EP0142012A1 - Process and means for the production of white and coloured reserve prints on textiles made of hydrophobic synthetic fibrous materials - Google Patents

Abstract

1. A process for producing white of colored patterns by discharge resist technique on a differently colored ground of textile sheet-like structures made of or containing hydrophobic synthetic fibers, in particular polyester fibers, by applying, in any order and with overlap, to the undyed cloth (i) at least one aqueous print paste which contains a discharge resist, non-coloring by oneself, and may also contain at least one hot-fixable dyestuff, in particular a disperse dyestuff, which is resistant to the diacharging and resisting agents, in the desired pattern and as background coloring, (ii) one or more, different aqueous print pastes or an aqueous padding liquor which each contain a dyestuff formulation of at least one hot-fixable dischargeable or resistable dyestuff, in particular a disperse dyestuff, and may also contain at least one hot-fixable dyestuff, in particular a disperse dyestuff, which is resistant to the discharging and resisting agents, subsequently exposing the textile material thus treated to the action of heat at temperatures of 150 degrees C to 230 degrees C, and then removing unfixed dyestuff and auxiliary residues by washing off, which comprises employing, as discharging and resisting agents in the print paste for the discharge resist patterns (i), mixtures of the following components : (a) hydrazino derivatives of arylcarboxylic, aralkylcarboxylic, arylsulfonic or aralkylsulfonic acids or salts thereof, preferably those which, in their free acid form and also free base form, have the general formula see diagramm : EP0142012,P6,F2 in which _n denotes a number from 1 to 3, X represents a group of the formula -COOH, -CH2 COOH, -SO3 H or -CH2 SO3 H where multiple X is identical or different, and in which the aromatic ring system can, if desired, contain fused-on further rings and/or can be substituted by non-ionic radicals, (b) polyalkylene glycols, preferably polyethylene glycols, of the general formula HO-(CH2 -CH2 O)m -H(B) in which _m denotes a number up to 100 and (c) nitrogen compounds of the general formula Ya N(CH2 -CH2 -OH)b (C) in which _a is not equal to _b and each is zero or a number between 1 and 3, provided _a+_b is always 3, and in which Y denotes a hydrogen atom or a low alkyl group, in particular -CH3 , -C2 H5 , -C3 H7 or -C4 H9 , multiple Y being identical or different.

Description

In the field of textile printing, it has always been a problem to achieve sharply defined white or colored patterns on a deep-colored background. In particular, if the production of filigree motifs on a dark background is desired, the direct pressure to pattern the textile material completely fails. In order to produce such designs, it has long been known to the person skilled in the art to print an etching paste in the desired pattern on a deep background color produced with a white-etchable dye and then to destroy the dye at the locations covered with the etching paste by dry or wet heat treatment. After washing out the prints, the desired pattern is obtained in white on a dark background. It is also known to add dyes that are resistant to the etchant to the etching printing pastes. At the same time as the background color is destroyed, the indestructible dye causes the textile material to color at the printed areas, in which case colored prints on a dark background are obtained. Colored prints on a dark background can, however, also be achieved if the dark etched base is made with a mixture of an etchable and a differently colored non-etchable dye and these two types of dye are brought into a common padding liquor.

When these process variants familiar from the cellulose area are transferred to synthetic fiber materials or textile material, which preferably consists of hydrophobic synthetic fibers, there is a complicated task in that the etching of For example, polyester fibers dyed with disperse dyes are associated with special efforts. This is due to the fact that disperse dyes, which were once fixed in the polyester fiber, ie have dissolved in it, are now largely removed from the access of aqueous agents and thus again from attack by aqueous etching agents. In the production of etching prints on textile materials containing hydrophobic fibers or consisting of hydrophobic fibers, the known etching printing process is therefore modified in such a way that the textile web is first padded with a dye liquor containing disperse dye and dried or dried, but without fixing the dye, ie solution of the dye in the hydrophobic fiber. The desired pattern is then printed on the so dried or dried on, padded fabric with the etching printing paste and the padded and printed fabric is then subjected to a heat treatment in which the base dye immerses in the non-printed areas in the polyester fiber, that is, is fixed there, and the dye is destroyed at the areas printed with the etching, ie no coloring takes place there. With regard to this mechanism, the technique just described is also referred to as etching reserve pressure.

