EP0607388B1 - Utilisation de polymeres greffes pour nourrir et fouler les cuirs et les peaux en poils - Google Patents

Utilisation de polymeres greffes pour nourrir et fouler les cuirs et les peaux en poils Download PDF

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Publication number
EP0607388B1
EP0607388B1 EP93915893A EP93915893A EP0607388B1 EP 0607388 B1 EP0607388 B1 EP 0607388B1 EP 93915893 A EP93915893 A EP 93915893A EP 93915893 A EP93915893 A EP 93915893A EP 0607388 B1 EP0607388 B1 EP 0607388B1
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EP
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Prior art keywords
monomers
acid
monoethylenically unsaturated
weight
leather
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Expired - Lifetime
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EP93915893A
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German (de)
English (en)
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EP0607388A1 (fr
Inventor
Hermann Birkhofer
Peter Danisch
Walter Denzinger
Heinrich Hartmann
Michael Kneip
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BASF SE
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BASF SE
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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

  • Greasing is a quality-determining process in the production of leather and is particularly important for very soft types of leather.
  • aqueous fat emulsions (licker) are used, which generally based on petrochemical products and natural oils and fats and made water-emulsifiable by partial sulphonation or with the help of emulsifiers.
  • DE-A 42 05 839 describes polymeric leather greasing agents based on esterified or amidated homo- or copolymers of monoethylenically unsaturated dicarboxylic acid anhydrides, which, depending on the degree of derivatization of the carboxyl groups and the polarity of the monomers in hydrophobicized leather, lead to a certain deterioration in the water-repellent properties of the leather can.
  • This application also describes further prior art.
  • EP-A 024 886 describes leather tanning agents based on polymers of (meth) acrylic acid, optionally (meth) acrylates and partially sulfated unsaturated fatty oils such as castor oil.
  • DE-AS 18 00 244 relates to the greasing and impregnation of leather with a mixture of an essentially hydrophobic synthetic resin and preferably sulfonated or sulfated animal or vegetable oils.
  • the synthetic resin has a maximum of 2% by weight of monomers containing carboxylate groups.
  • the post-published DE-A 41 42 318 relates to the use of copolymers and / or adducts of maleic anhydride with unsaturated fatty acids and / or their carboxyl group derivatives as neutral oil components in leather and fur greasing agents.
  • the invention was based on the object of providing improved means for greasing and filling leather and fur skins which no longer have the disadvantages of the prior art.
  • Monomers (a) are e.g. monoethylenically unsaturated mono- and dicarboxylic acids with preferably 3 to 12 carbon atoms in the molecule, such as acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, allylacetic acid, vinyl acetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or methylene malonic acid and the corresponding anhydrides.
  • monoethylenically unsaturated mono- and dicarboxylic acids with preferably 3 to 12 carbon atoms in the molecule, such as acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, allylacetic acid, vinyl acetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or methylene malonic acid and the corresponding anhydrides.
  • Examples of monomers containing sulfo groups include Vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, styrenesulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid.
  • Monomers with phosphonic acid groups are, for example, vinylphosphonic acid, allylphosphonic acid, phosphonomethylated allylamine and acrylamido-2-methylpropanephosphonic acid.
  • Preferred monomers of group (a) are acrylic acid, methacrylic acid and maleic acid. It can also be advantageous to use mixtures of the monomers (a).
  • the acids are preferably used as such or as anhydrides; in addition, alkali metal, alkaline earth metal or ammonium salts, such as the sodium, potassium, calcium, ammonium or substituted ammonium salts, can of course also be used, the acids in whole or in part as salts can be present.
  • olefins having 2 to 30 carbon atoms and vinyl alkyl ethers are also used as monomers (b) with 1 to 30 carbon atoms in the alkyl radical are particularly suitable.
  • olefins having 2 to 30 carbon atoms and vinyl alkyl ethers are also used as monomers (b) with 1 to 30 carbon atoms in the alkyl radical are particularly suitable.
  • a further modification of the graft copolymers can be achieved by carrying out the graft polymerization in the presence of monomers from group (c).
