterungsproduktes aus Polyethylenglykol mit einem Molgewicht von etwa 2000 und 1 Mol Stearinsäure,
• 60 Gewichtsteile eines Umsetzungsproduktes von 1 Mol t-Butanol mit 40 Mol 1,2-Propylenoxid,
• 120 Gewichtsteile einer 50%igen, wäßrigen Lösung von trichloressigsaurem Natrium,
• 30 Gewichtsteile Glyoxalbisulfit-monohydrat, 40 Gewichtsteile Polyethylenglykol mit einem Molgewicht von etwa 400,
• 100 Gewichtsteile einer 50%igen, wäßrigen Emulsion eines flüssigen Polyorganosiloxans,
• 10 Gewichtsteile hochdisperses Siliciumdioxid,
• 40 Gewichtsteile der Handelsform des Farbstoffes Disperse Blue 73 (ätzbeständig),
• 30 Gewichtsteile der Handelsform des Farbstoffes Reactive Blue 187 (reservebeständig),
• 10 Gewichtsteile m-nitrobenzolsulfonsaures Natrium,
• 80 Gewichtsteile Harnstoff und
• 60 Gewichtsteile Wasser
• 1000 Gewichtsteile.

An etching reserve paste, which has the following composition, is applied to a blended fabric made of polyester fibers / mercerized cotton (50:50) by means of a sample film printing stencil:

• 400 parts by weight of a 15% strength aqueous solution of a thickener mixture composed of a nonionic guar derivative and carboxymethyl starch,
• 20 parts by weight of a 10% strength aqueous solution of an esterification product made of polyethylene glycol with a molecular weight of about 2000 and 1 mole of stearic acid,
• 60 parts by weight of a reaction product of 1 mol of t-butanol with 40 mol of 1,2-propylene oxide,
• 120 parts by weight of a 50% strength aqueous solution of trichloroacetic acid sodium,
• 30 parts by weight of glyoxal bisulfite monohydrate, 40 parts by weight of polyethylene glycol with a molecular weight of about 400,
• 100 parts by weight of a 50% aqueous emulsion of a liquid polyorganosiloxane,
• 10 parts by weight of highly disperse silicon dioxide,
• 40 parts by weight of the commercial form of the dye Disperse Blue 73 (corrosion-resistant),
• 30 parts by weight of the commercial form of the dye Reactive Blue 187 (reserve-resistant),
• 10 parts by weight of sodium m-nitrobenzenesulfonate,
• 80 parts by weight of urea and
• 60 parts by weight of water
• 1000 parts by weight.

• 35 Gewichtsteile des durch Kuppeln von diazotiertem 3-Nitro-4-amino-anisol mit 2,6-Dihydroxy-3-cyan-4-methyl-pyridin entsprechend Beispiel 1 der DE-PS 1 544 446 hergestellten Dispersionsfarbstoffes (ätzbar),
• 25 Gewichtsteile des durch Kuppeln von diazotierter 1-Amino-2,4-dimethoxy-benzol-5-sulfonsäure (Natriumsalz) mit 3-Methyl-1-(4'-B-hydroxyäthylsulfonyl)-phenyl-5-pyrazolon sowie Veresterung mit Schwefelsäure gemäß Beispiel 1 der DE-PS 24 31 343 hergestellten Reaktivfarbstoffes (reservierbar),
• 477 Gewichtsteile Wasser,
• 450 Gewichtsteile einer 10%igen, wäßrigen Lösung eines Natriumalginats,
• 10 Gewichtsteile m-nitrobenzolsulfonsaures Natrium und
• 3 Gewichtsteile Zitronensäure 1000 Gewichtsteile.

