EP0757108A2 - Verfahren zum Hydrophobieren von Leder - Google Patents

Verfahren zum Hydrophobieren von Leder Download PDF

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Publication number
EP0757108A2
EP0757108A2 EP96305508A EP96305508A EP0757108A2 EP 0757108 A2 EP0757108 A2 EP 0757108A2 EP 96305508 A EP96305508 A EP 96305508A EP 96305508 A EP96305508 A EP 96305508A EP 0757108 A2 EP0757108 A2 EP 0757108A2
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EP
European Patent Office
Prior art keywords
weight
copolymer
weight percent
alkyl
meth
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Granted
Application number
EP96305508A
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English (en)
French (fr)
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EP0757108A3 (de
EP0757108B1 (de
Inventor
Anton Georges El A'mma
John David Whiteman
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.)
Rohm and Haas Co
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Rohm and Haas Co
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Publication of EP0757108A2 publication Critical patent/EP0757108A2/de
Publication of EP0757108A3 publication Critical patent/EP0757108A3/de
Application granted granted Critical
Publication of EP0757108B1 publication Critical patent/EP0757108B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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

  • This invention relates to a method for waterproofing leather.
  • This invention also relates to a composition suitable for use in waterproofing leather. More particularly, this invention relates to a method for waterproofing tanned leather by treating the leather with an aqueous dispersion of a silicone oil emulsified with a water-insoluble amphiphilic copolymer.
  • the present invention is involved with wet end leather processing which takes place after primary tanning, usually "chrome tanning", has been completed.
  • the method of this invention is practiced before, during, or after retanning the leather in order to provide enhanced waterproofing relative to that provided by the same amount of the amphiphilic polymer alone and, especially, enhanced waterproofing with firmness similar to that obtained by treating the leather with the amphiphilic copolymer alone or in conjunction with waterproofing fatliquors.
  • U.S. Patent No. 4,701,269 discloses a process for waterproofing leather and skins with a silicone oil and a salt of N-(C 9 -C 20 acyl)amino acid as an non-polymeric emulsifier for the silicone oil, which is carried out in the aqueous phase during or after retanning.
  • U.S. Patent No. 5,316,860 discloses a method for making leather water-resistant by treating tanned leather with an aqueous dispersion of a water-insoluble dispersed amphiphilic copolymer.
  • the problem faced by the inventors is the provision of a method for waterproofing leather using an aqueous dispersion of a silicone oil emulsified with a water-insoluble amphiphilic copolymer.
  • a method for waterproofing tanned leather by treating said leather with a composition comprising from 0.5 to 20 weight percent solids based on the weight of said leather of an aqueous dispersion of a silicone oil emulsified with a water-insoluble amphiphilic copolymer, said copolymer formed from 50 weight percent to 90 weight percent, based on the weight of said copolymer, of at least one ethylenically-unsaturated hydrophobic monomer selected from monomers consisting of hydrophobic alkyl (meth)acrylates; primary alkenes; vinyl esters of alkyl carboxylic acids; vinyl alkyl ethers; dialkyl esters, alkyl ester N-alkylamides, diN-alkylamides, hemi alkylesters.
  • an aqueous composition for use in waterproofing leather.
  • This invention relates to the use of an aqueous dispersion of silicone oil dispersed with a selected amphiphilic copolymer as a waterproofing leather treatment.
  • the silicone oil is dispersed in an aqueous medium, an "aqueous medium” defined herein as one containing more than 50% water.
  • the aqueous dispersion of silicone oil of this invention is substantially free from non-polymeric surfactants and contains lower organic solvent concentrations than silicone oil dissolved in a water-miscible solvent as practiced in the industry or than when the amphiphilic solution copolymers dissolved in at least one water-miscible solvent are used alone to achieve the same degree of waterproofing.
  • Silicone oils refers to polysiloxanes, substituted polysiloxanes, and mixtures thereof. Suitable are polysiloxanes in which the residual valencies of the silicon are satisfied by hydrocarbon radicals such as, for example, methyl, ethyl, propyl, and phenyl or by functionalized hydrocarbon radicals such as, for example, amino, thiol, or carboxy functional radicals.
  • silicone oils having a viscosity of from 25-1000 cSt.
  • the amphiphilic copolymer must contain at least one hydrophobic and at least one hydrophilic group.
  • the copolymer is formed from 10 percent by weight to 50 percent by weight of at least one hydrophilic monomer and from 50 percent by weight to 90 weight percent of at least one hydrophobic comonomer (All weight percents are based on the weight of the amphiphilic copolymer).
  • the copolymer is formed from 15 percent by weight to 45 percent by weight of at least one hydrophilic monomer and 55 percent by weight to 85 weight percent of at least one hydrophobic comonomer, and even more preferred that the copolymer is formed from 20 percent by weight to 40 percent by weight of at least one hydrophilic monomer and 60 percent by weight to 80 weight percent of at least one hydrophobic comonomer.
