EP0841405B1 - Utilisation de copolymères amphiphiles contenant des monomères fluorés pour imperméabiliser des cuirs - Google Patents

Utilisation de copolymères amphiphiles contenant des monomères fluorés pour imperméabiliser des cuirs Download PDF

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Publication number
EP0841405B1
EP0841405B1 EP96117814A EP96117814A EP0841405B1 EP 0841405 B1 EP0841405 B1 EP 0841405B1 EP 96117814 A EP96117814 A EP 96117814A EP 96117814 A EP96117814 A EP 96117814A EP 0841405 B1 EP0841405 B1 EP 0841405B1
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Prior art keywords
leather
amphiphilic copolymer
recurring units
weight
group
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EP96117814A
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German (de)
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EP0841405A1 (fr
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Dirk M.J. Coppens
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3M Co
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Minnesota Mining and Manufacturing Co
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Priority to ES96117814T priority Critical patent/ES2143125T3/es
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to EP96117814A priority patent/EP0841405B1/fr
Priority to DE69605925T priority patent/DE69605925T2/de
Priority to JP52140298A priority patent/JP3911549B2/ja
Priority to BR9712754-0A priority patent/BR9712754A/pt
Priority to AU48998/97A priority patent/AU4899897A/en
Priority to PCT/US1997/018386 priority patent/WO1998020170A1/fr
Priority to KR10-1999-7004022A priority patent/KR100475495B1/ko
Priority to US09/297,814 priority patent/US6294103B1/en
Priority to CNB971995338A priority patent/CN1152142C/zh
Priority to TW086116460A priority patent/TW419524B/zh
Priority to ARP970105170A priority patent/AR009410A1/es
Publication of EP0841405A1 publication Critical patent/EP0841405A1/fr
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    • 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 leather manufacture and the use of fluoroalkyl group containing amphiphilic copolymers therein. More in particular, the invention relates to fluoroalkyl group containing amphiphilic copolymers and their use in a waterproofness imparting composition for leather substrates. In another aspect, the invention relates to a method for imparting a high degree of waterproofness to leather substrates and to the resulting treated leather substrates.
  • the treatment of hides and skins to form leather involves a number of interdependent chemical and mechanical operations. These operations may be divided into a sequence of "wet end” steps followed by a sequence of “dry” steps. A description of each of these operations is provided in Fundamentals of Leather Manufacturing, Prof Dr Heidemann (Eduard Roether KG, 1993).
  • the primary tanning operation involves the treatment of the hide to preserve it and form useful leather. Chrome tanning salts are well known and widely used for this purpose. Chrome-tanned hides or skins are known in the art as 'wet blue leather'.
  • a second tanning step known as 'retanning', is employed.
  • Retanning can be accomplished using a variety of naturally derived materials including extracts from vegetables or plants, and synthetic tanning agents known as "syntans", or combinations thereof. After or during retanning, the leather can be colored and fatliquored.
  • the present invention relates to the wet end operations which take place after primary tanning, namely retanning and fatliquoring.
  • EP-A-372 746 discloses a method and process for treating leather utilizing selected amphiphilic copolymers for improving the strength, temper and water resistance of the leather.
  • the amphiphilic copolymers are formed from a predominant amount of at least one hydrophobic monomer and a minor amount of at least one copolymerizable hydrophilic monomer.
  • the application states that the process may be particularly useful as a one step substitute for conventional retanning and fatliquoring treatment steps.
  • EP-A-682 044 discloses copolymers comprising ethylenically unsaturated dicarboxylic acid anhydrides, long chain olefins and fluorolefins. Leathers treated with these polymers are shown to yield good waterproofness results according to the Bally-Penotrometer test.
  • US 5,124,181 discloses copolymers which contain a) from 50 to 90% by weight of C 8 -C 40 -alkyl methacrylates, vinyl esters of C 8 -C 40 -carboxylic acids or mixtures thereof and b) from 10 to 50% by weight of monoethylenically unsaturated C 3 -C 12 -carboxylic acids, monoethylenically unsaturated dicarboxylic anhydrides, monoesters or monoamides of monoethylenically unsaturated C 4 -C 12 -dicarboxylic acids, amides of C 3 -C 12 -monocarboxylic acids or mixtures thereof as copolymerized units and which have molecular weights of from 500 to 30 000.
  • the copolymers are used in at least partially neutralized form in aqueous solution or dispersion for making leather and furs water repellent.
  • WO 94/01587 discloses water-dispersible and/or water-emulsifiable co-oligomers containing (a) fatty crotonates ; (b) radically copolymerizable, hydrophilic, ethylenically unsaturated acids and/or their anhydrides, and possibly (c) minor amounts of other copolymerizable comonomers. These co-oligomers are used as amphiphilic agents for greasing leather and pelts.
  • a method of treating leather comprising contacting a leather, in particular a tanned leather, with an amphiphilic copolymer, said amphiphilic copolymer comprising the following recurring units: wherein:
  • the present invention further provides amphiphilic copolymers as defined above and aqueous compositions comprising them.