The process of etching reserve printing, which is simple in itself, involves a number of technical difficulties which often make it difficult to use. So it is fundamentally not easy to completely destroy the base dye with the etchant. If this does not succeed, then a colored residue remains on the etched areas, the shade of which can fluctuate between yellow-brown and dull violet or reddish gray tones and which soils the white background at the etched areas. This leads to untidy white etching or in the event that a colored etching should be produced, to falsify the shade of the caustic-resistant dye.

In order to remedy this shortcoming of the conventional method, etching pastes are used which contain relatively powerful reducing or oxidizing agents, e.g. Sodium dithionite in combination with alkali, alkali formaldehyde sulfoxylates or even heavy metal salts such as tin-2-chloride. With such strong etching agents, it is generally possible to achieve perfect white etching printing, but damage to the fiber material often occurs alongside it, especially if the polyester fiber fabric also contains accompanying fibers, such as those made of cellulose. Furthermore, these etchants are usually not cheap, and in the case of heavy metal etchants they also represent an ecological burden or cause additional expenditure in the purification of the waste water. In addition, there are relatively few types of dyes that are resistant to etchants on the aforementioned basis, and so the selection of etch-resistant dyes that can be used to produce colored etchings is relatively small.

To overcome the deficiencies shown, disperse dyes for background coloring are required, which can be etched with pure agents that are as mild as possible.

Disperse dyes are known from German published patent applications DE-A 26 12 740, 26 12 741, 26 12 742, 26 12 790, 26 12 791 and 26 12 792 which have at least two esterified carboxyl groups in their molecule. Such colorants saponify when treated with aqueous alkalis to form corresponding alkali-soluble compounds containing carboxyl groups.

The use of such products as a disperse dye for dyeing polyester fiber materials has the advantage that unfixed dye residues can be washed off the textile material again by simple treatment with alkaline agents.

A variation of the principle of the method explained, in which both the patterns and the funds are applied to the goods wet-on-wet with overlap in the same operation, is described in the two British patent applications GB-A 2 071 707 and GB-A 2 071 708 described. Alkaline water glass is used as an etching reserve. However, the processes modified in this way, just like the design technique mentioned at the outset with alkaline etching printing pastes, which may also contain reducing agents such as sodium dithionite or alkali formadehyde sulfoxylates, damage the polyester fiber material as a result of saponification of the fiber substance. The known acidic etching printing processes, which contain either tin-2-chloride or zinc salts of formaldehyde sulfoxyl acid as oxidative etching agents in the printing pastes, mean, in addition to the disadvantage of the corrosive effect on the fixing units, also the risk of wastewater pollution.

In continuing the efforts to solve the problems outlined above, to achieve filigree-like designs on a dark background of textile material consisting exclusively or predominantly of synthetic fibers, it has now surprisingly been found that the enumerated obstacles to obtaining flawless dyeing results in the course of the known Take measures to create such patterns with disperse dyes under disperse dyes by the etching reserve technique, if the etching reserves are composed so that they come into effect under largely neutral conditions.

• (i) mindestens eine wäßrige Druckpaste enthaltend selbst eine nicht-färbende Ätzreserve sowie gegebenenfalls noch mindestens einen heißfixierbaren, gegen das Ätz- bzw. Reservierungsmittel beständigen Färbstoff, insbesondere Dispersionsfarbstoff, in dem gewünschten Muster sowie als Fondcolorierung
• (ii) eine oder mehrere, unterschiedliche wäßrige Druckfarben bzw. eine wäßrige Klotzflotte jeweils enthaltend eine Farbstoffzubereitung aus mindestens einem heißfixierbaren, ätz- bzw. reservierbaren Farbstoff, insbesondere Dispersionsfarbstoff, sowie gegebenenfalls noch mindestens einen heißfixierbaren, gegen das Ätz- bzw. Reservierungsmittel beständigen Farbstoff, insbesondere Dispersionsfarbstoff, aufgetragen werden, anschließend das so behandelte Textilmaterial der Einwirkung von Hitze bei Temperaturen von 150° bis 230°C ausgesetzt und danach durch Auswaschen von nicht fixiertem Farbstoff und Hilfsmittelrückständen befreit wird,
  dadurch gekennzeichnet, daß man in der Druckpaste für die Xtzreservemuster (i) als Ätz- bzw. Reservierungsmittel Mischungen aus den folgenden Komponenten einsetzt:
  • (a) Hydrazino-Derivate von Aryl- bzw. Aralkyl-carbonsäuren oder -sulfonsäuren bzw. Salzen davon, vorzugsweise solche, die in ihrer freien Säureform und zugleich freien Baseform der allgemeinen Formel
    
