US3061473A - Process of and composition for producing improved textile materials having oil and water repellent and antistatic properties - Google Patents
Process of and composition for producing improved textile materials having oil and water repellent and antistatic properties Download PDFInfo
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- US3061473A US3061473A US38124A US3812460A US3061473A US 3061473 A US3061473 A US 3061473A US 38124 A US38124 A US 38124A US 3812460 A US3812460 A US 3812460A US 3061473 A US3061473 A US 3061473A
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- United States
- Prior art keywords
- oil
- water repellent
- repellent
- textile materials
- antistatic
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 50
- 230000002940 repellent Effects 0.000 title claims description 49
- 239000005871 repellent Substances 0.000 title claims description 49
- 238000000034 method Methods 0.000 title claims description 29
- 239000004753 textile Substances 0.000 title claims description 23
- 239000000463 material Substances 0.000 title claims description 21
- 239000000203 mixture Substances 0.000 title description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 238000001723 curing Methods 0.000 claims description 22
- 230000002209 hydrophobic effect Effects 0.000 claims description 14
- 239000002216 antistatic agent Substances 0.000 claims description 12
- -1 HYDROXYL COMPOUNDS Chemical class 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 239000012736 aqueous medium Substances 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 4
- 229920003169 water-soluble polymer Polymers 0.000 claims description 4
- 238000013007 heat curing Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 239000004744 fabric Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 12
- 239000000835 fiber Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 238000005108 dry cleaning Methods 0.000 description 9
- 238000004900 laundering Methods 0.000 description 7
- 125000002091 cationic group Chemical group 0.000 description 6
- 229920000867 polyelectrolyte Polymers 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 229920002994 synthetic fiber Polymers 0.000 description 5
- 239000012209 synthetic fiber Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical class OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229940054283 quartermaster Drugs 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920006304 triacetate fiber Polymers 0.000 description 1
- 229920006312 vinyl chloride fiber Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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
- 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
- D06M13/10—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 oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
- D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/213—Perfluoroalkyl carboxylic acids; Anhydrides, halides or salts thereof
-
- 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
- D06M13/10—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 oxygen
- D06M13/11—Compounds containing epoxy groups or precursors thereof
-
- 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
- D06M13/10—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 oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
- D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
-
- 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
- D06M13/372—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 containing etherified or esterified hydroxy groups ; Polyethers of low molecular weight
-
- 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
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- 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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/91—Antistatic compositions
-
- 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
-
- 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
- Y10T442/2418—Coating or impregnation increases electrical conductivity or anti-static quality
- Y10T442/2459—Nitrogen containing
Definitions
- the present invention relates to a novel process for imparting durable water repellent and antistatic properties in a single operation to textile materials manufactured from hydrophobic fibers. More specifically the present invention relates to a novel process for imparting water repellent, oil repellent, and antistatic properties to textile materials and fabrics manufactured wholly or in part from hydrophobic synthetic fibers.
- hydrophobic fibers are defined as synthetic fibers such as polyamide fibers, poly.- vinyl chloride fibers, triacetate fibers, acrylic fibers, polyester fibers and the like, which have a comparatively low capacity to retain moisture in comparison with such fibers as cotton, wool and rayon.
- Textile materials PIG p'aredfrom these hydrophobic fibers accumulate electrostatic charges when exposed to rubbing during processing or in use, and the use of suitable antistatic finishes is necessary in order to reduce or overcome the objectionable tendency to static accumulation.
- water repellent properties are essential when synthetic fibers are employed in the manufacture of fabrics which are to be exposed to rain and snow.
- novel process of the present invention comprise impregnating hydrophobic synthetic fibers with an aquer ous solution, dispersion or emulsion containing:
- the fluorochemical compounds which are used to im-. part water and oil repelleutproperties, can have chemical structures that vary widely. For example, acrylates and methacrylate of hydroxyl compounds containing'a highly fiuorinated residue and their polymers and copolymers can be used. Fluorochemical compounds of this typeare defined with greater particularity in U.S. Patents 2,642,416; 2,826,564; 2,839,513; 2,803,615.
- fluoro chemical compounds which can be employed as oil-and water repellent agents include the chromium cordination complexes of saturated perfluoromonocarboxylic acids of which the chromium complexes of perfluorobutyric-acid and perfluorooctanoic acid are presentative.
