MXPA99009885A - Treatment of fibrous substrates to impart repellency, stain resistance, and soil resistance - Google Patents

Abstract

A process is described which imparts exceptional antisoiling, anti-staining and repellent properties to carpets. The process makes use of a water-based exhaustion process wherein the water-based treating solution contains (1) glassy fluorochemical material, glassy hydrocarbon material, or combinations thereof;(2) a stainblocking material;(3) a polyvalent metal salt, acid, or combinations thereof;and (4) water. Subsequent to exhaustion, the wet treated carpet is heated, usually in a steaming step, rinsed, and dried in a dry heat oven.

Description

TREATMENT OF FIBROUS SUBSTRATES TO PROVIDE REPELENCE, RESISTANCE TO STAINS AND RESISTANCE TO DIRT FIELD OF THE INVENTION This invention relates generally to carpet treatments, and in particular to a method for imparting repellency, stain resistance and dirt resistance to carpeting by applying an aqueous treatment solution comprising a fluorochemical and / or a hydrocarbon to the carpet. , a blogging material for spots and a salt.

BACKGROUND OF THE INVENTION Several references disclose methods for emitting stain blocking materials, fluorochemical substances and / or waxes onto fibrous polyamide substrates to provide the substrate with good stain resistance to acid dyes and / or good water and oil repellency. U.S. Patent Number 4,875,901 (Payet et al.) Describes a method for providing fibrous substrates of polyamide with stain resistance by contacting the substrate with an aqueous solution comprising a partially sulfonated, water-soluble novolac resin, REF .: 31932 normally solid and a polyvalent metal salt soluble in water. U.S. Patent No. 4,940,757 (Moss et al.) And its continuation in part, U.S. Patent Number 5,310,828 (Williams et al.), Disclose polymeric compositions that impart stain resistance to polyamide fibers. The compositions are made by polymerizing an alpha-substituted acrylic acid or an ester, in the presence of a sulfonated aromatic formaldehyde condensation polymer. Optionally, this polymer can be combined with certain halogenated polymers such as perfluorinated urethanes and acrylates, and a small amount of a divalent metal salt such as a magnesium salt, can be applied together with the stain resistant composition. U.S. Patent Number 4,822,373 (Olson et al.) Describes treated fibrous polyamide substrates to which a partially sulfonated novolac resin and polymers containing methacrylic acid have been applied. U.S. Patent Number 5,001,004 (Fitgerald et al.) Discloses stain resistant polyamide textile substrates treated with compositions comprising hydrolyzed aromatic and ethylenically unsaturated polymers / maleic anhydride. Optionally, a repellent can be applied to oil, water and / or stains, polyfluoroorganic, before, during or after the application of the polymer. The hydrolyzed polymers can be applied to textile substrates in various ways, for example, during conventional dyeing and the continuous dyeing process, and are usually applied at an acidic pH. The published World Patent Application WO 92/10605 (Pechhold) describes fibrous substrates of polyamide to which they have been applied to them (by waterproofing, spraying, foaming, dye consumption or batch impregnation, or dye consumption or impregnation continuous) a hydrolyzed or monosterified alpha-olefin copolymer, water dispersible or water soluble / maleic anhydride. The coaplication of an oil, water and / or stain repellent material, organic polyfluoro, is also described. The application for World Patent number WO 93/19238 (Pechhold) describes a protective layer against stains which can be applied to polyamide textiles by waterproofing or spraying comprising mixtures of maleic anhydride / alpha-olefin polymer with condensation products of Sulfonated phenol-formaldehyde. Optionally, a repellent may be applied to the oil, water and / or the polyfluoroorganic stains before, during or after the application of the polymer.

U.S. Patent No. 4,925,707 (Vinod) describes the co-application of fluorochemicals against dirt with stain-blocking agents to nylon mats in which it is installed. U.S. Patent Number 5,252,232 (Vinod) describes an improved process for preparing freeze-thaw-stable aqueous compositions comprising an aqueous fluoroalkyl ester of citric acid and a hydrolyzed styrene / maleic anhydride copolymer which, when applied to a nylon carpet installed in such a manner It carefully moistens the hair fibers, imparts resistance to stains and dirt. U.S. Patent No. 5,073,442 (Knowlton et al.) Discloses a method for improving the soil and / or stain resistance characteristics of polyamide and wool fabrics by applying an aqueous solution containing various combinations of sulfonated phenolic compounds, sulfonated phenolic compounds and aldehydes, fluorochemical substances, modified wax emulsions, acrylic and organic acids of low molecular weight. U.S. Patent Number 5,520,962 (Jones) describes a method and composition for treating a carpet yarn to improve its repellency and stain resistance when treated by immersion in an aqueous medium acid that contains an anionic or nonionic fluorochemical substance, heating and removal of excess water. U.S. Patent Number 5,084,306 (McClellan et al.) Discloses a flexible narrowing process for coating binder with an aqueous emulsion containing fluorochemical substances and polyvalent ions and / or acidifying agents. U.S. Patent No. 4,680,212 (Blyth et al.) Discloses stain-resistant, unstained nylon fibers that have been coated on their surface with one or more stain blockers and one or more fluorochemical substances to impart resistance to the stain. the stains after commercial. The coating is preferably applied to the nylon fibers as an aqueous spin finish during the melt spinning process used to prepare the fibers. U.S. Patent Number 5,516,337 (Nguyen) describes a method for improving stain resistance to fibers, especially wool, by (a) treating the fibers with a mordant, (b) treating with a combination of a sulfonated or disulfonated surfactant together with a chemical protective for stains, and (c) provide a treatment with a fluorochemical substance in any of steps (a) or (b) in a sufficient amount to improve the properties of protective layer or resistance to stains. European published application EP-A-797699 discloses an aqueous treatment composition for providing stain release properties to fibrous materials, comprising (a) polymethacrylic acid [homopolymers] or copolymers containing methacrylic acid, (b) partially de novolac resin sulfonated, (c) a sulphated surfactant and (d) water, which may also contain divalent metal salts which may be co-applied with a fluorochemical composition. U.S. Patent No. 4,839,212 (Blyth et al.) Discloses nylon fibers coated with a sulfonated stain-blocking condensation product and an optional fluorochemical substance. U.S. Patent Number 4,959,248 (Oxenrider et al.) Discloses a process for imparting stain resistance properties to fibers formed from thermoplastic polymers by treating the fibers with a combination of a phenol condensation spot blocker and an agent Fluorochemical antisuciedad elaborated when reacting piromelitic anhydride with fluorinated and oxidized alcohol. European Patent Application 0 353 080 (Ingham et al.) Describes a process for improving the resistance to Tension of polyamide and keratinous fibers by treating the fibers in an aqueous bleach bath in a large liquor ratio first with a fluorochemical composition and subsequently with a spot blocker. The reference states that the applicants found that the simultaneous application results in interference between the fluorocarbon and the blocker. Various fatty derivatives have been described as useful repellents and dirt treatments for fibrous substrates. U.S. Patent Number 2,876,140 (Sheehan) describes softening agents for textile materials having improved resistance to dirt which are a combination of barium sulfate and cationic softening agents. These softening agents are of the amide and higher fatty acid type, such as the reaction products of polybasic organic acids with dialkylol substituted carbamido compounds having side chains containing polyamino acid radicals and their salts. U.S. Patent Number 4,076,631 (Caruso et al.) Describes textile treatment compositions to provide a soil-repellent, antistatic finish, consisting essentially of (1) an anti-static fatty amide agent, (2) an aqueous dispersion of hard particles, such as polystyrene , methacrylate polymethyl or colloidal hydrous metal oxide, (3) a fluorine-free inorganic or organic monobasic or polybasic acid, (4) an antimicrobial agent and (5) a fluorocarbon agent which provides a low free surface energy. In column 4, lines 37-50, the 'treatment of a carpet is described to provide an antistatic character and resistance to dirt on the floor (but not to oily dirt), although the method of treatment is not detailed. U.S. Patent No. 4,144,026 (Keller et al.) Discloses a process for simultaneously providing textile materials with an antistatic and grime-repellent finish by treating the textile materials with an aqueous solution containing (a) a copolymer of an acid. dicarboxylic, α, β unsaturated or an anhydride thereof, and at least one other ethylenically unsaturated compound, and (b) a fatty acid / alkanolamine reaction product or an alkylene oxide adduct of this reaction product, and subsequently drying it . U.S. Patent No. 4,153,561 (Hümüller et al.) Discloses storage stable aqueous emulsions for the treatment of textiles which contain N-alkyl-a-sulfosuccinic acid amide salts, fatty acid amide sulfates or fatty acid derivatives. glycerin ether, polyethylene glycols and nonionic dispersing agents. These emulsions can be applied to synthetic fiber carpets in waterproofed-continuous dyeing or printing processes, which provides good wetting, and before drying provides a soft and antisuciedad feeling to the fibers. U.S. Patent No. 4,329,390 (Danner) discloses aqueous dispersions of a microcrystalline wax, preferably together with one or more non-oxidized paraffins, having a cationic surfactant used as a dispersing agent. These aqueous dispersions, when applied to textile substrates such as a carpet by means of impregnation or dye consumption processes, provide a textile substrate with improved seam capacity and less damage in high speed sewing machines. U.S. Patent No. 4,883,188 (Kortmann et al.) Discloses stable water-resistant, oil-proof, and oil-resistant finishing agents for textiles, especially non-woven fabrics, containing (a) compounds containing a perfluoroalkyl group (preferably ( co) acrylate polymers), and (b) quaternary products of basic fatty acid amides. U.S. Patent Number 5,491,004 (Mudge et al) describes a method for applying a low dirt finish to spun synthetic textile fibers by applying a dry component, in a solid manner, comprising a fatty bisamide, a block copolymer of ethylene oxide and propylene oxide, the reaction product of a saturated fatty alcohol, a saturated fatty amine or an ethoxylated phenol and / or a fatty acid ester. None of the treatment compositions and methods described in the art imparts to a fibrous substrate a simultaneous combination of outstanding dynamic water and oil repellency, deep stain resistance and excellent performance against dirt, durable. These and other advantages are provided by the present invention, as described in the following.

