EP1416057A1 - Cuir sans chrome, imperméable à l'eau - Google Patents

Cuir sans chrome, imperméable à l'eau Download PDF

Info

Publication number
EP1416057A1
EP1416057A1 EP20030023284 EP03023284A EP1416057A1 EP 1416057 A1 EP1416057 A1 EP 1416057A1 EP 20030023284 EP20030023284 EP 20030023284 EP 03023284 A EP03023284 A EP 03023284A EP 1416057 A1 EP1416057 A1 EP 1416057A1
Authority
EP
European Patent Office
Prior art keywords
leather
water
free
chromium
chrome
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.)
Withdrawn
Application number
EP20030023284
Other languages
German (de)
English (en)
Inventor
Martin Dr. Kleban
Ahmet Kaplan
Jürgen Dr. Reiners
Henrik Winther
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.)
Lanxess Deutschland GmbH
Original Assignee
Bayer Chemicals 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 Chemicals AG filed Critical Bayer Chemicals AG
Publication of EP1416057A1 publication Critical patent/EP1416057A1/fr
Withdrawn legal-status Critical Current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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/04—Mineral tanning
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/4935—Impregnated naturally solid product [e.g., leather, stone, etc.]

Definitions

  • the invention relates to chrome-free leather with high water resistance, a method for its manufacture, its use as well as the use of silicones as Hydrophobing agent for chrome-free tanned leather.
  • chrome-free leather Applied to chrome-free leather, the desired water resistance can already be therefore cannot be achieved because the appropriate amount of chrome tanning agent replaced by large amounts of hydrophilic vegetable tannins and / or syntans must become.
  • hydrophilic ingredients in leather favor penetration from water to leather and not the opposite effect of water repellency.
  • chrome-tanned leather is complex.
  • leather waste generated during the manufacture of leather articles and leather at the end of its useful life in terms of waste disposal problematic, especially since chrome is no longer stored in certain landfills may.
  • chrome-tanned leather may have traces of Cr (VI) under certain Develop storage conditions or during combustion.
  • Chrome is tanned in the usual manufacturing process for waterproof leathers Leather with a combination of greasing agents and water repellents, in usually treated with silicone emulsions. Since this treatment is done in water the use of emulsifiers for the water repellent enhancers is also required, which in turn adversely affect water resistance.
  • the emulsification is carried out by means of compounds, their emulsifying, functional groups destroyed in a subsequent fixing step can be. This is usually done with chromium salts.
  • the object of the invention was therefore to provide waterproof, chrome-free tanned leather.
  • the invention relates to chrome-free leather with a water resistance measured as Penetration time according to DIN 53 338 of at least 30 min., Preferably of greater than 2 hours.
  • Chromium-free in the sense of the present invention means not with chromium salts tanned.
  • Chromium in leather is preferably less than 100 ppm.
  • the chrome-free leather according to the invention preferably has a shrinking temperature greater than 70 ° C, especially greater than 75 ° C.
  • the leather according to the invention is preferred which has an iron content of 1 to 7% by weight.
  • the iron content is determined as follows: A sample of the leather is to maintain the reference weight at 70 ° C in a vacuum to constant weight dried. It is then incinerated at 800 ° C, the Fe (III) content with a commercially available method determined by wet chemistry, and on the reference weight recalculated.
  • the iron content preferably results from tanning with iron salts.
  • Iron tanning is known in principle, see, for example, prior art Stather, Geranium chemistry and technology, Akademie Verlag, Berlin, 1957, 474-480; Heidemann E. at al., Possibilities and Limits of Iron Tanning, Das Leder, 1990, 8-14; Balasubramanian S. et al., Iron Complexes as Tanning Agents, JALCA, 12997, 218-224.