- -Fluorochemical compounds suitable for the process of our invention are available commercially, for example, those marketed under the trade name of Scotchgard by the Minnesota Mining and Manufacturing Company.
- the cationic polyelectrolytes which serve as antistatic agents, can be crosslinked and rendered insoluble (thermoset) by heating in the presence of a suitable curing agent. Their chemical structure can also vary widely. These compounds can be further described as Water soluble polymers containing reactive amino groups. Some examples of these polyelectrolytes are described in recent publications and patents. Cationic polyelectr'olytes suitable for the process of our invention are available commercially, for example those marketed under the trade name Aston by the Onyx Chemical Co. of Jersey City, NJ.
- the curing agents contemplated are polyfunctional alkylating agents, capable of reacting with the polyamine antistatic agent, rendering it insoluble and thus resistant to washing and drycleaning.
- the polyfunctional halides (ref. 3(a) supra) and polyfunctional epoxides are examples of curing agents which can be usefully employed 2,882,185, (0) US. Patent 2,914,427, a British Patent 797,175. v I
- Polyepoxides are available commercially under various trade names, for example Eponite 100 (a product of the Shell Chemical Corp.), Kopoxite 159 (a product of Koppers Company, Inc.) and many others. Polyepoxides are generally prepared by the reaction of aliphatic or aromatic polyhydroxyl compounds with epichlorohydrin, followed by dehydrohalogenation of the resulting poly-chlorohydrin. Among polyfunctional halides, the polyethylene glycol diiodides are preferred because of their high reactivity and solubility properties. A representative of this group is, for example, the compound known as Aston Catalyst which is a product of the Onyx Chemical Co.
- each material used in the impregnating solution may be varied within wide limits, depending on the type of fabric employed and on the end use requirements for water repellency, oil rcpellency, static propensity and durability. The following ranges are preferred, and give excellent results on many types of fabrics:
- Example 1 A woven 100% nylon fabric which has been dyed but not finished is impregnated with an aqueous solution containing 20 parts of a polymeric, cationic antistatic agent known as Aston 123 (product of the Onyx Oil and Chemical Co.), 1.7 parts of a curing agent consisting of Eponite l00 (product of the Shell Chemical Co.) and 8.6 parts of a fluorocarbon polymer known as Scotchgard FX204 (product of the Minnesota Mining and Manufacturing Co.) per 100 parts of solution. Care must be taken to adjust the pH of the Aston 123 to 6.0 7.0 before mixing.
- Aston 123 polymeric, cationic antistatic agent
- Eponite l00 product of the Shell Chemical Co.
- Scotchgard FX204 product of the Minnesota Mining and Manufacturing Co.
- Example 2 The fabric is then passed through the squeeze rolls of Example 2
- the procedure of Example 1 is repeated on the same fabric, using 20 parts Aston 108 (at pH 10.0) as the antistatic agent, 1.9 parts of Aston Catalyst as the curing agent, and 8.0 parts of Scotchgard FX-204 per 100 parts of solution as the water repellent agent. Excellent water repellent, oil repellent, and antistatic propperties are obtained.
- Example 3 The procedure of Example 1 is repeated on the same fabric, using 20 parts Aston 108 (at pH 10.0), 1.9 parts of Aston Catalyst and 9.0 parts of Scotchgard FC-154 as the water repellent agent per 100 parts of solution. The same excellent properties noted in Example 1 above are obtained.
- Example 4 A woven dyed 100% polyester fabric (Dacron, a trademark of the E. I. du Pont Corp), is treated according to the procedure of Example 1 with a solution containing 10 parts Aston 108 4 (pH 10.0), 1.0 part of Aston Catalyst 4 and 8.6 parts Scotchgard FX-208 5 as the water repellent agent per 100 parts of solution. Again excellent water repellent, oil repellent, and antistatic properties are obtained.
- Example 5 In this formula R is a lower alkyl (C to C n has a value of 2 to 3, and y has a value of 3 to 30.
