EP1481099A1 - Verwendung von acrylat-graft-polymeren im bereich von kollagensubstraten. substrate, häute und so erhaltene leder - Google Patents

Verwendung von acrylat-graft-polymeren im bereich von kollagensubstraten. substrate, häute und so erhaltene leder

Info

Publication number
EP1481099A1
EP1481099A1 EP03717418A EP03717418A EP1481099A1 EP 1481099 A1 EP1481099 A1 EP 1481099A1 EP 03717418 A EP03717418 A EP 03717418A EP 03717418 A EP03717418 A EP 03717418A EP 1481099 A1 EP1481099 A1 EP 1481099A1
Authority
EP
European Patent Office
Prior art keywords
acid
derivatives
sulfonic acid
weight
natural
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Withdrawn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
EP03717418A
Other languages
English (en)
French (fr)
Inventor
Yves Kensicher
Jean Moro
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.)
Coatex SAS
Original Assignee
Coatex SAS
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 Coatex SAS filed Critical Coatex SAS
Publication of EP1481099A1 publication Critical patent/EP1481099A1/de
Withdrawn legal-status Critical Current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
    • C14C11/00—Surface finishing of leather
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides

Definitions

  • the present invention relates to the technical sector of collagen-based substrates, in particular skins, leathers, crusts and reconstituted leathers, and more specifically the use of acrylic polymers grafted with one or more protein derivatives or natural or synthetic fatty derivatives. in order to allow the smoothing of said substrate without the use of crosslinker and in particular formalin.
  • the invention also relates to smoothing agents composed of said acrylic polymers grafted with one or more protein derivatives or natural or synthetic fatty derivatives.
  • the invention also relates to collagen-based substrates, in particular skins, leathers, crusts and reconstituted leathers smoothed using these said grafted acrylic polymers.
  • the invention further relates to smoothed leather objects using these so-called grafted acrylic polymers.
  • the first is a step of sorting passes or skins or substrates, which is carried out in slaughterhouses and / or in tanneries according to the customer's choice.
  • the Applicant has chosen to use the word skin to designate all types of collagen-based substrates including in particular the skins, leathers, crusts and reconstituted leathers.
  • the second step also called river work, constitutes a step of preparing the sorted skin which is, then, still putrescible.
  • This step includes firstly the tempering or re-greening of the skin in order to clean the said skin, then the depilation and the skinning of this cleaned skin to create sites for fixing the skin, sites which will make it possible to later fix the various skin treatment additives.
  • This skin tanning usually uses mineral derivatives such as in particular chromium, aluminum or zirconium-based salts as well as organic derivatives such as hydrolysable vegetable tannins such as, for example, chestnut-type glucosides, Vallonée, Sumac, Myrobolam or organic derivatives such as condensed vegetable tannins, among which, among others, catechic oligomers of the Québracho, mimosa, and gambier type.
  • mineral derivatives such as in particular chromium, aluminum or zirconium-based salts
  • organic derivatives such as hydrolysable vegetable tannins such as, for example, chestnut-type glucosides, Vallonée, Sumac, Myrobolam or organic derivatives such as condensed vegetable tannins, among which, among others, catechic oligomers of the Québracho, mimosa, and gambier type.
  • organic derivatives can also be synthetic tannins which can replace vegetable tannins. They are then called replacement tannins.
  • These replacement tannins are compounds rich in OH " in their structure and are mainly phenol formaldehyde or naphthol-phenol condensates.
  • These synthetic organic derivatives can also be auxiliary tannins used in addition to other tannins. They have less tanning power, but have other properties including, in particular, dispersing, filling or "full”, lightening or other properties.
  • auxiliary tannins are also naphthalene sulfonic condensates, aromatic sulfonic acid, urea-formaldehyde or even pre-condensed melamine and other condensates but are also other than synthetic tannins such as in particular aldehydes of the formaldehyde type, glyoxal, glutaraldehyde, aldehyde derivatives mainly multifunctional products such as aldehyde-alcohols, phosphoniums, sulfochlorides of fatty chains and other sulfochlorinated paraffins.
