EP0140525B2 - Behandlung von Leder - Google Patents

Behandlung von Leder Download PDF

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Publication number
EP0140525B2
EP0140525B2 EP84305847A EP84305847A EP0140525B2 EP 0140525 B2 EP0140525 B2 EP 0140525B2 EP 84305847 A EP84305847 A EP 84305847A EP 84305847 A EP84305847 A EP 84305847A EP 0140525 B2 EP0140525 B2 EP 0140525B2
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EP
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Prior art keywords
carbon atoms
leather
composition
group
water
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EP84305847A
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English (en)
French (fr)
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EP0140525B1 (de
EP0140525A1 (de
Inventor
Nathaniel P. C/O Minnesota Mining And Langford
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3M Co
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Minnesota Mining and Manufacturing Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes

Definitions

  • This invention in one aspect, relates to a composition comprising a fluorochemical compound useful for treating leather, textiles, and cellulosic materials. In another aspect, the invention relates to a method for treating these materials with the composition. In a third aspect, this invention relates to leather, textiles and cellulosic materials treated with the composition.
  • Leather has a combination of properties which has long made it useful and desirable for many applications, e.g. footwear, garments, and upholstery, requiring protection, comfort, durability, and esthetics. Such properties include long term flexibility, toughness, breathability, insulation, conformability, soft feel, and luxurious appearance. However, due to its porous, fibrous structure, leather absorbs water and oil, and the consequent unslightly spotting and stains detract from its usefulness and appearance. There had been considerable effort expended to overcome these drawbacks of leather. See Kirk-Othmer, Encycl. of Chem. Tech., Vol. 22, 1970, John Wiley & Sons, p 150, 151.
  • products that are used by consumers to impart water and oil repellancy to leather include waxes, e.g., beeswax, carnauba wax, paraffin wax; greases, e.g., lanolin; oils. e.g., fish oil, mink oil, neat's-foot oil, silicones, e.g., dimethylpolysiloxane, silicone resins; and fluorochemicals, e.g., FC-326 Scotchgard@ Brand Fabric Protector available from Minnesota Mining and Manufacturing Company, and FC-905 3M Brand Fluorochemical available from Minnesota Mining and Manufacturing Company.
  • waxes e.g., beeswax, carnauba wax, paraffin wax
  • greases e.g., lanolin
  • oils e.g., fish oil, mink oil, neat's-foot oil
  • silicones e.g., dimethylpolysiloxane, silicone resins
  • fluorochemicals e.g., FC-3
  • waxes, greases, oils, and silicones have been found to impart some degree of water and oil repellancy to leather; however, none of these are as effective as fluorochemicals in providing water and oil repellancy.
  • Fluorochemicals are somewhat less desirable to use them are waxes or oils, generally because certain of the solvents needed to apply fluorochemicals to leather are deleterius to leather or dyes that have been applied to the leather.
  • unlike waxes or oils presently available fluorochemical compounds are not known to condition or clean leather.
  • DE-A-1,418,985 discloses fluorochemical compounds for treating paper, textile, leather and other articles.
  • the compounds are incorporated in an emulsion or are dissolved in an organic solvent and are defined by a general formula which includes as one of many sub-classes of compounds those compounds defined by the formula: where R may be a hydrocarbon group, R 1 may be an alkyl group, R, is a fluoroinated aliphatic group, W may be an isocyarate, m is O or 1, 1 ⁇ b ⁇ 3,1 ⁇ p ⁇ 6 and (2 ⁇ -n + (p-l) ⁇ -6.
  • Table III lists various aromatic isocyanate reactants which can be utilised to form W.
  • FR-A-2,106,269 discloses organic solvent-based compositions containing fluorochemical compounds for treating textile and cellulose fibres.
  • the fluorochemical compounds are defined by a general formula which includes the sub-class of compounds defined by the formula: where R 1 is a perfluoroalkyl group having 3 to 11 carbon atoms and R 3 , R 4 , and R 5 are independently alkyl, aryl, aralkyl or lower cycloalkyl groups.
  • EP-A-0,107,948 which forms part of the state of the art against the present application by virtue of Article 54(3) EPC, discloses a general formula which includes the sub-class of compounds represented by the formula where
