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WO1992000336A1 - Utilisation de dispersions aqueuses de polyurethanne dans le corroyage du cuir - Google Patents

Utilisation de dispersions aqueuses de polyurethanne dans le corroyage du cuir Download PDF

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Publication number
WO1992000336A1
WO1992000336A1 PCT/EP1991/001132 EP9101132W WO9200336A1 WO 1992000336 A1 WO1992000336 A1 WO 1992000336A1 EP 9101132 W EP9101132 W EP 9101132W WO 9200336 A1 WO9200336 A1 WO 9200336A1
Authority
WO
WIPO (PCT)
Prior art keywords
oil
weight
parts
opened
polyurethane dispersion
Prior art date
Application number
PCT/EP1991/001132
Other languages
German (de)
English (en)
Inventor
Michael Marschner
Werner Krause
Horst Schulz
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 WO1992000336A1 publication Critical patent/WO1992000336A1/fr

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
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6407—Reaction products of epoxy resins with at least equivalent amounts of compounds containing active hydrogen

Definitions

  • the invention relates to the use of an aqueous polyurethane dispersion which, based on 100 parts by weight of di- and / or polyisocyanates, contains 61 to 450 parts by weight of castor oil and / or epoxidized fatty acid esters ring-opened with C 8 alkyl alcohols in the 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 (Ull anns Encyclopedia of Technical Chemistry, 4th edition, volume 16, pages 159-163, Verlag Chemie Weinheim, 1978).
  • the finishing film must adhere firmly to the leather and satisfy extremely high bending and expansion requirements during further processing and during later use. Furthermore, the surface of the
  • Dressing film must be hard enough to ensure adequate 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 priming and finishing liquors, with respective intermediate drying and, if necessary, intermediate hangers and embossing. In many cases, the finishing liquors contain polyurethanes, thermoplastic polyacrylates and / or butadiene copolymers as film-forming substances.
  • DE 37 02 615 describes polyurethane dispersions as coating and finishing agents for leather whose polyurethane solids, based on 100 parts by weight of isocyanate component, 6 to 60 parts by weight of castor oil, alkoxylated castor oil and / or epoxidized triglycerides which are ring-opened with C 8 alkyl alcohols are optionally alkoxylated.
  • leather that has been finished with these polyurethane dispersions have good fastness properties.
  • the subject of the invention is the use of an aqueous polyurethane dispersion with a solids content of between 10 and 50% by weight and a Brookfield viscosity at 20 ° C. of between 10 and 5000 mPas, the polyurethane solids, based on 100 parts by weight of di- and / or Contains polyisocyanates, 61 to 450 parts by weight of castor oil and / or epoxidized fatty acid esters ring-opened with C ⁇ _8-alkyl alcohols, in the leather finishing.
  • a polyurethane dispersion is used, the polyurethane solids, based on 100 parts by weight of di- and / or polyisocyanates, 80 to 200 parts by weight of castor oil and / or with Ci-8-alkyl alcohols contains ring-opened epoxidized fatty acid esters.
  • Epoxidized fatty acid esters are preferably epoxidized fatty acid mono-, di- and / or triglycerides which are obtained by epoxidation of unsaturated oils, especially soybean oil, linseed oil, talc oil, construction oil seed oil, peanut oil , Palm oil, sunflower oil, rape oil and / or claw oil are accessible.
  • unsaturated fatty acid esters can be epoxidized 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 fatty acid esters with monohydric C 8 alkyl alcohols for example methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, n-hexanol, 2-ethylhexanol, n-heptanol and / or n-octanol , but preferably with methanol in the presence of catalysts, for example sodium methylate or potassium hydroxide, at temperatures between 40 and 160 ° C and pressures between 10 4 and 3 * 10 ⁇ Pa.
  • catalysts for example sodium methylate or potassium hydroxide
  • the polyurethanes to be used according to the invention may contain polyester polyols which are composed of aliphatic and / or aromatic dicarboxylic acids and diols.
  • Suitable aliphatic dicarboxylic acids are, for example, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid and / or dimer fatty acids.
  • suitable aromatic dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and / or tetrahydrophthalic acid. Adipic acid is preferred as the aliphatic dicarboxylic acid and isophthalic acid is preferred as the aromatic dicarboxylic acid.
  • dicarboxylic acids mentioned are mixed in a manner known per se with diols, for example ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, dimerocenol (SovermolR 650NS, Henkel KGaA) and / or neopentylglycol, esterified.
  • diols for example ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, dimerocenol (SovermolR 650NS, Henkel KGaA) and / or neopentylglycol, esterified.
  • polyurethanes to be used according to the invention may also contain polyether polyols with average molecular weights between 1,000 and 20,000, 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 means a number between 0 and 8, with the proviso that the sum y + z is between 1 and 8
  • d is a number between 20 and 150
  • e is a number between 1 and 15, with the proviso that - based on all ethylene oxide and propylene oxide units of the polyether polyol - the sums a + c + e between 3 and 40, b + d are between 40 and 300 and c + e between 1 and 15.
  • the polyether polyols of the general formula are known compounds which are prepared 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 at temperatures between 110 and 200 ° C. and pressures between 10 ⁇ and 2-10 ⁇ Pa are accessible.
  • dihydroxy and / or diamino compounds which contain at least one anionic group, preferably one or more carboxylate, sulfonate and / or ammonium groups, for example dimethylolpropionic acid, are used in the production of polyurethanes to be used according to the invention.
  • anionic group preferably one or more carboxylate, sulfonate and / or ammonium groups, for example dimethylolpropionic acid
  • the polyurethanes to be used according to the invention contain, based on 100 parts by weight of isocyanate component, 61 to 450 parts by weight of castor oil and / or epoxidized fatty acid esters ring-opened with C8 -8 alkyl alcohols, 0 to 300 parts by weight of polyester polyols, 0 to 60 parts by weight of polyether polyols and 5 to 50 parts by weight bearing at least one anionic group Dihydroxy and / or diamino compounds, preferably 80 to 200 parts by weight of castor oil and / or epoxidized fatty acid esters opened with C 8 alkyl alcohols, 1 to 180 parts by weight of polyester polyols, 0 to 20 parts by weight of polyether polyols and 5 to 30 parts by weight of dihydroxy and at least one anionic group / or diamino compounds, with the proviso that the proportion of the OH equivalents of the polyester polyols, polyether polyols and at least one anionic group Dihydroxy compounds is between 10
  • 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-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate ( Isophorone diisocyanate), tetramethylene diisocyanates, trimethylhexamethylene diisocyanate, dimer fatty acid diisocyanates, 1,4-phenylene diisocyanate, diphenyl ethane diisocyanate, toluene-2,4- and / or toluene-2,6-diisocyanate, 2.4 f 4'- Tr ⁇ isocyanato-diphenyl ether and / or 4 ', 4'',4' -Triisocyanato-triphenyl ethane.
  • 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 be used alone or in combination with the above-mentioned unblocked di- and / or polyisocyanates.
  • the blocked di- and polyisocyanates are resistant to hydroxyl groups at room temperature and only react at temperatures above 50 ° C.
  • the content of blocked di- and / or polyisocyanates is preferably between 0 and 60% by weight, particularly preferably between 0 and 10% by weight.
  • Blocked di- and polyisocyanates are produced by reacting organic di- or polyisocyanates, for example isophorone diisocyanate, with an alcohol, for example phenol or m-cresol, in amounts such that all isocyanate groups are blocked.
  • organic di- or polyisocyanates for example isophorone diisocyanate
  • alcohol for example phenol or m-cresol
  • the polyurethanes to be used according to the invention can be produced by known processes (Ullmann's Encyclopedia of technical chemistry, volume 19, pages 302 ff., Verlag Chemie Wein ⁇ heim, 1980).
  • Di- and / or polyisocyanates with polyols and at least one anionic group containing dihydroxy and / or diamino compounds in the presence of solvents, for example N-methylpyrrolidone and / or methyl ethyl ketone, and, if appropriate, catalysts, such as N-methylmorpholine, are preferably added Temperatures between 60 and 120 ° C converted to prepolymers.
  • the polyurethane prepolymer composition is then dispersed in water and then, if appropriate, reacted with chain extenders, such as alkoxylated glycerols and / or diamines, for example ethylenediamine, hexamethylenediamine and / or piperazine.
  • chain extenders such as alkoxylated glycerols and / or diamines, for example ethylenediamine, hexamethylenediamine and / or piperazine.
  • the NCO groups still present in the polyurethane prepolymer react with water to form carbon dioxide, which leads to not inconsiderable, disruptive foam formation.
  • a polyurethane dispersion with a high content of castor oil and / or epoxidized fatty acid esters ring-opened with C8-alkyl alcohols as polyol component in the polyurethane solid, a solids content between 10 and 50 wt .-% and a Brookfield viscosity at 20 ° C between 10 and 5000 mPas can be used according to the invention in leather finishing in primer, color and / or finishing liquors.
  • the additive liquors may contain pigment preparations, film-forming substances in the form of aqueous dispersions, such as polyacrylates and / or polyurethanes, binders and fillers, matting agents, penetrators and / or plasticizers as further constituents.
  • finishing liquors can be applied using all of the technologies customary in leather finishing, for example by spraying, plushing, pouring and / or roller application.
  • the finishing liquors contain polyurethane dispersions to be used according to the invention in amounts of 1 to 60% by weight.
  • Tl means parts by weight
  • Base material natural crust leather
  • Head coloring 100 parts of metal complex dye solution 200 parts of polyglycol ether 200 parts of water

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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)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne l'utilisation dans le corroyage du cuir d'une dispersion aqueuse de polyuréthanne qui contient, par rapport à 100 parties en poids de diisocyanates et/ou de polyisocyanates, entre 61 à 450 parties en poids d'huile de ricin et/ou d'esters d'acides gras époxydés dont le cycle est ouvert avec des C1-8-alkylacools.
PCT/EP1991/001132 1990-06-27 1991-06-19 Utilisation de dispersions aqueuses de polyurethanne dans le corroyage du cuir WO1992000336A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4020456.1 1990-06-27
DE19904020456 DE4020456A1 (de) 1990-06-27 1990-06-27 Verwendung waessriger polyurethandispersionen in der lederzurichtung

Publications (1)

Publication Number Publication Date
WO1992000336A1 true WO1992000336A1 (fr) 1992-01-09

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ID=6409185

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/001132 WO1992000336A1 (fr) 1990-06-27 1991-06-19 Utilisation de dispersions aqueuses de polyurethanne dans le corroyage du cuir

Country Status (2)

Country Link
DE (1) DE4020456A1 (fr)
WO (1) WO1992000336A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8076001B2 (en) 2008-09-02 2011-12-13 Ppg Industries Ohio, Inc Crosslinked coatings comprising lactide
US8614286B2 (en) 2008-09-02 2013-12-24 Ppg Industries Ohio, Inc. Biomass derived radiation curable liquid coatings
US9650540B2 (en) 2008-09-02 2017-05-16 Ppg Industries Ohio, Inc. Radiation curable coating compositions comprising a lactide reaction product
CN118126278A (zh) * 2024-05-06 2024-06-04 旭川化学（苏州）有限公司 一种妥尔油基聚氨酯合成革及其制备方法和应用

Families Citing this family (1)

* 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, 30519 Hannover Ziegenleder mit einer genarbten Beschichtung

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0152585A1 (fr) * 1983-12-24 1985-08-28 Henkel Kommanditgesellschaft auf Aktien Matière adhésive de polyuréthane à deux composants
EP0260499A2 (fr) * 1986-09-06 1988-03-23 Henkel Kommanditgesellschaft auf Aktien Utilisation de polyols gras pour la préparation de dispersions aqueuses de polyuréthane
EP0278394A2 (fr) * 1987-02-12 1988-08-17 Henkel Kommanditgesellschaft auf Aktien Masse de revêtement diluable dans l'eau
EP0278278A1 (fr) * 1987-01-29 1988-08-17 Henkel Kommanditgesellschaft auf Aktien Agent de revêtement et d'apprêt pour le cuir

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0152585A1 (fr) * 1983-12-24 1985-08-28 Henkel Kommanditgesellschaft auf Aktien Matière adhésive de polyuréthane à deux composants
EP0260499A2 (fr) * 1986-09-06 1988-03-23 Henkel Kommanditgesellschaft auf Aktien Utilisation de polyols gras pour la préparation de dispersions aqueuses de polyuréthane
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 (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8076001B2 (en) 2008-09-02 2011-12-13 Ppg Industries Ohio, Inc Crosslinked coatings comprising lactide
US8614286B2 (en) 2008-09-02 2013-12-24 Ppg Industries Ohio, Inc. Biomass derived radiation curable liquid coatings
US9650540B2 (en) 2008-09-02 2017-05-16 Ppg Industries Ohio, Inc. Radiation curable coating compositions comprising a lactide reaction product
CN118126278A (zh) * 2024-05-06 2024-06-04 旭川化学（苏州）有限公司 一种妥尔油基聚氨酯合成革及其制备方法和应用

Also Published As

Publication number Publication date
DE4020456A1 (de) 1992-01-02

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