  • This wrinkling includes wet operations such as ripening which consists of leaving the skins stacked for 24 hours stacked to perfect the tanning, neutralization, retanning, dyeing, foods to soften the skin and mechanical operations such as draining, the dry, the setting in mood or rewetting, the palissonage which consists in stretching the skin to soften it at a humidity rate of about 23% to 28%, the framing consisting in stretching the skins palissonées on frames to flatten them, these frames being slid into a dryer in order to eliminate the previous humidity, trimming which is a manual operation consisting in eliminating the edges of frayed skin making the skin not very presentable or even the smoothing.
  • wet operations such as ripening which consists of leaving the skins stacked for 24 hours stacked to perfect the tanning, neutralization, retanning, dyeing, foods to soften the skin and mechanical operations such as draining, the dry, the setting in mood or rewetting, the palissonage which consists in stretching the skin
  • This mechanical smoothing operation consists in smoothing the skin using a metal, glass, agate or any other material cylinder, or even using a plate or any other means of brightening the skin.
  • This operation is accompanied by a heating which promotes the "rise” of the gloss, because it is carried out on dry skin during the wrought after trimming and framing or then after the fifth step of the process which is the finishing of the skin at the end of manufacturing.
  • a person skilled in the art must generally use casein to give the skin a shine and must spray a casein crosslinker, including in particular formalin to fix the casein and reach the friction resistance specifications required by the end user.
  • the handling problems consist of the need to implement the casein and then to spray in a second step the crosslinker of the said casein.
  • the Applicant has found that the use, on collagen-based substrates and in particular skins, leathers, crusts and reconstituted leathers, of acrylic polymers grafted with one or more protein derivatives or natural or synthetic fatty derivatives makes it possible to solve the aforementioned problems which arise for a person skilled in the art, that is to say firstly makes it possible to no longer have the handling problems due to the use of casein followed by spraying of crosslinking agent, secondly makes it possible to eliminate all or part of the crosslinking agent from casein whose formalin and thirdly allows the smoothing operation before the finishing operation thus having the advantage of providing the smoothed appearance which will reinforce the finishing.
  • German patent DE 44 16 877 which teaches him the use of polymers grafted by proteins to solve the problems of lightening of colors or resistance to light and heat.
  • these aims are achieved according to the invention thanks to the use as a smoothing agent, on collagen-based substrates and in particular skins, leathers, crusts and reconstituted leathers, of acrylic polymers grafted with one or more protein derivatives or natural or synthetic fatty derivatives.
  • This use is characterized in that the said grafted acrylic polymers are acrylic polymers grafted with one or more protein derivatives or natural or synthetic fatty derivatives.
  • this use is characterized in that it is used from 0.8% to 6% by dry weight, relative to the weight of the support known as "wet blue", and more particular from 1.2% to 2.4% by dry weight, relative to the weight of the so-called “wet blue” support, of said acrylic polymers grafted with one or more protein derivatives or natural or synthetic fatty derivatives.
  • the weight of the so-called "wet blue” support is the weight of the skin after the river work, chrome tanning, spinning and declutching operations.
  • these grafted acrylic polymers used according to the invention as a smoothing agent, result from various radical polymerization processes in the presence of the protein derivative (s) or of the natural or synthetic fatty derivative (s) to be grafted.
  • the use as a smoothing agent of these polymers resulting from the homopolymerization or from the radical copolymerization of unsaturated ethylenic monomers in the presence of the protein derivative (s) or of the natural or synthetic fatty derivative (s) to be grafted is characterized in that said agent is a product of radical polymerization of at least one of the monomers chosen from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride and / or 2-acrylamido-2-methyl-1-propane sulfonic acid, 2-methacrylamido-2-methyl-1-propane sulfonic acid, 3-methacrylamido-2-hydroxy-1-propane sulfonic acid , allylsulfonic acid, methallylsulfonic acid, allyloxybenzene sulfonic acid, methallyloxybenzene sulfonic acid, 2-hydroxy-3- (2-propen
  • the use as a smoothing agent of these polymers is characterized in that the acrylic or methacrylic acid esters are chosen from alkyloxypolyalkylene glycol acrylate or methacrylate and in particular is methoxypolyethylene glycol methacrylate .