  • the monomer mixtures contain up to 5% by weight of a monomer having at least two ethylenically unsaturated non-conjugated double bonds in the molecule.
  • These compounds are usually used as crosslinkers in copolymerizations. They can be added to the monomers of group (a) used for the copolymerization or to the monomer mixtures from (a) and (b). If they are used, the amount of monomers (c) used is preferably 0.05 to 2% by weight.
  • Suitable compounds of this type are, for example, methylene bisacrylamide, esters of acrylic acid and methacrylic acid with polyhydric alcohols, e.g. Glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, as well as polyols esterified at least twice with acrylic acid or methacrylic acid, such as pentaerythritol and glucose.
  • Suitable crosslinkers are also divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose. From this group of compounds, preference is given to using water-soluble monomers, such as glycol diacrylate or glycol diacrylates of polyethylene glycols having a molecular weight of up to 3,000.
  • component B includes all vegetable and animal oils. There are, for example, olive oil, rapeseed oil, soybean oil, sunflower oil, safflower oil, linseed oil, capelan oil or sperm oil.
  • the monomers (a) and optionally (b) and / or (c) are polymerized by free radicals in the presence of component B. It may be favorable for the effect of the graft polymer formed to use two or more of the oils specified under B.
  • the polymerization can be carried out in the presence or in the absence of inert solvents or diluents, with the absence of diluents being preferred.
  • Inert solvents are, for example, aromatic hydrocarbons such as toluene, xylene, o-, m-, p-xylene and isomer mixtures of xylene or ethylbenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, dodecane, cyclohexane, cyclooctane, methylcyclohexane or mixtures of the hydrocarbons mentioned and gasoline fractions which contain no polymerizable monomers.
  • Chlorinated hydrocarbons such as chloroform, carbon tetrachloride, hexachloroethane, dichloroethane or tetrachloroethane, alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol or sec-butanol as well as tetrahydrofuran, dioxane and mixtures of the inert solvents mentioned are also suitable.
  • chloroform such as chloroform, carbon tetrachloride, hexachloroethane, dichloroethane or tetrachloroethane
  • alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol or sec-butanol as well as tetrahydrofuran, dioxane and mixtures of the inert solvents mentioned are also suitable.
  • the graft polymerization can be carried out continuously or batchwise, generally using free-radical initiators.
  • Suitable free radical initiators are preferably those which have a half-life of less than 3 hours at the polymerization temperature chosen in each case. If the polymerization is initially started at a lower temperature and ends at a higher temperature, it is expedient to work with at least two initiators which decompose at different temperatures, namely firstly using an initiator which already decomposes at a lower temperature for the start of the polymerization and then the Complete the main polymerization with an initiator that decomposes at a higher temperature. For example, the following initiators can be used.
  • a redox system such as salts or complexes of heavy metals, for example copper, cobalt, manganese, iron, vanadium, cerium, nickel and chromium salts, or organic compounds such as benzoin, dimethylaniline or ascorbic acid are used , the half-lives of the radical initiators indicated can be reduced.
  • heavy metals for example copper, cobalt, manganese, iron, vanadium, cerium, nickel and chromium salts, or organic compounds such as benzoin, dimethylaniline or ascorbic acid
  • tert-butyl hydroperoxide with the addition of 5 ppm copper (II) acetylacetonate can be activated in such a way that polymerisation can take place at 100 ° C.
  • the reducing component of redox catalysts can also be formed, for example, from compounds such as sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine. Based on the monomers used in the polymerization, 0.01 to 20, preferably 0.05 to 10,% by weight of a polymerization initiator or a mixture of several polymerization initiators is used. 0.01 to 5% of the reducing compounds are added as redox components. Heavy metals are used in the range of 0.1 to 100 ppm, preferably 0.5 to 10 ppm. It is often beneficial to use a combination of peroxide, and Use reducing agent and heavy metal as a redox catalyst.
  • the polymerization of the monomers (a) and the monomers (b) and / or (c) which may also be used can also be carried out by the action of ultraviolet radiation, if appropriate in the presence of UV initiators.
