EP0107016A2 - Procédé pour l'impression de matière textile - Google Patents

Procédé pour l'impression de matière textile Download PDF

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Publication number
EP0107016A2
EP0107016A2 EP83109110A EP83109110A EP0107016A2 EP 0107016 A2 EP0107016 A2 EP 0107016A2 EP 83109110 A EP83109110 A EP 83109110A EP 83109110 A EP83109110 A EP 83109110A EP 0107016 A2 EP0107016 A2 EP 0107016A2
Authority
EP
European Patent Office
Prior art keywords
weight
parts
etching
reserve
dyes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP83109110A
Other languages
German (de)
English (en)
Other versions
EP0107016A3 (fr
Inventor
Kurt Roth
Ulrich Karsunky
Horst Dr. Tappe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19823235348 external-priority patent/DE3235348A1/de
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0107016A2 publication Critical patent/EP0107016A2/fr
Publication of EP0107016A3 publication Critical patent/EP0107016A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/12—Reserving parts of the material before dyeing or printing ; Locally decreasing dye affinity by chemical means
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/15—Locally discharging the dyes
    • D06P5/151—Locally discharging the dyes with acids or bases

Definitions

  • 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.
  • etching reserves on hydrophobic fiber material such as polyester fibers, or on mixtures thereof with other fibers, such as preferably polyester / cellulose fiber mixtures
  • hydrophobic fiber material such as polyester fibers
  • other fibers such as preferably polyester / cellulose fiber mixtures
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • nitro-thiazole or pyridone which can be cleaved under alkaline conditions and whose cleavage products are easy to eliminate.
  • 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.
  • 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
  • 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.
  • 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.
  • etching and preserving agents of both types 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.
  • a hygroscope e.g. Glycerin
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the etching of the disperse dye on the polyester component of the fiber mixture takes place at the points on the form.
  • 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.
  • 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
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Example 1 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Example 7 is followed for dye fixation and the final rinsing processes. You get a sharp white reserve on a red background.
  • a mixed fabric of polyester fibers / chlorinated wool (80:20) is printed in rotary film printing as indicated in Example 8.
  • 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.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP83109110A 1982-09-24 1983-09-15 Procédé pour l'impression de matière textile Withdrawn EP0107016A3 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3235348 1982-09-24
DE19823235348 DE3235348A1 (de) 1982-09-24 1982-09-24 Verfahren zum bedrucken von textilmaterial
DE19833325959 DE3325959A1 (de) 1982-09-24 1983-07-19 Verfahren zum bedrucken von textilmaterial
DE3325959 1983-07-19

Publications (2)

Publication Number Publication Date
EP0107016A2 true EP0107016A2 (fr) 1984-05-02
EP0107016A3 EP0107016A3 (fr) 1985-05-22

Family

ID=25804679

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83109110A Withdrawn EP0107016A3 (fr) 1982-09-24 1983-09-15 Procédé pour l'impression de matière textile

Country Status (3)

Country Link
EP (1) EP0107016A3 (fr)
DE (1) DE3325959A1 (fr)
ES (1) ES8405463A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1405948A1 (fr) * 2002-09-10 2004-04-07 Reinhold-Beitlich-Stiftung Procédé d'impression textile

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE794898A (fr) * 1972-02-04 1973-08-02 Montedison Fibre Spa Procede ameliore d'impression par decoloration ou decharge de fibres et de produits formes de telles fibres
JPS5930832B2 (ja) * 1976-09-03 1984-07-28 東洋紡績株式会社 防染法
DE2753696C3 (de) * 1977-12-02 1980-10-02 Basf Ag, 6700 Ludwigshafen Verfahren zum Bedrucken von Synthesefasern
GB2071708B (en) * 1980-03-13 1983-06-02 Ici Ltd Textile printing process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1405948A1 (fr) * 2002-09-10 2004-04-07 Reinhold-Beitlich-Stiftung Procédé d'impression textile

Also Published As

Publication number Publication date
ES525829A0 (es) 1984-06-01
EP0107016A3 (fr) 1985-05-22
DE3325959A1 (de) 1985-01-31
ES8405463A1 (es) 1984-06-01

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