  • polymers resulting, in a particular manner from the homopolymerization or from the radical copolymerization of the monomers previously listed in the presence of the protein derivative (s) or natural or synthetic fatty derivatives or of their mixtures previously mentioned, are characterized in an even more particular way in that that the mass content of protein derivatives or natural or synthetic fatty derivatives, relative to the total amount of the monomers is between 2.5% and 40%, preferably between 5% and 10%.
  • polymers can be obtained by radical polymerization or copolymerization of the abovementioned monomers in the acid state, partially neutralized or completely neutralized and preferably in the acid state in a polymerization medium which can be water, one or more alcohols or a hydroalcoholic mixture or also one or more solvents chosen from methanol, ethanol, propanol, isopropanol, butanols, or their mixtures or also dimethylformamide, dimethylsulfoxide, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, hexane, heptane, benzene, toluene, xylene, halogenated solvents such as carbon tetrachloride, chloroform, methylene chloride, or monopropylene glycol ethers, or mixtures thereof and the like.
  • a polymerization medium which can be water, one or more alcohols or a
  • neutralizing agents are chosen either from the group consisting of compounds containing alkali metal cations, in particular sodium and potassium, or else lithium, ammonium, or else primary or secondary aliphatic and / or cyclic amines such as for example ethanolamines, mono and diethylamine or cyclohexylamine, either in the group consisting of compounds containing divalent alkaline earth cations, in particular magnesium and calcium, or also zinc, as well as in the group constituted by the compounds containing trivalent cations, in particular aluminum, or also by certain compounds containing higher valence cations, either are a mixture of at least two of the abovementioned agents.
  • alkali metal cations in particular sodium and potassium
  • lithium, ammonium or else primary or secondary aliphatic and / or cyclic amines
  • primary or secondary aliphatic and / or cyclic amines such as for example ethanolamines, mono and diethylamine or cyclohexylamine, either
  • the homopolymer or the copolymer resulting from the polymerization reaction in the presence of the protein derivative (s) or of the natural or synthetic fatty derivative (s) can, be treated and separated into several phases, according to known static or dynamic processes skilled in the art, with one or more polar solvents belonging in particular to the group consisting of water, methanol, ethanol, propanol, isopropanol, butanols, acetone, tetrahydrofuran or their mixtures.
  • One of the phases corresponds to the polymer used according to the invention as a smoothing agent.
  • the invention also relates to the smoothing agents composed of said acrylic polymers grafted with said protein derivatives or natural or synthetic fatty derivatives.
  • the smoothing agents according to the invention are characterized in that they are products of radical polymerization of at least one of the monomers chosen from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride and / or 2-acrylamido-2-methyl-1-propane sulfonic acid in acid or partially neutralized form, 2-methacrylamido-2-methyl-1 acid - propane sulfonic acid or partially neutralized form, 3-methacrylamido-2-hydroxy-1-propane sulfonic acid form or partially neutralized, allylsulfonic acid, methallylsulfonic acid, allyloxybenzene sulfonic acid, acid methallyloxybenzene sulfonic, 2- hydroxy-3- (2-propenyloxy) propane sulfonic acid, 2-methyl-2-propene-1-sulfonic acid, ethylene sulfonic acid, propene sulfonic acid, acid 2-methyl
  • the smoothing agent according to the invention is characterized in that the acrylic or methacrylic acid esters are chosen from alkyloxypolyalkylene glycol acrylate or methacrylate and in particular is methoxypolyethylene glycol methacrylate.
  • the smoothing agents according to the invention are characterized in that the mass content of protein derivatives or natural or synthetic fatty derivatives or their mixtures, relative to the total amount of the monomers is between 2.5 % and 40%, preferably between 5% and 10%.
  • the smoothing agent according to the invention obtained by radical polymerization or copolymerization of the abovementioned monomers, is in the acid state, or in the partially neutralized state or the fully neutralized state and is preferably in the acid state i.e. at a pH below 7.
  • the neutralizing agents are chosen from those previously described.
  • the smoothing agent according to the invention resulting from the polymerization reaction in the presence of the protein derivative (s) or the natural or synthetic fatty derivative (s) can, as previously described, be treated and separated into several phases .