  • the photoinitiators or sensitizers that are normally used are used. These are, for example, compounds such as benzoin and benzoin ether, ⁇ -methylbenzoin or ⁇ -phenylbenzoin. So-called triplet sensitizers, such as benzene diketals, can also be used.
  • UV-low light sources such as fluorescent tubes with a high proportion of blue, also serve as UV radiation sources.
  • Suitable regulators are, for example, mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, butyl mercaptan and dodecyl mercaptan.
  • allyl compounds such as allyl alcohol, aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, propionic acid, hydrazine sulfate and butenols. If the polymerization is carried out in the presence of regulators, 0.05 to 20% by weight, based on the monomers used in the polymerization, are required.
  • the polymerization is carried out in the presence of water-soluble phosphorus compounds in which the phosphorus has an oxidation number of 1 to 4, the water-soluble alkali metal or ammonium salts, water-soluble Compounds containing PO (OH) "groups and / or their water-soluble salts.
  • Phosphorous acid is preferably used.
  • the phosphorus compounds in question are used to reduce the discoloration of the graft copolymers in amounts of from 0.01 to 5% by weight, based on the used monomers (A) Possible phosphorus compounds are described in EP-A-0 175 317.
  • the copolymerization of components (A) and (B) is usually carried out in an inert gas atmosphere with the exclusion of atmospheric oxygen. Good mixing of the reactants is generally ensured during the polymerization. In the case of smaller batches in which a reliable removal of the heat of polymerization is ensured, the reactants, which are preferably present in an inert diluent, can be copolymerized discontinuously by heating the reaction mixture to the polymerization temperature. These temperatures are in the range of 40 to 150 ° C. In order to be able to better control the course of the polymerization reaction, the monomers (A) are therefore added continuously or batchwise to the polymerizing mixture to the extent that the graft polymerization can be easily controlled in the desired temperature range.
  • a type of addition of the monomers of component (A) is preferred in which the compounds of component (B) or at least some of the compounds of component (B) are initially introduced into the reactor together with at least one monomer of group (a) in the polymerization reactor and heated therein to the desired polymerization temperature with stirring. As soon as this temperature is reached, the remaining monomers of group (a) and optionally the monomers (b) and optionally (c) and the initiator and optionally are added over a period of about 1 to 10, preferably 2 to 8 hours a controller too.
  • capelan oil with 1% ditertiary butyl peroxide can be heated to 150 ° C. in a weak stream of N 2 for 2 hours and then acrylic acid is metered in at 150 ° C. in the course of 3 hours.
  • the grafted vegetable or animal oil is converted into an aqueous dispersion.
  • the dispersion can be carried out using conventional emulsifiers such as fatty alcohol ethoxylates, dodecylbenzenesulfonates, Dioctyl sulfosuccinate or alkyl sulfonates can be made in suitable apparatus.
  • Emulsifier-free dispersion is particularly preferred by partially or completely neutralizing the carboxyl groups of the graft polymer with alkalis, alkaline earths, ammonia or amines and thus obtaining stable aqueous dispersions.
  • These dispersions have a solids content of 5 to 80% and preferably 20 to 70% and can thus be used directly for the treatment of leather and furskins.
  • the drying residue can be determined, for example, in a drying cabinet (2 h at 120 ° C).
  • graft polymers to be used according to the invention it is possible to produce very soft leather without the addition of conventional liquors.
  • the water-repellent properties of hydrophobized leather are not adversely affected when these products are used.
  • the mechanical properties, such as tensile strength, as well as the light fastness and heat yellowing resistance of such leathers are influenced very positively by the use of these graft polymers.
  • the good fixation in the leather results in great resistance to extractability with solvents or water.
  • washable leathers i.e. leathers that do not lose their properties such as softness, firmness and suppleness after washing; in contrast, this property is not to be expected for leathers that are greased with conventional licker.
  • aqueous dispersion to be used according to the invention preferably contains no additional emulsifiers. It is known that leather and furs, which are to be made hydrophobic and are treated with products containing emulsifiers, have to undergo complex processes after treatment with these agents, e.g. Post-treatment with polyvalent metal salts, to make the emulsifiers in the leather or in the fur skins ineffective, i.e. to fix.