- Eponite 100 is a bis-glycidyl ether of a polyethylene glycol and can be represented by the formula
- the Scotchgards are aqueous emulsions of polymers of perfluoroalkyl acrylates. Typical perfluoroalkyl acrylate monomers would be for example CH CHCO0CH (CF CF 1 in which n has a value of 2 to 8.
- an antistatic agent comprising a water soluble polymer containing amino groups and a curing agent selected from the group consisting of (1) polyfunctional halides and (2) polyfunctional epoxides, wherein said repellent, antistatic agent, and curing agent are all in an aqueous medium; removing the excess of solution, and thereafter heat curing the solution in the textile materials.
- a process for simultaneously imparting water repellent, oil repellent and antistatic properties to hydrophobic textile materials comprising impregnating said materials with an oil and water repellent selected from the group consisting of (1) acrylates and methacrylates of hydroxyl compounds containing a highly fluorinated residue and their polymers and copolymers and (2) chromium coordination complexes of saturated perfluoromono- 9.
- Water repellent, oil repellent and antistatic textile materials made by the process of claim 1.
- a composition for imparting water repellent, oil repellent, and antistatic properties to textile materials consisting of an oil and Water repellent selected from the group consisting of 1) acrylates and methacrylates of hydroxyl compounds containing a highly fluorinated residue and their polymers and (2) chromium coordination complexes of saturated perfiuoromonocarboxylic acids, an antistatic agent comprising a water soluble polymer containing amino groups and a curing agent selected from the group consisting of (1) polyfunctional halides and (2) polyfunctional polyepoxides, wherein said repellent, antistatic agent, and curing agent are all in an aqueous medium.
Description
United States Patent'O Delaware Filed June 23, 1960, Ser. No. 38,124
No Drawing.
11 Claims. (Cl. 117-1395) The present invention relates to a novel process for imparting durable water repellent and antistatic properties in a single operation to textile materials manufactured from hydrophobic fibers. More specifically the present invention relates to a novel process for imparting water repellent, oil repellent, and antistatic properties to textile materials and fabrics manufactured wholly or in part from hydrophobic synthetic fibers.
Many products and processes are known which may be used to render textiles or fabrics water repellent, and some are known to impart properties which are resistant to laundering and dry cleaning. There are also many known products and processes which are claimed to impart antistatic properties to hydrophobic textile materials. Some of the known antistatic finishes also withstand repeated launderings and drycleaning. However, the combination of durable water repellent and durable antistatic properties for hydrophobic fibers has not been possible heretofore. In fact, even very recently, experiments conducted by simultaneously applying the-water repellent and certain antistatic finishes, which are compatible in the treating bath, have shown that :both the water repellency and the static propensity sufier in degree of effectiveness. Thus, even in those instances in which there appears to be compatability of antistatic finishes with other functional finishes, in the bath, each combination' represents a special study, and there appears to be no fixed rules to guide the experimenter.
In the foregoing connection hydrophobic fibers are defined as synthetic fibers such as polyamide fibers, poly.- vinyl chloride fibers, triacetate fibers, acrylic fibers, polyester fibers and the like, which have a comparatively low capacity to retain moisture in comparison with such fibers as cotton, wool and rayon. Textile materials PIG: p'aredfrom these hydrophobic fibers accumulate electrostatic charges when exposed to rubbing during processing or in use, and the use of suitable antistatic finishes is necessary in order to reduce or overcome the objectionable tendency to static accumulation. On the other hand, water repellent properties are essential when synthetic fibers are employed in the manufacture of fabrics which are to be exposed to rain and snow.
The imparting of water repellent and antistatic properties to a given fabric, however desirable, would appear to be unattainable since the eifectiveness of an antistatic finish depends in large measure on its aflinity for water while the effectiveness of a water repellent finish depends on its lack of alfinity for water. It is known, for example, that a water repellent finish can lose its eifectiveness completely when contaminated by ionic im purities, such as residual detergent particles from wash or drycleaning solutions. For this reason the combination of a water repellent finish with a hydroscopic, ionic, antistatic finishing agent would be expected to lead to the complete loss of the water repellent properties, or of the antistatic properties, or possibly both. The Army Quartermaster Report cited above lends support to this theory. Accordingly, it would be highly beneficial to Measui-ing and Predicting the Generation of Static Electrlcity in Military Clothing, Textile Series, Report No. 110, Hqtrs, Quartermaster Research and Engineering Center, U .S. Army, Natiek, Mass. (September 1959).
the textile industry to provide a process for imparting both water repellent and antistatic properties to hydrophobic fibers in a single treatment.