BRIEF DESCRIPTION OF THE INVENTION In one aspect, the present invention relates to a treatment for carpets and other fibrous substrates which impart to the substrate an outstanding dynamic repellency to water and oil, deep stain resistance and excellent performance against dirt, durable. According to the invention, the substrate is treated with a (typically aqueous) mixture comprising (1) a repellent material that is selected from the group consisting of vitreous fluorochemicals having a backward contact angle of n-hexadecane plus 53 ° (preferably 65 ° or higher, and more preferably at least 70 ° or higher) and glassy hydrocarbons having an angle of recoil contact to n-hexadecane of 35 ° or higher; (2) a stain blocking material; and (3) a dye consumption aid that is selected from the group consisting of metal salts and acids. The aqueous mixture is typically applied by contacting the fibrous substrate with the treatment solution such that full contact is established on all the fibers of the substrate with the solution. The wet treated substrate is then exposed to steam or another water saturated atmosphere for a sufficient period of time and at a temperature high enough to fix the treatment materials on the fibrous substrate. The wet treated substrate is then moistened with water and dried in an oven at a high enough temperature to activate the materials. In another aspect, the present invention relates to fibrous substrates treated in accordance with the method described above which exhibit excellent performance against dirt, stains and repellency. The fibrous substrate, which has a total penetration of the fluorochemical, hydrocarbon and stain-blocking materials into and through each fiber, exhibits excellent dynamic water resistance (ie, resistance to penetration by water-based beverages spilled from a certain height). ), largely resists staining by aqueous acid staining agents such as the red drink KOOL-AIDHR, it prevents the penetration of oil in any proportion of the fiber, and in the case of carpets it offers significant protection against dry dirt when compared to an untreated carpet, as demonstrated by several cycles of "walking" tests. In another aspect, the present invention relates to a method for identifying hydrocarbon and fluorochemical materials which exhibit excellent properties against dirt when applied to a fibrous substrate. Surprisingly, it has been found that there is a strong correlation between the recoil contact angle and the antifouling properties for fluorochemical and hydrocarbon materials when used as carpet treatments. Consequently, backward contact angle measurements can be used to easily identify fluorochemical and hydrocarbon materials that have particularly good antifouling properties, without having to carry out prolonged walking fouling tests. For the purpose of the present invention, it is found that fluorochemical substances having a back-contact angle to n-hexadecane of at least about 53 °, preferably greater than about 65 °, and more preferably at least about 70 ° particularly good antifouling properties are shown. Similarly, hydrocarbon materials that have a Back-contact angle to n-hexadecane of at least about 35 ° is found to exhibit particularly good anti-fouling properties. When used as anti-fouling agents in carpets, it is preferred that the fluorochemical or hydrocarbon materials are hard, vitreous, non-adherent and non-cationic having a glass transition temperature from about 20 ° C to about 130 ° C. In an additional aspect, the present invention relates to an immersion process for treating carpets and other fibrous substrates to improve, for example, their antifouling properties, wherein the treatment solution comprises a material containing both fluorochemical and hydrocarbon portions. The substrates treated according to the method of the invention show excellent anti-fouling properties, but generally with a higher fluorine efficiency than the treatments using similar materials lacking the hydrocarbon groups. In still another aspect, the present invention relates to an immersion process for treating carpets and other fibrous substrates to improve, for example, their antifouling properties, wherein the treatment solution comprises a combination of fluorochemical and hydrocarbon materials. The substrates treated according to the method show excellent properties anti-fouling, but generally a higher fluorine efficiency than treatments using only fluorochemical materials. In still another aspect, the present invention pertains to a method for treating carpets and other fibrous substrates with a composition comprising a hydrocarbon material and, preferably, a blocker. The hydrocarbon material preferably has a back-to-n-hexadecane contact angle of at least about 35 °. Surprisingly, the substrates treated according to the method are found to have excellent anti-fouling properties, even when the treatment composition does not contain a fluorochemical substance.

