WO1992001817A1 - Polyurethanes pour l'appret de cuir - Google Patents

Polyurethanes pour l'appret de cuir Download PDF

Info

Publication number
WO1992001817A1
WO1992001817A1 PCT/EP1991/001271 EP9101271W WO9201817A1 WO 1992001817 A1 WO1992001817 A1 WO 1992001817A1 EP 9101271 W EP9101271 W EP 9101271W WO 9201817 A1 WO9201817 A1 WO 9201817A1
Authority
WO
WIPO (PCT)
Prior art keywords
leather
weight
use according
polyether polyols
parts
Prior art date
Application number
PCT/EP1991/001271
Other languages
German (de)
English (en)
Inventor
Rainer HÖFER
Hans-Herbert Friese
Roland Grützmacher
Gerhard Kaindl
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1992001817A1 publication Critical patent/WO1992001817A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • 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

Definitions

  • the invention relates to the use of special polyurethanes in the primer liquor of leather finishing.
  • Leather finishing is the protective layer that is applied to the leather that has been dried after tanning and oiling in order to protect it against moisture, dirt and damage (Ullmann's Encyklopadie der Technische Chemie, 4th edition, volume 16, pages 159-163 , Verlag Chemie Weinheim 1978).
  • the dressing film must adhere firmly to the leather and satisfy extremely high bending and stretching requirements during further processing and during later use. Furthermore, the surface of the dressing film must be hard enough to ensure sufficient resistance to damage from dry and wet rubbing, bumping and scratching. So that the dressing film can meet these different requirements, it is applied in several thin layers of different dressing liquors, in particular the primer and finishing liquors, with respective intermediate drying and, if necessary, intermediate hangers and embossing.
  • the primer is intended to conceal the defects visible in the undressed leather, to level the color and thus to improve the range.
  • the base fleets therefore contain in addition to the film-forming polymer dispersions, such as thermoplastic polyacrylates, butadiene copolymers and polyurethanes, pigments and other auxiliaries.
  • the primer For the use value of the finished leather, it is important that the primer withstand the mechanical stresses to which the leather is subjected during use, and in particular that it be highly flexible.
  • the object of the invention was to improve the physical fastness properties of finished leather.
  • the invention accordingly relates to the use of an aqueous polyurethane dispersion with a solids content of between 10 and 50% by weight and a Brookfield viscosity at 25 ° C. between 10 and 50,000 mPas, the polyurethane solids of which as components a) polyether polyols with at least 3 OH groups and an average molecular weight between 1,000 and 20,000, b) castor oil, alkoxylated castor oil, epoxidized glycerides ring-opened with C 1-6 alkyl alcohols and / or alkoxylated, epoxidized glycerides ring-opened with Ci-g alkyl alcohols, c) ionic groups bearing dihydroxy and / or diamino compounds and d) contains organic di- and / or polyisocyanates in the primer liquor of the leather finishing.
  • the polyurethanes to be used according to the invention in the primer liquor are known compounds which, according to DE 37 04 350, are used to produce
  • Prepared leathers have particularly good physical fastness properties, in particular cold flexibility and rub fastness properties, if they are primed with a polyurethane dispersion whose Brookfield viscosity at 25 ° C is between 10 and 10000 mPas.
  • the average molecular weight of the polyether polyols contained in the polyurethane solid is preferably between 3,000 and 12,000. Polyether polyols of the general formula are particularly preferred
  • R denotes an alkoxy radical which is derived from glycerol, diglycerol, polyglycerol with a degree of polymerization x between 3 and 6, trimethylolpropane or trimethylolethane
  • the index x means the degree of polymerization of the alkoxy radical
  • the indices y are a number between 1 and 8
  • z is a number between 0 and 7, with the proviso that the sum y + z is between 1 and 8
  • the indices a are a number between 1 and 15
  • b is a number between 20 and 150
  • c is a number between 1 and 15
  • d is a number between 20 and 150
  • e is a number between 1 and 15, with the proviso that the sums a + c + e between 3 and 40
  • b + d between 40 and 300 and c + e are between 2 and 30.
  • the polyether polyols of the general formula are known compounds which are obtainable in a manner known per se by alkoxylation of glycerol, diglycerol, polyglycerol with a degree of polymerization between 3 and 6, trimethylolpropane or trimethylolethane with ethylene oxide and propylene oxide.
  • the polyurethane solid preferably contains castor oil, alkoxylated castor oil, preferably alkoxylated with 1 to 50 mol of ethylene oxide and / or castor oil alkoxylated with 1 to 50 mol of propylene oxide, epoxidized glycerides ring-opened with Ci-g-alkyl alcohols and / or with 1 to 10 mol Ethylene oxide and 1 to 40 mol of propylene oxide alkoxylated, ring-opened with Ci.g-alkyl alcohols, epoxidized glycerides.
  • the epoxidized glycerides that is to say mixtures of epoxidized mono-, di- and / or triglycerides, required as starting materials for the production of the last two substance classes mentioned are epoxidized by unsaturated oils, for example soybean oil, linseed oil, tall oil, cottonseed oil, peanut oil, palm oil , Sunflower oil, rape oil and / or claw oil, accessible.
  • unsaturated glycerides can be obtained by Reaction with peracetic acid in the presence of acidic catalysts or with performic acid formed in situ from formic acid and hydrogen peroxide.
  • the epoxidized glycerides are then treated with monohydric C 8 alkyl alcohols, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol and / or 2-ethylhexanol, in the presence of catalysts, for example sodium methylate or potassium hydroxide, reacted with opening of the oxirane ring.