  • the leather according to the invention has an Si content of at least 0.2% by weight, in particular at least 1.0% by weight determined as silicate after combustion.
  • the leather according to the invention preferably contains silicones as water repellents, especially those used in the description of the manufacturing process below were used as water repellents.
  • the leather according to the invention has a water vapor permeability, measured according to DIN 53333, of greater than 0.8 mg / cm 2 h, in particular greater than 2 mg / cm 2 h.
  • the leather according to the invention is preferably by water absorption from less than 30 wt%, especially less than 20 wt% to Water penetration during the measurement according to DIN 53 338 or after 8 hours Marked water contact.
  • the invention further relates to a method for producing the invention leather, which is characterized by the fact that one chrome-tanned leather treated with a water repellent.
  • hydrophobizing agent which a) is self-emulsifying Is water and has ionic pH-sensitive groups and / or b) that in Combination with an emulsifier is used, the emulsifier being ionic has pH-sensitive groups.
  • Preferred ionic, pH-sensitive groups are within the scope of this application for example carboxylic acids and / or their salts or amines and / or their Salts, substituted sulfonylureas or cyanureas and / or their salts understand. That Reaction products from toluenesulfonyl isocyanate and amines or Cyanamide and isocyanates, and their salts, which are added when base is added (triethylamine, NaOH) form.
  • Suitable lubricants for water repellency are those that are free of electrolyte-stable anionic emulsifiers, e.g. sulfonated, sulfated or sulfited compounds with an emulsifying effect.
  • electrolyte-stable anionic emulsifiers e.g. sulfonated, sulfated or sulfited compounds with an emulsifying effect.
  • Fats and oils based on long-chain alkanes, alcohols, esters or other hydrophobic hydrocarbons e.g. Fats and oils based on long-chain alkanes, alcohols, esters or other hydrophobic hydrocarbons. These connections can be more natural or be of synthetic origin, such as, for example, fish oils, claw oils, vegetable oils or mineral oils.
  • these fatliquoring agents can be emulsifiers based on carboxylic acids, polycarboxylic acids or polyethers, to facilitate processing in an aqueous liquor.
  • the preferred hydrophobizing agents with ionic, pH-sensitive groups are to name appropriately modified silicones, especially polysiloxanes.
  • Suitable polysiloxanes are, for example, linear, branched or cyclic Polysiloxanes, which are optionally substituted. Polydimethylpolysiloxanes are preferred, which are optionally substituted. Suitable substituents are either via a spacer, optionally via heteroatoms or functional groups may be interrupted, connected to the main polysiloxane chain, or may also be bonded directly to a silicon atom of the polysiloxane main chain.
  • Suitable polysiloxanes are preferably polydialkylpolysiloxanes, polyalkylarylpolysiloxanes, with hydroxyalkyl, aminoalkyl, carboxyalkyl, hydroxyaryl, Carboxyaryl groups substituted polysiloxanes, which have a spacer with the polysiloxane main chain are connected, the spacer itself being an alkylene radical or a by functional groups, e.g. Ester, amide, urethane, carbonate, urea, ether, Imino, interrupted hydrocarbon residue can be.
  • the carboxyl group-containing compounds listed in EP-A 11 08 765 are particularly preferred Polysiloxanes and the polysiloxane raw materials used to manufacture them. Also preferred are those polysiloxanes that have hydrolyzable Residues have (Si-OR groups), which cross-link the Lead polysiloxane.
  • Polysiloxanes which are present as an aqueous dispersion are particularly preferred can therefore be used in an aqueous liquor.
  • the hydrophobizing agent is preferred in an amount of 0.1 to 10% by weight, based on fold weight, but especially 1 to 5% by weight.
  • pH-sensitive groups Using of water repellents without ionic, pH-sensitive groups is the Amount preferably 0.1 to 9 wt .-%. In the latter case, preferably Emulsifier with ionic, pH-sensitive groups in an amount of 5 to 25 wt .-%, based on the water repellant used.