DESCRIPTION OF THE DRAWINGS Figure 1 is a graph of dynamic repellency as a pH function for carpets treated according to the method of the present invention; Figures 2-5 are micrographs of treated fibers which illustrate the effects of the concentration of magnesium salt in the treatment process of the present invention; Y Figure 6 is a micrograph of a carpet fiber treated by a typical spray application process.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a treatment for carpets and other fibrous substrates which impart to the substrate an outstanding water and oil repellency, resistance to deep stains, and excellent durable anti-fouling performance. According to the invention, the substrate is treated with a composition (typically aqueous) comprising: (1) a repellent material that is selected from the group consisting of vitreous fluorochemical substances having a back-contact angle to n-hexadecane of 65 ° or greater and vitreous hydrocarbons having a receding contact angle to n-hexadecane of 35 ° or greater; (2) a stain blocking material; and (3) a dye consumption aid which is selected from the group consisting of metal salts (preferably polyvalent metal salts) and acids. The aqueous mixture is typically applied by contacting the fibrous substrate with the treatment solution such that there is complete contact with all the fibers of the substrate with the solution. The wet treated substrate is then exposed to steam or other atmosphere saturated in water for a sufficient period of time, and at a sufficiently high temperature, to fix the treatment materials on the fibrous substrate. The moist treated substrate is then rinsed with water and dried in an oven at a temperature high enough to activate the materials. Various dye consumption processes can be used to apply the treatment solution of the present invention to a fibrous substrate, the function of the dye consumption process is to make full contact of the entire fiber of the fiber substrate with the fiber. stain-blocking material and repellent fluorochemical material and / or hydrocarbon material. Examples of suitable dye consumption processes include dipping, flooding and foam application. Useful processes and equipment include the Kuster's Flexnip ™ machine, Kuster's foam applicator, Fluicon ™ flood applicator, Beck vat process, Fluidye ™ unit, hot sweeper, mud skimmer and waterproofing. In some cases, application at a sufficiently high bath temperature (eg, above 93 ° C (200 ° F)) can eliminate the subsequent vaporization operation.

FLUOROOUIMIC MATERIALS In order to impart oil and water repellency as well as dirt resistance to a fibrous substrate, the treatments of this invention must contain certain fluorochemical material and / or repellent hydrocarbon material. Fluorochemical materials suitable for use in the present invention should show a back-contact angle to n-hexadecane of at least 53 ° or greater, preferably at least 65 ° or higher, and more preferably at least 70 ° or higher, as measured by the back contact angle test described herein. Additionally, suitable fluorochemical materials are hard, vitreous, non-adherent and non-cationic materials having a glass transition temperature ranging from about 20 ° C to about 130 ° C. The fluorochemical material can be of any chemical class, but fluorochemical urethanes are preferred. The fluorochemical material preferably contains a fluoroaliphatic group, and more preferably, a perfluoroaliphatic group. The concentration of the fluorochemical material must be at least 0.03% SOF (solids in the fiber) and preferably at least 0.1% SOF. The following is a non-exhaustive list of fluorochemical substances to which reference is made in the Examples: F-1 - Scotchgard1 Fabric Guard ** FC-214-30 - a commercially available acrylate / urethane fluorochemical substance as an aqueous emulsion with 30% solids (by weight) from Minnesota Mining and Manufacturing Company.

F-2 - Scratch and Rain Repellent Scotchgard11 * FC-232 - an acrylate / fluorochemical urethane, commercially available as an aqueous emulsion with 30% solids (by weight) from Minnesota Mining and Manufacturing Company.

F-3 - Scotchgard Carpet Protector14 * FC-358 - a fluorochemical carbodiimide commercially available as a 20% solids (by weight) aqueous emulsion from Minnesota Mining and Manufacturing Company.

F-4 - 3M Carpet Protector FX-364 - a fluorochemical urethane commercially available as an aqueous emulsion with 23% solids (by weight) from Minnesota Mining and Manufacturing Company.

F-5 - 3M Carpet Protector FX-365 - a commercially available fluorochemical urethane as an aqueous emulsion with 24% solids (by weight) from Minnesota Mining and Manufacturing Company.

F-6 - Scotchgard ™ Carpet Protector * FC-1355 - a fluorochemical ester commercially available as an aqueous emulsion with 45% solids (by weight) from Minnesota Mining and Manufacturing Company.

F-7 - Scotchgard118 FC-1367F Carpet Protector - a fluorochemical ester commercially available as an aqueous emulsion with 41% solids (by weight) from Minnesota Mining and Manufacturing Company.

F-8 - Scotchgard KR FC-1373M Carpet Protector - a fluorochemical urethane commercially available as an aqueous emulsion with 29% solids (by weight) from Minnesota Mining and Manufacturing Company.

F-9 - Scotchgard Carpet Protector "* FC-1374 - a commercially available fluorochemical urethane as an aqueous emulsion with 31% solids (by weight) from Minnesota Mining and Manufacturing Company.

F-10 - Scotchgard ™ FC-1395 Carpet Protector - a fluorochemical urethane commercially available as an aqueous emulsion with 31% solids (by weight) from Minnesota Mining and Manufacturing Company.

F-ll - Carpet Treatment Duratcfr ™ is considered to be a fluorochemical urethane / urea substance, commercially available as an aqueous emulsion with 30% (by weight) of E.l. solids. duPont de Nemours & Co., Wilmington, Delaware.

F-11A - Carpet Treatment NRD-372 - is considered to be a fluorochemical substance of urethane / urea, commercially available as an aqueous emulsion with 27% (by weight) solids of E.l. duPont de Nemours & Co.

F-12 - Carpet Treatment Zonyl118 8779 - commercially available as an aqueous emulsion with 11% (by weight) of E.l. duPont de Nemours & Co.

F-13 - Softech11 * 97H Carpet Treatment - which is considered to be a fluoroalkyl acrylate polymer, commercially available as an aqueous emulsion with 15% (by weight) solids from Dyetech, Inc., Dalton, Georgia.

F-14 - Fluoroalkyl acrylate copolymer Shawguard "* 353 - commercially available as an aqueous emulsion with 13% (by weight) solids from Shaw Industries, Inc.

F-15 - Nuva Fluorochemical Acrylate Polymer "FT - commercially available as an emulsion with 22% (by weight) solids from Hoechst Celanese, Charlotte, North Carolina.

F-16 - Bartex Fluorochemical "* MAC - commercially available as an emulsion with 14% (by weight) solids from Trichromatic Carpet, Inc., Quebec, Canada.

F-17 - Fluoroalkyl acrylate polymer Bartex11 * TIIN - commercially available as an emulsion with 16% (by weight) solids from Trichromatic Carpet, Inc.