It is, therefore, an object of the present invention to provide a novel process whereby hydrophobic textile, materials are simultaneously provided with water repellent, oil repellent and antistatic properties.
It is a further object of this invention to provide a novel process whereby these desirable properties are imparted to the textile materials by a single treatment.
It is a further object of this invention to provide a novel composition which imparts water and oil repellent plus antistatic properties to hydrophobic textile materials.
It is a further object of this invention to provide a novel process whereby the aforementioned water repellent, oil repellent and antistatic properties imparted to the 1 textile materials are durable to repeated laundering and drycleaning cycles.
It is a further object of this invention to provide textile materials which exhibit satisfactory durable water repellency, oil repellency and antistatic properties without impairment of their appearance, hand, strengthor physical properties generally.
Other objects and advantages of the invention will be apparent from the description which follows.
The novel process of the present invention comprise impregnating hydrophobic synthetic fibers with an aquer ous solution, dispersion or emulsion containing:
(a) An oil and water repelling fluorochemical compound;
(b) A cationic polyelectrolyte; and
(c) A curing agent designed to crosslink and insolubilize the cationic polymer, thus rendering it durable to washing. v-.
The fluorochemical compounds, which are used to im-. part water and oil repelleutproperties, can have chemical structures that vary widely. For example, acrylates and methacrylate of hydroxyl compounds containing'a highly fiuorinated residue and their polymers and copolymers can be used. Fluorochemical compounds of this typeare defined with greater particularity in U.S. Patents 2,642,416; 2,826,564; 2,839,513; 2,803,615. Other fluoro chemical compounds which can be employed as oil-and water repellent agents include the chromium cordination complexes of saturated perfluoromonocarboxylic acids of which the chromium complexes of perfluorobutyric-acid and perfluorooctanoic acid are presentative. -Fluorochemical compounds suitable for the process of our invention are available commercially, for example, those marketed under the trade name of Scotchgard by the Minnesota Mining and Manufacturing Company.
The cationic polyelectrolytes, which serve as antistatic agents, can be crosslinked and rendered insoluble (thermoset) by heating in the presence of a suitable curing agent. Their chemical structure can also vary widely. These compounds can be further described as Water soluble polymers containing reactive amino groups. Some examples of these polyelectrolytes are described in recent publications and patents. Cationic polyelectr'olytes suitable for the process of our invention are available commercially, for example those marketed under the trade name Aston by the Onyx Chemical Co. of Jersey City, NJ.
The curing agents contemplated are polyfunctional alkylating agents, capable of reacting with the polyamine antistatic agent, rendering it insoluble and thus resistant to washing and drycleaning. The polyfunctional halides (ref. 3(a) supra) and polyfunctional epoxides are examples of curing agents which can be usefully employed 2,882,185, (0) US. Patent 2,914,427, a British Patent 797,175. v I
in the process of our invention. Polyepoxides are available commercially under various trade names, for example Eponite 100 (a product of the Shell Chemical Corp.), Kopoxite 159 (a product of Koppers Company, Inc.) and many others. Polyepoxides are generally prepared by the reaction of aliphatic or aromatic polyhydroxyl compounds with epichlorohydrin, followed by dehydrohalogenation of the resulting poly-chlorohydrin. Among polyfunctional halides, the polyethylene glycol diiodides are preferred because of their high reactivity and solubility properties. A representative of this group is, for example, the compound known as Aston Catalyst which is a product of the Onyx Chemical Co. of Jersey City, New Jersey, and which is a polyoxy alkylene glycol dihalide corresponding to the formula X(C,,H O) C H ,,X in which X is halogen, n has a value of 2 to 3, and y has a value of 3 to 30.
The amounts of each material used in the impregnating solution may be varied within wide limits, depending on the type of fabric employed and on the end use requirements for water repellency, oil rcpellency, static propensity and durability. The following ranges are preferred, and give excellent results on many types of fabrics:
(a) 1% to 5% of an aqueous dispersion of a fluorochemical compound (about 30% active ingredient);
(b) 2% to of a cationic polyelectrolyte product (containing about active ingredient); and
(c) 0.2 to 1.0% of a curing agent.