  • the graft polymer dispersions described above are suitable for the treatment of all conventional tanned hides.
  • the tanned hides are usually deacidified before treatment. They may have been stained before treatment. Coloring can, however, also be carried out only after the lubrication that takes place according to the invention.
  • the tanned skins are expediently mixed with the aqueous dispersions in aqueous liquors, which can be obtained by diluting the graft polymer dispersions with water, at pH values of 4 to 10, preferably 5 to 8 and temperatures of 20 to 60, preferably 30 to 50 ° C. treated for a period of 0.1 to 5, in particular 0.5 to 2 h. This treatment takes place, for example, by drumming in a barrel.
  • the required amount of graft polymer dispersion, based on the shaved weight of the leather or the wet weight of the fur skins is 0.1 to 30, preferably 1 to 20,% by weight.
  • the fleet length i.e. the percentage weight ratio of the treatment liquor to the goods, based on the shaved weight of the leather or the wet weight of the fur skins, is usually 10 to 1000, preferably 30 to 150%, for fur skins 50 to 500%.
  • the pH of the treatment liquor is adjusted to a value of 3 to 5, preferably 3.5 to 4, by adding acids, preferably an organic acid such as formic acid.
  • the treatment with the aqueous dispersions to be used according to the invention can be used before or after the retanning step.
  • Example 2 Similar to Example 1, 100 g of capelan oil and 1 g of tert-butyl perethylhexanoate are heated to 150 ° and stirred for 1 hour. Then 10 g of maleic anhydride and 1 g of tert-butyl perethylhexanoate are added and the mixture is heated at 150 ° C. for 6 hours. After cooling, the mixture is diluted with 310 g of water and 7.2 g of 50% sodium hydroxide solution and the mixture is intensively dispersed for 10 minutes with the Ultra-Turrax. The dispersion obtained has a pH of 8.9, a drying residue of 25% and a Brookfield viscosity of 16 mPa ⁇ s at 23 ° C.
  • rapeseed oil are heated to 150 ° C under a weak stream of N2. Then 20 g of acrylic acid (100%) and the solution of 1 g of tert-butyl perethylhexanoate in 10 g of rapeseed oil are metered in uniformly at 150 ° C. within 1 h. The mixture is then stirred at 150 ° for 2 h, a further 1 g of tert-butyl perethylhexanoate is added and the mixture is heated again at 150 ° C. for 2 h.
  • 100 g of the graft polymer thus obtained are diluted with 76 g of water and dispersed intensively for 10 minutes.
  • the white viscous dispersion has a pH of 3.5 and a drying residue of 55.9%.
  • methacrylic acid is used instead of acrylic acid, a dispersion with comparable properties is obtained.
  • Example 1 100 g of rapeseed oil and 1 g of tert-butyl perethylhexanoate are heated at 150 ° C. for 1 hour under a weak stream of N 2 . 18 g of maleic anhydride and 1 g of tert-butyl perethylhexanoate are then added and the mixture is heated at 150 ° C. for 6 h. Then it is cooled and 105 g of the product are mixed with 90 g of water and 8 g of 50% sodium hydroxide solution and intensively dispersed for 10 minutes with the Ultra-Turrax. A homogeneous viscous dispersion is formed with a drying residue of 52.7% and a pH of 5.5.
  • Example 1 100 g of capelan oil are heated to 150 ° in a weak N2 stream and then 20 g of acrylic acid and a solution of 1 g of tert-butyl perethylhexanoate in 10 g of capelan oil are uniformly added at 150 ° C. in the course of 1 h. The mixture is then heated for a further 1 h, another 1 g of tert-butyl perethylhexanoate is added and the mixture is heated for a further 1 h. The mixture is then cooled and 103 g of the product, after adding 90 g of water and 9 g of 50% sodium hydroxide solution, are dispersed intensively for 10 minutes using Ultra-Turrax. The viscous homogeneous dispersion has a pH of 7.0 and the drying residue is 49.1%.
  • Example 6 20 g of methacrylic acid are used instead of acrylic acid. 115 g of the graft polymer obtained, 95 g of water and 14 g of 50% sodium hydroxide solution are dispersed intensively for 10 minutes with the Ultra-Turrax. The viscous dispersion has a pH of 7.1 and a drying residue of 51.2%.
  • Example 4 The product from Example 4 was used analogously to the procedure given in Example 3.
  • the leather thus obtained showed soft and round grip properties.
  • Example 5 The product from Example 5 was used analogously to the procedure given in Example 1.
  • the leather thus obtained was characterized by a round, soft handle.
  • Example 6 The product from Example 6 was used analogously to the procedure given in Example 1. The result was similarly advantageous as in the previous examples.
  • Example 7 The product from Example 7 was used analogously to the procedure given in Example 3. The result was a soft leather with a comfortable grip.