F-18 - MeFOSE Urethane from Desmodur14 * N-75 Synthesis: 368 g (0.66 eq) of alcohol are added MeFOSE (C8F17S02N (CH3) C2H40H) and 176 g (0.68 eq) of DesmodurHR N75 triisocyanate (a biuret isocyanate trimer derived from hexamethylene triisocyanate, commercially available from Mobay Corp., Pittsburgh, Pennsylvania) together with 456 g of methyl ethyl ketone (MEK) per funnel to a 2000 ml three-necked round bottom flask fitted with a stirrer and a condenser. Heat is applied to the mixture using a heat lamp and stirring is initiated. 1 g of dibutyltin dilaurate is added, which results in a slight exotherm, and the mixture is refluxed for 2.5 hours. He Infrared spectrum analysis of the product shows a small peak at 2310 cm "1, which indicates the presence of residual NCO in the reaction.The reaction product is poured into aluminum trays and the MEK is removed in an oven at 121 ° C (250 ° F) When the solvent has been removed, the trays are cooled and the resulting solid urethane is placed in glass jars.

Emulsification: 100 g of the above solid urethane is added to 250 g of methyl isobutyl ketone (MIBK) and the mixture is heated to about 90 ° C to dissolve the urethane in the solvent. Another mixture consisting of 500 g of water and 5 g of Siponate ™ DS-10 surfactant (commercially available from Rhone-Poulenc Corp., Cranberry, New Jersey) is heated to 70 ° C to dissolve the surfactant. The two liquids are mixed with stirring and subjected for 12 minutes to emulsification using a Branson Sonifier ™ Ultrasonic Horn 450 system (commercially available from VWR Scientific). The solution is purified of the organic solvent in a rotary evaporator. MIBK codestila with a certain amount of water. When the inspection shows that there are no traces or any solvent odor, the amount of solids is measured and enough water is added to generate a final emulsion with a weight percent solids of 14.6%.

F-19 - Fluoroalkyl acrylate copolymer emulsion TG-232D - commercially available from Advanced Polymers, Inc., Carlstadt, New Jersey.

HYDROCARBON MATERIALS The hydrocarbon materials suitable for use in the present invention show a back-to-n-hexadecane contact angle of at least 35 ° or greater, as measured by the recoil contact angle test described herein. Additionally, suitable hydrocarbon materials are hard, glassy, non-sticky, non-cationic, fluorine-free materials having at least one aliphatic group and having a glass transition temperature ranging from about 20 ° C to about 130 ° C. . The aliphatic group is preferably a long-chain aliphatic group containing at least 10 carbon atoms and more preferably containing between about 12 and about 24 carbon atoms. The hydrocarbon material can be any of any chemical class, but urethanes and hydrocarbon amides are preferred. The concentration of the hydrocarbon material should be at least 0.1% SOF and is preferably at least 0.2% SOF. The following is a list of hydrocarbons which are referenced in the examples: H-l - Octadeciluretane from Desmodur "* N100 285 g (1.05 eq) of octadecanol and 228 g (1.12 eq) of Desmodur triisocyanate "11 N100 (a trimer of isocyanate of biuret derived from hexamethylene triisocyanate, commercially available from Mobay Corp., Pittsburgh, Pennsylvania) are added together with 500 g of methyl ethyl ketone (MEK) by means of a funnel to a 2000 ml three-necked round bottom flask with a stirrer and a condenser, heat is applied to the mixture using a heat lamp and started Agitation: 500 mg of dibutyltin dilaurate is added, resulting in a slight exotherm, and the mixture is refluxed for 2.5 hours.The infrared spectrum analysis of the product shows a small peak at 230 cm "1, which indicates the presence of residual NCO in the reaction. The reaction product is poured into aluminum trays and MEK is removed in an oven at 121 ° C (250 ° F). When the solvent has been removed, the trays are cooled and the resulting solid urethane is placed in glass jars. Essentially the same emulsification process is followed as described in the preparation of the emulsion for the fluorochemical material F-18. The solids in percent by weight of the final emulsion are 20.0%.

H-2 - Desmodur hexadecylurethane "15 N100 - Essentially the same procedure is used for synthesis and emulsification to prepare H-2, as used to prepare Hl, except that 72 g (1.12 eq) of hexadecanol replace the 285 g (1.06 eq) of octadecanol The solids in percent by weight of the final emulsion are 20.0%.

H-3 - Temodecylurethane from DesmodurKR N100 - Essentially the same procedure is used for synthesis and emulsification to prepare H-3, as used to prepare Hl, except that 256 g (1.20 eq) of tetradecanol replace the 285 g ( 1. 06 eq) of octadecanol and 244 g (1.28 eq) are used instead of 228 g (1.12 eq) of Desmodur triisocyanate "R N100.The solids in weight percent of the final emulsion are 20.0%.

H-4 - Dodecylurethane of Desmodur1111 N100 - Essentially the same procedure is used for emulsification synthesis to prepare H-4, based on that used to prepare Hl, except that 2.39 g (1.28 eq) of dodecanol replace the 285 g ( 1.06 eq) of octadecanol, and 261 g (1.37 eq) are used instead of the 2.28 g (1.12 eq) of DesmodurMR N100 triisocyanate. The solids in percent by weight of the final emulsion are 20.0%.

H-4A - Desmodur ™ Octadecilurethane 'N75 - Essentially the same procedure is used for the synthesis and emulsification to prepare H-4A, when used to prepare H-1, except that 284 g (1.10 eq) of Desmodur "R N75 replace the 228 g (1.12 eq) of Desmodur triisocyanate" 1 * N100. The solids in percent by weight of the final emulsion are 18.0%. H-5 - Octadecylurethane diisocyanate isophorone - Essentially the same procedure is used for the synthesis and emulsification to prepare H-5, when used to prepare Hl, except that 348 g (1.29 eq) are used instead of 285 g (1.06 eq) of octadecanol, and 152 g ( 1.12 eq) of isophorone isocyanate replace the 228 g (1.12 eq) of DesmodurMR N100 triisocyanate. The solids in percent by weight of the final emulsion are 20.0%.

H-6 - Isoxane Diisocyanate Hexadecyl-urethane - Essentially the same procedure is used for the synthesis and emulsification to prepare H-5, when used to prepare Hl, except that 336 g (1.39 eq) of hexanol are used to replace the 285 g (1.06 eq) of octadecanol, and 164 g (1.47 eq) of isophorone diisocyanate replace the 228 g (1.12 eq) of DesmodurMR N100 triisocyanate. The solids in percent by weight of the final emulsion are 20.0%.

H-7 - Octadecyl (2 mol / 1, -butanediol (1 mol) urethane of hexamethylene diisocyanate (2 moles) Synthesis: 274 g (1.39 eq) of octadecanol and 164 g (1.47 eq) of hexamethylene diisocyanate are added together with 500 g of MIBK by means of a funnel to a 2000 ml three-necked round bottom flask to which it has been placed. an agitator and a condenser. Heat is applied to the mixture using a heating lamp and stirring is initiated. 500 g of dibutyltin dilaurate (500 mg) are added, resulting in a slight exotherm, and the mixture is refluxed for 30 minutes. At this point, 48 g of butanediol are added and the mixture is refluxed for another 2 hours. The analysis of the infrared spectrum of the product shows a small peak at 2310 cm "1, which indicates the presence of residual NCO in the reaction.The reaction product is poured into aluminum trays and MEK is removed in a 121 ° C oven. (250 ° F) When the solvent has been removed, the trays are cooled and the resulting solid urethane is placed in glass bottles Emulsification: The same procedure is used for emulsification as described in the preparation of the hydrocarbon material Hl. solids in percent by weight of the final emulsion are 20.0%.