  • the ring opening is preferably carried out with methanol.
  • the ring-opened epoxidized glycerides can then be alkoxylated in a manner known per se with ethylene oxide and / or propylene oxide.
  • the alkylene oxides are preferably used in amounts such that 1 to 10 moles of ethylene oxide and 1 to 40 moles of propylene oxide accumulate per mole of ring-opened glyceride.
  • the polyurethanes to be used according to the invention contain dihydroxy and / or diamino compounds as an additional building block which preferably contain one or more carboxylate, sulfonate and / or ammonium groups as the ionic group, for example dimethylolpropionic acid, sulfonate group-containing aliphatic diols DE-OS 24 46 440 or anionic, built-in internal emulsifiers according to DE-OS 2651 506.
  • Suitable organic di- and / or polyisocyanates are aliphatic and / or aromatic di- and / or triisocyanates, for example dicyclohexylmethane-4,4'-diisocyanate, 1,6-hexane diisocyanate, 3-isocyanatometh l-3.5 , 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), tetramethylene diisocyanates, trimethylhexamethylene diisocyanate, dimer fatty acid diisocyanates, 1,4-phenylene diisocyanate, Diphenylmethane diisocyanates, toluene-2,4- and / or toluene-2,6-diisocyanate, 2,4,4'-triisocyanato-diphenyl ether and / or 4 ' ( 4'' f 4''' triisocyanato-triphenylmethane.
  • Aliphatic diisocyanates in particular isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,6-hexane diisocyanate and / or dimer fatty acid diisocyanates, are preferred.
  • blocked di- and / or polyisocyanates can also be used in combination with the above-mentioned non-blocked di- and / or polyisocyanates.
  • the blocked di- and polyisocyanates are resistant to hydroxyl groups at room temperature and only react at temperatures above 100 ° C. Based on the total amount of the di- and / or polyisocyanates used, the content of blocked di- and / or polyisocyanates is between 0 and 60% by weight, preferably between 0 and 10% by weight.
  • Blocked di- and polyisocyanates are prepared by reacting organic di- or polyisocyanates with one or more alcohols in amounts such that all isocyanate groups are blocked.
  • the polyurethanes can contain water-soluble diamines, for example ethylenediamine and / or isophoronediamine.
  • the weight ratio of components a) to components b) is between 90:10 and 10:90. Based on components a) and b), the polyurethanes contain 1 to 50% by weight. Dihydroxy and / or diamino compounds bearing ionic groups. The OH / NCO equivalent ratio is between 1: 0.5 and 1: 2.0.
  • the polyurethanes are produced in a manner known per se, in which, for example, di- and / or polyisocyanates with a) polyether polyols, b) castor oil, alkoxylated castor oil, ring-opened epoxidized glycerides and / or alkoxylated with C 1-6 alkyl alcohols Ci-8-alkyl alcohols ring-opened epoxidized glycerides and c) dihydroxy and / or diamino compounds bearing ionic groups, optionally in the presence of solvents such as N-methylpyrrolidone and optionally catalysts such as N-methyl-orpholine at temperatures between 50 and 100 ° C to a prepolymer with terminal isocyanate groups.
  • the prepolymer obtained is then dispersed in water at temperatures between 40 and 60 ° C. and, if appropriate, reacted with chain extenders such as diamines, for example ethylene diamine.
  • aqueous polyurethane dispersions to be used according to the invention with a solids content of between 10 and 50% by weight are used in aqueous primer liquors in amounts of 5 to 80% by weight.
  • the priming liquors can contain pigment preparations, film-forming substances in the form of aqueous dispersions, such as polyacrylates and / or polyurethanes, binders and fillers, for example wax dispersions or casein, matting agents, penetrators with solvent components and / or plasticizers.
  • the primer liquors can be applied to the leather in one work step or in several successive work steps, drying being carried out at temperatures between 50 ° C. and 120 ° C. after the individual work steps.
  • ironing or embossing can be carried out in a known manner at temperatures between 50 ° C. and 120 ° C. between the priming jobs or after the last priming job.
  • the priming liquors can be sprayed, plushed, poured, Scraps and / or roller application can be applied to the leather. This is then given a customary finish.
  • the leather treated with a polyurethane to be used in the primer liquor according to the invention has excellent physical fastness properties.
  • the finished leathers are not only characterized by a high degree of flexibility when wet and dry, but also at temperatures of -20 ° C and below. Furthermore, they have good fastness to rubbing both in the dry and in the wet state.
  • Parts by weight means “parts by weight”
  • composition of the primer fleet :
  • aqueous pigment preparation 50 parts by weight of matting agent based on silica 40 parts by weight of filler based on wax dispersion 130 parts by weight of the polyurethane dispersion I according to the invention 100 parts by weight of polyacrylate dispersion 160 parts by weight of water
  • the primer liquor was applied to the cover by roller application. After drying at 50 ° C was minted at 80 ° C and 150 bar.
  • Bally Flexometer dry 100,000 flexes wet 50,000 flexes
  • composition of the primer fleet 100 parts by weight of aqueous pigment preparation
  • the leather was sprayed 4 times with the primer liquor, after which
  • Bally flexometer dry 100,000 flexes
  • composition of the primer fleet :
  • the leather was sprayed 4 times with the primer liquor and then dried at 80 ° C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention se rapporte à l'utilisation de polyuréthanes spéciaux dans le bain d'apprêt pour le finissage du cuir.
PCT/EP1991/001271 1990-07-16 1991-07-08 Polyurethanes pour l'appret de cuir WO1992001817A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19904022539 DE4022539A1 (de) 1990-07-16 1990-07-16 Polyurethane fuer die ledergrundierug
DEP4022539.9 1990-07-16

