US3896251A - Outerwear fabric treatment - Google Patents

Outerwear fabric treatment Download PDF

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Publication number
US3896251A
US3896251A US38070273A US3896251A US 3896251 A US3896251 A US 3896251A US 38070273 A US38070273 A US 38070273A US 3896251 A US3896251 A US 3896251A
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groups
carbodiimide
fluoroaliphatic
radicals
percent
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Dennis P Landucci
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3M Co
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Minnesota Mining and Manufacturing Co
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Priority to GB5146874A priority Critical patent/GB1413052A/en
Priority to GB1062273A priority patent/GB1413051A/en
Priority to JP3050973A priority patent/JPS512560B2/ja
Priority to CH320273D priority patent/CH320273A4/xx
Priority to DE19732310801 priority patent/DE2310801C3/de
Priority to FR7307777A priority patent/FR2175027B1/fr
Priority to CH320273A priority patent/CH587381B5/xx
Priority to AU52962/73A priority patent/AU452397B2/en
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to US05380702 priority patent/US3896251A/en
Priority to US05/554,420 priority patent/US4024178A/en
Priority to FR7513873A priority patent/FR2259854B1/fr
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Publication of US3896251A publication Critical patent/US3896251A/en
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/395—Isocyanates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/425—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes
    • D06M13/428—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes containing fluorine atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2164—Coating or impregnation specified as water repellent
    • Y10T442/2172—Also specified as oil repellent

