EP0285898A2 - Préparations et procédé de finissage du cuir et de revêtement de matières textiles - Google Patents

Préparations et procédé de finissage du cuir et de revêtement de matières textiles Download PDF

Info

Publication number
EP0285898A2
EP0285898A2 EP88104538A EP88104538A EP0285898A2 EP 0285898 A2 EP0285898 A2 EP 0285898A2 EP 88104538 A EP88104538 A EP 88104538A EP 88104538 A EP88104538 A EP 88104538A EP 0285898 A2 EP0285898 A2 EP 0285898A2
Authority
EP
European Patent Office
Prior art keywords
acid
leather
weight
mixtures
aqueous
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.)
Granted
Application number
EP88104538A
Other languages
German (de)
English (en)
Other versions
EP0285898A3 (en
EP0285898B1 (fr
Inventor
Leo Dr. Tork
Ludwig Rottmaier
Wolfgang Höhne
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.)
Bayer AG
Original Assignee
Bayer 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
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0285898A2 publication Critical patent/EP0285898A2/fr
Publication of EP0285898A3 publication Critical patent/EP0285898A3/de
Application granted granted Critical
Publication of EP0285898B1 publication Critical patent/EP0285898B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
    • 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

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 leather is ironed between two paint jobs on continuous ironing machines at higher temperatures, which is common for nappa leather, or the leather is only given the following paint job after storage for several days (e.g. over the weekend), then the upper paint layer no longer adheres to the lower one.
  • 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 very quickly 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 important for leather finishing such as finishing and covering, grain throw and toughness, flexibility at low temperatures, dry and wet rub fastness, light fastness and heat resistance, but especially very good dry and wet buckling strengths, very good adhesion for leather and adhesion between the individual layers of color are obtained if the treatment of the leather is carried out with aqueous preparations which contain at least one polymer containing carboxyl groups and optionally casein as a binder and a special 1,2-polyepoxide compound as well as pigments and other auxiliaries and additives as a crosslinker .
  • the present invention thus relates to aqueous preparations for dressing leather and for textile purposes Layering based on a carboxyl group-containing polymer as a binder and a 1,2-polyepoxide compound as a crosslinking agent, which may contain conventional auxiliaries and additives, characterized in that the binder is a copolymer of 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 triglycidyl isocyanurate with an epoxy value of 0.5 to 1.01.
  • the binder is a copolymer of 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
  • the 1,2-polyepoxide compound is trig
  • the aqueous preparation additionally contains, if appropriate, base-digested casein.
  • the carboxyl groups can be present as free acid or as carboxylate groups. If the preparation contains casein, which is open to the base, the polymer contains carboxylate groups.
  • the triglycidyl isocyanurate contained in the aqueous preparations according to the invention corresponds to the formula (I) wherein R1 is hydrogen or methyl, preferably hydrogen.
  • the triglycidyl isocyanurate of the general formula (I) contained in the preparations according to the invention is known and can be obtained by treating cyanuric acid with excess epichlorohydrin or ⁇ -methylepichlorohydrin in the presence of a suitable catalyst, e.g. Triethylamine, converted in a known manner at 20-200 ° C to trichlorohydrin isocyanurate and then treated with hydrogen chloride-releasing agents such as aqueous sodium hydroxide solution at 20-120 ° C.
  • a suitable catalyst e.g. Triethylamine
  • the two isomers can be obtained from the crude product by fractional crystallization from suitable solvents, for example methanol or dichloromethane.
  • suitable solvents for example methanol or dichloromethane.
  • the crude product obtained in the preparation can generally be used.
  • This crude product can contain oligomeric parts of polyepoxides. Part of the epoxy groups can be hydrolyzed so that better solubility is achieved. However, the crude product should contain no less than two epoxy groups in the molecule, otherwise sufficient crosslinking will not be achieved.
  • the raw products generally have epoxy values from 0.5 to 1.01, preferably from 0.8 to 1.01.
  • 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 substance in grams that contains one 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.
  • 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.
  • triglycidyl isocyanurate with other polyglycidyl compounds, e.g. Glycidyl ethers from bisphenols, glycidyl esters from di- or polycarboxylic acids, basic glycidyl compounds such as N, N-diglycidylcyclohexylamine or N, N-diglycidylbenzylamine or heterocyclic epoxides such as glycidylhydantoins or polyglycidyltriazolidine-3,5-diones can be used.
  • Glycidyl ethers from bisphenols
  • glycidyl esters from di- or polycarboxylic acids
  • basic glycidyl compounds such as N, N-diglycidylcyclohexylamine or N, N-diglycidylbenzylamine or heterocyclic epoxides
  • glycidylhydantoins or polyglycidyltri
  • 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 whose one monomer component 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.
  • 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.
  • 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 nonionic 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 methods 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 29 46 435.