Publications (1)

Publication Number Publication Date
WO1992001817A1 true WO1992001817A1 (fr) 1992-02-06

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ID=6410351

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/001271 WO1992001817A1 (fr) 1990-07-16 1991-07-08 Polyurethanes pour l'appret de cuir

Country Status (2)

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DE (1) DE4022539A1 (fr)
WO (1) WO1992001817A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE9303951U1 (fr) * 1993-03-17 1993-06-17 Helcor-Leder-Tec Gmbh, 3452 Hehlen, De
EP0647665A2 (fr) * 1993-10-12 1995-04-12 The Thompson Minwax Company Composition de polyuréthane-urée autoréticulable et dispersable à l'eau
EP0682049A1 (fr) * 1994-05-09 1995-11-15 Hoechst Aktiengesellschaft Polyuréthane-polyurés et leur utilisation comme dispersant pour des résines synthétiques
EP0712877A1 (fr) 1994-11-16 1996-05-22 Sika AG, vorm. Kaspar Winkler & Co. Dispersions aqueuses de polymère, procédé pour leurs préparations et leurs utilisations
US5961495A (en) * 1998-02-20 1999-10-05 Becton, Dickinson And Company Medication delivery pen having a priming mechanism
US7754811B2 (en) 2007-08-22 2010-07-13 Bayer Materialscience Ag NC-PU dispersions with accelerated drying

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE29806416U1 (de) * 1998-04-08 1998-07-30 Schaefer Philipp Ziegenleder mit einer genarbten Beschichtung
ES2217642T3 (es) * 1999-04-15 2004-11-01 Alexander Dr. Harsanyi Procedimiento para la produccion de cuero a partir de piel de pez.
DE102010021465A1 (de) 2010-05-25 2011-12-01 Clariant International Ltd. Wässrige Polyurethan-Polyharnstoff-Dispersionen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1445204A1 (de) * 1960-08-01 1969-01-23 Allied Chem Lacke fuer Lackleder
EP0278278A1 (fr) * 1987-01-29 1988-08-17 Henkel Kommanditgesellschaft auf Aktien Agent de revêtement et d'apprêt pour le cuir
EP0278394A2 (fr) * 1987-02-12 1988-08-17 Henkel Kommanditgesellschaft auf Aktien Masse de revêtement diluable dans l'eau

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1445204A1 (de) * 1960-08-01 1969-01-23 Allied Chem Lacke fuer Lackleder
EP0278278A1 (fr) * 1987-01-29 1988-08-17 Henkel Kommanditgesellschaft auf Aktien Agent de revêtement et d'apprêt pour le cuir
EP0278394A2 (fr) * 1987-02-12 1988-08-17 Henkel Kommanditgesellschaft auf Aktien Masse de revêtement diluable dans l'eau

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE9303951U1 (fr) * 1993-03-17 1993-06-17 Helcor-Leder-Tec Gmbh, 3452 Hehlen, De
EP0647665A2 (fr) * 1993-10-12 1995-04-12 The Thompson Minwax Company Composition de polyuréthane-urée autoréticulable et dispersable à l'eau
EP0647665A3 (fr) * 1993-10-12 1995-09-27 Eastman Kodak Co Composition de polyuréthane-urée autoréticulable et dispersable à l'eau.
EP0682049A1 (fr) * 1994-05-09 1995-11-15 Hoechst Aktiengesellschaft Polyuréthane-polyurés et leur utilisation comme dispersant pour des résines synthétiques
EP0712877A1 (fr) 1994-11-16 1996-05-22 Sika AG, vorm. Kaspar Winkler & Co. Dispersions aqueuses de polymère, procédé pour leurs préparations et leurs utilisations
US5961495A (en) * 1998-02-20 1999-10-05 Becton, Dickinson And Company Medication delivery pen having a priming mechanism
US7754811B2 (en) 2007-08-22 2010-07-13 Bayer Materialscience Ag NC-PU dispersions with accelerated drying

Also Published As

Publication number Publication date
DE4022539A1 (de) 1992-01-23

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