  • the present invention provides a use of an above defined amphiphilic copolymer in treating leather to provide waterproofness thereto.
  • the present invention provides leathers comprising an amphiphilic copolymer as defined above.
  • the present invention provides a method for making above defined amphiphilic copolymers.
  • a particularly preferred amphiphilic copolymer for use in connection with this invention is a copolymer wherein the recurring unit having at least one carboxylic acid group or salt thereof corresponds to the following formula (III): wherein:
  • a fluorinated alkyl group R f in the fluorochemical containing recurring unit according to formula (I), is preferably a fluorinated, stable, inert, preferably saturated, non-polar, monovalent alkyl group. It can be straight chain, branched chain, or cyclic or combinations thereof. It can contain heteroatoms, bonded only to carbon atoms, such as oxygen, divalent or hexavalent sulfur, or nitrogen.
  • R f is preferably a fully-fluorinated alkyl group, but hydrogen or chlorine atoms can be present as substituents but preferably not more than one atom of either is present for every two carbon atoms.
  • the R f group has at least 3 carbon atoms, preferably 3 to 14 carbon atoms and more preferably at least 6 carbon atoms.
  • R f preferably contains about 40% to about 80% fluorine by weight, more preferably about 50% to about 78% fluorine by weight.
  • the terminal portion of the R f radical is preferably a perfluorinated moiety, preferably containing at least 7 fluorine atoms, e.g., CF 3 CF 2 CF 2 -, (CF 3 ) 2 CF-, F 5 SCF 2 -.
  • Preferred R f groups are fully or substantially fluorinated and are preferably those perfluorinated alkyls according to the formula C n F 2n+1 - where n is 3 to 14.
  • Linking groups Q, Q' and Y in the above formulas (I) to (III) preferably contain from 1 to about 20 carbon atoms. They can optionally contain oxygen, nitrogen, or sulfur-containing groups or a combination thereof, and are preferably free of functional groups that substantially interfere with free-radical polymerization (e.g., polymerizable olefinic double bonds, thiols, easily abstracted hydrogen atoms such as cumyl hydrogens, and other such functionality known to those skilled in the art).
  • functional groups e.g., polymerizable olefinic double bonds, thiols, easily abstracted hydrogen atoms such as cumyl hydrogens, and other such functionality known to those skilled in the art).
  • linking groups include straight chain, branched chain or cyclic alkylene, arylene, aralkylene, oxy, oxo, hydroxy, thio, sulfonyl, sulfoxy, amino, imino, sulfonamido, carboxyamido, carbonyloxy, urethanylene, ureylene, and combinations thereof such as sulfonamidoalkylene.
  • Preferred linking groups for Q and Q' include -(CH 2 CH 2 ) k O- and -SO 2 N(R)CH 2 CH 2 - wherein k is 1 or 2 and R is a C 1 -C 4 -alkyl group.
  • a preferred linking group Y is an aliphatic or aromatic linking group.
  • R h groups for use in connection with the present invention are hydrocarbon groups having at least 8 carbons and more preferably at least 12 carbon atoms. These hydrocarbon groups can contain 1 to 3 substituents such as e.g. a halogen, an amino group, an aryl group, an alkoxy group etc... More preferably however, the hydrocarbon group is unsubstituted and preferably saturated. Particularly preferred R h -groups for use in this invention are unsubstituted linear or branched alkyl groups preferably having at least 12 carbon atoms. Hydrocarbon groups R h for use in this invention may also contain cyclo aliphatic groups such as e.g. a cyclohexane.
  • Suitable cations M for use in the present invention include monovalent ions such as e.g. sodium ion, potassium ion or ammonium ion. It is also possible to use a mixture of two or more of such cations.
  • amphiphilic copolymers used in connection with the present invention can be prepared by free radical polymerisation e.g. by solution- or emulsion polymerization techniques of monomers (a), (b) and an ethylenically unsaturated monomer having a carboxylic acid group , a salt of a carboxylic acid group or a precursor of a carboxylic acid group using a free radical initiator:
  • the ethylenically unsaturated monomer corresponds to the following formula (c):
  • R f , R h, R 1,2,3 , Q, Q', Y and M have the same meaning as defined above.
  • Useful free radical initiators include azo compounds, such as azo-isobutyronitrile and azo-2-cyanovaleric acid, hydroperoxides such as cumene, t-butyl and t-amyl hydroperoxide, dialkyl peroxides such as di-t-butyl and dicumylperoxide, peroxyesters such as t-butylperbenzoate and di-t-butylperoxy phtalate, diacylperoxides such as benzoyl peroxide and lauroyl peroxide.
  • azo compounds such as azo-isobutyronitrile and azo-2-cyanovaleric acid
  • hydroperoxides such as cumene, t-butyl and t-amyl hydroperoxide
  • dialkyl peroxides such as di-t-butyl
  • Chain transfer agents can be used in order to control the molecular weight of the polymer.