  • the hydrophilic monomer used to prepare the amphiphilic copolymer is at least one monomer selected from water soluble ethylenically unsaturated, preferably monoethylenically unsaturated, acidic or basic monomers or mixtures thereof.
  • hydrophilic monomers examples include acrylic acid; methacrylic acid; itaconic acid; fumaric acid; maleic acid; and anhydrides of such acids; acid substituted (meth)acrylates, such as for example, phosphoethyl methacrylate and sulfoethyl methacrylate; acid substituted (meth)acrylamides such as, for example, 2-acrylamido-2-methylpropylsulfonic acid; and basic substituted (meth)acrylates and (meth)acrylamides, such as for example, amine substituted methacrylates including dimethylaminoethyl methacrylate, tertiary butyl-aminoethylmethacrylate, and dimethylaminopropyl methacrylamide and the like.
  • the preferred water soluble hydrophilic monomers used to prepare the amphiphilic copolymer are acrylic acid and methacrylic acid.
  • hydrophilic monomer and its level was made to enable the amphiphilic copolymer to function as a dispersant for silicone oil in the continuous phase, such as for example in water, and to enable the aqueous dispersion of silicone oil to be prepared at a high solids content such as, for example, 50% solids at a handleable or shearable viscosity without adversely affecting the ability of the dispersion to penetrate the leather.
  • the hydrophobic comonomer(s) used to prepare the amphiphilic copolymer includes at least one monomer selected from hydrophobic alkyl (meth)acrylates; primary alkenes; vinyl esters of alkyl carboxylic acids; vinyl alkyl ethers; dialkyl esters, alkyl ester N-alkylamides, diN-alkylamides, hemi alkylesters. or hemi N-alkylamides of unsaturated dicarboxylic acids, and mixtures thereof.
  • Suitable hydrophobic monomers include C 4 to C 22 alkyl acrylates; C 4 to C 22 alkyl methacrylates; C 4 to C 24 1-alkenes, vinyl esters of C 4 to C 22 alkyl carboxylic acids, vinyl C 4 to C 22 alkyl ethers, and di C 4 to C 22 alkyl esters, C 4 to C 22 alkyl ester N-C 4 to C 22 alkylamides, diN-C 4 to C 22 alkylamides, hemi C 4 to C 22 alkylesters. or hemi N-C 4 to C 22 alkylamides of unsaturated dicarboxylic acids.
  • the preferred hydrophobic monomers which have been found to provide the amphiphilic copolymer with the best performance characteristics are the C 4 to C 22 alkyl (meth) acrylates and mixtures thereof.
  • (meth) refers to both acrylates or acrylamides and methacrylates and methacrylamides, respectively.
  • Minor amounts of other ethylenically unsaturated copolymerizable hydrophobic monomers at levels less than 50 weight percent of the total hydrophobic comonomer concentration may be used in combination with a predominant amount (greater than 50 weight percent) of at least one of the above-listed hydrophobic comonomers.
  • These other hydrophobic comonomers have been found to be useful as diluents for the other hydrophobic comonomers without adversely affecting the retan/fatliquor properties obtained upon treatment with the treating composition.
  • Examples of such useful copolymerizable hydrophobic diluent comonomers include styrene, methylstyrenes, vinyl acetate, (meth)acrylonitrile, N-alkyl(meth)acrylamides, and olefins.
  • the amphiphilic copolymer may be prepared by the polymerization of the hydrophilic and hydrophobic monomers by any conventional polymerization technique such as, for example, solution polymerization, emulsion polymerization and melt bulk polymerization.
  • Polymerization of amphiphilic copolymers using conventional emulsion polymerization is taught in U.S. Patent No. 5,348,807, using a water soluble free radical initiator at a concentration of from 0.1 weight percent to 3 weight percent based on the total monomer weight.
  • the polymerization is preferably conducted at a temperature of from 40 degrees C to 100 degrees C, preferably from 50 to 70 degrees C, using a chain transfer agent , such as for example a mercaptan, to control the molecular weight.
  • the weight average molecular weight of the amphiphilic copolymer useful in the method of the invention can be as low as 2000 to as high as 100,000 weight average molecular weight, preferably less than 50,000.
  • the weight average molecular weight herein is that determined by Gel Permeation chromatography.
  • the polymerization may be conducted by polymerizing all monomers together or by the gradual addition of monomers until polymerization is essentially complete. Residual unreacted monomers can be incorporated into the polymer by the addition of subsequent initiator by techniques well known in the art.
  • the polymerization produces a concentration of amphiphilic polymer solids of 20 % solids to 75 % solids.
  • amphiphilic copolymers exemplified in the illustrative examples presented hereinafter were made according to the processes described in Example 1 of U.S. Patent No. 5316,860 for solution copolymers or Example 1 of U.S. Patent 5,348,807 for emulsion copolymers, by varying the selection and proportion of monomers and the relative amount of chain transfer agent to obtain different molecular weight polymers.