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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)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne l'utilisation de polymères greffés, solubles ou dispersibles dans l'eau, d'huiles végétales et animales, obtenus par polymérisation par promoteurs radicalaires A) d'un monomère ou d'un mélange de monomères comprenant a) 20 à 100 % en poids d'acides carboxyliques monoéthyléniquement insaturés, et/ou d'acides sulfoniques monoéthyléniquement insaturés, et/ou d'acides phosphoniques monoéthyléniquement insaturés, ou de leurs sels alcalins, alcalino-terreux ou d'ammonium, b) 0 à 80 % en poids d'autres monomères monoéthyléniquement insaturés, copolymérisables avec les monomères (a), et c) 0 à 5 % en poids de monomères insaturés non conjugués ayant au moins deux doubles liaisons éthyléniques, en présence B) d'huiles végétales et/ou animales, dans un rapport pondéral A:B de (80 à 1) : (20 à 99), pour nourrir et fouler les cuirs et les peaux en poils. On obtient ainsi des cuirs souples d'un toucher agréable.

Claims (7)

  1. Utilisation de polymères greffés solubles dans l'eau ou dispersibles dans l'eau, à base d'huiles végétales et animales, obtenus par polymérisation à amorçage radicalaire
    A) d'un monomère ou d'un mélange de monomères comprenant
    (a) 20 à 100 % en poids d'acides carboxyliques à insaturation monoéthylénique et/ou d'acides sulfoniques à insaturation monoéthylénique et/ou d'acides phosphoniques à insaturation monoéthylénique ou de leurs sels d'alcali, d'alcalino-terreux ou d'ammonium,
    (b) 0 à 80 % en poids d'autres monomères à insaturation monoéthylénique, copolymérisables avec les monomères (a) et
    (c) 0 à 5 % en poids de monomères ayant au moins deux insaturations éthyléniques non-conjuguées,
    en présence
    B) d'huiles végétales et/ou animales
    dans un rapport en poids A : B de (80 à 1) : (20 à 99), pour graisser et nourrir les cuirs et les fourrures, en excluant l'utilisation de copolymères et/ou de produits d'addition de l'anhydride maléique avec des acides gras insaturés et/ou leurs dérivés carboxylés, en tant que composés d'huile neutre dans des agents de graissage pour cuirs et fourrures.
  2. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise comme composés a) des acides carboxyliques ou des anhydrides d'acides carboxyliques.
  3. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise comme composés a) de l'acide acrylique, de l'acide méthacrylique ou de l'acide (anhydride) maléique.
  4. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise comme composés b) des dérivés d'acide (méth)acrylique ou maléique, en particulier les esters d'alkyle en C1-C20, ou du (méth)acrylamide.
  5. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise uniquement des composés a).
  6. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise des systèmes autoémulsifiants.
  7. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise les composants A et B dans un rapport en poids de (60 à 5) : (40 à 95).
EP93915893A 1992-07-24 1993-07-13 Utilisation de polymeres greffes pour nourrir et fouler les cuirs et les peaux en poils Expired - Lifetime EP0607388B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4224456A DE4224456A1 (de) 1992-07-24 1992-07-24 Verwendung von Pfropfpolymeren zum Fetten und Füllen von Leder und Pelzfellen
DE4224456 1992-07-24
PCT/EP1993/001831 WO1994002650A1 (fr) 1992-07-24 1993-07-13 Utilisation de polymeres greffes pour nourrir et fouler les cuirs et les peaux en poils

Publications (2)

Publication Number Publication Date
EP0607388A1 EP0607388A1 (fr) 1994-07-27
EP0607388B1 true EP0607388B1 (fr) 1997-10-08

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EP93915893A Expired - Lifetime EP0607388B1 (fr) 1992-07-24 1993-07-13 Utilisation de polymeres greffes pour nourrir et fouler les cuirs et les peaux en poils

Country Status (7)

Country Link
US (1) US5620748A (fr)
EP (1) EP0607388B1 (fr)
JP (1) JPH06511284A (fr)
AU (1) AU662071B2 (fr)
DE (2) DE4224456A1 (fr)
ES (1) ES2108289T3 (fr)
WO (1) WO1994002650A1 (fr)

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DE4402029A1 (de) * 1994-01-25 1995-07-27 Basf Ag Wäßrige Lösungen oder Dispersionen von Copolymerisaten
DE19625984C2 (de) * 1996-06-28 1999-07-29 Stockhausen Chem Fab Gmbh Wäßrige Polymerdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung in der Lederherstellung
KR100346466B1 (ko) * 1999-12-06 2002-07-27 현대자동차주식회사 페이스트형 방음용 밀봉재 조성물
FR2836485B1 (fr) * 2002-02-28 2004-07-30 Coatex Sas Utilisations de polymeres acryliques greffes dans le domaine des substrats a base de collagene. substrats, peaux et cuirs ainsi obtenus
AU2003298467A1 (en) * 2003-12-25 2005-08-11 Council Of Scientific And Industrial Research A process for making leather
US20060188729A1 (en) * 2005-02-22 2006-08-24 Kai-Volker Schubert Washable leather with repellency
FR2974578B1 (fr) * 2011-04-28 2015-10-30 Rhodia Operations Corps gras copolymerise, son procede de preparation et ses applications

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Publication number Publication date
AU662071B2 (en) 1995-08-17
EP0607388A1 (fr) 1994-07-27
JPH06511284A (ja) 1994-12-15
DE59307502D1 (de) 1997-11-13
AU4567993A (en) 1994-02-14
US5620748A (en) 1997-04-15
WO1994002650A1 (fr) 1994-02-03
DE4224456A1 (de) 1994-01-27
ES2108289T3 (es) 1997-12-16

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