H-8 - Octadecyl (2 moles) / 1, 4-butanediol (1 mol) urethane of isophorone diisocyanate In a 2-neck round bottom flask, equipped with agitator and condenser, "210 g are added. (4.12 eq) of isophorone diisocyanate, to this is added a solution of 248 g (0.92 eq) of stearyl alcohol in 500 g of MEK dry. The heating of the mixture starts and they are added 250 mg of dibutyltin dilaurate. The mixture generates exotherm, is refluxed for 1 hour, 41 g (0.92 eq) of 1,4-butanediol are added and the mixture is refluxed for an additional 2 hours. The infrared spectroscopy performed on the final mixture reveals a slight excess of isocyanate. The mixture is poured into shallow trays in an oven for 6 hours at 125 ° C. The material is harvested as hard white vitreous material and emulsified as described in the preparation of hydrocarbon material H-1.

H-9 - VesquatM triisocyanate hexadecylurethane T1890 In a three-necked flask, 75.0 g (0.071 eq) of Vestanat ™ T1890 triisocyanate (commercially available from Hüls America, are added to a stirred solution.

Inc., Piscataway, New Jersey), 31.9 g of MEK and 0.12 g of dibutyltin dilaurate, to a flask containing 51.9 g of hexadecanol in 50 g of MEK heated at 70 ° C under nitrogen. The temperature of the mixture is increased to 78 ° C over a period of 3 minutes, and then the mixture is stirred for an additional 3.3 hours. The resulting reaction product is poured into an aluminum tray. The yield is 104.7 g (96% of theory). Essentially the same emulsification process as described in the preparation of hydrocarbon material H-1 is used.

H-10 - Epon diepoxide octadecylaminoalcohol adduct ** 828 An aluminum can of 473 ml (one pint) is equipped with an overhead stirrer and a nitrogen purge line. The flask is charged with 152.6 g of epoxy resin EP01, R 828 (epoxy equivalent weight of 187, commercially available from Shell Chemical Co., Houston, Texas) and 42.4 g of bisphenol A (equivalent weight of 114). The reaction is heated to 125 ° C while purging with nitrogen. Then, 5 g of bisphenol A and 0.25 g of phosphonium iodide are charged to the flask, and the reaction is heated to 145 ° C. The reaction is exothermic at 175 ° C and is maintained at this temperature for 1 hour. The reaction is cooled to 130 ° C and 107.6 g of melted octadecylamine (equivalent weight of 269) are added to the reaction. The reaction is exothermic at 163 ° C and then cooled to 125 ° C. Finally, the reaction is heated to 125 ° -135 ° C for 1.5 hours. The reaction is cooled to room temperature and 307 g of a glassy solid are collected. Essentially the same emulsification process as described in the preparation of hydrocarbon material H-1 is used.

H-10A - Diepoxide octadecylaminoalcohol adduct Epon1"8 828 Aluminum of 473 ml (one pint) is equipped with an overhead stirrer and a nitrogen purge pipe. The flask is charged with 146 g of EP0N "R 828 and 50 g of bisphenol A. The reaction is heated to 125 ° C while purging the nitrogen, then 4 g of bisphenol A and 0.25 g of iodide are charged into the flask. The reaction is heated to 145 [deg.] C. The reaction is exothermic at 175 [deg.] C. and is maintained at this temperature for 1 hour.The reaction is cooled to 130 [deg.] C. and 82.8 g of melted octadecylamine are added to the reaction. equivalent weight of 269) The reaction is exothermic at 163 ° C and then cooled to 125 ° C. Finally, the reaction is heated at 125 ° -135 ° C for 1.5 hours. The reaction is cooled to room temperature and 282 g of a glassy solid are collected. Essentially the same emulsification process as described in the preparation of hydrocarbon material H-1 is used.

H-ll - Isophorone diamine octane acrylamide A 5000 ml three-necked flask is equipped with a Dean-Stark trap and an overhead stirrer. To the reaction flask is added 1854 g (6.52 moles) of stearic acid, 1.0 g of Irganox® 245. The reaction flask is purged with nitrogen for 30 minutes. Subsequently, the flask is heated slowly to 100 ° C, at which point all the stearic acid has melted. 554 g (3.26 moles) of isophorone diamine are added to the reaction. The reaction is heated at 190 ° C for 1 hour. There are 67 ml of water that are collected in the Dean-Stark trap after 2.5 hours. Subsequently, the reaction is cooled and allowed to sit at room temperature over the weekend. The reaction is then heated at 210 ° C for 1 hour and then cooled. 2271 g of a white solid are collected, and their identification is confirmed by the infrared and 13 C NMR spectrum. The melting point is measured and is 85 ° C.

H-12 - Isoform diamine azelaic diamine A 1000 ml three-necked flask is equipped with a Dean-Stark trap and an overhead stirrer. 94 g (0.5 mole) of azelaic acid and 170 g are added to the reaction flask. (1.0 moles) of isophorone amine. Afterwards, the flask was heat at 190 ° C for 2 hours. At this point, the required amount of water (18 g) has been collected in the Dean-Stark trap. Then 284 g (1.0 mol) of stearic acid are added to the reaction. The reaction is heated at 210 ° C for 1 hour. The reaction is cooled and 500 g of a glassy solid are collected. The identification of the product is confirmed by an infrared spectrum. Essentially the same emulsification process as described in the preparation of hydrocarbon material H-1 is used.

H-13 - Dytek / Bis-stearamide A three-necked flask of 1000 is equipped with a Dean-Stark trap and an overhead stirrer. 284 g are added (1.0 moles) of stearic acid, 1.4 g of Irganox® 245 (commercially available from Ciba Specialty Chemicals) to the reaction flask. The reaction flask is purged with nitrogen for 30 minutes. Then the flask is slowly heated to 100 ° C, at which point all the stearic acid has melted. 63 g (0.54 mol) of diamine DytekMR A (commercially available from E.l. duPont de Nemours, Wilmington, Delaware) and the reaction is heated to 170-180 ° C. There are 9 ml of water collected in the Dean-Stark trap after 1.5 hours. After, the reaction is heated at 200 ° C and placed under vacuum (6 mm torr) for 30 minutes. The reaction is cooled and 260 g of a white solid are collected. The identification of the product is confirmed by an infrared spectrum, and the melting point is 110 ° C. Essentially the same emulsification process as described in the H-1 hydrocarbon preparation is used.

H-14 - Octadecylurea of triisocyanate from Vestanat1 MR T1890 70.0 g (0.067 eq) of Vestanat ™ T1890 triisocyanate mixed with 41.6 g of toluene are added in one portion to a stirred solution of 53.8 g (0.20 eq) of Armeen ™ 18D flake (stearylamine, commercially available from Akzo Nobel Corp., Chicago , Illinois) in 40.0 g of toluene heated to 60 ° C under nitrogen. The temperature of the mixture is increased to 80 ° C and the mixture is stirred for an additional 2.25 hours. The resulting reaction product is poured into an aluminum tray. The yield is 11.9 g (98.1% of theory). Essentially the same emulsification process as described in the preparation of hydrocarbon material H-1 is used.