  • Emulsifying the silicone oil with the selected amphiphilic copolymer is accomplished by mixing the silicone oil and amphiphilic copolymer under low shear conditions such as by shaking a closed container containing the ingredients by hand.
  • the mixing may be carried out on ingredients which have been heated; typically the ingredients are heated in a hot water bath to a temperature of 60° C.
  • the amphiphilic copolymers are semi-solid or waxy materials it is preferred to heat the components to insure adequate fluidity for effective dispersion.
  • water miscible solvents such as, for example, the butyl ether of ethylene glycol and the butyl ether of propylene glycol may be incorporated to improve fluidity; preferred is the absence of organic solvents due to solvent emission restrictions.
  • compositions which retain a uniform appearance i.e., remain dispersed, for 10 days or more. More preferred are compositions which retain a uniform appearance, i.e., remain dispersed, for 10 days at 60 degrees C. , an accelerated test simulating 1-2 year dispersion stability.
  • the treatment process of the invention involves contacting the leather with the treatment composition containing the aqueous dispersion of silicone oil.
  • the composition used to treat the leather contains from 0.5 to 20 weight percent solids (silicone oil + amphiphilic copolymer) aqueous dispersion based on weight of leather, preferably in the range of from 1 to 5 weight percent and most preferably in the range of from 1 to 2 weight percent.
  • the ratio of silicone oil to amphiphilic copolymer by weight is from 1: 5 to 8:1.
  • Preferred is a ratio of silicone oil to amphiphilic copolymer by weight is from 1: 3 to 4:1.
  • the treatment composition may contain retanning agents, fatliquors, amphiphilic copolymers and other conventional adjuvants in addition to the aqueous dispersion of silicone oil.
  • additional amphiphilic copolymer typically for reasons of economics, the total amount of amphiphilic resin is in the range of from 0.5 to 20 weight percent solids based on leather weight, preferably from 2 to 15 weight percent solids based on leather weight.
  • One test used for determining the degree of waterproofing of leather was a dynamic saline water resistance test. This test used a Maeser water penetration tester according to ASTM D-2099-70. The number of Maeser flexes needed to cause water to penetrate the leather was recorded. A Maeser flex value of greater than 15,000 is the minimum criterion established by the U.S. military for waterproof boot leather.
  • a second test used for determining the degree of waterproofing of leather was a water uptake test.
  • a 5.1 cm by 5.1 cm. (2 inches by 2 inches) leather sample was weighed. It was then placed in a 1 L, jar with 10 times its weight of water and tumbled for 30 minutes. The leather was then removed and placed between two rigid plates the same size as the leather each of which has a square of paper blotter disposed between the plate and the leather.
  • a 1 kilogram weight was placed on the top of the assembly for 5 minutes. The weight was removed the assembly was turned over and the weight applied to the top of the inverted assembly for an additional 5 minutes. The leather was then removed from the assembly and reweighed. The weight % water uptake based on the dry weight of the leather on duplicate samples was reported. % Water uptake of 30% or less is acceptable as an industry standard.
  • Softness was determined by temper measurements. Readings were made using a BLC ST300 Softness Tester (British leather Confederation, Northampton, United Kingdom).
  • the leathers were prepared using the following procedure. Note that some of the steps have treatments that are specific to each Example to follow. Unless otherwise noted, all leathers were prepared using 1.58-1.74 kg./m. 2 (5.0-5.5 ounce/ft. 2 ) (approximately 2-2.5 mm. thick ) chrome tanned cowhides. The procedure is applicable to other types of hides and skins such as mineral (chrome, aluminum, zirconium, titanium, magnesium) tanned animal substrates such as pigskin, sheepskin, and the like. All weights are based on the weight of the bluestock (100% means a weight equal to the weight of the stock in the drum).
  • EXAMPLE 1 Effect of level of aqueous dispersion of silicone oil on waterproofing.
  • Samples 1.1 and 1.2 of this invention exhibited good waterproofing relative to Comparative A in which the treatment level was below 0.5 weight percent based on leather weight.
  • EXAMPLE 2 Effect of level of aqueous dispersion of silicone oil on waterproofing.
  • Sample 2-1 of this invention exhibited good waterproofing relative to Comparative B in which the treatment level was below 0.5 weight percent based on leather weight.
  • EXAMPLE 3 Waterproofing leather with an aqueous dispersion of a functional polyorganosiloxane.
  • Sample 3 of this invention provided good waterproofing of leather.
  • Samples 4.1 and 4.2 of this invention provided good waterproofing of leather.
  • Samples 5.1 and 5.2 of this invention exhibit waterproofing superior to that of Comparative Sample C in which silicone oil is absent.
  • EXAMPLE 6 Waterproofing leather with an aqueous dispersion of a polysiloxane. Preparation of Sample 6.
  • Comparative _ was prepared in the same manner without the silicone/amphiphilic copolymer emulsion. Exceptions to the preparation of leathers procedure herein were:
  • Sample 6 of this invention provided good waterproofing of leather without significant change in softness of the leather.