  • examples include mercaptoethanol, mercaptoacetic acid, stearylmercaptane, tert-dodecylmercaptane and the like.
  • the ethylenically unsaturated monomer comprises a precursor of a carboxylic acid group such as e.g. an anhydride
  • the precursor can be converted to a carboxylic acid group or salt thereof during or subsequent to the free radical polymerisation.
  • Fluorochemical monomers and in particular (meth)acrylate monomers corresponding to formula (a) and methods for the preparation thereof are known and disclosed, e.g., in U.S. Pat.No. 2,803,615.
  • Examples of such compounds include general classes of fluorochemical acrylates or methacrylates containing fluorinated sulfonamido groups, acrylates or methacrylates derived from telomer alcohols, acrylates or methacrylates derived from fluorochemical carboxylic acids and acrylates or methacrylates as disclosed in EP 526976.
  • Suitable monomers according to formula (b) for preparing amphiphilic copolymers in accordance with this invention include long chain C 8 -C 40 alkyl acrylates and C 8 -C 40 alkyl methacrylates.
  • suitable compounds of this type are 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, dodecyl (meth)acrylate, isotridecyl (meth)acrylate, tetradecyl (meth)acrylate, C 16/18 tallow fatty alcohol (meth)acrylate, octadecyl (meth)acrylate, palmityl (meth)acrylate, n-eicosyl (meth)acrylate.
  • mixtures of long chain alkyl(meth)acrylates Preferably used are acrylic and methacrylic esters derived from alcohols of 12 to 28 carbon atoms.
  • Suitable ethylenically unsaturated monomers having a carboxylic acid group, a salt of a carboxylic acid group or a precursor of a carboxylic acid group for preparing amphiphilic copolymers in accordance with this invention include dicarboxylic acid anhydrides, such as e.g. maleic acid anhydride, or monoethylenically unsaturated C 3 -C 12 carboxylic acids. Examples include acrylic acid, methacrylic acid, 2-carboxyethylacrylate, monomethacryloyloxyethyl phtalate.
  • an amphiphilic copolymer in connection with this invention consists of recurring units according to formulas (I) and (II) and recurring units having a carboxylic acid group or salt thereof.
  • the final leather properties can be selected as desired by balancing contents of carboxylic acid (or salt), the fluorine content and the long chain alkyl group content. Increasing the free acid (and salt) content will increase water solubility of an amphiphilic copolymer in connection with this invention and therefore also the hydrophilicity thereof. On the other hand, if the carboxylic acid content is low the copolymer may not adequately penetrate the leather structure and/or may not bind sufficiently into the leather. In accordance with the present invention it is highly preferred to incorporate sufficient free carboxylic acid (or salt) groups in the polymer in order to provide the polymer with sufficient crosslinking possibilities with the tanned leather, so as to irreversibly bond the polymer to the leather.
  • a particularly preferred amount of recurring units having at least one carboxylic acid group or salt thereof, in particular recurring units according to formula (III), is between 5% and 60% by weight and more preferably between 10% and 50% by weight based on the total weight of the recurring units according to formulas (I) and (II) and the recurring units having at least one carboxylic acid group or salt thereof.
  • the long chain alkyl group content is preferably high enough to assure the leather is lubricated properly.
  • the long chain alkyl group content is preferably such that there is still a desired level of penetration into the leather.
  • the amount of recurring units according to formula (II) is at least 20% by weight of the total weight of the recurring units according to formulas (I) and (II) and the recurring units having at least one carboxylic acid group or salt thereof.
  • fatty alkyl groups having an average chain length of at least 12 carbon atoms are preferably present in an amount of above 20% by weight.
  • the content of recurring units according to formula (I) is preferably at least 1% by weight, more preferably at least 5% by weight and most preferably at least 10 % by weight based on the total weight of the recurring units according to formulas (I) and (II) and the recurring units having at least one carboxylic acid group or salt thereof. If the fluorine content is too low, the water repellency of the leather may be insufficient. On the other hand, if the fluorine content is too high, the leather may become undesirable hard.
  • An amphiphilic copolymer in connection with the present invention is preferably used as an aqueous composition, in particular an aqueous dispersion in water. If the copolymer is made by solution polymerization, it can be dispersed in water, through vigorously mixing the solution polymer with water. A solvent free dispersion can be obtained by subsequent distillation of the polymerization solvent. A partial or complete neutralization of the acid groups present in the copolymer can be obtained by means of a suitable base, such as e.g. sodium hydroxide, potassium hydroxide, ammonium hydroxide or triethanolamine and the like.
  • a suitable base such as e.g. sodium hydroxide, potassium hydroxide, ammonium hydroxide or triethanolamine and the like.
  • a leather such as a tanned hide is contacted with an aqueous composition, preferably an aqueous dispersion, comprising amphiphilic copolymer.