H-15 - Hexadecylurea triisocyanate from Vestanat "* T1890 Essentially the same procedure is used for synthesis and emulsification to prepare H-15, when used to prepare H-14, except that 75.0 g (0.071 eq) is used instead of 70.0 g (0.067 eq) of VestanatMR T1890 and they use 51.6 g (0.214 eq) of Armeen ™ 16D flakes (cetylamine, commercially available from Akzo Nobel Corp.) instead of 53.8 g (0.20 eq) of Armeen ™ 18D flakes.

H-17 - Kenamide ™ E-180 - stearyl eruzamide, commercially available from Witco Corp., Memphis, Tennessee.

H-18 - Kenamide ** E-221 - erucil eruzamide, commercially available from Witco, Corp., Memephis, Tennessee.

H-19 - Koday Carnoba Wax Flakes "11 - commercially available from Eastman Fine Chemicals, Eastman Kodak Co., Rochester, New York.

H-10 - Polymer VybarÍIR 253 (Pill) - a highly branched hydrocarbon used as an additive for paraffin wax, commercially available from Petrolite Corp., Polymers Division, Tulsa, Oklaho a.

H-21 - Unirez ™ 221 - Polyamide based on dimeric acid, commercially available from Union Camp Corp., Jacksonville, Florida.

HYDROLOGICAL FLUOROUIMIC / HYDROCARBON MATERIALS In some cases, the material used in the present invention to impart oil repellency, water repellency and dirt resistance to a fibrous substrate may be a hybrid of the fluorochemical and hydrocarbon substances mentioned previously. Such materials may be, for example, the reaction product of a fluorochemical with a hydrocarbon material. Again, however, the resulting material must be a hard, vitreous, non-sticky material having a vitreous transition temperature ranging from about 20 ° C to about 130 ° C. The following is a non-exhaustive list of hybrid materials to which reference is made in the examples.

FH-1 - Desmodur N-75 urethane reaction product with 75% (mol) of MeFOSE and 25% (mol) of stearyl alcohol 276 g (0.49 eq) of alcohol MeFOSE, 72 g (0.27 eq) of octadecanol and 203 g (0.78 eq) of triisocyanate are added.

Desmodu: r.R N75, together with 449 of MIBK per funnel to a 2000 ml three-necked round bottom flask with stirrer and condenser. Heat is applied to the mixture using a heating lamp and stirring is initiated. 1 g of dibutyltin dilaurate is added, which results in a slight exotherm, and the mixture is refluxed for 2.5 h. The infrared spectrum analysis of the product shows a small peak at 2310 cm "1 which indicates the presence of residual NCO in the reaction, essentially following the same emulsification procedure as described in the preparation of the emulsion for the fluorochemical material F- 18. The solids in weight percent of the final emulsion are 15.2%.

FH-2 - Desmodur urethane reaction product N-75 with 50% (mol) of MeFOSE and 50% (mol) of stearyl alcohol Essentially the same procedure is used for the synthesis and emulsification to prepare FH-2 when used to prepare FH-1, except that 184 g (0.33 eq) of alcohol MeFOSE, 144 g (0.53 eq) of octadecanol, 230 g ( 0.89 eq) of DesmodurMR N75 triisocyanate and 443 g of MIBK. The solids in percent by weight of the final emulsion are 15.3%.

FH-3 - Desmodur N-75 urethane reaction product with 25% (mol) of MeFOSE and 75% (mol) of stearyl alcohol Essentially the same procedure is used for synthesis and emulsification to prepare FH-3, when used to prepare FH-1, except that 92 g (0.16 eq) of alcohol MeFOSE, 216 g (0.80 eq) of octadecanol, 257 g ( 0.99 eq) of Desmodur triisocyanate "R N75 and 436 g of MIBK The solids in percent by weight of the final emulsion are 15.3%.

FH-4 - Desmodur N-75 urethane reaction product with 10% (mol) of MeFOSE and 90% (mol) of stearyl alcohol Essentially the same procedure is used for the synthesis and emulsification to prepare FH-4 when used to prepare FH-1, except that 37 g (0.07 eq) of alcohol MeFOSE, 258 g (0.96 eq) of octadecanol, 273 g ( 1.05 eg) of DesmodurMR N75 triisocyanate and 432 g of MIBK. The solids in percent by weight of the final emulsion are 15.3%.

STAINLESS BLOCKING MATERIALS In most embodiments, the treatment solution of the present invention will include at least one stain blocker. However, in some substrates, such As polypropylene, the stain blocker can be omitted completely without significantly affecting oil and water repellency (see Table 14). The following is a non-exhaustive list of blotters which are suitable for use in the present invention, of which FX-661 is especially preferred: S-1 - 3M Brand Stain Release Concentrate FX-661 - Carpet Stain Removal Material consisting of sulfonated and acrylic phenolic resins, commercially available from Minnesota Mining and Manufacturing Company as an aqueous emulsion with 29% (by weight) of solid S-2 - 3M Brand Stain Release Concentrate FC-369 - Stain-blocking material for carpet composed of sulfonated phenolic resins, commercially available from the Minnesota Mining and Manufacturing Company as an aqueous emulsion of 34% (by weight) solids.

. S-3 - 3M Brand Stain Release Concentrate FX-657 - carpet stain blocking material made from modified acrylic resins, commercially available from the Minnesota Mining and Manufacturing Company as an aqueous emulsion with 30% (by weight) solids.

S-4 - 3M Brand Stain Release Concentrate FX-670 - carpet stain blocking material made of acrylic resins, commercially available from Minnesota Mining and Manufacturing Company as an aqueous emulsion of 30% solids (by weight).

S-6 - SR-300 - Stain blocking material consisting of a combination of a sulfonated aromatic compound and a hydrolyzed copolymer of an unsaturated maleic anhydride aromatic monomer, commercially available as a 30% (by weight) solution of E.l. solids. duPont de Nemours & Co. S-7 - Stain blocking material which is the sodium salt of the hydrolyzed stearylmaleic anhydride copolymer (SMA-1000, commercially available from Elf Atochem, Birdsboro, Pennsylvania), which can be prepared using the procedure described in Example 1 of the U.S. patent No. 5,001,004 (Fitzgerald et al.).

YOU GO OUT Various salts (for example metal salts) can be used in the present invention to improve the deposition of the fluorochemical substance or the hydrocarbons on the fibrous substrate. The salts of divalent metals (for example MgSO, although good results can also be obtained under certain conditions by the use of monovalent salts or polyvalent salts) Suitable salts for use in the present invention include LiCl, NaCl, NaBr, Nal, KCl, CsCl, LÍ2S04 , Na2SO4, NH4C1, (NH4) 2S04, (CH3) 4NC1, MgCl2, MgSO4, CaCl2, Ca (CH3COO) 2, SrCl2, BaCl2, ZnCl2, ZnSO4, FeSO4 and CuSO4.