Definitions

  • This invention relates to textile materials and, in particular, to the class of materials including those known as outerwear fabrics which consist essentially of hydrophobic synthetic fibers. This invention relates more particularly to processes for treating synthetic fibercontaining materials to impart durable water and oil repellency and materials so protected.
  • a preferred fluoroaliphatic radical-containing material is a substantially linear vinyl polymer containing from 10 to 60 percent by weight of the polymer of fluorine in the form of fluoroaliphatic groups terminating in CR, groups and containing at least three fully fluorinated carbon atoms.
  • Acrylates and methacrylates are readily available and very convenient vinyl polymers and are particularly preferred.
  • the carbodiimides consist essentially of from I to a plurality, preferably not over 20, of carbodiimide groups, terminal organic radicals free from isocyanatereactive hydrogen atoms connected to carbodiimide and, when two or more carbodiimide groups are pres ent, also polyvalent, preferably divalent, organic linking groups which are residues of a polyisocyanate between successive carbodiimide groups. Fluoroaliphatic groups may form parts of terminal or linking groups.
  • the treating solution is applied by padding, spraying or other conventional means a perfluoroalkoxyl group having up to 4 carbon atoms, cyano, carboxy, carbamoyl, or solvent is vaporized to leave a coating of the blend on the fibers.
  • the components can be applied in a series of applications or, more conveniently, as a single blend.
  • a blend of vinyl polymer and carbodiimide combined in a ratio of 10:90 to :5 may be prepared in the desired aqueous or nonaqueous medium and diluted as needed to form the treating solution.
  • the fabric is found to be oil and water repellent, launderable and dry-cleanable with substantial retention of repellent properties and to possess a pleasant hand.
  • fluoroaliphatic radicalcontaining polymers useful for the treatment of fabrics to obtain oil and water-born stain repellency
  • condensation polymers such as polyesters, polyamides, polyepoxides and the like
  • vinyl polymers such as acrylates, methacrylates, polyvinyl ethers and the like. Many of these are disclosed in the reference in Table l.
  • the preferred class of fluoroaliphatic radicalcontaining vinyl polymers is composed of the acrylate and methacrylate polymers and random copolymers. ln any event, it is essential that the vinyl polymer contain a fluoroaliphatic radical terminating in a CF group and containing at least three fully fluorinated carbon atoms, preferably a perfluoroalkyl group.
  • the polymer may contain as little as 10 percent of its weight of fluorine in the form of fluoroaliphatic radicals, and as much as 60 percent for maximum resistance to dry cleaning. it is preferred that the polymer contain from about 15 percent to 45 percent by weight of fluorine.
  • the fluoroaliphatic polymer is applied to the treated fabric so as to provide between 0.02 and 0.5 percent by weight of carbon-bonded fluorine on the fabric, preferably 0.05 0.25 percent by weight. Although higher levels of fluorine can be applied to provide useful products, the increased cost is not usually warranted by increase in performance.
  • the carbodiimides employed in the invention can be of more or less conventional types including terminal hydrocarbon radicals or they may include fluoroaliphatic radicals as noted above. Fluoroaliphatic radicalcontaining carbodiimides were not known heretofore and are particularly useful in fabric treatments.
  • the carbon-bonded fluorine of these polymers which ranges from about l5 to about 45 percent is included within the totals of fluorine applied to the fabric, i.e., 0.02 to 0.5 percent by weight.
  • n O or an integer from I to at least 20 and preferably from 1 to 10.
  • a and B are as defined below.
  • the A groups or B groups may each be the same or different. Carbodiimides in which n is 20 and higher are useful but offer no known advantages.
  • A is a divalent organic group which may include pendent fluoroaliphatic radicals linking successive carbodiimide groups when n is I or more.
  • Illustrative linking groups include alkylene, such as ethylene, isobutylene. and the like of 2 to about l0 carbon atoms, aralkylene, such as CH,C,H.C- H,, of up to l0 carbon atoms, arylene, such as tolylene, C.H,(Cl-l;), of up to about 10 carbon atoms.
  • polyoxaalkylene such as (C,H O),C,H containing up to about 5 oxa groups and combinations of the various types.
  • the A group is the residue of an organic diisocyanate. That is, the divalent radical obtained by removal of the isocyanate group from an organic diisocyanate.