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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)
EP96305508A 1995-08-03 1996-07-26 Verfahren zum Hydrophobieren von Leder Expired - Lifetime EP0757108B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US183295P 1995-08-03 1995-08-03
US1832 1995-08-03

Publications (3)

Publication Number Publication Date
EP0757108A2 true EP0757108A2 (de) 1997-02-05
EP0757108A3 EP0757108A3 (de) 1998-03-18
EP0757108B1 EP0757108B1 (de) 1999-09-29

Family

ID=21698041

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96305508A Expired - Lifetime EP0757108B1 (de) 1995-08-03 1996-07-26 Verfahren zum Hydrophobieren von Leder

Country Status (7)

Country Link
EP (1) EP0757108B1 (de)
KR (1) KR970010978A (de)
CN (1) CN1140635C (de)
AU (1) AU713882B2 (de)
BR (1) BR9603228A (de)
DE (1) DE69604461T2 (de)
ES (1) ES2138294T3 (de)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1087021A1 (de) * 1999-09-18 2001-03-28 Trumpler GmbH & Co. Chemische Fabrik Lederbehandlungsmittel
US6379751B1 (en) 1999-12-13 2002-04-30 Bayer Aktiengesellschaft Imparting water-repellency with polysiloxanes containing carboxyl groups
US7060363B2 (en) * 2002-10-28 2006-06-13 Bayer Aktiengesellschaft Chromium-free, waterproof leather
US20090176070A1 (en) * 2005-12-22 2009-07-09 Hiroshi Goto Pigment Dispersion, Recording Ink, Ink Cartridge, Ink-Jet Recording Method and Ink-Jet Recording Apparatus
US7637961B2 (en) 2002-03-05 2009-12-29 Rohm And Haas Company Composition and method for preparing leather
WO2011147959A2 (en) 2010-05-28 2011-12-01 Momentive Performance Materials Gmbh Hydrophobizing of fibrous materials with polyorganosiloxanes
EP2557181A1 (de) 2011-08-12 2013-02-13 LANXESS Deutschland GmbH Verfahren zum Hydrophobieren von collagenfaserhaltigen Substraten
CN108035161A (zh) * 2018-01-10 2018-05-15 广东天跃新材料股份有限公司 一种无挥发性有机物的硅橡胶皮革及其涂布工艺
EP3336202A1 (de) 2016-12-13 2018-06-20 LANXESS Deutschland GmbH Verfahren zur herstellung hydrophobierender lederbehandlungsmittel
IT202000024793A1 (it) * 2020-10-21 2022-04-21 Gsc Group S P A Procedimento conciario e relativo agente conciante
WO2022154662A1 (en) 2021-01-18 2022-07-21 Stahl International B.V. Composition and process for waterproofing leather

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100449278B1 (ko) * 2001-09-21 2004-09-18 스톨베르그 앤드 삼일 주식회사 형광엑스선을 이용한 몰드플럭스 중의 불소 함량 분석 방법
KR100674471B1 (ko) * 2004-05-25 2007-01-25 한국기초과학지원연구원 폴리에틸렌 수지 분석용 표준시편 및 이를 이용한 ｐｅ수지의 미량 원소 비파괴 분석법
JP5122215B2 (ja) 2006-08-31 2013-01-16 ローム アンド ハース カンパニー 調整された粘度を有する水性両親媒性コポリマーエマルジョンおよびその製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0213480A2 (de) * 1985-08-21 1987-03-11 BASF Aktiengesellschaft Verfahren zum Hydrophobieren von Leder und Pelzen
EP0498634A2 (de) * 1991-02-05 1992-08-12 Rohm And Haas Company Die Verwendung von polymeren Nachgerbemitteln zum Fetten von Möbelleder mit verminderter Beschlagsneigung