  • Amphiphilic copolymer aqueous dispersions in accordance with the invention are suitable for the treatment of all conventional tanned hides, in particular hides tanned with mineral tanning agents, such as chromium(III)salts.
  • the tanned hides are usually neutralized before treatment. They may be dyed before treatment. However, dyeing may also be carried out after a waterproofing treatment in accordance with this invention.
  • the tanned hides can be treated with an aqueous dispersion comprising an amphiphilic copolymer in accordance with the invention preferably in an aqueous liquor obtained by diluting the amphiphilic copolymer dispersions with water, at a pH of from 3 to 10, preferably from 5 to 8, and at from 20°C to 70°C, preferably from 40°C to 60°C.
  • the amount of the amphiphilic copolymer dispersion applied to the leather in accordance with this invention is chosen so that sufficiently high or desirable water repellency is imparted to the substrate, said amount usually being between 0.1% and 30% by weight, preferably between 0.5% and 15% by weight, based on the shaved weight of the leather or the wet weight of the hide or wet blue leather.
  • the amount which is sufficient to impart desired repellency can be determined empirically and can be increased as necessary or desired.
  • the treatment is effected, for example, by drumming. After the treatment with the aqueous dispersion described above, the pH of the treatment liquor is preferably brought to 3-5, preferably 3.3-4, by addition of an acid in particular an organic acid, such as formic acid.
  • an aqueous composition according to the present invention In order to increase repellency properties and the durability thereof and to aid in the application of an aqueous composition according to the present invention to a leather substrate to be treated therewith, it may be advantageous to incorporate into an aqueous composition according to this invention, one or more other substances such as oil and/or water repellent compositions and/or siloxane softening agents. Also other additives such as conventional leather finishing agents e.g. retanning, fatliquoring agents can be added.
  • Particularly preferred aqueous compositions for use in connection with the present invention include a water and/or oil repellent composition in addition to the amphiphilic copolymer in connection with the present invention.
  • Preferred water and/or oil repellent compositions for use in this invention are fluorochemical compositions comprising a mixture of normally solid compounds and/or polymers, each of the compounds having at least two fluoroaliphatic groups and a large hydrocarbon moiety and each of the polymers having at least one fluoroaliphatic group and a plurality of said hydrocarbon moiety.
  • Particularly preferred are compositions comprising compounds that are fluoroaliphatic esters of dimer acids and/or trimer acids. Examples of fluorochemical compositions that can be used in an aqueous composition in accordance with this invention are described in WO 93/10085.
  • Step treatment solution Temperature Time 1. Rewetting (2x) 500% water 30°C 60 min 2. Neutralization 150% water + 30°C overnight 1.5% Tanigan Pak N + during 2% Sodiumformiate + 5min/hour 0.5% Sodiumbicarbonate 3. Wash (3x) 300% Water 50°C 5 min 4. Retanning/Fatliquoring 100% water + 60°C 4% Chesnut + 40 min 4% amphiphilic 90 min fluorochemical copolymer 30 min Formic Acid to pH 3.5 5. Wash 300% Water 50°C 5 min 6. Fixation 200% Water + 40°C 60 min 4% Baychrom F 7. Wash 200% Water 40°C 10 min
  • the so treated leather sample was horsed-up overnight, dried at 60°C during 60 min, staked in the conventional manner and conditioned at room temperature during 2 weeks.
  • the leather substrates used for the evaluation of the treatment according to the invention are all commercially available and are listed below :
  • Respective data of water and oil repellency shown in the Examples and Comparative Examples are based on the following methods of measurement and evaluation criteria :
  • the water resistance of the leathers was tested according to ASTM D-2009-70, using a Maeser water penetration tester. The number of Maeser flexes needed to cause water to penetrate the leather is recorded. Since this test utilizes saline water, it is useful for predicting the resistance of leather to damage not only from water, but also from perspiration. A Maeser flex value of greater than 15.000 is the minimum criterion established by the U.S. Military for waterproof boot leather.
  • the water repellency (WR) of a treated substrate was measured using a series of water-isopropyl alcohol test liquids and was expressed in terms of the WR rating of the treated substrate.
  • the WR rating corresponds to the most penetrating test liquid which does not penetrate or wet the substrate surface after 15 seconds exposure. Treated subtrates which are penetrated by or are resistant only to a 100% water (0% isopropyl alcohol) test liquid, the least penetrating test liquid, are given a rating of 0, whereas treated substrates resistant to a 100% isopropyl alcohol (0% water) test liquid, the most penetrating test liquid, are given a rating of 10.
  • the spray rating of a treated substrate is a value indicative of the dynamic repellency of the treated substrate to water that impinges on the treated substrate.
  • the repellency is measured by Standard Test Number 22, published in the 1985 Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists (AATCC), and is expressed in terms of 'spray rating' of the tested substrate.
  • the spray rating is obtained by spraying 250 ml water on the substrate from a distance of 15 cm.
  • the wetting pattern is visually rated : using a 0 to 100 scale, where 0 means complete wetting and 100 means no wetting at all.