Without intermediate drying, a background color is overlapped in an overlapping manner on the pre-printed form that is still moist, and is structured as follows:

• 35 parts by weight of the disperse dye prepared by coupling diazotized 3-nitro-4-amino-anisole with 2,6-dihydroxy-3-cyan-4-methyl-pyridine according to Example 1 of DE-PS 1 544 446 (etchable),
• 25 parts by weight of the by coupling diazotized 1-amino-2,4-dimethoxy-benzene-5-sulfonic acid (sodium salt) with 3-methyl-1- (4'-B-hydroxyethylsulfonyl) phenyl-5-pyrazolone and esterification with sulfuric acid reactive dye prepared according to Example 1 of DE-PS 24 31 343 (can be reserved),
• 477 parts by weight of water,
• 450 parts by weight of a 10% aqueous solution of sodium alginate,
• 10 parts by weight of sodium m-nitrobenzenesulfonate and
• 3 parts by weight of citric acid 1000 parts by weight.

The textile material treated in this way is then dried and the etching reserves produced are fixed and aftertreated as indicated in Example 1.

You get a blue print on a golden yellow background.

Example 4

• 400 Gewichtsteilen einer 15%igen, wäßrigen Lösung einer Verdickermischung aus einem nichtionischen Guarderivat und Carboxymethylstärke,
• 20 Gewichtsteilen einer 10%igen, wäßrigen Lösung eines Veresterungsproduktes aus Polyethylenglykol mit einem Molgewicht von etwa 2000 und 1 Mol Stearinsäure,
• 60 Gewichtsteilendes Umsetzungsproduktes aus t-Butanol und Propylenoxid aus Beispiel 3,
• 60 Gewichtsteilen Natriumcarbonat,
• 30 GewichtsteilenGlyoxalbisulfit-monohydrat,
• 40 Gewichtsteilen Polyethylenglykol mit einem Molgewicht von etwa 400,
• 100 Gewichtsteilen einer 50%igen, wäßrigen Emulsion eines flüssigen Polyorganosiloxans,
• 10 Gewichtsteilen hochdispersem Siliciumdioxid,
• 100 Gewichtsteilen Zinkformaldehydsulfoxylat, 5 Gewichtsteilen eines optischen Aufhellers und
• 175 Gewichtsteilen Wasser
• 1000 Gewichtsteile,

auf einem Mischgewebe aus Polyesterfasern / Baumwolle (65 : 35) ein kleinflächiges Dessin aufgedruckt.Using a rotary film printing machine, using an etching reserve paste consisting of

• 400 parts by weight of a 15% strength aqueous solution of a thickener mixture composed of a nonionic guar derivative and carboxymethyl starch,
• 20 parts by weight of a 10% strength aqueous solution of an esterification product made of polyethylene glycol with a molecular weight of about 2000 and 1 mole of stearic acid,
• 60 parts by weight of the reaction product of t-butanol and propylene oxide from Example 3,
• 60 parts by weight of sodium carbonate,
• 30 parts by weight glyoxal bisulfite monohydrate,
• 40 parts by weight of polyethylene glycol with a molecular weight of about 400,
• 100 parts by weight of a 50% aqueous emulsion of a liquid polyorganosiloxane,
• 10 parts by weight of highly disperse silicon dioxide,
• 100 parts by weight of zinc formaldehyde sulfoxylate, 5 parts by weight of an optical brightener and
• 175 parts by weight of water
• 1000 parts by weight,

a small-area design is printed on a blended fabric made of polyester fibers / cotton (65: 35).

Immediately afterwards, this pre-printed pattern is overprinted over a large area without intermediate drying with the base color specified in Example 3, and the web thus treated is then dried.

Now that the disperse dye of the base color and the optical brightener of the reserve have been caused to fix by the action of moist heat on the textile material in the high-temperature steamer for 6 minutes at 180 ° C., the fiber material is then fixed in accordance with the method described in German Offenlegungsschrift DE-OS 31 47 318 explained methods using liquid spray heads, which rotate at about 5000 revolutions per minute, with a liquor absorption of 30% (based on the weight of the dry goods) sprayed with an alkaline fixing solution, which consists of
400 ml water glass from 38 - 40 ° Be, 150 ml sodium hydroxide solution from 50 ° Be and 450 ml water consists.