All percentages are given on the weight of fabric treated. The actual percentage deposited on the fabric in the course of treatment can be calculated from the percent concentration of each material in the treating solution and the percent wet pick-up of the fabric. After impregnation with the solution or emulsion, the textile is passed through the squeeze rolls of a padder or other similar device, dried and heated in a curing oven to bring about polymerization of the resins. The time and temperature of curing may be varied widely. Curing temperatures of 280 F. to 350 F. for 1 minute to 5 minutes give excellent results. After curing, the treated textile can be rinsed or subjected to a mild detergent wash in order to remove soluble residues.
The present invention will be more completely illustrated by the following examples, which are illustrative of the excellent results that can be obtained when fabrics manufactured from hydrophobic fibers are treated according to the process of the invention and which examples are not to be construed as being limitative. All parts are by weight unless otherwise specified.
Example 1 A woven 100% nylon fabric which has been dyed but not finished is impregnated with an aqueous solution containing 20 parts of a polymeric, cationic antistatic agent known as Aston 123 (product of the Onyx Oil and Chemical Co.), 1.7 parts of a curing agent consisting of Eponite l00 (product of the Shell Chemical Co.) and 8.6 parts of a fluorocarbon polymer known as Scotchgard FX204 (product of the Minnesota Mining and Manufacturing Co.) per 100 parts of solution. Care must be taken to adjust the pH of the Aston 123 to 6.0 7.0 before mixing.
The fabric is then passed through the squeeze rolls of Example 2 The procedure of Example 1 is repeated on the same fabric, using 20 parts Aston 108 (at pH 10.0) as the antistatic agent, 1.9 parts of Aston Catalyst as the curing agent, and 8.0 parts of Scotchgard FX-204 per 100 parts of solution as the water repellent agent. Excellent water repellent, oil repellent, and antistatic propperties are obtained.
Example 3 The procedure of Example 1 is repeated on the same fabric, using 20 parts Aston 108 (at pH 10.0), 1.9 parts of Aston Catalyst and 9.0 parts of Scotchgard FC-154 as the water repellent agent per 100 parts of solution. The same excellent properties noted in Example 1 above are obtained.
Example 4 A woven dyed 100% polyester fabric (Dacron, a trademark of the E. I. du Pont Corp), is treated according to the procedure of Example 1 with a solution containing 10 parts Aston 108 4 (pH 10.0), 1.0 part of Aston Catalyst 4 and 8.6 parts Scotchgard FX-208 5 as the water repellent agent per 100 parts of solution. Again excellent water repellent, oil repellent, and antistatic properties are obtained.
Example 5 In this formula R is a lower alkyl (C to C n has a value of 2 to 3, and y has a value of 3 to 30.
For a further description of these polyamines, see U.S. Patent No. 3,021,232. Eponite 100 is a bis-glycidyl ether of a polyethylene glycol and can be represented by the formula For a further discussion of these compounds see U.S. Patent No. 2,982,751. The Scotchgards are aqueous emulsions of polymers of perfluoroalkyl acrylates. Typical perfluoroalkyl acrylate monomers would be for example CH CHCO0CH (CF CF 1 in which n has a value of 2 to 8.
a padder. The wet pick-up of the fabric is 33%, indicat- Several tests can be employed to establish the effectiveness of the present process for imparting water repellent, oil repellent, and antistatic properties to synthetic fibers. Some of the accepted test procedures are as follows.
For water repellency:
(a) AATCC spray test, Test Method 22-1952. Manual of the American Association of Textile Chemists and Colorists (AATCC), 1959 edition, p. 164.
Product of the Onyx Chemical Co. 5 Product of Minnesota Mining and Manufacturing Co. 6 Product of the Shell Chemical Co.
(b) Water penetration test, Federal Specification CCC-T-191, Modification POD-112, p. 3. For static properties (electrical resistivity):
AATCC Test Method 7 61959 (adopted as tentative 76-1954, revised 195 8, approved as standard 1959). Manual of the AATCC, 1959 edition, p. 138.