  • the invention provides a method of treating a material selected from the group consisting of leather, textiles, and cellulosics in order to provide enhanced water and oil repellancy thereto comprising the step of applying to said material a composition comprising a compound represented by the formula: wherein:
  • the invention provides a composition for treating leather textiles, and cellulosic materials in order to provide enhanced water and oil repellancy thereto, said composition comprising:
  • the fluorochemical compounds useful in this invention confer durable water and oil repellancy to leather while not adversely affecting the appearance, feel, hand, and other desirable qualities of the leather.
  • the fluorochemical compounds useful in the practice of this invention are capable of providing up to about 30 times as much water repellancy to leather as the best commercially available leather treatment products.
  • the fluorochemical compounds are also useful for imparting water and oil repellancy to textiles, including both natural materials, e.g, cotton, silk, and synthetic materials, e.g. nylon, polyester.
  • the fluorochemical compounds have been found to be useful for imparting water and oil repellancy to cellulosic materials, e.g. wood, paper.
  • the sites of unsaturation in the fluorochemical compounds of the invention allow crosslinking after the composition is applied to the surface of the leather.
  • the preferred solvents from which these fluorochemical compounds can be applied are not only not harmful to leather, but they are also capable of cleaning and conditioning the leather.
  • the solvents perform the additional function of supressing cross-linking of the fluorochemical compounds before the composition is applied to the leather. Upon evaporation of the solvent after application of the composition, the fluorochemical compound cross-links to cure in air at normal room temperature.
  • the fluorochemical compounds of this invention can be applied from solvent that are hot harmful to the health of the consumer, to leather itself, to dyes previously applied to leather, or to textiles and cellulosic materials. While not preferred, the fluorochemical compounds can also be applied from chlorinated hydrocarbon solvents. Compositions of the present invention can be readily formulated into a variety of preparations for various modes of application to leather and/or textiles and/or cellulosic materials.
  • the fluorochemicals useful in this invention preferably contain at least 20 weight percent, preferably 25 to 50 weight percent. fluorine in the form of said fluoroaliphatic radical.
  • R is -CH 3 and R 1 is -CH 2 CH 2 -, or
  • the chain in the radical A may be straight, branched, or cyclic.
  • the radical preferably contains two or more unsaturated sites.
  • Compositions of the present invention containing fluorochemical compounds having unsaturated sites are easy to formulate, because the fluorochemical compounds readily dissolves in solvents that are not harmful to leather.
  • the unsaturated fluorochemical compounds begin to cross-link as the solvent evaporates and continue to cross-link even several days after application.
  • the aliphatic moiety A can be substituted with one or more pendant hydroxyl groups (-OH) or one or more pendant carboxyl groups (-COOH) or both.
  • the organic linking group, Q can have a wide variety of structures, serving as it does the function of bonding together in the same molecule the R, and A moieties.
  • the Q linkages should be free of moieties, particularly hydrophilic groups, such as acid functional groups and salts thereof, e.g. -COOH and -COONa, polyoxyethylene, polyethyleneimine, and aliphatic hydroxyl groups, which would interfere with the ability of the fluorochemical compounds to impart the desired oil and water repellancy to the substrate treated therewith in accordance with this invention.
  • the products of the present invention can be prepared by any of the following method:
  • the fluoroaliphatic sulfonamido alcohols and the fatty acid can be replaced by a fluoroaliphatic sulfonamido carboxylic acid and a fatty alcohol respectively. Because of the nature of such intermediates and such reactions, the fluorochemicals so prepared and useful in this invention will often be mixtures of isomers and homologs.
  • the fluoroaliphatic reactants may be chemically combined with the aforementioned coreactants through the condensation of their hydroxyl or carboxyl groups with available carboxyl and hydroxyl groups in fatty acids or fatty alcohols to form an ester linkages or bridging radical or through the addition of their hydroxyl or carboxyl groups to an isocyanate group to form a urethane linkage and amine linkage respectively.