ACIDS In some embodiments of the present invention, it will be necessary or desirable to adjust the pH of the treatment solution (e.g. by making it more acidic) so as to facilitate the consumption of dye of fluorochemical substances or other materials on the fibrous substrate. Suitable acids that can be used in this regard include sulfuric acid, sulfamic acid, citric acid, hydrochloric acid, oxalic acid and autoacid (a mixture of urea and sulfuric acid). Although the optimum pH for the treatment solution may vary based on the choice of materials, optimum results are generally obtained with a pH of less than about 5, and more preferably, a pH of less than about 3.

CARPETS The following are the carpets referred to in the examples Nylon carpet MO-678 - whitish in color, having a front weight of 1.3-1.4 kg / m2 (38-40 ounces / yard2), commercially available from Shaw Industries, Dalton, Georgia Nyalon 6 Wolf-Laurel carpet - white in color, having a 1.3 kg / m2 (38 oz / yard2) frontal weight, commercially available from Shaw Industries.

Upbeat'1 * nylon carpet 6 - light cream color, color no. 45101, style 51145, which has a front weight of 0.9 kg / m2 (25 oz / m2).

Chesapeake Bay polypropylene carpet ** - a style carpet 53176, commercially available from Shaw Industries, Inc., characterized by a 100% cut hair style and a front weight of 1.8 kg / m2 (52 oz / yard2). The color of the carpet is Vellum and is designated by the color code 76113. Polyester carpet Venus11 * - orange carpet, commercially available from Terza Corp., Mexico.

TEST METHODS The following is a description of the test procedures referenced in the Examples and the specification.

Application procedure simulated bending-narrowing The simulated bending-nipping application procedure described in the following is used to simulate the bending-nipping operations used by the folder mills to apply a stain-blocking composition to a carpet. In this test, a carpet sample measuring approximately 13 cm x 10 cm (5 inches by 4 inches) is immersed in deionized water at room temperature until it drips wet. The water is extracted from the wet sample by rotating it in a centrifugal Bock extractor until the sample is moist to the touch. The wet carpet sample is then subjected to steam for 2 minutes at atmospheric pressure, at a temperature of 90-100 ° C and 100% relative humidity in a closed steam chamber. After the steam treatment, the carpet sample is allowed to cool to almost the temperature environment, and the aqueous treatment composition is applied by placing the carpet sample, with the fibers of the carpet pointing down, in a glass tray containing the treatment composition. The treatment composition contains sufficient fluorochemical and / or vitreous hydrocarbon material and sufficient stain blocking material to provide the desired percent solids on the fiber (% SOF) and is prepared by dissolving or dispersing two types of materials and (optionally) the desired amount of salt in deionized water and adjust the pH to a value of 2 (unless otherwise specified) using 10% aqueous sulfamic acid. The weight of the aqueous treatment solution in the vitreous tray is approximately 3.5 to 4 times the weight of the carpet. The carpet sample absorbs the entire volume of the treatment solution over a period of 1 to 2 minutes to provide a percent wet pickup of 350-400%. Afterwards, the treated carpet sample is subjected to steam a second time for 2 minutes (using the same conditions and equipment as described above), it is briefly immersed in a 5 liter (5 gallon) bucket filled in half with deionized water, Rinse carefully under a stream of deionized water to remove excess waste treatment composition, centrifuge until it is moist to the touch using a centrifugal extractor, and allow air dry overnight at room temperature before testing.

Spray application and curing procedure The aqueous treatment solution is applied to a carpet by means of spraying at approximately 15% by weight of wet pickup, using a laboratory-sized spray booth with a conveyor belt designed to mimic the operation of a commercial spray booth to large scale as conventionally used in carpet mills. The wet sprayed carpet is then dried at 120 ° C until it is dry (typically for 10-20 minutes) in a powered air oven. The application rate (in% of SOF) is controlled by varying the speed of the conveyor belt.

Application of foam and curing process The frothing applicator used in the present invention consists of a foam preparation device and a vacuum frame device. The foam preparation device is a Hobart Kitchen-Aid ™ mixer manufactured by Kitchen-Aid Division of Hobart Corporation, Troy, Ohio.

The vacuum frame device is a small stainless steel cabinet with a vacuum plenum and a vacuum bed. The carpet to be treated is placed on the bed, together with the foamed material that is to be deposited on the carpet. The vacuum bed forms a cabinet that has an exhaust hole placed in a Duty Shop Vac Dayton Tradesman ™ 94.6 liter (25 gallon) vacuum machine. The size of the bed is 20 cm x 30 cm x 4 cm (8"x 12" x 1.5") The plenum is separated from the rest of the bed by an aluminum plate in which holes are drilled approximately 1.7 mm apart ( 1/16"). The plate is of a structure similar to a strainer or screen. The portion of the carpet to be treated is weighed. The carpet can then be pre-moistened with water. The various application parameters must be adjusted by trial and error. In particular, the test foams should be prepared in order to determine the blowing rate, which is determined by the equation: blowing rate - foam volume / foam weight In general, the foam should be adjusted so that the foam pick-up is about 60% of the weight of the dry carpet, although other wet pick-up values may be used as required for an application particular. A doctor blade can be prepared from any thin rigid material. A thin vinyl laminate, of a thickness of approximately 2.5 mm (100 thousandths of an inch) is especially suitable, since it can be easily cut to any size. The notch portion of the blade should be approximately 20 cm (8 inches) wide so that it can be placed within the slot of the vacuum bed. In a typical application, approximately 150 g of liquid is foamed and placed in a Kitchen-Aid ™ mixer bowl. The wire whisk attachment is used and the mixer is adjusted at its highest speed (10). 2-3 minutes are allowed to elapse to form the foam and stabilize at a certain blowing rate. The blowing rate can be calculated by placing volume marks on one side of the bowl. An excess of the foam is placed on top of the carpet sample lying flat on a vacuum bed. Caution must be exercised so that no air pockets are formed in the foam structure. The foam is then removed by the doctor blade. The vacuum is subsequently turned on and applied to the carpet. At this point, the carpet can be dried in the oven.

The treated carpet samples are subjected to the following tests that are considered conventional or standard in the carpet industry.

Water repellency test Treated carpet samples are evaluated for water repellency using the 3M water repellency test V for floor coverings (February 1994), available from Minnesota Mining and Manufacturing Company. In this test, the treated carpet samples are exposed to penetrations by mixing deionized water and isopropyl alcohol (IPA). Each combination is assigned a qualification number as shown below: Classification number Water / IPA combination of adhesion repellency (% by volume) F Water failure 0 100% water 1 90/10 water / l ASPEA 2 80/20 water / lEA 3 3 70/30 water / IPEA 4 60/40 water / IPEA 5 50/50 water / IPEA 6 40/60 water / IPEA 7 30/70 water / IPEA 8 20/80 water / IPEA 9 10/90 water / lEA 10 100% IPEA In carrying out the water repellency test, a treated carpet sample is placed on a flat horizontal surface, and the piece of carpet is manually brushed in the direction that provides the largest layer of yarn. Five small drops of water or the IPEA / water mixture are placed gently in separate spots at least 5 cm (two inches) above the carpet sample. If, after observing for 10 seconds at a 45 ° angle, four of the five drops are visible as spheres or hemispheres, the carpet is considered to pass the test. The reported water repellency corresponds to the highest number of water or water / lPEA mixture for which the treated carpet sample passes the test described.