  • the oil repellency of a treated substrate is measured by the American Association of Textile Chemists and Colorists (AATCC) Standard Test Method No. 118-1983, which test is based on the resistance of a treated substrate to penetration by oils of varying surface tensions. Treated substrates resistant only to Nujol R , mineral oil (the least penetrating of the test oils) are given a rating of 1, whereas treated substrates resistant to heptane (the most penetrating of the test oils) are given a rating of 8. Other intermediate values are determined by use of other pure oils or mixtures of oils, as shown in the following table.
  • a Bally Penetrometer test was done according to DIN 53338.
  • a Bally Penetrometer Model 5023 (a standardized dynamic testing machine for shoe upper leather) was used.
  • the test piece was alternatively buckled and stretched by the machine, like an upper leather in actual use, while in contact with water on one side.
  • the values measured in this test are :
  • the repellency of an abraded treated substrate is measured on 5cmx12.5cm test pieces of treated substrate which has been abraded using 10 back and forth rubs over a 5-second period with abrasive paper ("WETORDRY - TRI-M-ITE" No600C) in an AATCC crockmeter (Model CM-1).
  • the above-described OR and WR repellency tests are performed on the abraded test pieces and the repellency ratings recorded as Abraded Oil Repellency (AOR) and Abraded Water Repellency (AWR) values.
  • amphiphilic fluorochemical copolymers impart a high degree of waterproofness to leather treated therewith.
  • the use of small amounts (10 % by weight) of fluorochemical (meth)acrylate in the polymer increases the waterproofness dramatically.
  • the amount of long chain alkyl hydrocarbon monomer is preferably more than 20% by weight.
  • example 7 a polymer was prepared from MeFOSEMA/ODMA/AA (30/40/30) using mercaptoacetic acid, according to the general procedure outlined above. The polymer dispersion was applied to a new batch of wet blue leather (2.0-2.2 mm thickness). The performance of the treated leather was compared to the performance of the same wet blue leather treated with a commercial available acrylic syntan (LubritanTM WP, available from Rohm and Haas). The application conditions were as described above. Of each treatment, six leather samples were evaluated. The 6 comparative examples C-3 treated with LubritanTM WP showed a large variation in Maeser flex results (min 24.500 - max 156.000) ; with an average value of 70.000. In contrast therewith, the 6 pieces of example 7 reached more than 500.000 Maeser flexes.
  • a commercial available acrylic syntan LibritanTM WP
  • an amphiphilic fluorochemical copolymer was prepared from MeFOSEMA/ODMA/IBMA/AA 20/40/10/30 according to the general procedure and neutralized with triethanolamine.
  • Wet blue leather (1.7 mm) was treated with the amphiphilic fluorochemical copolymer dispersion at 4% by weight based on the shaved weight of the leather.
  • the leather was tested for its waterproofness. The test was stopped after 140.000 Maeser flexes were obtained. This result indicates that also short chain alkyl acrylates can be incorporated in the amphiphilic fluorochemical copolymers without damaging the waterproofing properties of the leather treated therewith.
  • amphiphilic fluorochemical copolymers were made from 23 parts MeFOSEA, 23 parts ODMA, 30 parts AA and 23 parts siloxane macromer.
  • the polymers were made according to the general procedure, but using DPM as solvent.
  • the polymers were dispersed using triethanolamine or sodiumhydroxide.
  • the dispersions were applied to wet blue leather (1.7 mm) at 4% by weight based on the shaved weight of the leather.
  • the results of water repellency (mean values of 3 measurements) are given in table 3.
  • an amphiphilic fluorochemical copolymer was made from 30 parts MeFOSEMA, 40 parts ODMA and 30 parts AA. The polymer was neutralized with triethanolamine. A blend of 80 parts of the polymer dispersion and 20 parts of a conventional fluorochemical oil-and water repellent leather protector FC was applied to wet blue leather (1.7 mm) at 4% based on the shaved weight of the leather. The treated leather was tested for oil and water repellency. The results are given in table 4. Overall repellency properties of wet blue leather treated with amphiphilic fluorochemical copolymers Ex No OR AOR SR WR AWR Maeser flexes 18 6 5 90 10 10 100.000+
  • example 19 The same kind of experiment was repeated in example 19 and comparative example C-4 but with Bovine nubuck leather (for shoe upper leather).
  • Bovine nubuck leather for shoe upper leather.
  • the leather was treated with a mixture of 4% amphiphilic fluorochemical copolymer and 4% of a conventional fluorochemical oil- and water repellent leather protector FC.
  • Comparative example C-4 was made using 4% LubritanTM WP in combination with 4% FC.