  • the reaction of these fluoroaliphatic acids and alcohols with the coreactants may be carried out in a manner similar to that conventionally employed with nonfluorinated carboxyl or hydroxyl containing components.
  • the reaction (1) can be conducted by introducing the reactants into a vessel containing a catalyst.
  • Catalysts that are suitable for the reactions include sulfuric acid and ion exchange resins.
  • Commercially available ion exchange resins that are useful as catalysts in the reactions include Amberlite@ IR 120, a strongly acidic, sulfonated polystyrene cation exchange resin, and Amberlite@ 15, a strongly acid, sulfonic functional cation exchange resin, both of which are available from Mallinckrodt.
  • the reaction medium can include a solvent or it can be solvent free.
  • Solvents suitable for the reaction include xylene and mixtures of hydrocarbons. A commercially available mixture of hydrocarbons useful as a solvent for the reaction medium is sonar L, avilable from Exxon.
  • the reaction is preferably conducted under an atmosphere of nitrogen and refluxed until no additonal water is generated.
  • Monofunctional alcohols useful in this invention include the N-alkanol perfluoroalkanesulfonamides described in U.S. Patent 2,803,656, which have the general formula wherein R t is a perfluoroalkyl group (including perfluorocycloalkyl) having 4 to 10 carbon atoms, R 1 is an alkylene radical having 1 to 12 carbon atoms, and R is a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms.
  • These monofunctional alcohols are prepared by reactions of an acetate ester of halohydrin with a sodium or potassium salt of the corresponding perfluoroalkanesulfonamide.
  • Illustrative alcohols include the following:
  • monofunctional alcohols include the N-[-hydroxypoly(oxaalkylene)]perfluoroalkane sulfonamides of U.S. Patent 2,915,554, such as
  • Suitable carboxyl-containing fluoroaliphatic reactants include the monofunctional perfluoroalkanesul- fonamidoalkylene-carboxylic acids of U.S. Patent 2,809,990, which have the general formula: wherein R t is a perfluoroalkyl (including perfluorocycloalkyl) group having from 4 to 10 carbon atoms, R is hydrogen or an alkyl group having from 1 to 4 carbon atoms and R 2 is an alkylene group having from 1 to 12 carbon atoms.
  • Illustrative acids include the following:
  • Fatty acid and fatty alcohol reactants useful in the practice of this invention preferably have at least one to three unsaturated sites, and more if available.
  • Representative examples of fatty acids suitable for the practice of this invention include, but are not limited, to, linseed fatty acid, linolenic acid, eleostearic acid, ricinoleic acid, oleic acid, linoleic acid, sorbic acid, dimer acid, and mixtures thereof.
  • Representative fatty alcohols that are suitable for the practice of this invention are the analogs of the fatty acids mentioned above.
  • the fluorochemical compounds useful in the practice of this invention can be dissolved in an appropriate organic solvent or mixture of organic solvents, and applied directly from the resulting solution.
  • Solvents that are suitable for dissolving the fluorochemicals include chlorinated hydrocarbons, e.g. tetrachlorethane, trichloroethane, isoparaffinic hydrocarbons, alcohols, e.g., isopropyl alcohol, ketones, e.g., methyl isobutyl ketone, and mixtures thereof.
  • chlorinated hydrocarbons can be used to dissolve the fluorochemicals, they are not recommended because they can damage leather and dyes that are used on leather. Furthermore, chlorinated hydrocarbons can be objectionable to user of the composition of this invention.
  • the composition can be applied in any of several alternative formulations, including, for example, aerosols, water/oil emulsions, and anhydrous gels. Aerosols will require a propellant, e.g. isobutane. Anhydrous gels will require a gelling agent, e.g. aluminum oleate. Water/oil emulsions will require water and an emulsifying agent, e.g. sorbitan sesquioleate.
  • Water/oil emulsions and anhydrous gels can further employ mild solvents, e.g. isoparaffinic hydrocarbons, which can serve the dual purpose of carrying the fluorochemical and acting as a cleaning aid for the leather.
  • mild solvents e.g. isoparaffinic hydrocarbons
  • Conditioners and softeners e.g. mineral oil, can also be included in compositions of the present invention.
  • the composition of this invention can be used to treat such leather articles as show uppers, garments, gloves, luggage, handbags, upholstery, and the like.
  • the composition is particularly useful for leathers having porous surfaces, such as natural smooth leathers having no finish and suede leathers.
  • the composition can also be used with finished skins, e.g. those having a sprayed on leather finish.
  • the composition can also be used to treat textile articles such as clothing, shoes, and the like.