    entsprechen, worin n eine Zahl von 1 bis 3 bedeutet, X eine Gruppe der Formel
    
    darstellt, wobei mehrfaches X gleich oder verschieden ist, und in welcher das aromatische Ringsystem gegebenenfalls ankondensierte weitere Ringe enthalten und/oder durch nicht-ionische Reste substituiert sein kann,
  • (b) Polyalkylenglykole, vorzugsweise Polyethylenglykole entsprechend der allgemeinen Formel
    
    worin m eine Zahl zwischen 1 und 100 bedeutet und
  • (c) Stickstoff-Verbindungen entsprechend der allgemeinen Formel
    
    worin a ungleich b ist und jedes davon Null oder eine Zahl zwischen 1 und 3 darstellt - unter der Voraussetzung, daß die Summe von a + b immer 3 beträgt - und in welcher Y ein Wasserstoffatom oder eine niedere Alkylgruppe, insbesondere -CH₃, -C₂H₅, -^C ₃ ^H ₇ oder -C₄H₉ bedeutet, wobei mehrfaches Y gleich oder verschieden ist.

The present invention thus relates to the production of white or colored patterns according to the etching reserve technique on a different colored background of textile fabrics containing or consisting of hydrophobic synthetic fibers, in particular polyester fibers, with the undyed web in any order and with overlap

• (i) at least one aqueous printing paste itself containing a non-coloring etching reserve and, if appropriate, at least one heat-fixable dye which is resistant to the etching or reservation agent, in particular disperse dye, in the desired pattern and as a base color
• (ii) one or more different aqueous printing inks or an aqueous padding liquor each containing a dye preparation comprising at least one heat-fixable, etchable or reservable dye, in particular disperse dye, and, if appropriate, at least one heat-fixable dye which is resistant to the etching or reservation agent , in particular disperse dye, are applied, then the textile material treated in this way is exposed to heat at temperatures of 150 ° to 230 ° C. and then freed from unfixed dye and auxiliary residues,
  characterized in that mixtures of the following components are used in the printing paste for the Xtz reserve pattern (i) as the etching or reservation agent:
  • (a) Hydrazino derivatives of aryl or aralkyl carboxylic acids or sulfonic acids or salts thereof, preferably those which are in their free acid form and at the same time free base form of the general formula
    
    correspond in which n is a number from 1 to 3, X is a group of the formula
    
    where multiple X is the same or different, and in which the aromatic ring system may contain further fused rings and / or may be substituted by non-ionic radicals,
  • (b) Polyalkylene glycols, preferably polyethylene glycols according to the general formula
    
    where m is a number between 1 and 100 and
  • (c) nitrogen compounds according to the general formula
    
    in which a is not equal to b and each represents zero or a number between 1 and 3 - provided that the sum of a + b is always 3 - and in which Y is a hydrogen atom or a lower alkyl group, in particular -CH ₃ , - C ₂ H ₅ , - ^C ₃ ^H ₇ or -C ₄ H ₉ , where multiple Y is the same or different.

The present invention also relates to etching reserve means for carrying out the claimed method, characterized in that it contains a mixture of components (a), (b) and (c).