After spraying, the goods are wrapped in plastic wrap and left at room temperature overnight. In the course of this time, the reactive dye of the base color fixes by cold dwelling wherever it is not exposed to the influence of the reserve and is prevented from doing so. Finally, the pattern is post-treated and finished as indicated in Example 1.

You get white reserve effects on a golden yellow background.

Example 5

• In 530 Gewichtsteile kaltes Wasser werden
• • 50 Gewichtsteile einer Paraffin-Zirkonsalz-Emulsion und
  • 50 Gewichtsteile einer Verdickermischuna aus einem nichtionischen Guarderivat und Carboxymethylstärke eingerührt.

In film printing, a fabric made of polyester fibers is printed with an etching reserve paste, which is produced as follows:

• Be cold water in 530 parts by weight
• • 50 parts by weight of a paraffin-zirconium salt emulsion and
  • 50 parts by weight of a thickener mixture from a nonionic guar derivative and carboxymethyl starch were stirred in.

• 120 Gewichtsteile einer 50%igen, wäßrigen Lösung von trichloressigsaurem Natrium,
• 20 Gewichtsteile einer 10%igen, wäßrigen Lösung des Veresterungsproduktes von Polyethylenglykol mit einem Molgewicht von etwa 2000 und 1 Mol Stearinsäure,
• 60 Gewichtsteile des Umsetzungsproduktes aus n-Butanol und Propylenoxid gemäß Beispiel 1,
• 50 Gewichtsteile Glycerin,
• 50 Gewichtsteile Polyethylenglykol mit einem Molgewicht von etwa 400,
• 30 Gewichtsteile der Handelsform des Farbstoffes Disperse Red 200 (ätzbeständig),
• 30 Gewichtsteile der Handelsform des Farbstoffes Disperse Red 132 (ätzbeständig) und
• 10 Gewichtsteile hochdisperses Siliciumdioxid hinzu.

After thorough stirring, this approach is added

• 120 parts by weight of a 50% strength aqueous solution of trichloroacetic acid sodium,
• 20 parts by weight of a 10% strength aqueous solution of the esterification product of polyethylene glycol with a molecular weight of about 2000 and 1 mole of stearic acid,
• 60 parts by weight of the reaction product of n-butanol and propylene oxide according to Example 1,
• 50 parts by weight of glycerin,
• 50 parts by weight of polyethylene glycol with a molecular weight of about 400,
• 30 parts by weight of the commercial form of the dye Disperse Red 200 (resistant to etching),
• 30 parts by weight of the commercial form of the dye Disperse Red 132 (caustic) and
• Add 10 parts by weight of highly disperse silicon dioxide.

• 80 Gewichtsteile der Handelsform des Farbstoffes Disperse Blue 96 (ätzbar),
• 415 Gewichtsteile einer 10%igen, wäßrigen Lösung eines Natriumalginats,
• 5 Gewichtsteile Zitronensäure und
• 500 Gewichtsteile Wasser.

Immediately afterwards, a background color is printed on this form without intermediate drying and has the following composition:

• 80 parts by weight of the commercial form of the dye Disperse Blue 96 (etchable),
• 415 parts by weight of a 10% strength aqueous solution of sodium alginate,
• 5 parts by weight of citric acid and
• 500 parts by weight of water.

The fiber material treated in this way is then dried immediately and steamed in a high-temperature steamer at 175 ° C. for 7 minutes in order to fix the base color and the color reserve. The goods are then rinsed cold with water, reductively cleaned and aftertreated at 80 ° C. with an aqueous bath with the addition of an auxiliary based on fatty acid polyglycol ester. Finally, the pattern created is rinsed again with water and dried.

You get a sharp red reserve on a blue background.

Example 6

• In 717 Gewichtsteile kaltes Wasser werden
• • 50 Gewichtsteile einer Paraffin-Zirkonsalz-Emulsion,
  • 18 Gewichtsteile eines hochviskosen Alginats und
  • 100 Gewichtsteile Harnstoff eingerührt.