  • the composition is especially useful for articles comprising leather and textiles, e.g. shoes, fashion accessories.
  • the composition can be used to treat cellulosic materials such as wood and paper.
  • the amount of the fluorochemical deposited on the leather can vary, but functionally stated that amount will be sufficient to impart oil and water repellency to the leather. Generally that amount will be about 0.05 to 1.0 percent by weight, preferably 0.1 to 0.2 percent by weight based on the weight of the leather after it is dried. More can be applied, but a greater effect will probably not be noticed. With such amounts of fluorochemical deposited on the leather, the leather will have oil and water repellency that is durable, that is, the repellency will last a long time during active use of the article made from such finished leather, the fluorochemical penetrating to a significant depth into the leather.
  • Such durable repellency is obtained without adversely affecting the appearance, feel, hand, flexibility, breathability, or other desirable properties of leather. And such desirable properties are obtained not only by treated cattlehide in accordance with this invension but other finished hides and skins, such as sheepskin and pigskin.
  • the amount of fluorochemical required to impart water and oil repellancy to textiles and cellulosic materials is substantially similar to that amount required to impart those properties to leather.
  • Examples 1-11 illustrated the preparation of various fluorochemicals of this invention
  • Examples 12-13 illustrating the effectiveness of various fluorochemicals in the treatment of leather
  • Examples 14-16 illustrating various formulations into which the fluorochemicals can be incorporated.
  • samples of leather were treated with various fluorochemical compositions in accordance with this invention and the properties of the treated leather tested.
  • similar tests were made on untreated samples or on samples treated with products not within the scope of the invention.
  • a Bally Penetrometer Model 5022 (a dynamic testing machine for shoe leather uppers was used, in which test the test piece was alternatively buckled and stretched by a machine, like an upper leather in actual use, while in contact with water on one side.
  • the leather-treating test method was as follows:
  • This example compares the efficacy of the product of the present invention with commercially available water-repellants for leather.
  • the following ingredients, in the amounts indicated, were mixed in a beaker to form a gel-type leather treating composition:
  • This treating agent, referred to as Formulation A was compared with the commercially available leather treating agents listed in Table III.
  • the leather-treating test method was the same as that employed in Example 12, and the results of the treatment comparison is shown in Table III. From the foregong Table, it is apparent that the product of the present invention is much better than commercially available products with respect to water repellancy.
  • This Example describes a leather treatment composition that can be applied as a clear liquid.
  • the following ingredients in the amounts indicated were introduced into a beaker:
  • This Example describes a leather treatment composition that an be applied as an aerosol foam.
  • the following ingredients in the amounts indicated were introduced into a container suitable for aerosol compositions:
  • This Example describes a leather treatment composition that can be applied as an aerosol spray.
  • the following ingredients in the amounts indicated were introduced into a container suitable for aerosol compositions:
  • This Example describes a leather treatment composition that can be applied as a water/oil emulsion.
  • the following ingredients in the amounts indicated were introduced into a beaker:
  • samples of textiles were treated with the following composition in accordance with this invention and properties of the treated textiles tested.
  • wooden tongue depressors were treated with the following compositions in accordance with this invention and properties of the treated articles tested.
  • the effectiveness of these compositions for water repellancy was tested by measuring the weight percent of water absorbed by the untreated and treated tongue depressors.
  • the tongue depressors were immersed in a water bath having a temperature of 15.6 ° C (60 ° F) for 45 minutes. Upon removal, the excess water was removed by shaking. The percentage of water absorbed was determined by weighing the tongue depressors before and after immersion, and multiplying the difference divided by original weight by 100.

