Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
• • C—CHEMISTRY; METALLURGY
  • C14—SKINS; HIDES; PELTS; LEATHER
  • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
  • C14C11/00—Surface finishing of leather
  • C14C11/003—Surface finishing of leather using macromolecular compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
  • D06M15/15—Proteins or derivatives thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof

Definitions

• binders When dressing full-grain, sanded or split leather, dressing agents made from pigments, binders and other auxiliaries are applied to their surface, so that the pores of the leather are sealed on the surface.
• Alkaline-digested casein solutions and aqueous copolymer dispersions are generally used as binders. These copolymer dispersions are polyacrylate dispersions, dispersions of copolymers of vinyl acetate with acrylic esters or ethylene, synthetic rubber dispersions or polyurethane dispersions.
• Inorganic and organic pigments are used as pigments, for example iron oxide, titanium dioxide, azo pigments and phthalocyanines.
• the aqueous dressing liquors must be alkaline because the color mixtures generally contain aqueous alkaline casein solutions in more or less large proportions.
• Crosslinking component A (meth) acrylic acid
• crosslinking component B acrolein
• glycidyl methacrylate or dichlorotriazinylaminoethyl methacrylate - have not proven themselves due to the poor stability in storage of the polymer dispersions.
• the crosslinking of carboxylated aqueous dispersions of polyacrylates, polybutadienes, polyurethanes and casein solutions with polyfunctional aziridine compounds is carried out as a further aqueous reactive finish for leather finishing.
• the physical fastness properties are significantly improved by this process, but because of the high reactivity of the aziridine derivatives, the processing conditions must be observed extremely carefully even at room temperature, a requirement that is difficult to implement in practice.
• Adhesion difficulties also occur between the polymer primer and the finish, namely because the commonly used finishes based on collodion or acetobutyrate or also non-reactive PUR lacquers are not applied immediately after the last primer application.
• Embossed leather is particularly difficult to produce using this crosslinking system because the embossability of the leather decreases rapidly with the degree of crosslinking.
• the leather In order to be able to be embossed at all, the leather must always be embossed at the same stage of cross-linking immediately after the color application. Since these requirements are difficult to meet in a leather factory, the reproducibility of the embossing effect is practically non-existent.
• top layers on leather with particularly good properties which are important for leather finishing, such as finishing and covering, grain throw and toughness, flexibility at low temperatures, dry and wet rub fastness, fastness and heat resistance, but in particular very good dry and wet buckling strengths, very good adhesion for leather and adhesion between the individual layers of paint can be obtained if the leather is treated with aqueous preparations which contain at least one polymer containing carboxyl groups and optionally casein as a binder and a 1,2-polyepoxide compound as well as pigments and other auxiliaries and additives as a crosslinking agent.
• the present invention thus relates to aqueous preparations for finishing leather and for textile coating based on a polymer containing carboxyl groups as a binder and a 1,2-polyepoxide compound as a crosslinking agent, which may contain customary auxiliaries and additives, characterized in that the binder comprises a copolymer monoolefinically unsaturated monomers with an acid number of 5-150 mg KOH / g substance and / or a polyurethane with an acid number of 5-150 mg KOH / g substance and that the 1,2-polyepoxide compound is a polyglycidyl-triazolidine-3,5-dione with an epoxy value of 0.2 to 1.12.
• R 2 Possible substituents on R 2 are: C 1 -C 4 alkoxy, CN, N0 2 , C 1 -C 4 alkyl mercapto, halogen, preferably fluorine, chlorine, bromine, and in the case of the cycloaliphatic and aromatic radicals also C 1 -C 4 alkyl.
• cycloaliphatic Cs-Cs aliphatic-aromatic C 7 -C 10 - or aromatic C 6 -C 10 - and for the case that m is 1, a divalent, optionally substituted aliphatic C 2 -C 18 -, cycloaliphatic C S -C 12 -, aliphatic-aromatic C 7 -C l o or aromatic C 6 -C 12 radical,
• polyglycidyl compounds are e.g. Described in more detail in U.S. Patent Nos. 4,283,546 and 4,467,099.
• the poly-glycidyl-triazolidine-3,5-diones obtained have epoxy values from 0.2 to 1.12, preferably from 0.6 to 1.12.
• the epoxy value is understood to mean the number of 1,2-epoxy groups contained in 100 g of substance.
• the epoxy equivalent is defined as the amount of grams of substance that contains an equivalent of 1,2-epoxy groups. The determination is carried out by titration with hydrochloric acid, one mole of 1,2-epoxide groups being equivalent to one mole of hydrogen halide.