  • the invention also relates to collagen substrates smoothed using the said acrylic polymers grafted with the said protein derivative (s) or natural or synthetic fatty derivatives.
  • These skins are characterized in that they contain the said acrylic polymers grafted with the said protein derivatives or natural or synthetic fatty derivatives or their mixtures, and are more particularly characterized in that '' they contain from 0.8% to 6% by dry weight, relative to the weight of the so-called “wet blue” support, and in a very specific manner from 1.2% to 2.4% by dry weight relative to the weight of the so-called “wet blue” support, said acrylic polymers grafted with protein derivatives or natural or synthetic fatty derivatives.
  • the invention further relates to smoothed leather objects using said acrylic polymers grafted with said protein derivative (s) or natural or synthetic fatty derivatives.
  • EXAMPLE 1 The purpose of this example is to demonstrate the gloss properties obtained by the use of acrylic polymers grafted with one or more protein derivatives or natural or synthetic fatty derivatives according to the invention.
  • the "wet blue” skin is then weighed, which is the reference weight for the neutralization, retanning, dyeing and nourishing steps which follow.
  • the "wet blue” skin is introduced into a degreasing drum at 40 ° C. containing a degreasing bath composed of 150% by weight of water relative to the weight of the "wet blue” skin and 1% by weight, relative to the weight of the "wet blue” skin, of the Actol DB degreaser sold by the company ATC.
  • This bath containing the skin is stirred for 20 minutes at a speed of between 10 and 12 revolutions per minute before being emptied of the fuller.
  • the neutralization step is then carried out at 35 ° C. and up to a pH equal to 4.5, by addition, in the fuller, of the neutralizing medium, composed of 100% by weight of water relative to the weight of the "wet blue” skin and 1% by weight, relative to the weight of the "wet blue” skin, of the neutralizer Actan NH sold by the company ATC.
  • the neutralizing bath is in turn emptied of the fuller to make room for the retanning step.
  • the retanning operation then continues for all the tests by adding 50% by weight of water relative to the weight of the "wet blue” skin and 0.1% by weight, relative to the weight, at 50 ° C. "wet blue” skin, a biocide sold by the company ATC under the name of Biocide C3, then by stirring the mixture for 5 minutes at a speed of between 10 and 12 revolutions per minute.
  • the smoothing is carried out by means of a straightener equipped with a glass cylinder.
  • a measurement of the gloss of the smoothed skin is then carried out by simple application, on the smoothed skin, of a gloss meter of the "micro Tri gloss” type from BYK-GARDNER GmbH. '
  • Test No. 1 This test is a control test which uses 1.2% by dry weight, relative to the skin weight "wet blue" of a homopolymer of acrylic acid.
  • the value of the gloss obtained is equal to 4.1.
  • This test illustrates the invention and uses 1.2% by dry weight, relative to the weight of the "wet blue" skin, of a polymer of casein grafted acrylic acid in a weight ratio equal to 92.5 % acrylic acid and 7.5% casein.
  • the value of the gloss obtained is equal to 4.8.
  • This test illustrates the invention and uses 4.5% by dry weight, relative to the weight of the "wet blue" skin, of a polymer of casein grafted acrylic acid in a weight ratio equal to 97.5 % acrylic acid and 2.5% casein.
  • the value of the gloss obtained is equal to 5.3.
  • This test illustrates the invention and uses 0.8% by dry weight, relative to the weight of the "wet blue" skin, of a polymer of casein grafted acrylic acid in a weight ratio equal to 80% d acrylic acid and 20% casein.
  • the value of the gloss obtained is equal to 4.7.
  • This test illustrates the invention and uses 1.2% by dry weight, relative to the weight of the "wet blue" skin, of a polymer of casein grafted acrylic acid in a weight ratio equal to 95% d acrylic acid and 5% casein.
  • the value of the gloss obtained is equal to 5.2.
  • This test illustrates the invention and uses 1.2% by dry weight, relative to the weight of the "wet blue" skin, of a polymer of casein grafted acrylic acid in a weight ratio equal to 90% d acrylic acid and 10% casein.
  • the value of the gloss obtained is equal to 8.1.
  • Test No. 7 This test illustrates the invention and uses 0.9% by dry weight, relative to the weight of the "wet blue" skin, of a polymer of acrylic acid grafted with linseed oil in a ratio by weight equal to 90% acrylic acid and 10% linseed oil.
  • This test illustrates the invention and uses 1.8% by dry weight, relative to the weight of the "wet blue" skin, of a polymer of acrylic acid grafted with linseed oil in a weight ratio equal to 90 % acrylic acid and 10% linseed oil.
  • the value of the gloss obtained is equal to 6.3.