  • Suitable organic diisocyanates may be simple, e.g.. toluene diisocyanate. or complex, as formed by the reaction ofa simple diisocyanate with a dior polyol in proportions to give an isocyanate terminated polyurethane.
  • carbodiimides generally and preferably include divalent A groups
  • some of the A groups can be, for example trivalent or tetravalent derived from triisocyanates or tetraisocyanates such as polymethylenepolyphenyl isocyanates. e.g., OCNC l-l CH,C H (NCO)CH C H NCO.
  • A is trivalent or tetravalent, branched or even crosslinked polycarbodiimides result.
  • a mixture of A groups containing some trivalent groups can be used to provide branched polycarbodiimides which retain the desirable solubility and thermoplasticity of the linear carbodiimides resulting from carbodiimides having divalent A groups.
  • Substituents may be present in A groups provided they contain no isocyanate-reactive hydrogen atoms; that is, groups such as -OH are normally excluded. Simple unsubstituted organic linking groups free from nonaromatic unsaturation are preferred.
  • the organic linking group depends on the polyisocyanate compound employed such as:
  • the terminal groups, or B-groups are preferably monovalent radicals of monoisocyanate compounds which may be aliphatic as C l-l aralkyl as C,H,CH,-. aryl as C H and preferably fluoroaliphatic such as C F C ll and C F, Cl-l O,CNHC,l-l.(Cl-l,). (derived from tolylene diisocyanate and l,ldihydroperfluorooctanol). Numerous other terminal groups are operable in the compounds and process of the invention.
  • the B groups are monovalent radicals derived from diisocyanates and include an isocyanate group (or an hydrolysis product of such a group).
  • the terminal B groups may be the .same or different.
  • the relative proportion of monoisocyanate to diisocyanate used in the reaction determines the average value of n in the above formula, 0 when no diisocyanate is used upwards so that with about mole percent of monoisocyanate and 90 percent of diisocyanate n will average about as will be readily apparent.
  • Synthetic fabrics of 100% filament nylon and 100 percent spun and 100 percent filament polyester are treated with the blended formulation at a predetermined level of fluoroaliphatic component on the fabric. This level is conveniently set to give a particular weight of carbon-bonded fluorine on the fabric, usually of the order of 0.05 to about 0.5 percent by weight.
  • the water repellency of the tested fabrics is measured by Standard Test Number 22-52, published in the 1952 Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists, Vol. 28, page 136.
  • the spray rating is expressed on a 0 to 100 scale where 100 is the highest possible rating. For outerwear fabrics particularly, a spray rating of 70 or higher is considered desirable.
  • the oil repellency test American Association of Textile Chemists and Colorists Standard Test 1 18-196 is based on the resistance to penetration of oils of varying viscosities. Treated fabrics resistant only to Nujol, a common type of mineral oil, and the least penetrating of the test oils, are given a rating of 1, whereas fabrics resistant to heptane, the most conventionally of the test oils, are given a value of 8. Other intermediate values are determined by use of other pure substances.
  • the oil repellency corresponds to the oil which does not penetrate or wet the fabric after 3 minutes contact. Higher numbers temperatures better oil repellency. In general, an oil repellency of 3 or greater is desirable.
  • the laundering cycle employed is as follows: The treated fabrics are laundered in a mechanically agitated automatic washing machine capable of containing a 4 kg. load, using water at 60 C. and a commercial detergent and then tumble-dried in an automatic dryer for 20 minutes at 88 C. before being tested. They are not ironed after drying.
  • Drycleaning is performed by a commercial drycleaning establishment and the fabrics are not pressed or heated after the drycleaning process.
  • Perchloroethylene (C Cl is the solvent used for the drycleaning procedure.
  • Carbodiimides are usually made from diisocyanates and monoisocyanates in an inert solvent such as methyl isobutyl ketone, conveniently at a concentration of about 40 percent of dissolved materials, to which is added about 1% of the weight of the materials of a phospholine oxide or other suitable catalyst.
  • the reaction mixture is prepared so that any water is removed before addition of isocyanates and is heated until reac tion is essentially complete.
  • the reaction mixture can be emulsified in water and further diluted with water before application.
  • the fabric treating solution can be prepared by blending emulsions of carbodiimide and fluoroaliphatic radical-containing polymers, together with any desired compatible adjuvents.