• the polyglycidyl compounds contained in the aqueous preparations according to the invention can be used both without a solvent and as a solution and / or dispersion.
• the polyepoxides are preferably used as a solution or dispersion depending on their solubility in the medium used in each case.
• Suitable solvents are water and water-miscible organic solvents.
• examples include: amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, alcohols such as methanol, ethanol, isopropanol, ethylene glycol monomethyl ether or ethyl ether, ketones such as acetone, diacetone alcohol, esters such as glycol acetate or glycerol acetate.
• Dimethylformamide, N-methylpyrrolidone and diacetone alcohol are preferably used.
• mixtures of several polyglycidyl-triazolidine-3,5-dions or mixtures of a polyglycidyl-triazolidine-3,5-dione with other polyglycidyl compounds e.g. B. glycidyl ethers from bisphenols, glycidyl esters of di- or polycarboxylic acids, basic glycidyl compounds such as N, N-diglycidylcyclohexylamine or N, N-diglycidylbenzylamine or heterocyclic epoxides such as glycidylhydantoins or triglycidyl isocyanurate can be used.
• the carboxyl group-containing polymers contained in the aqueous preparations according to the invention have an acid number of 5-150 mg KOH / g substance, the average molecular weight being 1,000 to 25,000.
• the OH numbers are preferably below 20, in particular below 10.
• the carboxyl group-containing polymers to be used according to the invention can be copolymers, one monomer component of which is an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, or polyurethanes containing carboxyl groups.
• copolymers containing carboxyl groups should consist of 1-25% by weight of at least one copolymerizable ⁇ , ⁇ -ethylenically unsaturated carboxylic acid having 3 to 5 carbon atoms and 75-99% by weight of at least one further copolymerizable monomer.
• the ⁇ , ⁇ -ethylenically unsaturated carboxylic acids can be monocarboxylic acids or dicarboxylic acids or half-esters of dicarboxylic acids with 1 to 12 carbon atoms in the alcohol component.
• Preferred copolymers containing carboxyl groups consist of polymerized units of
• Copolymers are understood not only as copolymers with a statistical distribution of the copolymerized monomers or block copolymers, but also as graft copolymers in which monomers have been grafted onto a preformed homopolymer or copolymer. Statistical copolymers are preferred.
• the copolymers containing carboxyl groups to be used according to the invention are prepared by known processes of bulk, solution or dispersion polymerization, preferably by dispersion polymerization.
• the copolymers prepared in bulk or solution polymerization must be converted into a dispersion in a second step.
• Anionic, cationic or non-ionic emulsifiers and dispersants can be used in an amount of 0.1 to 20% by weight, based on monomers, to produce such stable dispersions.
• Such processes have been described, for example, in 'Methods of Organic Chemistry', Houben-Weyl, 4th edition, volume 14/1, pages 24-556 (1961) and in DE-OS-2 946 435.
• the polymerizations can be carried out at temperatures from 0 ° C. to about 100 ° C.
• initiators which can be used are percarbonates, peresters such as tert-butyl perpivalate, perctoate, benzoyl peroxide, o-methoxybenzoyl peroxide, dichlorobenzoyl peroxide, azodiisobutyronitrile in amounts of 0.5 to 3% by weight, based on the amount of monomer.
• molecular weight regulators such as thioglycol, thioglycerol or tert-dodecyl mercaptan can also be used.
• Polyurethanes containing carboxyl groups are also known.
• the preparation of these polyurethanes or their aqueous dispersions can, for. B. in such a way that prepolymers in organic solvents such as. B. acetone, and after addition and reaction with carboxyl group-containing chain extenders dispersed in water. Since the systems are self-emulsifying, no emulsifiers and only low shear forces are required. After the solvent has been distilled off, the polyurethane dispersions remain.
• Hydroxycarboxylic acids and / or aminocarboxylic acids are preferably used as chain extenders containing carboxyl groups. Care must be taken, particularly in the case of hydroxycarboxylic acids, to ensure that there is no significant reaction between the carboxylic acids and the isocyanate. This can be done in particular by using sterically hindered hydroxycarboxylic acids, such as. B. of 2,2-di (hydroxymethyl) propionic acid can be achieved. Suitable chain extenders are, for. B.
• glycolic acid lactic acid, tartaric acid, citric acid, glycine, a- or ⁇ -alanine, sarcosine, methionine, 4-aminobutyric acid, 6-aminocaproic acid, glutamic acid.