  • This test illustrates the invention and uses 1.8% by dry weight, relative to the weight of the "wet blue" skin, of a polymer of casein grafted acrylic acid in a weight ratio equal to 90% d acrylic acid and 10% casein.
  • This test illustrates the invention and uses 1.8% by dry weight, relative to the weight of the "wet blue" skin, of a polymer of acrylic acid and methacrylic acid grafted lecithin in a ratio by weight equal to 45% acrylic acid, 45% methacrylic acid and 10% lecithin.
  • the value of the gloss obtained is equal to 5.5.
  • This test illustrates the invention and uses 1.8% by dry weight, relative to the weight of the "wet blue" skin, of a polymer of acrylic acid grafted with linseed oil in a weight ratio equal to 60 % acrylic acid and 40% linseed oil.
  • the value of the gloss obtained is equal to 4.9.
  • This test illustrates the invention and uses 2.3% by dry weight, relative to the weight of the "wet blue" skin, of a copolymer, at pH equal to 5, of acrylic acid grafted olein in a weight ratio equal to 75.6% acrylic acid, 14.4% maleic anhydride and 10% olein.
  • the value of the gloss obtained is equal to 7.9.
  • Test No. 13 This test illustrates the invention and uses 2.3% by dry weight, relative to the weight of the "wet blue" skin, of a copolymer, at pH equal to 5, of acrylic acid grafted casein in a weight ratio equal to 85.5% acrylic acid, 9.5% 2-acrylamido-2-methyl-1-propane sulfonic acid and 5% casein.
  • the value of the gloss obtained is equal to 8.6.
  • This test illustrates the invention and uses 2.3% by dry weight, relative to the weight of the "wet blue" skin, of a copolymer, at pH equal to 5, of acrylic acid grafted with linseed oil. in a weight ratio equal to 68% acrylic acid, 15.3% acrylamide, 1.7% sodium methallylsulfonate and 15% linseed oil.
  • the value of the gloss obtained is equal to 5.6.
  • This test illustrates the invention and uses 2.3% by dry weight, relative to the weight of the "wet blue" skin, of a copolymer, at pH equal to 5, of lanolin-grafted acrylic acid in a weight ratio equal to 73.6% acrylic acid, 13.8% methacrylic acid, 4.6% methacrylamide and 8% lanolin.
  • the value of the gloss obtained is equal to 6.1.
  • This test illustrates the invention and uses 2.3% by dry weight, relative to the weight of the "wet blue" skin, of a copolymer, at pH equal to 6.5, of grafted methacrylic acid oil of castor oil in a weight ratio equal to 81% methacrylic acid, 4.5% butyl acrylate, 4.5% styrene and 10% castor oil.
  • This test illustrates the invention and uses 2.3% by dry weight, relative to the weight of the "wet blue" skin, of a polymer, at pH equal to 5, of acrylic acid grafted with fish oil. in a weight ratio equal to 80% acrylic acid and 20% fish oil.
  • This test illustrates the invention and uses 2.3% by dry weight, relative to the weight of the "wet blue" skin, of a copolymer, at pH equal to 5, of acrylic acid grafted with coconut oil. in a weight ratio equal to 76% of acrylic acid, 4.75% of ethylene glycol methacrylate phosphate, 14.25% of methoxypolyethylene glycol methacrylate of molecular weight equal to 750 and 5% of coconut oil.
  • the value of the gloss obtained is equal to 8.7.
  • Test No. 19 This test illustrates the invention and uses 2.3% by dry weight, relative to the weight of "wet blue" skin, of a copolymer, at pH equal to 5, of acrylic acid grafted beef foot oil in a weight ratio equal to 85.5% acrylic acid, 4.5% vinyl acetate and 10% beef foot oil.
  • the value of the gloss obtained is equal to 8.1.
  • This test illustrates the invention and uses 1.8% by dry weight, relative to the weight of "wet blue" skin, of a polymer, at pH equal to 5, of acrylic acid grafted with casein and oil. flax in a weight ratio equal to 90% acrylic acid, 5% casein and 5% linseed oil.
  • This test illustrates the invention and uses 0.9% by dry weight, relative to the weight of the "wet blue” skin, of a polymer, at pH equal to 5, of acrylic acid grafted lecithin in a weight ratio equal to 90% acrylic acid and 10% lecithin and 0.9% by dry weight, relative to the weight of "wet blue” skin, of a polymer, at pH equal to 5, of lanolin-grafted acrylic acid in a weight ratio equal to 90% acrylic acid and 10% lanolin.
  • This shine value keeps the skin looking natural.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
EP03717418A 2002-02-28 2003-02-20 Verwendung von acrylat-graft-polymeren im bereich von kollagensubstraten. substrate, häute und so erhaltene leder Withdrawn EP1481099A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0202527A FR2836485B1 (fr) 2002-02-28 2002-02-28 Utilisations de polymeres acryliques greffes dans le domaine des substrats a base de collagene. substrats, peaux et cuirs ainsi obtenus
FR0202527 2002-02-28
PCT/FR2003/000565 WO2003072834A1 (fr) 2002-02-28 2003-02-20 Utilisation de polymeres acryliques greffes dans le domaine des substrats a base de collagene. substrats, peaux et cuirs ainsi obtenus