  • the self-emulsifying water repellent with ionic, pH-sensitive groups is preferably in an amount of 0.1 to 10 wt .-%, but especially 1 to 5% by weight based on the shaved weight.
  • the chrome-free leather which may be retanned with the water repellent is preferably tanned with iron compounds Service.
  • the iron salt can either be of the nakedness Salt or as an aqueous solution.
  • Preferred iron salts are those of iron in the +3 oxidation state, for example iron chloride, iron sulfate, basic iron sulfate as well as iron in the oxidation state +2 as Ferrous sulfate.
  • the amount of iron is preferably from 0.3 to 5% by weight, in particular 1 to 3% by weight.
  • the tanning is preferably done in water at a temperature of 0 - 60 ° C, preferably 20-37 ° C.
  • the tanning liquor After adding the iron salts for tanning, the tanning liquor should have a pH of 1.0 to 3.2, preferably from 1.4 to 2.5. After a reasonable time to Penetration of 30 min. up to 24 h, preferably 1 h to 12 h, the pH of the tanning liquor raised to fix the iron salts.
  • a basic one is preferably used Connection, e.g. B. sodium hydroxide, carbonate, bicarbonate, formate, calcium carbonate or magnesium oxide is used.
  • the iron-tanned leather thus obtained has a shrinking temperature of greater than 70 ° C, preferably greater than 75 ° C. It also has a uniform one Yellow color. For example, it can be mechanically aftertreated by wilting, folding, etc. on conventional tanneries.
  • “retanning” means post-treatment from chrome-free tanned leather to color, levelness, softness, fullness but especially to optimize the behavior against water (hydrophobicity) and Fix tannins and auxiliaries.
  • the pH is generally in the range from 4.1 to 8.0 and is therefore suitable for penetration of the retanning products into the Leather.
  • any retanning agents used as well as those with pH-sensitive Fixing group-provided hydrophobizing agents or emulsifiers becomes the pH after the hydrophobization, preferably to 2.5 to 4.0, in particular to 3.3 lowered to 3.9.
  • Organic acids such as formic acid, Acetic acid or oxalic acid, optionally in combination with inorganic acids such as sulfuric acid or phosphoric acid.
  • the water content of the iron-tanned leather preferably reduced by withering, and then the thickness of the leather corrected by folding if necessary.
  • the retanning process is preferably carried out in a tanning drum in an aqueous liquor a temperature of 0 to 70 ° C, especially from 20 to 50 ° C instead and includes optionally, other than the hydrophobicizing and lubricating agents according to the invention Tools such as Polymers, synthetic retanning agents, vegetable retanning agents, Colorants, acids and bases.
  • the synthetic tanning agents suitable for this application are e.g. B. water-soluble condensation products from sulfonated aromatics, formaldehyde and optionally further substances from the groups of aromatics, urea, or urea derivatives.
  • Vegetable tannins are tannins obtained from vegetable sources from the Classes of condensed tannins or hydrolyzable tannins e.g. Chestnut extract, Mimosa, Tara or Quebracho.
  • the dyes are common water-soluble in leather applications Dyes, e.g. from the groups of acid dyes, direct dyes, Metal complex dyes or substantive dyes.
  • the preferred polymers for use are high molecular weight water soluble or water dispersible products e.g. from the (Co) polymerization reaction of unsaturated acids and their derivatives with e.g. filling or greasing effect on leather.
  • Acids and bases are used to change the pH of the aqueous liquor to influence the penetration properties of the compounds used or to fix them.
  • the hydrophobizing and fatliquoring agents according to the invention are used in Generally in 20 to 1000, preferably 50 to 200% aqueous liquor, based on Weight of the leather used, in a pH range from 4.1 to 8.0, preferably 5.0 applied to 7.5.
  • the addition of 0.1 to 10% by weight, preferably 1-5% by weight of the Hydrophobing agents and 1 - 20%, preferably 2 - 12% of the fatliquor can in one or more steps.