  • the polycarbodiimide and fluoroaliphatic radical containing polymer can be prepared in solution and the solution blended, diluted if necessary and applied, for example, to fabrics that would be undesirably affected by water.
  • the proportions depend on the amount needed to givea treating solution which will provide the correct concentration of solids, carbodiimides plus fluoroaIiphatic-radical containing polymer, to attain the desired weight of treatment at the level of wet pickup chosen. This level is herein set at 50 percent where not otherwise denominated to give comparability of results.
  • a 0.3 percent concentration provides 0. l 5 percent solids pickup which at 50 percent fluorine content gives 0.075 percent fluorine on the fabric.
  • the latter fluorine content is used in these examples, unless otherwise indicated, to permit ready comparisons.
  • EXAMPLE 1 A solution of l0l.6 parts (0.17 mol) of C,F SO,N(CH CH OH in 265 parts of methyl isobutyl ketone (MIBK) is first dried by distilling 30 parts of the solvent. Then 54 parts (0.31 mol) of 2,4-toluene diisocyanate are added and the solution refluxed for 2 hours to form a prepolymer diisocyanate. The solution is then cooled to 6575 C., and 1 part of 3-methyl-lphenyl-B-phospholine-l-oxide is added followed by 3 hours further refluxing. A film cast from this solution is weak and brittle and contains the characteristic carbodiimide infrared absorption peak at 4.69 microns.
  • MIBK methyl isobutyl ketone
  • the solution contains the carbodiimide designated Polymer A which is predominantly represented by the and the B" group is -A-NCO.
  • Polymer A which is predominantly represented by the and the B" group is -A-NCO.
  • the mixture is then emulsified using a high shear mixer.
  • the emulsion is employed in fabric treatments.
  • the A" group is C H C- H;
  • the 8" group is C F -,SO,N(C H )C H O,CNHC H;,(CH To I00 parts of this polycarbodiimide in 138 parts of methyl isobutyl ketone is added 2.5 parts of polyoxyethylene sorbitan monooleate emulsifier (available under the Trademark Tween 80), 2.5 parts of C F SO N(CH )C H..N(CH CI and 265 parts of distilled water. The mixture is then emulsified.
  • Example 4 The procedure of Example 2 is repeated using C F SO N(CH )C H OH and a lower amount (27.5 parts; 0.16 mol) of tolylene diisocyanate.
  • the resultant carbodiimide designated Polymer D is represented by the structure:
  • Polymer V designates a 50/50 blend of two polymers.
  • Polymer U designates a commercially available mate- 65 One is made by emulsion polymerizing for 16 hours at rial believed to be a 50/50 blend of poly( Z-ethylhexyl methacrylate) and poly( l l ,2,Z-tetrahydroperfluoroalkyl methacrylate) in which the alkyl group has an aver- 50 C. a mixture of 50 parts methyl methacrylate and 60 parts of tridecyl acrylate in I26 parts of water and 54 parts of acetone in the presence of 2 parts of Polymer W is like the latter polymer used in Polymer V, but prepared from equal amounts of C F SO N(C,.
  • Polymer X is prepared as in the above procedures,
  • the fabrics are treated to contain h in a reac1i0nmim f90 -r C F SO N(CH 0.075 percent carbon bonded fluorine.
  • the ratings are given for conciseness as a fraction. e.g.. 5/100. in which the nary ammonium chloride emulsifier at 65 C. for 16 nllmel'illor 1 15 Oil rating and denominator i hours spray rating.
  • the kettle is cooled to about 90 C., 52 parts of 2,4-toluene diisocyanate added and the solution heated to 1 l" C. for a further 3 hours.
  • the solution is next cooled to 50 C. and 5 parts of a by weight solution of 2,2,14,4- pentamethyl-l-phenylphosphetane oxide in methylene chloride added, and the solution is then again slowly heated to 1 15 C., care being taken to avoid excessive foaming.
  • the solution is maintained at 1 15 C., with agitation for about 3 hours, or until the isocyanate groups are essentially completely reacted as indicated by the EXAMPLE 24
  • the product is a percent by weight solution of:
  • a fabric-treating concentrate is prepared by dissolving parts of a fluoroaliphatic radical-containing methacrylate copolymer (35 percent fluorine in the form of fluoroaliphatic radicals) in l l parts of MIBK and 260 parts of C F Cl and adding 25 parts of the above polycarbodiimide product solution.
  • a solvent system is preferred for treatment of fabrics whose structure would be damaged by exposure to water, such as textured or velvet upholstry fabrics.
  • a solvent system is preferred for treatment of a medium-weight 100 percent nylon velvet, for example, the above concentrate, is diluted to about 0.4 percent solids with trichloroethylene.
  • lmproved water resistance can be obtained by the addition of a fluorine-free water repellant, such as 0.1 percent by weight of the solution of a stearato-chrome complex.