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

Claims (20)

  1. Procédé pour le traitement du cuir comprenant la mise en contact d'un cuir avec un copolymère amphiphile, ledit copolymère amphiphile comprenant les unités récurrentes suivantes :
    Figure 00290001
    Figure 00290002
    dans lesquelles :
    Rf représente un groupement alkyle fluoré présentant au moins 3 atomes de carbone;
    Q et Q' représentent chacun indépendamment un groupement organique de liaison ou une liaison chimique;
    R1 et R2 représentent chacun indépendamment un hydrogène ou un groupement alkyle en C1-C4, et
    Rh représente un groupement hydrocarboné présentant au moins 8 atomes de carbone et contenant facultativement 1 à 3 substituants, et
    une unité récurrente comprenant au moins un groupement acide carboxylique ou un sel de celui-ci.
  2. Procédé suivant la revendication 1 dans lequel ladite unité récurrente comprenant au moins un groupement acide carboxylique ou un sel de celui-ci est une unité récurrente correspondant à la formule suivante :
    Figure 00300001
    dans laquelle :
    R3 représente un hydrogène ou un groupement alkyle en C1-C4;
    Y représente un groupement organique de liaison ou une liaison chimique, et
    M représente un hydrogène ou un cation.
  3. Procédé suivant la revendication 1, dans lequel ledit copolymère amphiphile comprend en outre un siloxane contenant des unités récurrentes.
  4. Procédé suivant la revendication 1 ou 2, dans lequel Rh représente un groupement alkyle non substitué et Rf correspond à CnF2n+1- dans lequel n est un entier compris entre 3 et 14.
  5. Procédé suivant la revendication 2 dans lequel ledit copolymère amphiphile comprend des unités récurrentes suivant la formule (I) en une quantité d'au moins 1% en poids, lesdites unités récurrentes suivant la formule (II) en une quantité d'au moins 20% en poids et lesdites unités récurrentes suivant la formule (III) en une quantité comprise entre 5% et 60% en poids, lesdits pourcentages en poids étant par rapport au poids total des unités récurrentes suivant les formules (I), (II) et (III).
  6. Procédé suivant la revendication 1, dans lequel ledit cuir est également mis en contact avec une composition hydrofuge et/ou oléofuge.
  7. Procédé suivant la revendication 1, dans lequel ledit copolymère amphiphile est sous la forme d'une dispersion aqueuse.
  8. Procédé suivant la revendication 7, dans lequel ledit cuir est mis en contact avec ladite dispersion aqueuse pendant le retannage.
  9. Copolymère amphiphile comprenant les unités récurrentes suivantes :
    Figure 00310001
    Figure 00310002
    dans lesquelles :
    Rf représente un groupement alkyle fluoré présentant au moins 3 atomes de carbone;
    Q et Q' représentent chacun indépendamment un groupement organique de liaison ou une liaison chimique;
    R1 et R2 représentent chacun indépendamment un hydrogène ou un groupement alkyle en C1-C4 et;
    Rh représente un groupement hydrocarboné présentant au moins 8 atomes de carbone et contenant facultativement 1 à 3 substituants, et
    une unité récurrente comprenant au moins un groupement acide carboxylique ou un sel de celui-ci.
  10. Copolymère amphiphile suivant la revendication 9, dans lequel ladite unité récurrente comprenant au moins un groupement acide carboxylique ou un sel de celui-ci est une unité récurrente correspondant à la formule suivante
    Figure 00320001
    dans laquelle :
    R3 représente un hydrogène ou un groupement alkyle en C1-C4;
    Y représente un groupement organique de liaison ou une liaison chimique, et
    M représente un hydrogène ou un cation.
  11. Copolymère amphiphile suivant la revendication 9, comprenant en outre des unités récurrentes contenant du siloxane.
  12. Copolymère amphiphile suivant la revendication 9 ou 10, dans lequel Rh représente un groupement alkyle non substitué et Rf correspond à CnF2n+1 dans lequel n est un entier compris entre 3 et 14.
  13. Copolymère amphiphile suivant la revendication 10, dans lequel ledit copolymère amphiphile comprend des unités récurrentes suivant la formule (I) en une quantité d'au moins 1% en poids, lesdites unités récurrentes suivant la formule (II) en une quantité d'au moins 20% en poids et lesdites unités récurrentes suivant la formule (III) en une quantité comprise entre 5% et 60% en poids, lesdits pourcentages en poids étant par rapport au poids total des unités récurrentes suivant les formules (I), (II) et (III).
  14. Composition aqueuse, comprenant un copolymère amphiphile suivant l'une quelconque des revendications 9 à 13.
  15. Composition aqueuse suivant la revendication 14, comprenant en outre une composition hydrofuge et/ou oléofuge.
  16. Composition aqueuse suivant la revendication 15, dans laquelle ladite composition hydrofuge et/ou oléofuge comprend des esters fluoroaliphatiques et des acides dimères et/ou des acides trimères.
  17. Cuir comprenant un copolymère amphiphile suivant l'une quelconque des revendications 9 à 13.
  18. Utilisation d'un copolymère amphiphile suivant l'une quelconque des revendications 9 à 13 dans un traitement du cuir pour lui conférer une imperméabilisation.