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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)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paper (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Claims (14)

1. Verfahren zum Behandeln eines Werkstoffs, der aus der Gruppe ausgewählt ist, die aus Leder, Textilien und Zelluloseprodukten besteht, um ihm stärkeres Wasser- und Ölabweisungsvermögen zu verleihen, in dem auf den Werkstoff eine Zusammensetzung aufgetragen wird, die mindestens teilweise aus einer Verbindung der Formel
Figure imgb0039
besteht, in der
Rf ein gesättigtes einwertiges nichtaromatisches aliphatisches Radikal mit bis zu 20 Kohlenstoffatomen ist, das eine endständige Perfluoromethylgruppe, mindestens, drei vollständig fluorierte, miteinander verbundene Kohlenstoffatome in einer geraden, verzweigten oder zyklischen Kette und gegebenenfalls Cl-Substituenten enthält, wobei Rf pro zwei in (Rf+R+R1) enthaltene Kohlenstoffatome nicht mehr als
ein CI-Atom enthält,
R ein Alkylradikal mit 1 bis 4 Kohlenstoffatomen darstellt,
R1 ein Alkylenradikal mit 1 bis 12 Kohlenstoffatomen darstellt,
R2 ein Alkylenradikal mit 1 bis 4 Kohlenstoffatomen darstellt,
A eine Kohlenwasserstoff- oder Carboxylatgruppe darstellt, die 5 bis 36 Kohlenstoffatome besitzt und
die von einer Fettsäure oder einem Fettalkohol abgeleitet ist, mindestens einen ungesättigten Bindungsplatz besitzt und gegebenenfalls mit einer oder mehreren Hydroxylgruppen (-OH) oder Carboxylgruppen (-COOH) substituiert ist,
Q ein Glied darstellt, das aus der Gruppe ausgewählt ist, die aus
Figure imgb0040
besteht.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Zusammensetzung ferner mindestens ein organisches Lösungsmittel als Träger für die genannte Verbindung enthält.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Zusammensetzung ferner ein Treibmittel enthält.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß die Zusammensetzung ferner ein Geliermittel enthält.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Zusammensetzung ferner Wasser enthält.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Zusammensetzung ferner ein Emulgiermittel enthält.
7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das zu behandelnde Material Leder ist.
8. Gegenstand aus einem Werkstoff, der aus der Gruppe ausgewählt ist, die aus Leder, Textilien, Zelluloseprodukten und Kombinationen derselben besteht, und der mit einem nach dem Verfahren nach Anspruch 1 aufgetragenen Überzug versehen ist.
9. Zusammensetzung zum Behandeln von Leder, Textilien und Zelluloseprodukte, um ihnen ein stärkeres Wasser- und Ölabweisungsvermogen zu erteilen, wobei die Zusammensetzung enthält
(a) eine Verbindung der Formel
Figure imgb0041
in der
Rf ein gesättigtes einwertiges nichtaromatisches aliphatisches Radikal mit bis zu 20 Kohlenstoffatomen ist, das eine endständige Perfluoromethylgruppe, mindestens, drei vollständig fluorierte, miteinander verbundene Kohlenstoffatome in einer geraden, verzweigten oder zyklischen Kette und gegebenenfalls CI-Substituenten enthält, wobei Rf pro zwei in (Rf + R + Rl) enthaltene Kohlenstoffatome nicht mehr als ein CI-Atom enthält,
R ein Alkylradikal mit 1 bis 4 Kohlenstoffatomen darstellt,
R1 ein Alkylenradikal mit 1 bis 12 Kohlenstoffatomen darstellt,
R2 ein Alkylenradikal mit 1 bis 4 Kohlenstoffatomen darstellt,
A eine Kohlenwasserstoff- oder Carboxylatgruppe darstellt, die 5 bis 36 Kohlenstoffatome besitzt und die von einer Fettsäure oder einem Fettalkohol abgeleitet ist, mindestens einen ungesättigten Bindungsplatz besitzt und gegebenenfalls mit einer oder mehreren Hydroxylgruppen (-OH) oder Carboxylgruppen (-COOH) substituiert ist,
Q ein Glied darstellt, das aus der Gruppe ausgewählt ist, die aus
Figure imgb0042
besteht, und
(b) einen Träger, der für das Leder, die auf das Leder aufgetragenen Farbstoffe, die genannten Textilien oder die genannten Zelluloseprodukte unschädlich ist.
10. Zusammensetzung nach Anspruch 9, dadurch gekennzeichnet, daß der Träger mindestens teilweise aus mindestens einem organischen Lösungsmittel für die genannte Verbindung besteht.
11. Zusammensetzung nach Anspruch 10, dadurch gekennzeichnet, daß der Träger ferner ein Treibmittel enthält.
12. Zusammensetzung nach Anspruch 10, dadurch gekennzeichnet, daß der Träger ferner ein Geliermittel enthält.
13. Zusammensetzung nach Anspruch 12, die ferner Wasser enthält.
14. Zusammensetzung nach Anspruch 13, die ferner ein Emulgiermittel enthält.
EP84305847A 1983-09-13 1984-08-28 Behandlung von Leder Expired - Lifetime EP0140525B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US53193283A 1983-09-13 1983-09-13
US531932 1983-09-13