  • the polymerizations can be carried out at temperatures from 0 ° C. to about 100 ° C.
  • Percarbonates peresters such as tert-butyl perpivalate can be used as initiators.
  • -Peroctoate benzoyl peroxide, o-methoxy benzoyl 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 production of these polyurethanes or their aqueous dispersions can e.g. in such a way that prepolymers in organic solvents, e.g. Acetone, dissolves and disperses in water after addition and reaction with chain extender containing carboxyl groups. 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.
  • Hydroxyarboxylic 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 hydroxy carboxylic acids, e.g. of 2,2-di (hydroximethyl) propionic acid can be achieved. Suitable chain extenders are e.g.
  • glycolic acid lactic acid, tartaric acid, citric acid, glycine, ⁇ - 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 aliphatic, cycloaliphatic, aromatic diisocyanates or mixtures thereof, such as e.g. 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.
  • 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 obtained by reacting aliphatic di- or triols, such as ethylene glycol, propylene glycol kol, glycerol or trimethylolpropane, or by reacting bisphenols such as 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, base-digested, ie water to understand solubilized casein.
  • the preparation of the digested casein is described, for example, in "W. Griffmann, Handbuch der Gerschenemie und Lederfabrikation I / 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 triglycidyl isocyanurate are used in proportions such 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 in the preparations according to the invention.
  • Suitable catalysts are tertiary amines, for example triethylamine, quaternary ammonium salts, for example tetraethylammonium chloride, sulfides or sulfonium 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.
  • the preparations according to the invention can contain further auxiliaries and additives such as thickeners, e.g. those based on cellulose such as carboxymethyl cellulose, polyvinyl alcohol or poly-N-vinylpyrrolidone.
  • thickeners e.g. those based on cellulose such as carboxymethyl 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 primer is carried out in one or more orders.
  • intermediate ironing or embossing 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, optionally together with casein solutions and crosslinking agents according to the invention, by spraying, printing and casting processes.
  • the crosslinking reaction is slower than the crosslinking of carboxylated polymers with divalent metal oxides, e.g. Zinc oxide, as well as with aziridine derivatives, but significantly faster than the reaction with epoxides of the "Dian" type.
  • the crosslinking is complete after 5 to 15 days. In contrast to the process described in EP-B-29 170, this favorable crosslinking time ensures good adhesion of the Zurich layer not only to split and sanded leathers, but also to full-grain sanding 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 and the solvent resistance 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 are not intended to appear coated, for example 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 errors with a thinner deck layers can be covered, whereby the elegant grain of the thin coated leather surface is preserved 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 NH3 with 250 g of a commercially available 13.5% aqueous ammoniacal casein solution, 100 g water and 25 g of a conventional 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 application amount is 150 - 300 g / m2.
  • the leather After drying, the leather is ironed or scarred at 100 ° C and 300 bar with a delay of 2 to 5 seconds. Then the top color is applied with the same Fleet (order approx. 100-200 g / m2). Finally, a common collodion varnish is applied as a finish by pouring.
  • the finish obtained shows excellent values for the wet and dry kink resistance, good adhesion to the leather, good water swell resistance, and very good embossability. Even very fine embossments do not come out when the hot leather is stacked.
  • the rubber latex was produced as follows: A mixture of 18,000 g of water, 5,000 g of butadiene- (1,3), 3,000 g of acrylonitrile, 1,700 g of styrene and 333 g of 90% methacrylic acid is mixed in a 40-liter stainless steel autoclave with a cross-bar stirrer 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 sulfoxylate dihydrate as a redox initiator system at 35 ° C.
  • 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 NH3) 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 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 copolymers, with aminoethanol to pH 10-10 , 5) are intensively stirred with 60 g of an ammoniacal 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 water.
  • the finish obtained has very good dry and wet kink strengths as well as good layer adhesion and water swell resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Paints Or Removers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP88104538A 1987-04-04 1988-03-22 Préparations et procédé de finissage du cuir et de revêtement de matières textiles Expired - Lifetime EP0285898B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873711415 DE3711415A1 (de) 1987-04-04 1987-04-04 Zubereitung und verfahren zum zurichten von leder und zur textilbeschichtung
DE3711415 1987-04-04

Publications (3)

Publication Number Publication Date
EP0285898A2 true EP0285898A2 (fr) 1988-10-12
EP0285898A3 EP0285898A3 (en) 1990-05-23
EP0285898B1 EP0285898B1 (fr) 1993-05-12