For oil repellency:
Minnesota Mining and Manufacturing Scotchgard technical bulletin, Appendix A. Durability to laundering:
Test before and after laundering in ahome style automatic washer, agitator type, water temperature 140 F., with detergent.
Durability to drycleaning:
Commercial drycleaning, either perchloroethylene or Stoddard solvent.
Accepted standards of performance for treated fabrics by the test methods listed above are- For water repellency:
(a) Spray test80 or higher.
(b) Water penetration-60 minutes or longer. For electrical resistivity:
x ohms or lower. For oil repellency:
Spray ratings of 80 or higher.
carboxylic acids, an antistatic agent comprising a water soluble polymer containing amino groups and a curing agent selected from the group consisting of (1) polyfunctional halides and (2) polyfunctional epoxides, wherein said repellent, antistatic agent, and curing agent are all in an aqueous medium; removing the excess of solution, and thereafter heat curing the solution in the textile materials.
2. The process of claim 1 in which the oil and water repellent, the antistatic agent, and the curing agent are in an aqueous medium selected from the group consisting of an aqueous solution, an aqueous dispersion, and an emulsion.
3. The process of claim 1 in which the heat curing takes place at temperatures from about 280 F. to 350 F. for a period of about 1 to 5 minutes.
4. The process of claim 3 in which the curing agent is a polyfunctional halide.
5. The process of claim 3 in which the curing agent is a dihalide of a polyethylene glycol.
6. The process of claim 3 in which the curing agent is a polyfunctional polyepoxide.
7. The process of claim 17in which the oil and water repellent consists of the acrylates and methacrylates of hydroxyl compounds containing a highly fluorinated residue and their polymers and copolymers.
8. The process of claim 1 in which the oil and water The test results obtained on the fabrics treated as derepellent conslsts of chromium coordination complexes scribed in Examples 1-5 are summarized below. of perfluoromonocarboxylic acids.
Water Oil Resisrepel- Water penetration, repeltivity Fabric Treatment leney time lency ohms at;
spray spray RH 1 rating rating Woven nylon None (control) 0 0 (immediate) 0 10 Do Example 1 Over 120 1111115.... 100 1X10 Example 1 after 5L 90 1 l0 Example 2 mins 100 3X10 Example 2 after 5L 30 mins 90 3X10 Example 3 Over 120 mins 100 4 10 None (contro 0 0 10 Example 4 80 4X10 Example 4 after 5 dry cleanings 80 4X10 None (control) 0 10 Example 5 100 6X10" Example 5 after 5L 100 2 10 1 RH relative humidity. 2 L=laundering.
The foregoing experimental data demonstrate that certain water and oil repellent finishes plus antistatic finishes can be simultaneously applied to hydrophobic fibers so as to impart excellent water repellent, oil repellent, and antistatic properties to said fibers and which properties are durable to subsequent laundering and dry cleaning treat- While the illustrative embodiments of the invention have been described hereinbefore with particularity, it will be understood that various other modifications will be apparent to and can readily be made by those skilled in the art without departing from the scope and spirit of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and description set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention including all features which would be treated as patentable equivalents thereof by those skilled in the art to which the invention pertains.
What I claim is:
1. A process for simultaneously imparting water repellent, oil repellent and antistatic properties to hydrophobic textile materials comprising impregnating said materials with an oil and water repellent selected from the group consisting of (1) acrylates and methacrylates of hydroxyl compounds containing a highly fluorinated residue and their polymers and copolymers and (2) chromium coordination complexes of saturated perfluoromono- 9. Water repellent, oil repellent and antistatic textile materials made by the process of claim 1.
10. The process of claim 1 in which 1% to 5% of the oil and water repellent; 2% to 10% of a cationic polyelectrolyte product as the antistatic agent; and 0.2 to 1.0% of the curing agent are employed in the aqueous medium, said percentages being in terms of the weight of the textile materials'treated.
11. A composition for imparting water repellent, oil repellent, and antistatic properties to textile materials consisting of an oil and Water repellent selected from the group consisting of 1) acrylates and methacrylates of hydroxyl compounds containing a highly fluorinated residue and their polymers and (2) chromium coordination complexes of saturated perfiuoromonocarboxylic acids, an antistatic agent comprising a water soluble polymer containing amino groups and a curing agent selected from the group consisting of (1) polyfunctional halides and (2) polyfunctional polyepoxides, wherein said repellent, antistatic agent, and curing agent are all in an aqueous medium.