Using a roller engraved in accordance with the pattern, a fabric made of mercerized cotton is printed on the Rouleaux printing machine with a reserve paste which is produced as follows:

• Be cold water in 717 parts by weight
• • 50 parts by weight of a paraffin-zirconium salt emulsion,
  • 18 parts by weight of a highly viscous alginate and
  • 100 parts by weight of urea are stirred in.

• 30 Gewichtsteilen Natriumbicarbonat,
• 5 Gewichtsteilen m-nitrobenzolsulfonsaurem Natrium,
• 30 Gewichtsteilen Glyoxalbisulfit-monohydrat und
• 50 Gewichtsteilen der Handelsform des Farbstoffes
• Reactive Blue 159 (reservebeständig).

After thorough stirring, this mixture is added

• 30 parts by weight of sodium bicarbonate,
• 5 parts by weight of sodium m-nitrobenzenesulfonate,
• 30 parts by weight of glyoxal bisulfite monohydrate and
• 50 parts by weight of the commercial form of the dye
• Reactive Blue 159 (reserve-resistant).

• 450 Gewichtsteile einer 10%igen, wäßrigen Lösung eines Natriumalginats,
• 360 Gewichtsteile Wasser,
• 100 Gewichtsteile Harnstoff,
• 60 Gewichtsteile der Handelsform des Farbstoffes Reactive Black 5 (reservierbar),
• 5 Gewichtsteile m-nitrobenzolsulfonsaures Natrium und
• 25 Gewichtsteile Natriumbicarbonat.

A wet color is then printed on this form, wet-on-wet and with an overlap, which is composed of the following components:

• 450 parts by weight of a 10% aqueous solution of sodium alginate,
• 360 parts by weight of water,
• 100 parts by weight of urea,
• 60 parts by weight of the commercial form of the dye Reactive Black 5 (reservable),
• 5 parts by weight of sodium m-nitrobenzenesulfonate and
• 25 parts by weight of sodium bicarbonate.

The textile material printed in this way is now dried and then steamed for 8 minutes at 102 ° C. in a hanging loop damper; the dye of the base color and the dye of the colored reserve are fixed on the goods. Finally, the pattern is aftertreated and dried as usual with reactive dyes.

You get a sharp, turquoise reserve on a black background.

Example 7

• 520 Gewichtsteile kaltes Wasser
• 50 Gewichtsteile einer Paraffin-Zirkonsalz-Emulsion und
• 40 Gewichtsteile eine Verdickermischung aus einem nichtionischen Guarderivat und Carboxymethylstärke eingerührt.

To produce an etching reserve paste, in

• 520 parts by weight of cold water
• 50 parts by weight of a paraffin-zirconium salt emulsion and
• 40 parts by weight of a thickener mixture of a nonionic guar derivative and carboxymethyl starch.

• 180 Gewichtsteile einer 50 %igen, wäßrigen Lösung von trichloressigsaurem Natrium,
• 10 Gewichtsteile Kaliumcarbonat,
• 50 Gewichtsteile Glycerin,
• 80 Gewichtsteile Polyethylenglykol mit einem Molgewicht von etwa 400,
• 30 Gewichtsteile der Handelsform des Farbstoffes Disperse Red 200 (ätzbeständig),
• 30 Gewichtsteile der Handelsform des Farbstoffes Disperse Red 132 (ätzbeständig) und
• 10 Gewichtsteile hochdisperses Siliciumdioxid hinzu.

After thorough stirring, this approach is added

• 180 parts by weight of a 50% strength aqueous solution of trichloroacetic acid sodium,
• 10 parts by weight of potassium carbonate,
• 50 parts by weight of glycerin,
• 80 parts by weight of polyethylene glycol with a molecular weight of about 400,
• 30 parts by weight of the commercial form of the dye Disperse Red 200 (resistant to etching),
• 30 parts by weight of the commercial form of the dye Disperse Red 132 (caustic) and
• Add 10 parts by weight of highly disperse silicon dioxide.