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EP0140525A1 EP0140525A1 (de) 1985-05-08
EP0140525B1 EP0140525B1 (de) 1989-06-21
EP0140525B2 true EP0140525B2 (de) 1994-08-24

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EP (1) EP0140525B2 (de)
JP (1) JP2516899B2 (de)
AU (1) AU582346B2 (de)
DE (1) DE3478754D1 (de)
ES (1) ES9100005A1 (de)
MX (1) MX161563A (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6479612B1 (en) 1999-08-10 2002-11-12 E. I. Du Pont De Nemours And Company Fluorochemical water and oil repellents
US7160480B2 (en) 2005-02-22 2007-01-09 E. I. Du Pont De Nemours And Company Leather treated with fluorochemicals

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5098446A (en) * 1989-10-13 1992-03-24 Minnesota Mining And Manufacturing Company Use of fluorochemicals in leather manufacture
DE69207779T2 (de) 1991-11-12 1996-05-30 Minnesota Mining & Mfg Derivate fluoroaliphatischer dimer-säuren und deren verwendung
JP3875400B2 (ja) * 1998-05-11 2007-01-31 スリーエム カンパニー 撥水撥油剤組成物
US6491745B1 (en) 1999-05-07 2002-12-10 3M Innovative Properties Company Water/oil repellent composition

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US2809990A (en) 1955-12-29 1957-10-15 Minnesota Mining & Mfg Fluorocarbon acids and derivatives
US2951051A (en) 1957-06-26 1960-08-30 Minnesota Mining & Mfg Perfluoro-substituted aliphatic acids and derivatives thereof
US2915554A (en) 1957-07-23 1959-12-01 Minnesota Mining & Mfg Non-ionic surfactant derivatives of perfluoro alkane-sulfonamides
NL280258A (de) * 1961-09-07
NL268543A (de) 1962-06-22 1900-01-01
US3330812A (en) 1964-04-27 1967-07-11 Minnesota Mining & Mfg Vinyl polymers containing perfluorocarbon groups and acyl halide groups
US3573952A (en) 1968-10-21 1971-04-06 Minnesota Mining & Mfg Process for imparting oil repellency to suede leather
CH260770D (de) * 1969-02-25
GB1301942A (de) * 1969-07-11 1973-01-04
CH1187671D (de) 1970-09-09
US3987227A (en) * 1973-04-02 1976-10-19 Minnesota Mining And Manufacturing Company Durably stain-repellant and soil-resistant pile fabric and process
US3922143A (en) * 1973-07-25 1975-11-25 Minnesota Mining & Mfg Polycarbodiimide treatments
US4035506A (en) * 1974-07-26 1977-07-12 Minnesota Mining And Manufacturing Company Fluorocarbon dermal protective compositions
DE2653602A1 (de) * 1976-11-25 1978-06-01 Bayer Ag Perfluoralkylgruppen enthaltende carbodiimide
US4525305A (en) * 1982-10-25 1985-06-25 Minnesota Mining And Manufacturing Company Leather with fluorochemical finish
CA1248273A (en) * 1982-11-09 1989-01-03 Robert W. Brinkley Blends of fluorochemicals and fibrous substrates treated therewith
EP0113217A3 (de) * 1982-12-30 1985-08-28 Minnesota Mining And Manufacturing Company Fluorchemikalien auf Polyesterbasis und damit behandelte faserige Substrate
DE3311165A1 (de) * 1983-03-26 1984-09-27 Gödecke AG, 1000 Berlin Feinkristallines isoxicam

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6479612B1 (en) 1999-08-10 2002-11-12 E. I. Du Pont De Nemours And Company Fluorochemical water and oil repellents
US7160480B2 (en) 2005-02-22 2007-01-09 E. I. Du Pont De Nemours And Company Leather treated with fluorochemicals

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JPS6096683A (ja) 1985-05-30
EP0140525B1 (de) 1989-06-21
MX161563A (es) 1990-11-06
DE3478754D1 (en) 1989-07-27
AU582346B2 (en) 1989-03-23
AU3189984A (en) 1985-03-21
EP0140525A1 (de) 1985-05-08
JP2516899B2 (ja) 1996-07-24
ES9100005A1 (es) 1990-11-01

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