Family

ID=6324889

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88104538A Expired - Lifetime EP0285898B1 (fr) 1987-04-04 1988-03-22 Préparations et procédé de finissage du cuir et de revêtement de matières textiles

Country Status (7)

Country Link
US (1) US5087646A (fr)
EP (1) EP0285898B1 (fr)
JP (1) JPS63264978A (fr)
BR (1) BR8801572A (fr)
DE (2) DE3711415A1 (fr)
ES (1) ES2041720T3 (fr)
PT (1) PT87098B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0309221A2 (fr) * 1987-09-21 1989-03-29 Eagle-Picher Industries, Inc. Résines époxydes modifiées par un élastomère
EP0458243A1 (fr) * 1990-05-21 1991-11-27 Nippon Paint Co., Ltd. Composition de revêtement aqueuse
EP0466136A1 (fr) * 1990-07-12 1992-01-15 Kansai Paint Co., Ltd. Composition de revêtement aqueuse pour substrats de plastique et méthode de revêtement
DE9107770U1 (fr) * 1991-06-24 1992-06-11 Mueller, Peter, 4300 Essen, De
EP0528874B2 (fr) † 1990-05-17 2001-10-17 Henkel Kommanditgesellschaft auf Aktien L'utilisation d'un système reactif capable de former un film, à base de dispersion, comprenant deux composés
WO2006000385A2 (fr) * 2004-06-28 2006-01-05 Basf Aktiengesellschaft Copolymeres et leur utilisation pour traiter des substrats souples

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4217716A1 (de) * 1992-05-29 1993-12-02 Bayer Ag Vernetzer für Textildruck-Bindemittel
US5853859A (en) * 1995-07-07 1998-12-29 Kimberly-Clark Worldwide, Inc. Room temperature latex printing
DE19652145A1 (de) * 1996-12-14 1998-06-18 Herberts Gmbh Bindemittelzusammensetzung, diese enthaltende Überzugsmittel, deren Herstellung und Verwendung
US6187140B1 (en) 1997-12-31 2001-02-13 Kimberly-Clark Worldwide, Inc. Creping process utilizing low temperature-curing adhesive
US7815995B2 (en) * 2003-03-03 2010-10-19 Kimberly-Clark Worldwide, Inc. Textured fabrics applied with a treatment composition
DE102004027415A1 (de) * 2004-06-04 2005-12-22 Basf Ag Copolymerisate und ihre Verwendung zur Behandlung von flexiblen Substraten
DE102004032304A1 (de) * 2004-07-03 2006-02-16 Construction Research & Technology Gmbh Wasserlösliche sulfogruppenhaltige Copolymere, Verfahren zu deren Herstellung und ihre Verwendung
GB0605895D0 (en) * 2006-03-27 2006-05-03 Blc Leather Technology Ct Epoxide-based tannage system
JP5708286B2 (ja) * 2011-06-14 2015-04-30 トヨタ紡織株式会社 ヒータ構造体
JP6247492B2 (ja) * 2012-11-06 2017-12-13 ダウ グローバル テクノロジーズ エルエルシー 水性皮革コーティング組成物および皮革をコーティングするための方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0036639A2 (fr) * 1980-03-25 1981-09-30 Doncroft Colors & Chemicals, Inc. c/o Joseph Bancroft & Sons Co., Inc. Impression de tissus par transfert à sec de colorants sublimables
EP0226108A2 (fr) * 1985-12-13 1987-06-24 Bayer Ag Compositions et procédé pour l'apprêt du cuir et le revêtement des matières textiles

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5840367A (ja) * 1981-08-26 1983-03-09 日本ペイント株式会社 水性塗料組成物およびその製法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0036639A2 (fr) * 1980-03-25 1981-09-30 Doncroft Colors & Chemicals, Inc. c/o Joseph Bancroft & Sons Co., Inc. Impression de tissus par transfert à sec de colorants sublimables
EP0226108A2 (fr) * 1985-12-13 1987-06-24 Bayer Ag Compositions et procédé pour l'apprêt du cuir et le revêtement des matières textiles