The mixture component (a) in the etching reserve according to the invention is, for example, 2-, 3- or 4-hydrazino-benzene-carboxylic acid; 2-hydrazino-phenylacetic acid; Hydrazino-naphthalene carboxylic acids; 2-, 3- or 4-hydrazino-benzenesulfonic acid- (5); 4-, 5- or 8-hydrazino-naphthalenesulfonic acid (1); 1- or 6-hydrazino-naphthalenesulfonic acid- (2); 4-hydrazino-toluenesulfonic acid- (2); 2-or 3-hydrazino _- benzene-disulfonic acid (1,4) and 4-hydrazino-benzene-disulfonic acid (1,3) as well as corresponding alkali metal or ammonium salts on the acid residue or salts of hydrohalic acids on the hydrazo group. The mixture component (a) is used in amounts between 5 and 60 g, preferably between 10 and 30 g, per kilogram of the etching printing paste. This amount is mainly based on the intended color depth of the fund.

Mixture component (c), in particular N, N-dimethyl-N-ethanolamine, serves to neutralize compound (a); therefore the amount of (c) used depends mainly on the amount of the mixture component (a) present. The pH of the aqueous solution of these neutralized phenylhydrazine derivatives must be adjusted so that the solutions are transparent and clear in water. The aqueous solutions of the 3-component mixture for the etching reserve in the printing paste (i) should expediently have a pH in the range between 6.5 and 8.8.

Suitable polyalkylene glycols corresponding to component (b) for the etching reserve according to the invention are primarily polyethylene glycols with an average molecular weight of between 300 and 4500. The amount of the mixture component (b) required in the printing paste (i) is between 30 and 500 g, preferably between 60 and 200 g, per kilogram of the etching printing paste.

In view of the preparation of the printing pastes (i) it has proven to be rational if one prepares before the same produces an aqueous stock solution from the mixture of the three components (a), (b) and (c). By this measure, the neutralization process is anticipated and thus there is an etching reserve that functions well at all times in the form of the stock solution, which only has to be processed into printing paste and into which aqueous formulations of dyestuffs which are resistant to the etching reserve can be introduced without any particular effort .

Suitable textile fabrics, in particular woven or knitted fabrics, made of synthetic fibers with a hydrophobic character are, according to the process, all materials which can be dyed by heat-fixable dyes, in particular disperse dyes, especially from fibers of linear aromatic polyesters such as polyethylene 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 or other synthetic fibers can also be used.

For the production of background colors and colored effects using the process of the present invention, the compounds known from this class and suitable for application to the synthetic fibers described above are used from the class of disperse dyes, for example those described in the COLOR INDEX, 3rd edition 1971 and additions in 1975 are listed under the generic name "Disperse Dyes".

The selection of the etchable dyes for the claimed process can only be made experimentally due to the mild effect of the etching reserve. The range of disperse dyes that can be etched according to the present invention is sufficient and ranges from yellow to blue.

In terms of printing technology, the process for generating the etching reserves can be carried out in such a way that the undyed textile fabric or knitted fabric is first padded with a dye liquor containing an etchable disperse dye and dried or dried, but no fixation of the dye, i.e. Solution of the dye in the hydrophobic fiber, may take place, and then prints the desired pattern with the etching printing paste on the dried fabric. Conversely, it is also possible to pre-print the printing pastes containing the caustic agent on the goods and to apply the base dye preparation as overlapping pastes or printing pastes. With regard to the feasibility, there are also no restrictions imposed on the practitioner as to whether the orders of the pastes containing the etching agent and the fond dye are carried out wet-on-wet on the goods or with intermediate drying. In the case of wet-on-wet application, however, the patterns are less sharply defined, which is often even desirable in order to obtain special effects.

A further advantage of the method according to the invention is the possibility of storing the goods printed with the printing pastes containing the etching agent after drying. The fund dyes can then be applied in an overlapping manner with a time delay. Equivalent results can be obtained if the application of the fund dyes is carried out by means of a block process and intermediate drying and the application of the printing pastes containing caustic is carried out on other machines with a time delay.