References Cited in the file of this patent UNITED STATES PATENTS 2,803,615 Ahlbrecht et al. Aug. 20, 1957 2,820,719 Trusler et a1. Jan. 21, 1958 2,965,517 Albrecht et a1. Dec. 20, 1960
Claims (1)
1. A PROCESS FOR SIMULTANEOUSLY IMPARTING WATER REPELLENT, OIL REPELLENT AND ANTISTIC PROPERTIES TO HYDROPHOBIC TEXTILE MATERIALS COMPRISING IMPREGNATING SAID MATERIALS WITH AN OIL AND WATER REPELLENT SELECTED FROM THE GROUP CONSISTING OF (1) ACRYLATES AND METHACRYLATES OF HYDROXYL COMPOUNDS CONTAINING A HIGHLY FLUORINATED RESIDUE AND THEIR POLYMERS AND COPOLYMERS AND (2) CHROMIUM COORDINATION COMPLEXES OF SATURATED PERFLUOROMONOCARBOXYLIC ACIDS, AN ANTISTATIC AGENT COMPRISING A WATER SOLUBLE POLYMER CONTAINING AMINO GROUPS AND A CURING AGENT SELECTED FROM THE GROUP CONSISTING OF (1) POLYFUNSTIONAL HALIDES AND (2) POLYFUNCTIONAL EPOXIDES, WHEREIN SAID REPELLENT, ANTISTATIC AGENT, AND CURING AGENT ARE ALL IN AN AQUEOUS MEDIUM; REMOVING THE EXCESS OF SOLUTION, AND THEREAFTER HEAT CURING THE SOLUTION IN THE TEXTILE MATERIALS.
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Cited By (16)
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US3212931A (en) * | 1961-05-31 | 1965-10-19 | Nippon Telegraph & Telephone | Electrostatographic recording medium and a method of making the same |
US3236672A (en) * | 1962-02-12 | 1966-02-22 | Arkansas Company Inc | Durable water and oil repellency |
US3385812A (en) * | 1965-06-25 | 1968-05-28 | Du Pont | Finishing composition comprising a fluorochemical and a polyorganosiloxane |
US3502537A (en) * | 1966-01-04 | 1970-03-24 | Bondina Ltd | Air-permeable protective materials |
US3903330A (en) * | 1973-12-03 | 1975-09-02 | Gisen Co | Process of treating polyester fibers with resins |
US3968066A (en) * | 1974-04-18 | 1976-07-06 | Ciba-Geigy Corporation | Oil and water repellent textile composition containing a fluorochemical polyurethane resin and a quaternary ammonium salt |
US4115605A (en) * | 1975-08-04 | 1978-09-19 | Kimberly-Clark Corporation | Anti-static compositions comprising a copolymer or perfluoroalkyl acrylate and polyoxyalkylene acrylate, wetting agent, and a salt selected from the group consisting of potassium acetate and lithium chloride in aqueous medium |
JPS5538385B1 (en) * | 1971-05-18 | 1980-10-03 | ||
US4565717A (en) * | 1983-10-20 | 1986-01-21 | E. I. Dupont De Nemours And Company | Antisoiling treatment of synthetic filaments |
EP0737773A1 (en) * | 1993-12-28 | 1996-10-16 | Daikin Industries, Ltd. | Method of treating textile products and textile products thus treated |
US20040123853A1 (en) * | 2001-06-06 | 2004-07-01 | Ralf Forster | Ignition system for an internal combustion engine |
US20050112969A1 (en) * | 2003-11-25 | 2005-05-26 | Kimberly-Clark Worldwide, Inc. | Method of treating substrates with ionic fluoropolymers |
US20050112970A1 (en) * | 2003-11-25 | 2005-05-26 | Kimberly-Clark Worldwide, Inc. | Method of treating nonwoven fabrics with non-ionic fluoropolymers |
US20060110997A1 (en) * | 2004-11-24 | 2006-05-25 | Snowden Hue S | Treated nonwoven fabrics and method of treating nonwoven fabrics |
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US2820719A (en) * | 1952-08-27 | 1958-01-21 | Davies Young Soap Company | Process for rendering fabrics water repellent |
US2965517A (en) * | 1958-01-21 | 1960-12-20 | Ciba Ltd | Process for producing antistatic dressings on synthetic fibers |