• isocyanates are reacted with hydroxyl-containing compounds such as hydroxyl-containing polyesters, polyethers or polycarbonates.
• the isocyanates used to prepare the prepolymers are preferably the technically readily available, for example the aromatic, cycloaliphatic, aromatic diisocyanates or mixtures thereof, such as, for. B. tolylene-2,4-diisocyanate, toluene-2,6-diisocyanate, phenylene diisocyanate, methylene bis (4-phenyl isocyanate); Hexamethylene diisocyanate, cyclohexylene-1,4-diisocyanate, methylene bis (4-cyclohexyl) isocyanate, isophorone diisocyanate.
• aromatic, cycloaliphatic, aromatic diisocyanates or mixtures thereof such as, for. B. tolylene-2,4-diisocyanate, toluene-2,6-diisocyanate, phenylene diisocyanate, methylene bis (4-phenyl isocyanate); Hexamethylene diisocyanate,
• the hydroxyl group-containing polyesters used for the preparation of the prepolymers can be terminated or substituted on the main chain by hydroxyl groups.
• polyesters are those which are prepared by reacting acids, esters, anhydrides or acid chlorides with glycols, polyglycols and, if appropriate, small amounts of triplets.
• Suitable glycols and polyglycols are ethylene glycol, di- and triethylene glycol, propylene glycol, 2,2-dimethyl-1,3-propanediol.
• Glycerol, trimethylolpropane or trimethylolethane are particularly suitable as triols.
• polystyrene resin e.g., polystyrene resin
• aliphatic, cycloaliphatic or aromatic dicarboxylic acids or their derivatives such as phthalic, maleic, succinic, adipic, cork, sebacic and hexahydrophthalic acid.
• the hydroxyl-containing polyethers used to prepare the prepolymers are preferably those which are prepared by reacting aliphatic di- or triols, such as, for example, ethylene glycol, propylene glycol, glycerol or trimethylolpropane, or by reacting bisphenols, such as, for example, bisphenol A or hydroquinone, with ethylene oxide or propylene oxide .
• the carboxyl group-containing polymers to be used according to the invention preferably have an acid number of 10-100 mg KOH / g substance, in particular 10 to 50 mg KOH / g substance.
• the water-dispersible polymers are preferably used in the form of their aqueous dispersions, the carboxyl groups advantageously being neutralized with amines such as triethylamine, triethanolamine, dimethylethanolamine or with ammonia.
• casein to be used for the preparation of the preparations according to the invention is the commercially available, basic digested, i.e. to understand casein made water-soluble.
• the preparation of the digested casein is e.g. B. in "W. Grettermann, Handbook of Gerreichemie und Lederfabrikation 1/1. Part", 2nd edition (1961), p. 724 ff.
• basic digested casein it should be noted that the polymers containing carboxyl groups are neutralized with amines.
• the casein solutions can contain the usual casein plasticizers such as glycols, polyols, polyether glycols.
• the carboxyl group-containing polymers and the polyglycidyftriazolidin-3,5-diones are used in such proportions that 0.5 to 1.5, preferably 0.9 to 1.1, epoxy groups are accounted for by one carboxyl group.
• a butadiene binder requires significantly more crosslinking agents than an acrylate binder, a strongly acidic binder (e.g. itaconic acid) with a higher content of carboxylic acid groups less than a weakly acidic binder (e.g. methacrylic acid) with a lower content of carboxylic acid groups.
• a strongly acidic binder e.g. itaconic acid
• a weakly acidic binder e.g. methacrylic acid
• catalysts such as are known from the reaction of epoxides with carboxylic acids can be used to accelerate the crosslinking reaction.
• Suitable catalysts are tertiary amines, e.g. B. triethylamine, quaternary ammonium salts, e.g. B. tetraethylammonium chloride, sulfides or suffonium salts.
• carboxyl groups are generally neutralized with amines, an additional catalyst can be dispensed with for the crosslinking reaction, so that the crosslinking on the leather surface or on the textile surface is preferably not catalyzed.
• Inorganic or organic pigments can be added to the preparations according to the invention in their usually effective proportions up to 150% by weight, based on the binder.
• pigments are: titanium dioxide, iron oxides, carbon black, chromium oxide, phthalocyanine and azo pigments.
• the preparations according to the invention can contain further auxiliaries and additives such as thickeners, e.g. B. those based on cellulose such as carboxmethyl cellulose, polyvinyl alcohol or poly-N-vinylpyrrolidone.