  19. Procédé de fabrication d'un copolymère amphiphile comprenant une polymérisation par radicaux libres d'un mélange comprenant des monomères (a), (b) et un monomère éthyléniquement insaturé présentant au moins un groupement acide carboxylique ou un sel de celui-ci ou un précurseur d'un groupement acide carboxylique:
    Figure 00340001
    Figure 00340002
    dans lesquels
    Rf représente un groupement alkyle fluoré présentant au moins 3 atomes de carbone;
    Q et Q' représentent chacun indépendamment un groupement organique de liaison ou une liaison chimique;
    R1 et R2 représentent chacun indépendamment un hydrogène ou un groupement alkyle en C1-C4 et;
    Rh représente un groupement hydrocarboné présentant au moins 8 atomes de carbone et contenant facultativement 1 à 3 substituants.
  20. Procédé suivant la revendication 19, dans lequel ledit monomère éthyléniquement insaturé correspond à la formule suivante (c) :
    Figure 00340003
    dans laquelle :
    Y représente un groupement organique de liaison ou une liaison chimique;
    R3 représente un hydrogène ou un groupement alkyle en C1-C4 et;
    M représente un hydrogène ou un cation.
EP96117814A 1996-11-07 1996-11-07 Utilisation de copolymères amphiphiles contenant des monomères fluorés pour imperméabiliser des cuirs Expired - Lifetime EP0841405B1 (fr)

Priority Applications (12)

Application Number Priority Date Filing Date Title
EP96117814A EP0841405B1 (fr) 1996-11-07 1996-11-07 Utilisation de copolymères amphiphiles contenant des monomères fluorés pour imperméabiliser des cuirs
DE69605925T DE69605925T2 (de) 1996-11-07 1996-11-07 Verwendung amphiphiler Copolymere, enthaltend fluorhaltige Monomer zur wasserfesten Ausrüstung von Leder
ES96117814T ES2143125T3 (es) 1996-11-07 1996-11-07 Uso de copolimeros anfifilicos que contienen un monomero fluorado para impartir impermeabilidad al cuero.
PCT/US1997/018386 WO1998020170A1 (fr) 1996-11-07 1997-10-15 Utilisation de copolymeres amphiphiles contenant un monomere fluore pour rendre un cuir impermeable
BR9712754-0A BR9712754A (pt) 1996-11-07 1997-10-15 Processo de tratamento de couro, copolìmero anfifìlico, uso e processo de obtenção do mesmo, couro, e, composição aquosa.
AU48998/97A AU4899897A (en) 1996-11-07 1997-10-15 Use of amphiphilic copolymers containing a fluorinated monomer to impart waterproofness to leather
JP52140298A JP3911549B2 (ja) 1996-11-07 1997-10-15 皮革に防水性を与えるためのフッ素化モノマー含有両親媒性コポリマーの使用法
KR10-1999-7004022A KR100475495B1 (ko) 1996-11-07 1997-10-15 플루오르화 단량체를 함유하는 양친매성 공중합체를 사용하여 피혁에 방수성을 부여하는 방법
US09/297,814 US6294103B1 (en) 1996-11-07 1997-10-15 Use of amphiphilic copolymers containing a fluorinated monomer to impart waterproofness to leather
CNB971995338A CN1152142C (zh) 1996-11-07 1997-10-15 含氟化单体的亲油亲水共聚物在使皮革产生防水性能上的应用
TW086116460A TW419524B (en) 1996-11-07 1997-11-05 Amphiphilic copolymers, method for making the same, and its use in treating leather
ARP970105170A AR009410A1 (es) 1996-11-07 1997-11-06 Fabricacion de cuero y utilizacion de un grupo fluoroalquilo que contiene copolimeros anfifilicos en el mismo

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP96117814A EP0841405B1 (fr) 1996-11-07 1996-11-07 Utilisation de copolymères amphiphiles contenant des monomères fluorés pour imperméabiliser des cuirs

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EP0841405A1 EP0841405A1 (fr) 1998-05-13
EP0841405B1 true EP0841405B1 (fr) 1999-12-29

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KR (1) KR100475495B1 (fr)
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Publication number Priority date Publication date Assignee Title
US6525127B1 (en) 1999-05-11 2003-02-25 3M Innovative Properties Company Alkylated fluorochemical oligomers and use thereof in the treatment of fibrous substrates
WO2003064707A1 (fr) * 2002-01-31 2003-08-07 Tfl Ledertechnik Gmbh Compositions et leur utilisation afin de d'impermeabiliser le cuir ou les fourrures, les textiles et autres matieres fibreuses
KR20030073514A (ko) * 2002-03-12 2003-09-19 강석일 방수막을 가지는 먹장어 가죽 및 그 제조방법
EP1801133A1 (fr) 2005-12-19 2007-06-27 Lanxess Deutschland GmbH Copolymères durcissables fluorés et revêtements ainsi que leur procèdé de préparation
EP1820809A1 (fr) 2006-02-17 2007-08-22 Lanxess Deutschland GmbH Revêtement de substrats à base de polymères fluorés réticulables
DE102006027400A1 (de) * 2006-06-13 2007-12-20 Wacker Chemie Ag Verfahren zur Behandlung von proteinhaltigen, faserartigen Stoffen mit beta-Ketocarbonyl-funktionellen Siloxanpolymeren

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2803615A (en) 1956-01-23 1957-08-20 Minnesota Mining & Mfg Fluorocarbon acrylate and methacrylate esters and polymers
US3923715A (en) 1973-07-26 1975-12-02 Du Pont Aqueous dispersions of perfluoroalkyl esters and vinyl polymers for treating textiles
US4525305A (en) 1982-10-25 1985-06-25 Minnesota Mining And Manufacturing Company Leather with fluorochemical finish
US4539006A (en) 1983-09-13 1985-09-03 Minnesota Mining And Manufacturing Company Leather treatment
DE3672718D1 (de) 1985-08-30 1990-08-23 Hoechst Ag Perfluoralkyl- und epichlorhydrin-gruppen enthaltende urethane, diese urethane enthaltende waessrige dispersionen und ihre verwendung.