The fixation of the printed and optionally over-splashed or over-printed goods takes place, as usual, in hot air or superheated steam at temperatures between 160 ° and 220 ° C for 45 seconds to 8 minutes, or in pressurized steam at 1.2 to 1.4 atm for 10 to 30 minutes, preferably 15 to 20 minutes. The completion of the fixed prints requires, after rinsing with water, as usual, a reductive aftertreatment as well as a final rinsing and drying.

example 1

• a) A fabric made of polyester fibers is made with a liquor
  
  padded at room temperature and then carefully dried below the fixation temperature for the dye in question.
• b) Fabric of the same type of fiber as in Example 1 a) is made according to the procedure given there with a liquor of the above composition, but here as a dye containing 40 g of C.I. Disperse Red 160, padded and dried.
• c) For the preparation of the etching reserve pastes, a stock solution is prepared from:
  
• d) The padded fabrics from Examples 1 a) and 1 b) are with the following etching reserves
  
  
  printed in punctiform patterns, dried and then treated for 7 minutes in a high-temperature steamer at 180 ° C. to etch or fix the applied dyes. The goods are then rinsed with water, reductively aftertreated in an aqueous liquor with sodium dithionite, sodium hydroxide solution and a nonionic surfactant, rinsed again with water and finally dried.

After the completion of the etching reserve prints, yellow and white dot-shaped patterns on a violet background are obtained on the goods from example 1 a), and yellow and white dot-shaped patterns on a red background are obtained on the goods from example 1 b).

Example 2

A polyester fabric is printed with the printing paste 1 according to Example 1 d) in any pattern and grafted over this pre-printing wet-on-wet in the same operation a paste of the following composition:

The process product is then dried as in example 1, fixed and then finished.

You get yellow print samples on a green background.

Claims (6)

1. Process for the production of white or colored patterns according to the etching reserve technique on a different colored background of textile fabrics containing or consisting of hydrophobic synthetic fibers, in particular polyester fibers, with the undyed web in any order and with overlap (i) at least one aqueous printing paste itself containing a non-coloring etching reserve and optionally at least one heat-fixable dye which is resistant to the etching or reservation agent, in particular disperse dye, in the desired pattern and as a base color (ii) one or more different aqueous printing inks or an aqueous padding liquor each containing a dye preparation comprising at least one heat-fixable, etchable or reservable dye, in particular disperse dye, and, if appropriate, at least one heat-fixable dye which is resistant to the etching or reservation agent Dye, especially disperse dye, are applied, then the textile material treated in this way is exposed to heat at temperatures of 150 ° to 230 ° C and then freed of non-fixed dye and auxiliary residues by washing, characterized in that the printing paste for the etching reserve pattern (i) as Etching or reservation agent uses mixtures of the following components: (a) Hydrazino derivatives of aryl or aralkyl carboxylic acids or sulfonic acids or salts thereof, preferably those which are in their free acid form and at the same time free base form of the general formula

correspond in which n is a number from 1 to 3, X is a group of the formula -COOH, -CH ₂ COOH, -SO ₃ H or -CH ₂ SO ₃ H, where multiple X is the same or different, and in which the aromatic ring system optionally contain fused further rings and / or can be substituted by non-ionic radicals, (b) Polyalkylene glycols, preferably polyethylene glycols according to the general formula

where m is a number between 1 and 100 and (e) nitrogen compounds according to the general formula

in which a is not equal to b and each represents zero or a number between 1 and 3 - provided that the sum of a + b is always 3 - and in which Y is a hydrogen atom or a lower alkyl group, in particular -CH ₃ , - C ₂ H ₅ , -C ₃ H ₇ or -C ₄ H ₉ , where multiple Y is the same or different. 2. The method according to claim 1, characterized in that the printing pastes containing the etching reserve are pre-printed on the goods and the base dye preparation is applied as an overlapping paste or printing paste. 3. The method according to claims 1 and 2, characterized in that the orders of the pastes containing etchant and fond dye pastes take place wet-on-wet on the goods in one operation. 4. The method according to claim 1, characterized in that the application of the base dyes takes place by means of a padding process and intermediate drying and. that the application of the printing pastes containing the caustic reserve is carried out on other machines with a time delay. 5. The method according to claim 1, characterized in that the aqueous solutions of the Xtz reserve mixture have a pH between 6.5 and 8.8. 6. etching reserve for carrying out the method according to claims 1 to 5, characterized by a content of a mixture of components (a), (b) and (c).