  • Other tools used can also be added in one or more steps together with or separately from the products according to the invention.
  • the retanning process is carried out in 1 - 48 h, preferably in 1.5 - 24 h, especially in 2 - 8 h.
  • the wet leather obtained from retanning can be processed using the usual technical methods Methods and machines are dried and finished, e.g. through vacuum drying, stenter drying or hanging drying and optional Subsequent tunneling, milling, grinding or polishing.
  • the leather obtained can improve the surface properties and physical fastness with commercially available products and machines with a polymeric film layer, such as e.g. described by W. Wenzel in Aqueous Finishing of Leather, JALCA, 1991, 442-455.
  • the preferably used pickled pelts for iron tanning are preferred acid pretreated, especially at pH 2-5, especially preferred at 3-4. This acid pretreatment is preferably decalcified and pickled nakedness used.
  • Compounds such as carboxylic acids are particularly used for pimples such as formic acid, acetic acid or oxalic acid or inorganic acids such as Sulfuric acid or acidic salts of sulfuric acid or mixtures thereof.
  • non-polymeric acids are difunctional carboxylic acids such as tartaric acid, maleic acid, glutaric acid, phthalic acid and / or adipic acid; trifunctional carboxylic acids such as citric acid.
  • Preferred polymeric carboxylic acids are copolymers which can be obtained by radical polymerization using (meth) acrylic acid, maleic acid or itaconic acid, maleic anhydride or their derivatives with other comonomers which contain no carboxyl groups.
  • Terpolymers or copolymers which are composed of more than 3 comonomers are also suitable.
  • These acids are preferably obtained in an amount of 0.5 to 10% by weight used on the nakedness used, in particular 1-4 wt .-%.
  • the acidic pretreatment preferably proceeds in such a way that to the nakedness used Pimples are given in an amount so that the pH of the pickled bare on a value of 2-5, in particular reduced to 3-4.
  • the pimple connections are preferably added to the nakedness in a tanning drum in aqueous solution. This is generally done at a temperature of 0 to 60 ° C, especially at 20 to 37 ° C. It is preferably 10 min. up to 24 h, especially 30 min. up to 2 h pretreated.
  • a fatty agent is particularly preferred for the acidic pretreatment added.
  • Preferred lubricants for this use are those that are free of electrolyte stable anionic emulsifiers, e.g. sulfonated, sulfated or sulfited compounds with an emulsifying effect.
  • electrolyte stable anionic emulsifiers e.g. sulfonated, sulfated or sulfited compounds with an emulsifying effect.
  • these fatliquoring agents can be emulsifiers based on carboxylic acids.
  • Polycarboxylic acids or polyethers are added, to facilitate processing in an aqueous liquor.
  • the fatliquor used in the pretreatment can have the properties of affect the finished leather, especially in terms of softness and Water resistance. Based on the pelt weight, 0.1 - 5% by weight are particularly important preferably 0.5-3% by weight added.
  • the aminopolysiloxane thus produced is initially charged at 55 ° C. and 15.6 g of caprolactone and 130 g of ethyl acetate are added. Then 0.2 g of titanium tetrabutylate or dibutyltin dilaurate and 10 g of ethyl acetate are added. The mixture is stirred for 10 hours at about 75 ° C. (The carbonyl band of the lactone (no longer present at 1722 cm -1 ) is in the IR spectrum. Then the ethyl acetate is distilled off (about 140 g).
  • the prepolymer is diluted with 6000 g acetone. 18.0 g of ethylenediamine and 12.5 g of hydrazine hydrate in 300 g of water are added to this solution and the mixture is stirred at 50 ° C. for 15 minutes. A solution of 33.6 g of cyanamide in 400 g of water is then added. Another 20 minutes later, 80.7 g of triethylamine are added. The CO 2 evolution is ended after 45 minutes. The mixture is diluted with 6000 g of water and then the acetone is distilled off under reduced pressure. The result is a finely divided dispersion with an average particle size of the disperse phase of approx. 95 nm, a solids content of 32.5% and an outlet viscosity of 12 seconds.