With the printing ink prepared in this way, a fabric made of polyester fibers is then printed in rotary film printing using a pattern-like template.

• 80 Gewichtsteile der Handelsform des Farbstoffes Disperse Blue 96 (ätzbar),
• 400 Gewichtsteile einer 10 %igen, wäßrigen Lösung eines Natriumalginats, 2 Gewichtsteile Zitronensäure,
• 10 Gewichtsteile Zinksulfat und
• 508 Gewichtsteile Wasser.

A wet-in-wet and overlapping manner is then printed on this form, which has the following composition:

• 80 parts by weight of the commercial form of the dye Disperse Blue 96 (etchable),
• 400 parts by weight of a 10% aqueous solution of sodium alginate, 2 parts by weight of citric acid,
• 10 parts by weight of zinc sulfate and
• 508 parts by weight of water.

The fiber material treated in this way is then dried immediately and steamed in a high-temperature steamer at 175 ° C. for 7 minutes in order to fix the base color and the color reserve. The goods are then rinsed cold with water, reductively cleaned and aftertreated at 80 ° C. with an aqueous bath with the addition of an auxiliary based on fatty acid polyglycol ester. Finally, the pattern created is rinsed again with water and dried.

You get a sharp red reserve on a blue background.

Example 8

• In 640 Gewichtsteile kaltes Wasser werden
  • 50 Gewichtsteile einer Paraffin-Zirkonsalz-Emulsion und
  • 50 Gewichtsteile einer Verdickermischung aus einem nichtionischen Guarderivat und Carboxymethylstärke eingerührt.

A knitted fabric made from a mixture of polyester fibers and chlorinated wool in a ratio of 85:15 is treated using a rotary film printing machine with an etching reserve printing paste, which is obtained in the following manner:

• Be cold water in 640 parts by weight
  • 50 parts by weight of a paraffin-zirconium salt emulsion and
  • 50 parts by weight of a thickener mixture of a nonionic guar derivative and carboxymethyl starch were stirred in.

• 60 Gewichtsteilen einer 50 %igen, wäßrigen Lösung von trichloressigsaurem Natrium, 50 Gewichtsteilen Glycerin,
• 80 Gewichtsteilen Polyethylenglykol mit einem Molgewicht von etwa 400,
• 30 Gewichtsteilen der Handelsform des Farbstoffes Disperse Red 200 (ätzbeständig),
• 30 Gewichtsteilen der Handelsform des Farbstoffes Disperse Red 132 (ätzbeständig) und
• 10 Gewichtsteilen hochdispersem Siliciumdioxid.

After thorough stirring, this mixture is still mixed with

• 60 parts by weight of a 50% strength aqueous solution of sodium trichloroacetic acid, 50 parts by weight of glycerin,
• 80 parts by weight of polyethylene glycol with a molecular weight of about 400,
• 30 parts by weight of the commercial form of the Disperse Red 200 dye (resistant to etching),
• 30 parts by weight of the commercial form of the dye Disperse Red 132 (corrosion-resistant) and
• 10 parts by weight of highly disperse silicon dioxide.

• 30 Gewichtsteile der Handelsform des Farbstoffes Disperse Blue 96 (ätzbar),
• 415 Gewichtsteile einer 10 %igen, wäßrigen Lösung eines Natriumalginats,
• 2 Gewichtsteile Zitronensäure,
• 50 Gewichtsteile Natriumsulfat kalz. und
• 503 Gewichtsteile Wasser

Immediately afterwards, a background color is printed on this form without intermediate drying, which has the following components:

• 30 parts by weight of the commercial form of the dye Disperse Blue 96 (etchable),
• 415 parts by weight of a 10% strength aqueous solution of sodium alginate,
• 2 parts by weight of citric acid,
• 50 parts by weight of sodium sulfate calc. and
• 503 parts by weight of water

The further measures for dye fixation and finishing of the design thus produced are carried out as in Example 7.

You get a sharp red reserve on a blue background.