  • the fabric is sprayed in a ventilated spray booth with the dilute solution to about 50% wet pick up, then dried in a circulating air oven at ll0 C. for about 3 minutes, until the solvent has evaporated and the fabric has reached oven temperature.
  • the resulting treated fabric has an oil rating of 6 and a spray rating of 75. The stain resistance remains even after extensive abrasion.
  • EXAMPLE 25 A branched polycarbodiimide is prepared by adding to 57.5 parts of dry MIBK (Methyl lsobutyl Ketone) The solution is refluxed for 3 hours, then cooled to 90 C. and 1.7 parts of a 22 percent by weight solution of pentamethyll -phenylphosphetane oxide added. The resulting solution is heated to reflux and maintained there for two hours. A further 0.86 parts of catalyst solution is added because the presence of unreacted NCO is shown by infrared absorption and refluxing is continued for an additional hour. The resulting clear solution is free from NCO, but exhibits the characteristic absorption peak of carbodiimide at 4.69 microns. Emulsions and solutions containing this polycarbodiimide product and a fluoroaliphatic group containing acrylate copolymer confer durable oil and water resistance on treated fabrics.
  • MIBK Metal l lsobutyl Ketone
  • fluoroaliphatic radical-containing substantially linear vinyl polymer containing from ID to 60 percent by weight thereof of fluorine in the form of fluoroaliphatic radicals terminating in CF groups, said fluoroaliphatic radicals containing at least three fully fluorinated carbon atoms, and
  • B a solvent-soluble carbodiimide consisting essentially of from I to a plurality of carbodiimide groups, terminal organic radicals free from isocyanate-reactive hydrogen atoms connected to carbodiimide and, when two or more carbodiimide groups are present, polyvalent organic groups, residues of polyisocyanates, linking successive carbodiimide groups, and thereafter vaporizing said medium whereby a coating of said blend is deposited on said synthetic fibers.
  • fluoroaliphatic radical-containing substantially linear vinyl polymer containing from l0 to 60 percent by weight thereof of fluorine in the form of fluoroaliphatic radicals terminating in CF, groups, said fluoroaliphatic radicals containing at least three fully fluorinated carbon atoms, and
  • B. a carbodiimide consisting essentially of from I to a plurality of carbodiimide groups, terminal hydrocarbon or fluoroaliphatic radicals free from isocyanate-reactive hydrogen atoms and connected to carbodiimide and, when two or more carbodiimide groups are present, polyvalent organic groups, residues of polyisocyanates, linking successive carbodiimide groups, and
  • fluoroaliphatic radicals contain from 3 to 18 fully fluorinated carbon atoms.
  • a durably launderable and dry-cleanable, oil and water repellent fabric consisting substantially completely of hydrophobic synthetic fibers having a coating thereon of a blend, in proportions of from about l0:90 to 95:5, of
  • fluoroaliphatic radical-containing substantially linear vinyl polymer containing from 10 to 60 percent by weight thereof of fluorine in the form of fluoroaliphatic groups terminating in CF, groups, said fluoroaliphatic groups containing at least three fully fluorinated carbon atoms,
  • B. a carbodiimide consisting essentially of from l to a plurality of carbodiimide groups, terminal organic radicals free from isocyanatereactive hydrogen atoms connected to carbodiimide and, when two or more carbodiimide groups are present, polyvalent organic groups, residues of polyisocyanates, linking successive carbodiimide groups;
  • said coating being in amount to provide from 0.02 to 0.5 percent by weight of carbon-bonded fluorine on the fabric.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US05380702 1972-03-06 1973-07-19 Outerwear fabric treatment Expired - Lifetime US3896251A (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
JP3050973A JPS512560B2 (enrdf_load_stackoverflow) 1972-03-06 1973-03-05
CH320273D CH320273A4 (enrdf_load_stackoverflow) 1972-03-06 1973-03-05
DE19732310801 DE2310801C3 (de) 1972-03-06 1973-03-05 Verfahren zur Erzeugung einer öl- und wasserabweisenden Ausrüstung auf Textilgut aus synthetischen Fasern
FR7307777A FR2175027B1 (enrdf_load_stackoverflow) 1972-03-06 1973-03-05
GB1062273A GB1413051A (en) 1972-03-06 1973-03-05 Fabric treatment
CH320273A CH587381B5 (enrdf_load_stackoverflow) 1972-03-06 1973-03-05
GB5146874A GB1413052A (en) 1972-03-06 1973-03-05 Fluoroaliphatic radical-containing carbodiimides
AU52962/73A AU452397B2 (en) 1972-03-06 1973-03-06 Carbodimide having fluoroliphatic radicals and its use in textile treatment
US05380702 US3896251A (en) 1972-03-06 1973-07-19 Outerwear fabric treatment
US05/554,420 US4024178A (en) 1972-03-06 1975-03-03 Fluoroaliphatic radical containing carbodiimides
FR7513873A FR2259854B1 (enrdf_load_stackoverflow) 1972-03-06 1975-05-02