  • composition of suitable cyanamide polyadducts is like that The following example shows, not to the already mentioned composition of C-PUR limited.
  • the prepolymer is diluted with 663 g acetone. After an NCO content of 1.1% has been reached, a solution of 1.43 g of hydrazine hydrate and 5.69 g of isophoronediamine in 42.1 g of water is added at 50-55 ° C. and the mixture is stirred at 50 ° C. for 15 minutes. Then 36.6 g of a 10% aqueous solution of cyanamide are added. Another 10 minutes later, 8.7 g of triethylamine are added. The CO 2 evolution is ended after 1 hour. The mixture is diluted with 632 g of water and then the acetone is distilled off under reduced pressure.
  • the result is a finely divided dispersion with an average particle size of the disperse phase of approx. 70 nm, a solids content of 30% and a viscosity of approx. 10 mPas at 20 ° C./10 s -1 .
  • a linear dimethylpolysiloxane with pendant 2-aminoethylaminopropyl substituents and trimethylsilyl end group and / or dimethylsilyl methoxy end group characterized by a base nitrogen content of 0.20% and a viscosity of 650-700 mPas at 20 ° C, with at 20 ° C 15.4 g of an emulsifier, e.g. Emulsifier ASN (25% in water) from Bayer AG, 12.8 g of cyclohexanol or isobutanol and 0.3 g of acetic acid are stirred. Then be 180 g of water are metered in within 30 minutes.
  • an emulsifier e.g. Emulsifier ASN (25% in water) from Bayer AG
  • a mixture of 300 g mineral oil, viscosity 100 mPas, 80 g of a neutralized Acrylic acid / stearyl methacrylate copolymer and 620 g of water are mixed using a Dissolver blended. High pressure dispersion at 700 bar makes it stable Emulsion with particle size ⁇ 200 nm generated.
  • Purified fish oil and water are mixed in a ratio of 1: 3 using a jet disperser processed into an emulsion with particle size ⁇ 100 nm.
  • the emulsion will by adding 10% acrylic acid / methacrylic acid / ethylhexyl methacrylate copolymer and 2% PVA 26/88 stabilized.
  • Tanning process A tanning with iron salts using a fatliquor.
  • Base product split cowhide, 3.0 mm. All quantities refer to the weight of the sheer.
  • % product ° C Time min comment do the washing up water 35 deliming 100 water 35 2.0 ammonium sulfate 0.3 sodium bisulfite 10 stain 1.1
  • Protease 90 pH: 9.1 Fleet off do the washing up water 20 preparation 20 water 20 pimple 6.0 sodium chloride 5 ° Bé:> 6 0.3 Preservative (active ingredient CMK) 2.0 Fatliquor (Ex.
  • Retanning process A production of a watertight saddle leather, thickness 3.5-4 mm, starting from example 7; all quantities used relate to rebate weight.
  • Retanning process B production of a shoe upper leather thickness 1.6-1.8 mm based on tanning process A; all quantities used relate to rebate weight.
  • process + % product ° C Time min comment To wash 200 water 35 15 Fleet off Neutralization 100 water 35 3.0 Neutralization tanning agent, ditolyl ether sulfonic acid condensate 1.0 sodium 60 pH 5.8 4.0 Polymeric retanning agent, polyaspartic acid derivative ü.N. pH 5.8 Fleet off To wash 100 water 35 Fleet off retanning 50 water 35 4.0 Fatliquor Ex 6 2.0 Hydrophobing agent Ex.
  • Retanning process B production of a split shoe upper leather thickness 1.3 - 1.5 mm based on tanning analogous to tanning process A; all quantities used relate to rebate weight.
  • process + % product ° C Time min comment To wash 200 water 35 15 Fleet off Neutralization 50 water 40 4.0 Synthetic tanning agent, phenolsulfonic acid condensate 30 4.0 Polymeric retanning agent, methacrylic acid copolymer 30 1.0 sodium 3.0 Natrimbicarbonat 60 pH 5.6 3.0 Lubricant Ex 5 60 pH 5.6 Fleet off To wash 200 water 40 5 Fleet off retanning 100 water 40 3.0 Lubricant Ex 5 40 6.0 Synthetic tanning agent, diphenyl sulfone condensate 20 4.0 Polymeric retanning agent, polyaspartic acid derivative 40 pH 6.0 1.0 Pigment white 200 water 30 5 Fleet off?
  • Retanning process B production of a sheep's clothing leather 0.8 mm based on tanning analogous to tanning process A; all quantities used relate to rebate weight.