Example 9

• 50 Gewichtsteile einer Paraffin-Zirkonsalz-Emulsion und
• 40 Gewichtsteile einer Verdickermischung aus einem nichtionischen Guarderivat und Carboxymethylstärke eingetragen und nach gutem Durchrühren werden diesem Ansatz noch
• 180 Gewichtsteile einer 50 %igen, wäßrigen Lösung von trichloressigsaurem Natrium,
• 10 Gewichtsteile Natriumcarbonat,
• 50 Gewichtsteile Glycerin,
• 80 Gewichtsteile Polyethylenglykol mit einem Molgewicht von etwa 400 und
• 10 Gewichtsteile hochdisperses Siliciumdioxid zugefügt.

Be cold water in 580 parts by weight

• 50 parts by weight of a paraffin-zirconium salt emulsion and
• 40 parts by weight of a thickener mixture of a nonionic guar derivative and carboxymethyl starch are added and after thorough stirring, this is Approach yet
• 180 parts by weight of a 50% strength aqueous solution of trichloroacetic acid sodium,
• 10 parts by weight of sodium carbonate,
• 50 parts by weight of glycerin,
• 80 parts by weight of polyethylene glycol with a molecular weight of about 400 and
• 10 parts by weight of highly disperse silicon dioxide were added.

The etching reserve paste obtained in this way is then applied to a fabric made of polyester fibers by means of a sample film printing template.

• 40 Gewichtsteilen des durch Kuppeln von diazotiertem 3-Nitro-4-amino-5-brombcnzoesäure-ethylester mit N,N-Dihydroxyethyl-m-toluidin entsprechend Beispiel 2 der DE-OS 30 41 013 hergestellten Dispersionsfarbstoffes (ätzbar) ,
• 300 Gewichtsteilen einer 10 %igen, wäßrigen Lösung eines Natriumalginats,
• 100 Gewichtsteilen einer 10 %igen, wäßrigen Lösung eines Stärkeethers,
• 2 Gewichtsteilen Zitronensäure,
• 30 Gewichtsteilen Calciumhydrogenphosphat,
• 15 Gewichtsteilen eines handelsüblichen Fixierbeschleunigers und
• 513 Gewichtsteilen Wasser besteht.

Without intermediate drying, the still moist pre-print created in this way is overprinted over a large area with a background color using a blind stencil

• 40 parts by weight of the disperse dye prepared by coupling diazotized 3-nitro-4-amino-5-bromocenzoate with N, N-dihydroxyethyl-m-toluidine according to Example 2 of DE-OS 30 41 013 (etchable),
• 300 parts by weight of a 10% aqueous solution of sodium alginate,
• 100 parts by weight of a 10% strength aqueous solution of a starch ether,
• 2 parts by weight of citric acid,
• 30 parts by weight of calcium hydrogen phosphate,
• 15 parts by weight of a commercially available fixing accelerator and
• 513 parts by weight of water.

Example 7 is followed for dye fixation and the final rinsing processes. You get a sharp white reserve on a red background.

Example 10

A mixed fabric of polyester fibers / chlorinated wool (80:20) is printed in rotary film printing as indicated in Example 8. However, the etching reserve paste contains an additional 50 g / kg of a commercially available reducing agent based on sulfoxylate instead of a corresponding amount of water.

• 30 Gewichtsteilen der Handelsform des Farbstoffes Disperse Blue 96 (ätzbar),
• 8 Gewichtsteilen der Handelsform des Farbstoffes Reactive Blue 122 (reservierbar),
• 300 Gewichtsteilen einer 4 %igen, wäßrigen Lösung eines Natriumalginates,
• 100 Gewichtsteilen einer 10 %igen, wäßrigen Lösung eines Stärkeethers,
• 10 Gewichtsteilen eines Hilfsmittels auf Polyphosphatbasis,
• 10 Gewichtsteilen Zinksulfat,
• 10 Gewichtsteilen eines handelsüblichen Fixierbeschleunigers auf Alkylaryl-oxethylatbasis,
• 2 Gewichtsteilen Zitronensäure und
• 530 Gewichtsteilen Wasser.