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US2820719A (en) * | 1952-08-27 | 1958-01-21 | Davies Young Soap Company | Process for rendering fabrics water repellent |
US2803615A (en) * | 1956-01-23 | 1957-08-20 | Minnesota Mining & Mfg | Fluorocarbon acrylate and methacrylate esters and polymers |
US2965517A (en) * | 1958-01-21 | 1960-12-20 | Ciba Ltd | Process for producing antistatic dressings on synthetic fibers |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
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US3212931A (en) * | 1961-05-31 | 1965-10-19 | Nippon Telegraph & Telephone | Electrostatographic recording medium and a method of making the same |
US3236672A (en) * | 1962-02-12 | 1966-02-22 | Arkansas Company Inc | Durable water and oil repellency |
US3385812A (en) * | 1965-06-25 | 1968-05-28 | Du Pont | Finishing composition comprising a fluorochemical and a polyorganosiloxane |
US3502537A (en) * | 1966-01-04 | 1970-03-24 | Bondina Ltd | Air-permeable protective materials |
JPS5538385B1 (en) * | 1971-05-18 | 1980-10-03 | ||
US3903330A (en) * | 1973-12-03 | 1975-09-02 | Gisen Co | Process of treating polyester fibers with resins |
US3968066A (en) * | 1974-04-18 | 1976-07-06 | Ciba-Geigy Corporation | Oil and water repellent textile composition containing a fluorochemical polyurethane resin and a quaternary ammonium salt |
US4115605A (en) * | 1975-08-04 | 1978-09-19 | Kimberly-Clark Corporation | Anti-static compositions comprising a copolymer or perfluoroalkyl acrylate and polyoxyalkylene acrylate, wetting agent, and a salt selected from the group consisting of potassium acetate and lithium chloride in aqueous medium |
US4565717A (en) * | 1983-10-20 | 1986-01-21 | E. I. Dupont De Nemours And Company | Antisoiling treatment of synthetic filaments |
EP0737773A4 (en) * | 1993-12-28 | 1998-06-10 | Daikin Ind Ltd | Method of treating textile products and textile products thus treated |
EP0737773A1 (en) * | 1993-12-28 | 1996-10-16 | Daikin Industries, Ltd. | Method of treating textile products and textile products thus treated |
EP1039018A1 (en) * | 1993-12-28 | 2000-09-27 | Daikin Industries, Ltd. | Method of treating textile products and textiles products thus treated |
US20040123853A1 (en) * | 2001-06-06 | 2004-07-01 | Ralf Forster | Ignition system for an internal combustion engine |
US7931944B2 (en) | 2003-11-25 | 2011-04-26 | Kimberly-Clark Worldwide, Inc. | Method of treating substrates with ionic fluoropolymers |
US20050112970A1 (en) * | 2003-11-25 | 2005-05-26 | Kimberly-Clark Worldwide, Inc. | Method of treating nonwoven fabrics with non-ionic fluoropolymers |
US7811949B2 (en) | 2003-11-25 | 2010-10-12 | Kimberly-Clark Worldwide, Inc. | Method of treating nonwoven fabrics with non-ionic fluoropolymers |
US20050112969A1 (en) * | 2003-11-25 | 2005-05-26 | Kimberly-Clark Worldwide, Inc. | Method of treating substrates with ionic fluoropolymers |
US20060110997A1 (en) * | 2004-11-24 | 2006-05-25 | Snowden Hue S | Treated nonwoven fabrics and method of treating nonwoven fabrics |
WO2006057681A1 (en) * | 2004-11-24 | 2006-06-01 | Kimberly-Clark Worldwide, Inc. | Treated nonwoven fabrics and method of treating nonwoven fabrics |
AU2005310043B2 (en) * | 2004-11-24 | 2010-08-26 | Kimberly-Clark Worldwide, Inc. | Treated nonwoven fabrics and method of treating nonwoven fabrics |
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