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)
EP20030023284 2002-10-28 2003-10-15 Cuir sans chrome, imperméable à l'eau Withdrawn EP1416057A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10250111 2002-10-28
DE2002150111 DE10250111A1 (de) 2002-10-28 2002-10-28 Chromfreies, wasserdichtes Leder

Publications (1)

Publication Number Publication Date
EP1416057A1 true EP1416057A1 (fr) 2004-05-06

Family

ID=32087252

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20030023284 Withdrawn EP1416057A1 (fr) 2002-10-28 2003-10-15 Cuir sans chrome, imperméable à l'eau

Country Status (8)

Country Link
US (2) US7060363B2 (fr)
EP (1) EP1416057A1 (fr)
JP (1) JP2004149798A (fr)
KR (1) KR20040038696A (fr)
CN (1) CN1498973A (fr)
AR (1) AR041681A1 (fr)
DE (1) DE10250111A1 (fr)
ZA (1) ZA200308302B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007003264A3 (fr) * 2005-07-02 2007-06-07 Lanxess Deutschland Gmbh Derives d'acide polyaspartique dans des produits de revetement contenant du polysiloxane
EP1702991A3 (fr) * 2005-03-17 2008-03-19 Lanxess Deutschland GmbH Procédé pour le traitement hydrophobique du cuir en utilisant des silanes ayant des groupes alkyl et alkoxy et le cuir hydrophobe ainsi obtenu
WO2011147959A2 (fr) 2010-05-28 2011-12-01 Momentive Performance Materials Gmbh Hydrophobisation de matériaux fibreux au moyen de polyorganosiloxanes
CN112376297A (zh) * 2020-08-26 2021-02-19 焦作隆丰皮草企业有限公司 一种用于无铬鞣羊剪绒毛革的防水剂、染毛剂及无铬鞣羊剪绒毛革的环保染色工艺
US10947605B2 (en) 2016-01-12 2021-03-16 Fraunhofer-Gesellschaft Zur Forderung Der Angewand Method for hydrophobising leather, and leather produced by means of same
WO2022154662A1 (fr) 2021-01-18 2022-07-21 Stahl International B.V. Composition et procédé d'imperméabilisation de cuir

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10250111A1 (de) * 2002-10-28 2004-05-06 Bayer Ag Chromfreies, wasserdichtes Leder
DE102004024798A1 (de) * 2004-05-17 2005-12-08 Basf Ag Zusammensetzungen, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2006015978A1 (fr) * 2004-08-10 2006-02-16 Tfl Ledertechnik Gmbh Cuir imperméabilisé et autonettoyant
JP5456700B2 (ja) * 2008-02-29 2014-04-02 レザーテック リミテッド ハイド及びスキンを保存する方法
NZ592201A (en) * 2008-10-17 2012-08-31 Leatherteq Ltd Preservation of hides without salt curing and performed before tanning
JP5460028B2 (ja) * 2008-11-18 2014-04-02 ミドリホクヨー株式会社 インパネ用皮革
KR101136547B1 (ko) * 2009-06-23 2012-04-24 정경민 연어 어피를 활용한 친환경적인 연어가죽의 제조방법 및 이 방법에 의해 제조된 연어가죽
GB2488353A (en) * 2011-02-24 2012-08-29 Darryl Miles Cassingham Coated fibrous based substrates
EP2607500A1 (fr) 2011-12-23 2013-06-26 Hermes Sellier Procédé de fabrication de cuivre utilisant un polysaccharide dérivé d'amidon oxydé et compositions le contenant
CN105671221B (zh) * 2015-07-08 2018-05-04 四川大学 双防水层黄牛鞋面革及其制备方法
KR101877529B1 (ko) * 2016-08-12 2018-07-11 (주)수문상사 자동차 대쉬보드용 천연피혁의 제조방법
CN106148591A (zh) * 2016-08-30 2016-11-23 四川达威科技股份有限公司 一种防水加脂剂及其制备方法
EP3336202A1 (fr) * 2016-12-13 2018-06-20 LANXESS Deutschland GmbH Procédé de préparation d'agents à effet hydrophobe pour le traitement de cuir
CN112694565B (zh) * 2020-12-23 2022-04-29 齐河力厚化工有限公司 一种两性有机硅聚合物及其制备方法和应用
CN113372475B (zh) * 2021-06-24 2023-03-24 齐鲁工业大学 一种制备防水聚合物加脂剂的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1178545B (de) * 1963-08-08 1964-09-24 Boehme Fettchemie Gmbh Verfahren zum Wasserfestmaschen von Leder oder Pelzen
DE19629986A1 (de) * 1996-07-25 1998-01-29 Basf Ag Verfahren zum Hydrophobieren von mit Polymergerbstoffen gegerbten Ledern und Pelzfellen
EP1108765A2 (fr) * 1999-12-13 2001-06-20 Bayer Ag Hydrophobisation avec des polysiloxanes ayant des groupes carboxyliques