Publications (1)

Publication Number Publication Date
EP1481099A1 true EP1481099A1 (de) 2004-12-01

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EP03717418A Withdrawn EP1481099A1 (de) 2002-02-28 2003-02-20 Verwendung von acrylat-graft-polymeren im bereich von kollagensubstraten. substrate, häute und so erhaltene leder

Country Status (7)

Country Link
US (1) US20050155157A1 (de)
EP (1) EP1481099A1 (de)
KR (1) KR20040094733A (de)
AU (1) AU2003222585A1 (de)
CA (1) CA2476649A1 (de)
FR (1) FR2836485B1 (de)
WO (1) WO2003072834A1 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2893031B1 (fr) * 2005-11-04 2008-02-08 Coatex Sas Procede de fabrication d'une resine thermoplastique avec une resistance a l'impact amelioree mettant en oeuvre un polymere peigne avec au moins une fonction greffee oxyde de polyalkylene et resines obtenues.
CN101649361B (zh) * 2009-08-27 2012-10-24 陕西科技大学 丹宁酸改性乙烯基类聚合物鞣剂的制备方法
PT2714756T (pt) 2011-06-02 2018-07-16 Lanxess Deutschland Gmbh Polímeros de enxerto à base de polissacárido e/ou polipéptido como taninos sintéticos
CN102504131A (zh) * 2011-12-02 2012-06-20 陕西科技大学 双原位法制备酪素基纳米二氧化硅复合皮革涂饰剂的方法
CN102796831B (zh) * 2012-09-04 2014-10-08 陕西科技大学 复合型丙烯酸复鞣剂的制备方法
CN103589812B (zh) * 2013-11-28 2015-07-29 兴业皮革科技股份有限公司 一种油蜡水染软面革的制备方法
US10676618B2 (en) 2015-07-14 2020-06-09 Clariant International Ltd Polar-modified rice husk wax
CN109252374A (zh) * 2018-09-14 2019-01-22 桐乡市濮院毛针织技术服务中心 一种棉麻混纺纱染色用平滑剂的制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3651210A (en) * 1970-05-15 1972-03-21 Ashland Oil Inc Synthetic emulsion-graft copolymers further reacted with protein
US3761435A (en) * 1971-10-28 1973-09-25 Goodrich B Polymers of acrylic ester and vinyl halide monomers with alkyd monomers
DE3013912A1 (de) * 1980-04-11 1981-10-29 Röhm GmbH, 6100 Darmstadt Polymerprodukte zur behandlung von bloessen und leder
DE3344354A1 (de) * 1983-12-08 1985-06-13 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von waessrigen polyacrylat-copolymer-dispersionen und ihre verwendung bei der zurichtung von leder
DE4224456A1 (de) * 1992-07-24 1994-01-27 Basf Ag Verwendung von Pfropfpolymeren zum Fetten und Füllen von Leder und Pelzfellen
DE4242039A1 (de) * 1992-12-12 1994-06-16 Stockhausen Chem Fab Gmbh Copolymerisate und ihre Verwendung zur Behandlung von Leder
DE4416877A1 (de) * 1994-05-13 1995-11-16 Basf Ag Wasserlöslich oder wasserdispergierbare Pfropfpolymerisate von Proteinen als Ledergerbstoffe
JPH09328616A (ja) * 1996-06-10 1997-12-22 Toshiba Silicone Co Ltd 艶出し保護剤

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03072834A1 *

Also Published As

Publication number Publication date
US20050155157A1 (en) 2005-07-21
CA2476649A1 (fr) 2003-09-04
AU2003222585A1 (en) 2003-09-09
FR2836485B1 (fr) 2004-07-30
KR20040094733A (ko) 2004-11-10
WO2003072834A1 (fr) 2003-09-04
FR2836485A1 (fr) 2003-08-29

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