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TNSN89128A1 (fr) * 1988-12-02 1991-02-04 Rohn And Haas Company Independance Mall West Traitement du cuir avec des copolymeres amphiphites choisis

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0213480A2 (de) * 1985-08-21 1987-03-11 BASF Aktiengesellschaft Verfahren zum Hydrophobieren von Leder und Pelzen
EP0498634A2 (de) * 1991-02-05 1992-08-12 Rohm And Haas Company Die Verwendung von polymeren Nachgerbemitteln zum Fetten von Möbelleder mit verminderter Beschlagsneigung

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1087021A1 (de) * 1999-09-18 2001-03-28 Trumpler GmbH & Co. Chemische Fabrik Lederbehandlungsmittel
US6379751B1 (en) 1999-12-13 2002-04-30 Bayer Aktiengesellschaft Imparting water-repellency with polysiloxanes containing carboxyl groups
EP1892274A2 (de) 1999-12-13 2008-02-27 Lanxess Deutschland GmbH Hydrophobierung mit carboxylgruppenhaltigen Polysiloxanen
US7637961B2 (en) 2002-03-05 2009-12-29 Rohm And Haas Company Composition and method for preparing leather
US7060363B2 (en) * 2002-10-28 2006-06-13 Bayer Aktiengesellschaft Chromium-free, waterproof leather
US7208016B2 (en) * 2002-10-28 2007-04-24 Lanxess Deutschland Gmbh Chromium-free, waterproof leather
US20090176070A1 (en) * 2005-12-22 2009-07-09 Hiroshi Goto Pigment Dispersion, Recording Ink, Ink Cartridge, Ink-Jet Recording Method and Ink-Jet Recording Apparatus
US8242201B2 (en) * 2005-12-22 2012-08-14 Ricoh Company, Ltd. Pigment dispersion, recording ink, ink cartridge, ink-jet recording method and ink-jet recording apparatus
US8383700B2 (en) 2005-12-22 2013-02-26 Ricoh Company, Ltd. Pigment dispersion, recording ink, ink cartridge, ink-jet recording method and ink-jet recording apparatus
WO2011147959A2 (en) 2010-05-28 2011-12-01 Momentive Performance Materials Gmbh Hydrophobizing of fibrous materials with polyorganosiloxanes
WO2013023980A1 (de) 2011-08-12 2013-02-21 Lanxess Deutschland Gmbh Verfahren zum hydrophobieren von collagenfaserhaltigen substraten
EP2557181A1 (de) 2011-08-12 2013-02-13 LANXESS Deutschland GmbH Verfahren zum Hydrophobieren von collagenfaserhaltigen Substraten
EP3336202A1 (de) 2016-12-13 2018-06-20 LANXESS Deutschland GmbH Verfahren zur herstellung hydrophobierender lederbehandlungsmittel
WO2018108595A1 (de) 2016-12-13 2018-06-21 Lanxess Deutschland Gmbh Verfahren zur herstellung hydrophobierender lederbehandlungsmittel
US11365456B2 (en) 2016-12-13 2022-06-21 Tfl Ledertechnik Gmbh Method for producing hydrophobicizing leather treatment agents
CN108035161A (zh) * 2018-01-10 2018-05-15 广东天跃新材料股份有限公司 一种无挥发性有机物的硅橡胶皮革及其涂布工艺
IT202000024793A1 (it) * 2020-10-21 2022-04-21 Gsc Group S P A Procedimento conciario e relativo agente conciante
WO2022084910A1 (en) * 2020-10-21 2022-04-28 Gsc Group S.P.A. Tanning process and related tanning agent
WO2022154662A1 (en) 2021-01-18 2022-07-21 Stahl International B.V. Composition and process for waterproofing leather
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
DE69604461T2 (de) 2000-05-25
ES2138294T3 (es) 2000-01-01
CN1146490A (zh) 1997-04-02
BR9603228A (pt) 1998-09-29
CN1140635C (zh) 2004-03-03
AU713882B2 (en) 1999-12-16
DE69604461D1 (de) 1999-11-04
EP0757108A3 (de) 1998-03-18
MX9603158A (es) 1997-07-31
AU6061896A (en) 1997-02-06
EP0757108B1 (de) 1999-09-29
KR970010978A (ko) 1997-03-27

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