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR212876A1 (es) * 1976-03-05 1978-10-31 Union Carbide Corp Procedimiento mejorado para el tratamiento de cuero curtido con licor graso y el cuero curtido asi tratado
DE3529869A1 (de) * 1985-08-21 1987-02-26 Basf Ag Verfahren zum hydrophobieren von leder und pelzen
US4740211A (en) * 1985-09-09 1988-04-26 Seton Company, Inc. Chromium-free tanning process
US4784664A (en) * 1986-06-24 1988-11-15 Seton Company Non-chrome tanning method
US4762522A (en) * 1987-03-02 1988-08-09 Gaf Corporation Agent for treatment of hides and pelts
DE3800629A1 (de) * 1988-01-12 1989-07-20 Basf Ag Verfahren zum hydrophobieren von leder, pelzen und lederaustauschmaterialien
US5117509A (en) * 1990-07-05 1992-06-02 Bowers Steven M Sport glove
DE4125983A1 (de) * 1991-08-06 1993-02-11 Bayer Ag Verfahren zum fuellenden gerben und/oder nachgerben von leder
DE4404890A1 (de) * 1994-02-16 1995-08-17 Basf Ag Verfahren zum Hydrophobieren von Leder und Pelzfellen mit kammartig carboxylfunktionalisierten Polysiloxanen
DE19516961A1 (de) * 1995-05-12 1996-11-28 Stockhausen Chem Fab Gmbh Verfahren zur Hydrophobierung von Leder bei niedrigen pH-Werten und damit hergestellte Leder
AU713882B2 (en) * 1995-08-03 1999-12-16 Rohm And Haas Company Method for waterproofing leather
DE19629988A1 (de) 1996-07-25 1998-01-29 Basf Ag Verfahren zur Polymerisation von Vinylchlorid
DE19639782A1 (de) * 1996-09-27 1998-04-02 Huels Chemische Werke Ag Glycidether-, Acryl- und/oder Methacryl-funktionelle Organopolysiloxan-haltige Zusammensetzungen auf Wasser-Basis, Verfahren zu deren Herstellung sowie deren Verwendung
DE19646916C1 (de) * 1996-11-13 1998-04-23 Basf Ag Verwendung von Carboxyamid-Polysiloxanen zur Hydrophobierung von Materialien faseriger Struktur und Verfahren zur Durchführung
DE19707970A1 (de) * 1997-02-27 1998-09-03 Wacker Chemie Gmbh Polycarbonsäurefunktionelle Polyorganosiloxane
DE10250112A1 (de) * 2002-10-28 2004-05-06 Bayer Ag Kondensationsprodukt zum Nachgeben von Fe-gegerbtem Leder
DE10250111A1 (de) * 2002-10-28 2004-05-06 Bayer Ag Chromfreies, wasserdichtes Leder

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1178545B (de) * 1963-08-08 1964-09-24 Boehme Fettchemie Gmbh Verfahren zum Wasserfestmaschen von Leder oder Pelzen
DE19629986A1 (de) * 1996-07-25 1998-01-29 Basf Ag Verfahren zum Hydrophobieren von mit Polymergerbstoffen gegerbten Ledern und Pelzfellen
EP1108765A2 (fr) * 1999-12-13 2001-06-20 Bayer Ag Hydrophobisation avec des polysiloxanes ayant des groupes carboxyliques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TONIGOLD L ET AL: "MOGLICHKEITEN UND GRENZEN DER EISENGERBUNG", LEDER, EDUARD ROETHER VERLAG. DARMSTADT, DE, vol. 41, no. 1, 1990, pages 8 - 14, XP000113346, ISSN: 0024-0176 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1702991A3 (fr) * 2005-03-17 2008-03-19 Lanxess Deutschland GmbH Procédé pour le traitement hydrophobique du cuir en utilisant des silanes ayant des groupes alkyl et alkoxy et le cuir hydrophobe ainsi obtenu
WO2007003264A3 (fr) * 2005-07-02 2007-06-07 Lanxess Deutschland Gmbh Derives d'acide polyaspartique dans des produits de revetement contenant du polysiloxane
WO2011147959A2 (fr) 2010-05-28 2011-12-01 Momentive Performance Materials Gmbh Hydrophobisation de matériaux fibreux au moyen de polyorganosiloxanes
US10947605B2 (en) 2016-01-12 2021-03-16 Fraunhofer-Gesellschaft Zur Forderung Der Angewand Method for hydrophobising leather, and leather produced by means of same
CN112376297A (zh) * 2020-08-26 2021-02-19 焦作隆丰皮草企业有限公司 一种用于无铬鞣羊剪绒毛革的防水剂、染毛剂及无铬鞣羊剪绒毛革的环保染色工艺
CN112376297B (zh) * 2020-08-26 2023-08-01 焦作隆丰皮草企业有限公司 一种用于无铬鞣羊剪绒毛革的防水剂、染毛剂及无铬鞣羊剪绒毛革的环保染色工艺
WO2022154662A1 (fr) 2021-01-18 2022-07-21 Stahl International B.V. Composition et procédé d'imperméabilisation de cuir
NL2027334B1 (en) 2021-01-18 2022-07-25 Stahl Int B V Composition and process for waterproofing leather