FR2588555B1 (fr) 1985-10-16 1987-12-11 Atochem Monomeres acryliques fluores, polymeres en derivant et leur application au traitement hydrofuge et oleofuge de substrats divers
FR2590895B1 (fr) 1985-12-03 1988-01-15 Atochem Monomeres acryliques fluores, polymeres en derivant et leur application comme agents hydrophobes et oleophobes
DE3622284A1 (de) 1986-07-03 1988-01-07 Hoechst Ag Urethane aus aliphatischen fluoralkoholen, isocyanaten und aromatischen verbindungen, verfahren zu ihrer herstellung und ihre verwendung
DE3722375A1 (de) 1987-07-07 1989-01-19 Hoechst Ag Fluor und polysiloxan enthaltende urethane, verfahren zu ihrer herstellung und ihre verwendung
DE3800629A1 (de) 1988-01-12 1989-07-20 Basf Ag Verfahren zum hydrophobieren von leder, pelzen und lederaustauschmaterialien
DE3800845A1 (de) * 1988-01-14 1989-07-27 Bayer Ag Pfropfcopolymerisate, ein verfahren zu deren herstellung und deren verwendung
TNSN89128A1 (fr) 1988-12-02 1991-02-04 Rohn And Haas Company Independance Mall West Traitement du cuir avec des copolymeres amphiphites choisis
DE3931039A1 (de) 1989-09-16 1991-03-28 Basf Ag Verwendung von copolymerisaten auf basis von langkettigen ungesaettigten estern und ethylenisch ungesaettigten carbonsaeuren zum hydrophobieren von leder und pelzfellen
FR2653772B1 (fr) * 1989-11-02 1992-01-17 Atochem Telomeres acryliques fluores et leur application au traitement hydrofuge et oleofuge de substrats divers.
CA2071596A1 (fr) 1991-07-10 1993-01-11 Frederick E. Behr Halogenures de perfluoroalkyle et leurs derives
ES2082514T3 (es) 1991-11-12 1996-03-16 Minnesota Mining & Mfg Derivados de acidos dimeros fluoroalifaticos y su uso.
DE4223111A1 (de) 1992-07-14 1994-01-20 Henkel Kgaa Neue Lederfettungsmittel und ihre Verwendung
DE4244951C2 (de) 1992-12-01 1998-08-06 Minnesota Mining & Mfg Fasersubstrat mit Wasser-, Öl-, Schmutzabweisungsvermögen und Weichgriffigkeit
DE4240274B4 (de) * 1992-12-01 2004-02-12 Minnesota Mining And Manufacturing Co., Saint Paul Polysiloxane mit fluoraliphaten- und carboxylhaltigen terminalen Gruppen, ihre Herstellung und ihre Verwendung bei der Behandlung von Fasersubstraten
DE4416415A1 (de) 1994-05-10 1995-11-16 Hoechst Ag Copolymere auf Basis von ethylenisch ungesättigten Dicarbonsäureanhydriden, langkettigen Olefinen und Fluorolefinen

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EP0841405A1 (fr) 1998-05-13
WO1998020170A1 (fr) 1998-05-14
AU4899897A (en) 1998-05-29
ES2143125T3 (es) 2000-05-01
CN1152142C (zh) 2004-06-02
KR100475495B1 (ko) 2005-03-10
JP3911549B2 (ja) 2007-05-09
JP2001504874A (ja) 2001-04-10
DE69605925D1 (de) 2000-02-03
CN1236397A (zh) 1999-11-24
DE69605925T2 (de) 2000-07-20
AR009410A1 (es) 2000-04-12
KR20000053098A (ko) 2000-08-25
TW419524B (en) 2001-01-21
BR9712754A (pt) 1999-10-19

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