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US23218672A 1972-03-06 1972-03-06
US05380702 US3896251A (en) 1972-03-06 1973-07-19 Outerwear fabric treatment

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US23218672A Continuation-In-Part 1972-03-06 1972-03-06

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US05/554,420 Division US4024178A (en) 1972-03-06 1975-03-03 Fluoroaliphatic radical containing carbodiimides

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US3896251A true US3896251A (en) 1975-07-22

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US (1) US3896251A (enrdf_load_stackoverflow)
JP (1) JPS512560B2 (enrdf_load_stackoverflow)
AU (1) AU452397B2 (enrdf_load_stackoverflow)
CH (2) CH320273A4 (enrdf_load_stackoverflow)
FR (2) FR2175027B1 (enrdf_load_stackoverflow)
GB (2) GB1413052A (enrdf_load_stackoverflow)

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US4414355A (en) * 1981-07-14 1983-11-08 Minnesota Mining And Manufacturing Company Wire coating composition
US4415694A (en) * 1981-07-14 1983-11-15 Minnesota Mining And Manufacturing Company Contact enhancing composition
US4455348A (en) * 1981-07-14 1984-06-19 Minnesota Mining And Manufacturing Company Wire coating composition
US4487876A (en) * 1981-07-14 1984-12-11 Minnesota Mining & Mfg Wire coating composition
US4540497A (en) * 1982-11-09 1985-09-10 Minnesota Mining And Manufacturing Company Fluoroaliphatic radical-containing, substituted guanidines and fibrous substrates treated therewith
EP0157611A1 (en) * 1984-04-02 1985-10-09 Minnesota Mining And Manufacturing Company Fluorochemical biuret compositions and fibrous substrates treated therewith
US4560487A (en) * 1982-12-20 1985-12-24 Minnesota Mining And Manufacturing Company Blends of fluorochemicals and fibrous substrates treated therewith
US4565641A (en) * 1982-11-09 1986-01-21 Minnesota Mining And Manufacturing Company Blend of fluorochemical guanidines and poly(oxyalkylenes)
US4566981A (en) * 1984-03-30 1986-01-28 Minnesota Mining And Manufacturing Company Fluorochemicals and fibrous substrates treated therewith: compositions of cationic and non-ionic fluorochemicals
US4606737A (en) * 1984-06-26 1986-08-19 Minnesota Mining And Manufacturing Company Fluorochemical allophanate compositions and fibrous substrates treated therewith
US4668726A (en) * 1984-03-30 1987-05-26 Minnesota Mining And Manufacturing Company Cationic and non-ionic fluorochemicals and fibrous substrates treated therewith
DE3607773A1 (de) * 1986-03-08 1987-09-10 Cassella Ag Fluoralkylliganden enthaltende polyurethane, verfahren zu ihrer herstellung und ihre zubereitungen und ihre verwendung
US4778915A (en) * 1985-10-16 1988-10-18 Atochem Fluoroacrylic monomers and polymers
US4920190A (en) * 1985-12-03 1990-04-24 Atochem Fluorinated carbamate polymers as hydrophobic and oleophobic agents
US5144056A (en) * 1985-12-03 1992-09-01 Atochem Fluorinated acrylic monomers as hydrophobic and oleophobic agents
US5258458A (en) * 1991-02-28 1993-11-02 Minnesota Mining And Manufacturing Company Composition for providing oil and water repellency
US5672651A (en) * 1995-10-20 1997-09-30 Minnesota Mining And Manufacturing Company Durable repellent fluorochemical compositions
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US5728432A (en) * 1994-08-11 1998-03-17 Nisshinbo Industries, Inc. Treating reinforcing fibers with carbodiimide aqueous dispersion
US5817249A (en) * 1994-11-24 1998-10-06 Minnesota Minning And Manufacturing Company Carbodiimide compound and water repellent compositions
US5846604A (en) * 1988-03-14 1998-12-08 Nextec Applications, Inc. Controlling the porosity and permeation of a web
US5856245A (en) * 1988-03-14 1999-01-05 Nextec Applications, Inc. Articles of barrier webs
US5874164A (en) * 1988-03-14 1999-02-23 Nextec Applications, Inc. Barrier webs having bioactive surfaces
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FR2175027A1 (enrdf_load_stackoverflow) 1973-10-19
GB1413051A (en) 1975-11-05
FR2259854B1 (enrdf_load_stackoverflow) 1979-06-08
DE2310801A1 (de) 1973-09-20
FR2259854A1 (enrdf_load_stackoverflow) 1975-08-29
CH320273A4 (enrdf_load_stackoverflow) 1976-09-15
FR2175027B1 (enrdf_load_stackoverflow) 1981-01-09
DE2310801B2 (de) 1975-04-03
AU5296273A (en) 1974-09-05
AU452397B2 (en) 1974-08-16
CH587381B5 (enrdf_load_stackoverflow) 1977-04-29
JPS48103900A (enrdf_load_stackoverflow) 1973-12-26
JPS512560B2 (enrdf_load_stackoverflow) 1976-01-27
GB1413052A (en) 1975-11-05

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