The base color is composed of:

• 30 parts by weight of the commercial form of the dye Disperse Blue 96 (etchable),
• 8 parts by weight of the commercial form of the reactive blue 122 dye (can be reserved),
• 300 parts by weight of a 4% aqueous solution of sodium alginate,
• 100 parts by weight of a 10% strength aqueous solution of a starch ether,
• 10 parts by weight of a polyphosphate-based auxiliary,
• 10 parts by weight of zinc sulfate,
• 10 parts by weight of a commercially available fixing accelerator based on alkylaryl oxyethylate,
• 2 parts by weight of citric acid and
• 530 parts by weight of water.

Fixation and aftertreatment are carried out as indicated in Example 7.

You get a sharp red reserve on a blue background.

Claims (8)

1. Process for the production of etching reserve effects on a colored background. of textile fabrics, which consist of or contain hydrophobic synthetic fibers, by printing a printing paste, which contains an alkaline etching or reservation agent, in the desired pattern on the undyed web, then - without intermediate drying - overprinting or padding in a separate sequence or spraying this pre-printed, not yet fixed pattern overlapping with one or more different, aqueous printing pastes or an aqueous dyeing liquor which, in addition to conventional printing or dyeing aids, also contain at least one alkali-caustic or reservable disperse dye, subsequent heat exposure to the sun treated textile material at temperatures from 100 ° to 230 ° C and then washing out of unfixed dye and auxiliary residues, characterized in that an aqueous printing paste is used as the pre-pressure reserve, which in addition to alkaline agents or alkali donors as well as usual Thickenings and optionally other printing aids additionally contain a water-repellent emulsion based on paraffin and / or polyorganosiloxanes, optionally in a mixture with highly disperse silicon dioxide. 2. The method according to claim 1, characterized in that the overprinting paste or dyeing liquor for over-padding or over-spraying the alkali-etchable or reservable disperse dyes for coloring the background also has water-soluble sulfates or phosphates. 3. Use of the method according to claim 1 or 2, for the production of colored etching reserve effects on a different colored background using disperse dyes which are resistant to the alkaline etching or reservation agent in the form paste in addition to the alkaline etching or reservation agent. 4. Use of the method according to claim 1 or 2, for the production of colorful etching reserve effects on a different colored background using disperse dyes which are resistant to the alkaline etching or reservation agent in the overprinting paste or dyeing liquor to block or spray over in addition to the alkaline etchable or reservable Disperse dyes. 5. Use of the method according to claim 1 or 2 for the production of white and / or colored etching reserve effects on a different colored background of textile fabrics made of polyester / cellulose fiber mixtures using alkaline fixable reactive dyes which react with the cellulose according to the substitution mechanism in the Pre-printing paste in addition to the alkaline etching or reservation agents and optionally also in addition to disperse dyes which are resistant to the alkaline etching or reservation agent, and fixation of the reactive dyes by a single-phase or two-phase process. 6. Use of the method according to claim 1 or 2 for the production of white and / or colored etching reserve effects on a different colored background of textile fabrics made of polyester / cellulose fiber mixtures using alkaline fixable reactive dyes with the cellulose according to the addition mechanism react, and possibly also of alkali-fixable reactive dyes, which react with the cellulose according to the substitution mechanism, in the overprinting paste or dye liquor to block or spray in addition to alkali-etchable or reservable dispersion dyes and, if appropriate, also resistant to the alkaline etchant or reservation agent Disperse dyes, and fixation of the reactive dyes by a single-phase or two-phase process. 7. Use of the method according to claim 1 and 2 for the production of white and / or colored etching reserve effects on a different colored background of textile fabrics made of polyester / wool fiber mixtures using sulfates or phosphates for the base color, optionally with the addition of a commercially available fixing accelerator. 8. Use of the method according to claim 7, with the additional use of a commercially available reducing agent based on sulfoxylate in the etching reserve paste and / or the additional use of a reactive dye in the base color.