Also Published As

Publication number Publication date
KR20040038696A (ko) 2004-05-08
DE10250111A1 (de) 2004-05-06
US7208016B2 (en) 2007-04-24
AR041681A1 (es) 2005-05-26
US20040232376A1 (en) 2004-11-25
CN1498973A (zh) 2004-05-26
US7060363B2 (en) 2006-06-13
ZA200308302B (en) 2004-10-25
US20060151738A1 (en) 2006-07-13
JP2004149798A (ja) 2004-05-27

Similar Documents

Publication Publication Date Title
EP1416057A1 (fr) Cuir sans chrome, imperméable à l'eau
EP1892274B1 (fr) Imperméabilisation à l'aide de polysiloxanes comprenant des groupes carboxyles
EP0324345B1 (fr) Procédé pour rendre hydrophobes le cuir, les fourrures et les cuirs synthétiques
US4762522A (en) Agent for treatment of hides and pelts
DE3013912A1 (de) Polymerprodukte zur behandlung von bloessen und leder
EP1263992B1 (fr) Polysiloxanes utilises pour l'impermeabilisation
WO1998038340A1 (fr) Cuir biodegradable
WO2013023979A1 (fr) Procédé pour teinter des substrats à base de fibres de collagène
DE102004050284A1 (de) Isocyanat-basierende Gerbstoffe
DE102005012329A1 (de) Verfahren zur Hydrophobierung von Leder mittels Alkylalkoxysilanen sowie hydrophobiertes Leder
EP1873176A1 (fr) Produits de condensation dialdéhydes contenant des groupes acides
EP1693393B1 (fr) Produits de condensation contenant des groupes acides
EP0526815B1 (fr) Procédé de tannage/imprégnation et/ou post-tannage du cuir
EP1416058A1 (fr) Produits de condensation pour le retannage de cuir tanné au fer
EP2540753A1 (fr) Composition à base de composés contenant des groupes de carbamoylsulfonate
WO2013023980A1 (fr) Procédé d'hydrophobisation de substrats contenant des fibres de collagène
EP3390673B1 (fr) Procede destine a la fabrication de semi-produits en cuir ou en fourrure
EP1896620B1 (fr) Procede de fabrication de cuir
WO1996035815A9 (fr) Procede d'impermeabilisation de cuirs sous de faibles valeurs de ph et cuirs ainsi impermeabilises
EP2580356A1 (fr) Procédé de fabrication de cuir
WO2002000942A1 (fr) Utilisation d'hydrolysats de tannins vegetaux pour la stabilisation de chrome iii contre l'oxydation dans du cuir tanne au chrome
EP0151290A1 (fr) Produits de condensation amphotères et leur application au retannage
DE3248485A1 (de) Verfahren zur nachgerbung von ledern
DE3248484A1 (de) Verfahren zur gewinnung neutral gestellter, carboxylgruppenhaltiger polymerisate nach alkalischer hydrolyse

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

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

17P Request for examination filed

Effective date: 20041108

AKX Designation fees paid

Designated state(s): AT DE ES GB IT

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: LANXESS DEUTSCHLAND GMBH

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20080501