• thickeners e.g. B. those based on cellulose such as carboxmethyl cellulose, polyvinyl alcohol or poly-N-vinylpyrrolidone.
• the method according to the invention is suitable for leather primers and finishes as well as for textile coating.
• Commercially available opaque paint pastes are also used for the priming orders.
• the processing can be done on full-grain, sanded and split leather or leather fiber materials of any kind.
• the finishes are applied to the leather in a manner known per se using the copolymers according to the invention, the crosslinking agent, the casein, pigment preparations of the abovementioned type and further additives.
• the dressings can be applied by casting, printing, knife coating, brushing, spraying, brushing or plushing processes. The quantity required depends on the type and pretreatment of the leather and can easily be determined by preliminary tests.
• the primer is carried out in one or more orders.
• intermediate ironing or scar stamping at 70 to 110 ° C, a good fusion and thus a good finish of the primer is achieved.
• Subsequent opaque paint applications can then be carried out.
• the viscosity of the dye liquors can be adjusted as required, depending on the type of leather and application technique.
• Full-grain leather which should only be thinly coated, is primed with low-viscosity liquors using air guns, while for heavily sanded leather and split leather, the viscosity of the paint mixtures is increased due to the better filling effect with thickeners.
• the paint is applied to this leather using airless guns, printing or casting machines.
• polyurethane one- and two-component lacquers, acetobutyrate lacquers, collodion lacquers or collodion lacquer emulsions of the oil-in-water and water-in-oil type are suitable.
• aqueous polyacrylate or polyurethane dispersions according to the invention can also be applied by spraying, printing and casting processes.
• the crosslinking reaction is slower than the crosslinking of carboxylated polymers with divalent metal oxides, e.g. B. zinc oxide, and with aziridine derivatives, but significantly faster than the reaction with epoxides of the "Dian" type.
• the crosslinking is complete after 5 to 15 days.
• this favorable crosslinking time ensures good adhesion of the Zurich layer not only to split and sanded leathers, but also to full-grain abrasive box leathers impregnated with acrylate binders.
• the crosslinking does not adversely affect the cold resistance of the dressing, the lightfastness and the film transparency.
• the dry and wet kink resistance, the dry, wet and rub-through resistance as well as the resistance to solvents achieve very good values that cannot be achieved by other processes from aqueous systems. It is also noteworthy that the known undesirable hydrophilicity of acrylate binders is significantly reduced by the crosslinking.
• the method according to the invention offers a particular advantage for the finishing of full-grain and weakly sanded leathers which should not appear coated, e.g. B. Furniture and clothing nappa.
• the crosslinking according to the invention has the effect that the binder film becomes "load-bearing" for larger proportions of pigment, matting and gripping agents without incisive losses in the fastness properties. This means that with pigment-rich, low-binder color approaches, defects can be covered with thinner cover layers, which means that the elegant grain of the thinner coated leather surface is retained and the finish does not look plastic.
• Leather can be trimmed with fewer work steps than usual, which despite its strong coverage appear very natural and not coated.
• a color paste aqueous dispersion with 55% by weight iron oxide pigment, 5% by weight binder based on butyl acrylate, methyl methacrylate, N-vinyl pyrrolidone, acrylic acid, vinyl acetate
• a color paste aqueous dispersion with 55% by weight iron oxide pigment, 5% by weight binder based on butyl acrylate, methyl methacrylate, N-vinyl pyrrolidone, acrylic acid, vinyl acetate
• Copolymer adjusted to pH 9-9.5 with NH 3
• 250 g of a commercially available 13.5% aqueous ammoniacal casein solution 100 g water and 25 g of a customary 60% aqueous peanut oil emulsion.
• the split leather or polished vachettes to be treated receive 1 to 2 jobs using a brush, plush board, airless gun, spraying, printing or casting machine.
• the total amount applied is 150-300 g / m 2
• the leathers are ironed or scarred at 100 ° C and 300 bar with a delay of 2 to 5 s. Then the top color is applied with the same liquor (application approx. 100 - 200 g / m 2 ). Finally, a common collodion varnish is applied as a finish by pouring.
• the dressing obtained shows excellent values for the hate and dry kink resistance, good adhesion to the leather, good water swell resistance, and its very good embossability. Even very fine embossments do not come out when the hot leather is stacked.