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0309221A2 (fr) * 1987-09-21 1989-03-29 Eagle-Picher Industries, Inc. Résines époxydes modifiées par un élastomère
EP0309221A3 (fr) * 1987-09-21 1990-04-18 Eagle-Picher Industries, Inc. Résines époxydes modifiées par un élastomère
EP0528874B2 (fr) † 1990-05-17 2001-10-17 Henkel Kommanditgesellschaft auf Aktien L'utilisation d'un système reactif capable de former un film, à base de dispersion, comprenant deux composés
EP0458243A1 (fr) * 1990-05-21 1991-11-27 Nippon Paint Co., Ltd. Composition de revêtement aqueuse
US5183504A (en) * 1990-05-21 1993-02-02 Nippon Paint Co., Ltd. Aqueous coating composition
AU634387B2 (en) * 1990-05-21 1993-02-18 Nippon Paint Co., Ltd. Aqueous coating composition
EP0466136A1 (fr) * 1990-07-12 1992-01-15 Kansai Paint Co., Ltd. Composition de revêtement aqueuse pour substrats de plastique et méthode de revêtement
DE9107770U1 (fr) * 1991-06-24 1992-06-11 Mueller, Peter, 4300 Essen, De
WO2006000385A2 (fr) * 2004-06-28 2006-01-05 Basf Aktiengesellschaft Copolymeres et leur utilisation pour traiter des substrats souples
WO2006000385A3 (fr) * 2004-06-28 2006-03-30 Basf Ag Copolymeres et leur utilisation pour traiter des substrats souples

Also Published As

Publication number Publication date
EP0285898A3 (en) 1990-05-23
BR8801572A (pt) 1988-11-08
US5087646A (en) 1992-02-11
ES2041720T3 (es) 1993-12-01
JPS63264978A (ja) 1988-11-01
DE3711415A1 (de) 1988-10-20
EP0285898B1 (fr) 1993-05-12
PT87098A (pt) 1988-04-01
DE3880872D1 (de) 1993-06-17
PT87098B (pt) 1992-07-31

Similar Documents

Publication Publication Date Title
EP0285898B1 (fr) Préparations et procédé de finissage du cuir et de revêtement de matières textiles
DE3915459C2 (fr)
EP2057293B1 (fr) Cuir corroyé
DE2926001C3 (de) Lacksystem zum kathodischen Elektrotauch-Lackieren
DE4122265A1 (de) Polyurethan-dispersionen
DE60020878T2 (de) Additionspolymer und polyurethan enthaltende wässrige beschichtungszusammensetzung
DE1953345A1 (de) Verfahren zur Herstellung von modifizierten kationischen Emulsionspolymerisaten
DE2734576A1 (de) Verfahren zur herstellung von waessrigen dispersionen oder loesungen von isocyanat-polyadditionsprodukten
EP0226108B1 (fr) Compositions et procédé pour l'apprêt du cuir et le revêtement des matières textiles
DE2708442A1 (de) Verfahren zur herstellung von modifizierten, waessrigen kunststoff- dispersionen
EP0244602B1 (fr) Procès du finissage du cuir
US2828222A (en) Method of coating leather with polymers containing units of acrylyl or methacrylyl dicyandiamide and the resulting article
EP0437742B1 (fr) Compositions de polymère aqueux
DE3534874A1 (de) Loesliches, vernetzbares acrylatcopolymerisat, verfahren zu seiner herstellung und ueberzugsmittel auf der basis des acrylatcopolymerisats
Szycher Waterborne polyurethanes
DE3235044C2 (de) Kationische Acryllatexzusammensetzung und ihre Verwendung
EP0086354A2 (fr) Préparations pigmentaires et leur application à la pigmentation et/ou au bébustrage des agents d'apprêt pour cuir et simili-cuirs
DE3700571A1 (de) Mischungen aus waessrigen polymerdispersionen und deren verwendung als beschichtungsmasse
DE2843780A1 (de) Polymerdispersionen zur behandlung von leder
DE1816395A1 (de) Verfahren zur Zurichtung von Leder und synthetischem Lederaustauschmaterial
DE1236202B (de) Verfahren zur Herstellung stabiler, waessriger Emulsionen bzw. Dispersionen von AEthylen-Mischpolymerisaten
DE2041550A1 (de) Verfahren zum Behandeln von Flaechengebilden mit anionischen waessrigen Polyurethandispersionen
DE2801817A1 (de) Pigmentpraeparationen
EP0814102A2 (fr) Polymères greffés de monomères insaturés sur des polyurées modifiées, leur procédé de préparation et leur utilisation
DE1235496B (de) Verfahren zum Behandeln von Leder

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19880322

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): CH DE ES FR GB IT LI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): CH DE ES FR GB IT LI

17Q First examination report despatched

Effective date: 19921027

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

ITTA It: last paid annual fee
AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE ES FR GB IT LI

REF Corresponds to:

Ref document number: 3880872

Country of ref document: DE

Date of ref document: 19930617

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19930525

ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2041720

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19940322

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19940322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19941130

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20020215

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20020311

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20020314

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030324

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031001

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030324

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050322

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT