WO1998039488A1 - Utilisation de polymeres pour le nourrissage a l'huile du cuir - Google Patents

Utilisation de polymeres pour le nourrissage a l'huile du cuir Download PDF

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Publication number
WO1998039488A1
WO1998039488A1 PCT/EP1998/001012 EP9801012W WO9839488A1 WO 1998039488 A1 WO1998039488 A1 WO 1998039488A1 EP 9801012 W EP9801012 W EP 9801012W WO 9839488 A1 WO9839488 A1 WO 9839488A1
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WO
WIPO (PCT)
Prior art keywords
leather
polymers
acrylic acid
acid
methoxy
Prior art date
Application number
PCT/EP1998/001012
Other languages
German (de)
English (en)
Inventor
Arno Behr
Wolfgang Ritter
Rudolf Zauns-Huber
Oliver Pietsch
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 WO1998039488A1 publication Critical patent/WO1998039488A1/fr

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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
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes

Definitions

  • the invention relates to the use of special polymers based on methoxy (polyethylene glycol) methacrylate for greasing leather.
  • the greasing of vegetable and / or mineral-tanned leather or fur skins is an essential process step in the finishing of the ready-to-use material.
  • the shape of the fat distribution in the skin substance and the extent to which the fat components are incorporated into the skin substance have a decisive influence on the properties and usability of the finished products.
  • the special structure of the fatliquor - for example the extent of their lipophilic groups and any reactive groups present for reaction with suitable reactive components in the tanned leather - determine, among other things, the durability and effect of the greasing finish in practical use of the leather and fur products.
  • a very important need in practice is to provide greasy substances or finishing agents that can be bound so reliably in the tanned skin substance that a sufficient resistance to washing and cleaning of the leather and fur products is ensured for the practical need .
  • High-quality leather goods for example from the clothing industry, should be accessible to both aqueous-surfactant laundry and, if necessary, chemical cleaning without a significant loss in quality. Finally, for special cases further condition of sufficient waterproofness of the finished leather is desired.
  • EP-A-372 746 discloses amphiphilic copolymers which are formed from a predominant proportion of at least one hydrophobic monomer and a minor proportion of at least one copolymerizable hydrophilic monomer.
  • hydrophobic monomers long-chain alkyl (meth) acrylates, long-chain alkoxy- or alkylphenoxy (polyethylene oxide) - (meth) acrylates, primary alkenes, vinyl esters of long-chain alkyl carboxylic acids and their mixtures.
  • the minor proportion of hydrophilic comonomers are ethylenically unsaturated water-soluble acids or hydrophilic basic comonomers.
  • the molecular weight (weight average) of the copolymers is in the range from 2,000 to 100,000. The copolymers are said to be suitable for waterproofing leather.
  • EP-A-412 389 describes the use of copolymers as agents for the hydrophobization of leather and fur skins which are obtained by radical copolymerization of (a) Cg_4 () monoolefins with (b) ethylenically unsaturated C4_g-dicarboxylic acid anhydrides in the manner of a bulk polymerization at temperatures of 80 up to 300 ° C to copolymers with molecular weights of 500 to 20,000 g / mol, subsequent solvolysis of the anhydride groups of the copolymers and at least partial neutralization of the carboxyl groups formed in the solvolysis have been prepared in an aqueous medium with bases and which are in the form of aqueous dispersions or solutions .
  • monoethylenically unsaturated dicarboxylic acid anhydrides half esters or half amides of monoethylenically unsaturated C4_i 2-dicarboxylic acids, amides of C3..12-monocarboxylic acids or mixtures thereof, in copolymerized form and having molar masses of 500 to 30,000 g / mol.
  • WO 93/05188 relates to the use of aqueous dispersions of co-oligomers from the radical-triggered emulsion copolymerization of (a) half-esters of maleic acid with oleophilic alcohols and / or their lower alkylene oxide adducts and (b) acrylic and / or methacrylic acid as an amphiphilic agent for greasing equipment of leather.
  • WO 94/01587 describes co-oligomers based on (a) crotonic acid esters and (b) free-radically copolymerizable hydrophilic ethylenically unsaturated acids and / or their anhydrides for the finishing of leather.
  • co-oligomers which have been prepared by reacting the two obligatory monomers in an organic solvent (xylene) are specifically disclosed.
  • EP-A-583 973 describes special copolymers for rendering leather repellent. These copolymers are said to contain free carboxylate groups and fatty alkyl groups and contain (a) ethylenically unsaturated dicarboxylic acids and (b) ethylenically unsaturated monofunctional compounds, for example maleic acid semiesters, as monomer units. Description of the invention
  • the object of the present invention was to provide substances for the greasing of leather, furs and the like. These substances should in particular be able to give the leather or furs treated with them good wash fastness and good fastness to cleaning.
  • greying equipment means on the one hand leather greasing in the narrower sense of the word, and also the hydrophobization of leather.
  • Another task was to ensure that these substances are well absorbed by leather and are particularly characterized by a high leach liquor consumption. In addition to its purely technical relevance, the latter point is also useful from an ecological point of view.
  • CH2 C (CH 3 ) COO (CH 2 - CH 2 -0) n - CH3
  • n is a number ranging from 1 to 100.
  • polymer encompasses both homopolymers which are composed exclusively of methoxy (polyethylene glycol) methacrylate units and copolymers which, in addition to methoxy (polyethylene glycol) methacrylate units, also contain one or more other monomer units which can be copolymerized therewith polymerized included.
  • the present application relates to the use of polymers based on methoxy (polyethylene glycol) methacrylate for greasing leather.
  • a polymer that contains polymerized as building blocks a) methoxy (polyethylene glycol) methacrylate and b 1) esters or ester mixtures of crotonic acid and C ⁇ ⁇ -40 fatty alcohols and / or b2) acrylic acid and / or methacrylic acid and / or b3) esters or ester mixtures of acrylic acid and / or methacrylic acid and C ⁇ Q.
  • methoxy (polyethylene glycol) methacrylates whose molecular weights are in the range from 300 to 2000 and in particular from 300 to 500.
  • the polymers to be used according to the invention can be prepared per se by all methods known to the person skilled in the art from the prior art.
  • the polymers according to the invention are particularly suitable for finishing chrome-tanned leather.
  • the good greasing or hydrophobizing properties of the polymers according to the invention are based essentially on their amphiphilic character: the greasing or water-repellent effect of the polymers is brought about by the alkyl radicals present in the polymers, the anchoring in the leather structure is brought about by the fact that the polymers have sufficient carboxyl extinctions Number contain that there is a stable interaction between the carboxyl groups of the fatty polymer and the chromium present in the leather structure.
  • C16 / C18 fat acrylate acrylic acid ester of Ci6 / i8 fatty alcohol (Sidobre Sinnova)
  • V50 2,2-azobis (2-amidinopropane) dichloride (from Wako)
  • Dehydrophen 100 adduct of 10 moles of ethylene oxide per mole of nonylphenol (from Henkel)
  • Acrylic acid 25 g of 100 dehydrophenes and 0.1 g of mercaptopropionic acid.
  • a subsequent reaction was then carried out at 90 ° C. for 1 h. After cooling, the product was neutralized with 25% ammonia.
  • the aqueous dispersion had a pH of 7.2 and a solids content of 52.8%.
  • This variant of the production corresponds to a final monomer composition of 50% bisomer MPEG 350 MA, 30% C16 / C18 fat acrylate and 20% acrylic acid.
  • a subsequent reaction was then carried out at 90 ° C. for 1 h. After cooling, the product was neutralized with 25% ammonia.
  • the aqueous dispersion had a pH of 8.5 and a solids content of 47.9%.
  • This variant of the preparation corresponds to a final monomer composition of 40% bisomer MPEG 350 MA, 30% C16 / C18 fat acrylate and 30% acrylic acid.
  • a subsequent reaction was then carried out at 90 ° C. for 1 h. After cooling, the product was neutralized with 25% ammonia.
  • the aqueous dispersion had a pH of 7.1 and a solids content of 51.0%.
  • This variant of the production corresponds to a final monomer composition of 30% bisomer MPEG 350 MA, 30% C16 / C18 fat acrylate and 40% acrylic acid.
  • a subsequent reaction was then carried out at 90 ° C. for 1 h. After cooling, the product was neutralized with 25% ammonia.
  • the aqueous dispersion had a pH of 7.3 and a solids content of 50.6%.
  • This variant of the production corresponds to a final monomer composition of 60% bisomer MPEG 350 MA, 10% C16 / C18 fat acrylate and 30% acrylic acid.
  • a subsequent reaction was then carried out at 90 ° C. for 1 h. After cooling, the product was neutralized with 25% ammonia.
  • the aqueous dispersion had a pH of 7.3 and a solids content of 51.5%.
  • a subsequent reaction was then carried out at 90 ° C. for 1 h. After cooling, the product was neutralized with 25% ammonia.
  • the aqueous dispersion had a pH of 7.4 and a solids content of 52.9%.

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  • 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)

Abstract

Ces polymères à base de méthoxy(polyéthylèneglycol)méthacrylate se prêtent au nourrissage à l'huile du cuir.
PCT/EP1998/001012 1997-03-03 1998-02-21 Utilisation de polymeres pour le nourrissage a l'huile du cuir WO1998039488A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1997108501 DE19708501A1 (de) 1997-03-03 1997-03-03 Verwendung von Polymeren zur fettenden Ausrüstung von Leder
DE19708501.6 1997-03-03

Publications (1)

Publication Number Publication Date
WO1998039488A1 true WO1998039488A1 (fr) 1998-09-11

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ID=7822031

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/001012 WO1998039488A1 (fr) 1997-03-03 1998-02-21 Utilisation de polymeres pour le nourrissage a l'huile du cuir

Country Status (2)

Country Link
DE (1) DE19708501A1 (fr)
WO (1) WO1998039488A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH369596A (fr) * 1956-01-09 1963-05-31 Goodrich Co B F Procédé pour la préparation de copolymères
US4230844A (en) * 1978-09-28 1980-10-28 E. I. Du Pont De Nemours And Company Processes for the preparation of polymeric thickeners and uses thereof
EP0372146A1 (fr) * 1988-11-24 1990-06-13 SORIN BIOMEDICA S.p.A. Procédé d'enroulement de filaments pour dispositifs d'échange, comme d'oxygénateurs de sang ou similaires, et dispositif d'échange fabriqué selon ce procédé
EP0418661A1 (fr) * 1989-09-16 1991-03-27 BASF Aktiengesellschaft Utilisation de copolymérisates à base d'esters non saturés à longue chaîne et d'acides carboxyliques à liaison éthylénique pour hydrophober du cuir ou des peaux
WO1994001587A1 (fr) * 1992-07-14 1994-01-20 Henkel Kommanditgesellschaft Auf Aktien Nouveaux agents de graissage du cuir et leur utilisation
EP0583973A2 (fr) * 1992-08-18 1994-02-23 Ciba Specialty Chemicals Water Treatments Limited Composition d'imprégnation pour cuir
DE19513521A1 (de) * 1995-04-10 1996-10-17 Henkel Kgaa Verwendung von amphiphilen Copolymeren zur Verbesserung der Beständigkeit von Leder gegenüber Hydrotropen

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH369596A (fr) * 1956-01-09 1963-05-31 Goodrich Co B F Procédé pour la préparation de copolymères
US4230844A (en) * 1978-09-28 1980-10-28 E. I. Du Pont De Nemours And Company Processes for the preparation of polymeric thickeners and uses thereof
EP0372146A1 (fr) * 1988-11-24 1990-06-13 SORIN BIOMEDICA S.p.A. Procédé d'enroulement de filaments pour dispositifs d'échange, comme d'oxygénateurs de sang ou similaires, et dispositif d'échange fabriqué selon ce procédé
EP0418661A1 (fr) * 1989-09-16 1991-03-27 BASF Aktiengesellschaft Utilisation de copolymérisates à base d'esters non saturés à longue chaîne et d'acides carboxyliques à liaison éthylénique pour hydrophober du cuir ou des peaux
WO1994001587A1 (fr) * 1992-07-14 1994-01-20 Henkel Kommanditgesellschaft Auf Aktien Nouveaux agents de graissage du cuir et leur utilisation
EP0583973A2 (fr) * 1992-08-18 1994-02-23 Ciba Specialty Chemicals Water Treatments Limited Composition d'imprégnation pour cuir
DE19513521A1 (de) * 1995-04-10 1996-10-17 Henkel Kgaa Verwendung von amphiphilen Copolymeren zur Verbesserung der Beständigkeit von Leder gegenüber Hydrotropen

Also Published As

Publication number Publication date
DE19708501A1 (de) 1998-09-10

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