• the rubber latex was made as follows: In a 40 liter stainless steel autoclave with crossbar stirrer, a mixture of 18,000 g water, 5,000 g butadiene (1,3), 3,000 g acrylonitrile, 1,700 g styrene, 333 g 90% methacrylic acid and 50 g of tert-dodecyl mercaptan in the presence of 200 g of a sodium sulfonate of a mixture of long-chain paraffin hydrocarbons with an average chain length of 15 carbon atoms as an emulsifier and 5 g of 70% tert-butyl hydroperoxide and 2.5 g of sodium formaldehyde sulfoxy Polymerized latdihydrate as redox initiator system at 35 ° C until a solids concentration of 20% is reached.
• a solution of 100 g of a reaction product of isononylphenol with 20 moles of ethylene oxide and 2.5 g of sodium formaldehyde sulfoxylate dihydrate in 500 g of water is then pressed in and the polymerization is continued at 35 ° C. After a solids concentration of about 31% by weight (about 86% conversion) has been reached, the polymerization with a solution of 200 g is 25%. % By weight diethylhydroxylamine stopped in 200 g of water. The latex obtained is freed of residual monomers and has a solids concentration of 31%.
• the acid number of the binder is 19.5 mg KOH / g solid.
• a white pigment paste (aqueous dispersion with 65% by weight of titanium dioxide pigment, 5% by weight of binder based on an ethyl acrylate, methyl methacrylate, N-vinylpyrrolidone, acrylic acid) are used for the preparation of synthetically retanned white split leather or polished Vachettes -, Vinyl acetate copolymer, adjusted to pH 9 - 9.5 with NH 3 ) with 250 g of water, 10 g of 25% ammonia water and 25 g of a conventional 60% peanut oil emulsion.
• a white pigment paste aqueous dispersion with 65% by weight of titanium dioxide pigment, 5% by weight of binder based on an ethyl acrylate, methyl methacrylate, N-vinylpyrrolidone, acrylic acid
• the dressing is carried out as described in Example 1, but a white pigmented acetobutyrate-based lacquer is applied by spraying instead of a collodion lacquer.
• the application properties of the dressing correspond to the advantageous properties described in the general part.
• the finish is lightfast and resistant to yellowing even at 160 ° C.
• a carbon black paste aqueous dispersion with 16% by weight of carbon black and 20% by weight of a binder based on an isopropyl acrylate, methyl methacrylate, N-vinylpyrrolidone, acrylic acid, vinyl acetate copolymer, with aminoethanol to pH 10 - 10.5
• a carbon black paste aqueous dispersion with 16% by weight of carbon black and 20% by weight of a binder based on an isopropyl acrylate, methyl methacrylate, N-vinylpyrrolidone, acrylic acid, vinyl acetate copolymer, with aminoethanol to pH 10 - 10.5
• 60 g of an ammonical 13.5% by weight casein solution and with 30 g of a matting paste with 30% by weight of precipitated silica and 5% by weight of the binder of the color paste according to Example 1 and then diluted with 400 g of water.
• the paint is used in its present form; if you want to apply the paint by plushing, the paint liquor is previously diluted with water in a ratio of 2: 1, if the paint is to be applied with a casting machine or an airless gun, the liquor is adjusted to a viscosity with a suitable thickener that has a run-off time of 16 to 28 s from a Ford cup with a 4 mm nozzle.
• the finish obtained has very good dry and wet kink strengths as well as good layer adhesion and water swell resistance.
• Example 1 is repeated with the proviso that 30 g of a 50% by weight solution of 1,2-diglycidyl-4-methyftriazolidine-3,5-dione in dimethylacetamide are used as the crosslinking agent.
• the finish obtained has properties comparable to those described in Example 1.
• Example 2 is repeated with the proviso that 25 g of a 50 G 3 % by weight solution of 1,4-butane-bis-oxipropyl-3-diyl-4,4'-bis - [(1, 2-diglycidyl) triazolidine-3,5-dione] can be used in ethyl glycol.
• the finish obtained has the same good properties as that described in Example 2.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Paints Or Removers (AREA)
• Treatment And Processing Of Natural Fur Or Leather (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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• 1985
  • 1985-12-13 DE DE19853544001 patent/DE3544001A1/de not_active Withdrawn
• 1986
  • 1986-11-29 ES ES86116644T patent/ES2014408B3/es not_active Expired - Lifetime
  • 1986-11-29 DE DE8686116644T patent/DE3669737D1/de not_active Expired - Lifetime
  • 1986-11-29 EP EP86116644A patent/EP0226108B1/de not_active Expired - Lifetime
  • 1986-12-03 PT PT83866A patent/PT83866B/pt unknown
  • 1986-12-10 JP JP61292668A patent/JPS62147000A/ja active Pending

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