Oil repellency test Samples of treated carpet are evaluated for oil repellency using 3M oil repellency test III (February 1994), available from Minnesota Mining and Manufacturing Company, St. Paul, Minnesota. In this test, treated carpet samples are exposed to oil penetration or oil mixtures of varying surface tensions. The oils and mixtures of oils are provided with a classification that corresponds to the following: Oil repellency classification number Oil composition F (mineral oil failure) 1 mineral oil 1.5 85/15 (volume) mineral oil n-hexadecane 65/35 (volume) mineral oil / hexadecane 3 n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-dean The oil repellency test is carried out in the same way as the water repellency test, with a reported oil repellency rating corresponding to the highest oil or oil mixture for which the treated carpet sample passes the test .

Dynamic test of water resistance The dynamic resistance to water is determined using the following test procedure. A sample of treated carpet is tilted (15.2 cm x 15. "2 cm) at an angle of 45 ° with respect to the horizontal and 20 ml of deionized water is incised on the center of the carpet sample through a tube of glass with an inner diameter of 5 mm, placed 45.7 cm above the test sample The increase in weight (g) of the test sample is measured, where a lower weight gain indicates better repellency properties dynamic to water.

Spotting test The stain resistance is determined using the following test procedure. A treated carpet sample of 13 cm x 10 cm is stained for 2 minutes by immersing the carpet sample in an aqueous solution of 0.007% (by weight) of red dye FD &C # 40 in deionized water, adjusted to a pH of 2.8 with 10% aqueous sulfamic acid. The dye solution is heated to a temperature of 55-70 ° C. The treated and stained carpet sample is then briefly immersed in a 5-gallon (19-liter) bucket filled in half with deionized water, followed by wetting under a stream of deionized water until the running water is clear. The wet carpet sample is then removed until it is wet to the touch using a Bock centrifugal extractor and air-dried overnight at room temperature. The degree of staining of the carpet sample is determined numerically using a color analyzer of three compact stimuli Minolta 310 Chroma Meter ™. The color analyzer measures the red-stained color autochromatically on a red-green coordinate as a "delta a" (? A) value as compared to the color of a non-stained and untreated carpet sample. The measurements reported in the tables below are provided to place a place after the decimal point and represent the average of three measurements, unless stated otherwise. A larger indicates a greater amount of staining by the red dye. The readings typically vary from 0 (no staining) to 50 (severe staining).

Soiled "walking" test The relative fouling potential of each treatment is determined by exposing the treated and untreated carpet samples (control) under "dirty" defined soiling test conditions and by comparing their levels of relative soiling The test is carried out by assembling the treated and untreated carpet squares on a particle board, by placing the samples on the floor of one of two chosen commercial positions, and by allowing the samples to be soiled by normal foot traffic. . The amount of foot traffic in each of these areas is monitored, and the position of each sample within a given position is changed daily using a pattern designed to minimize the effects of position and orientation to fouling. After a period of specific exposure to dirt, measured in number of cycles where one cycle is equal to approximately 10,000 feet of traffic, the treated samples are removed and the amount of dirt present in a given sample is determined using colorimetric measurements, establishing the assumption that the amount of dirt in a given sample is directly proportional to the color difference between the unsoiled sample and the corresponding sample after being soiled. The three CIÉ L * a * b * color coordinates of the unsoiled and subsequently fouled samples are measured using a Chroma Minolta 310 meter with a D65 light source. Calculate the color difference value, E using the equation that follows: ? E = [(? L *) 2+ (? A *) 2+ (? B *) 2] 12 where? L * L * soiled-L * not soiled? a * a * soiled-a * not soiled? b * b * soiled-b * not soiled It has been shown that the ΔE values calculated from these colorimetric measurements are qualitatively in agreement with values of previous visual evaluations such as the fouling evaluation suggested by the AATCC, and have additional advantages of greater precision, are not affected by the evaluation environment. or by subjective differences to the operator. The final values of? E for each sample are calculated as an average of between five and seven duplicates.

Reverse contact angle test The recoil contact angle test provides a quick and accurate prediction of the potential that prevents soiling of a treated nylon carpet. The receding contact angle values measured with n-hexadecane using this test correlate well with the anti-soiling values measured for actual foot traffic using the "walking" soiling test. To perform this test, a solution, emulsion or suspension is applied (typically at approximately 3% solids) to a nylon film by dip coating. The nylon film is prepared as follows. A nylon film is cut into rectangular strips of 85 mm x 13 mm. Each strip is cleaned by immersing it in methyl alcohol, rubbing with a Kimwipe ™ brush (commercially available from Kimberly Clark Corp., Boswell, Georgia), being careful not to touch the surface of the strip, and allowing the strip to dry for 15 minutes. Then, using a small clasp to hold the end of the strip, the strip is immersed in the treatment solution, and the strip is then extracted slowly and evenly from the solution. The coated film strip is tilted to allow any solution to slip to accumulate at the corner of the strip, and a piece of Kimwipe® tissue paper makes contact with the corner to remove the accumulation of solution. The coated film strip is allowed to air dry in a protected place for a minimum of 30 minutes and then cured for 10 minutes at 121 ° C. After the treatment is dried and cured, a drop of n-hexadecane is applied to the treated film and the receding contact angle of the drop is measured using a CAHN dynamic contact angle analyzer, model DCA 322 (a Wilhelmy balancing apparatus equipped with a computer for data and control processing, commercially available from ATI, Madison, Wisconsin). The analyzer of Dynamic contact angle DAHN is calibrated using a weight of 500 mg. An alligator clip is attached to a piece of coated film strip approximately 30 mm long, and the clip and the piece of film are left hanging from the bracket of a scale. A 30 ml glass beaker containing approximately 25 ml of n-hexadecane is placed under the stirrup of the scale, and the beaker is placed so that the strip of coated film is centered on the beaker and its content, but without making contact with the walls of the beaker. Using the lever on the left side of the apparatus, the platform holding the beaker is carefully raised until the n-hexadecane surface is 2-3 mm from the bottom edge of the film strip. The appliance door is closed, the "configure" option of the "initialize" menu of the computer is chosen, the "automatic" option of the "experiment" menu is chosen, and the computer program then calculates the time for a total of three scans. The result should be a time interval of 1 second and estimate the total time of 5 minutes, which are acceptable settings to show the baseline weight of the sample. The return button is pressed to start an automatic measurement cycle. 10 readings are taken from the baseline before the exploration begins. The device then makes the liquid rise and fall so that they are taken 3 scans. Then the "least squares" option of the "analysis" menu is selected, and the average backward contact angle is calculated from the 3 scans of the film sample. The 95% confidence interval for the average of three scans' is typically approximately ± 1.2 °.

Fluorine analysis combustion test This procedure for measuring the amount of fluorochemical substance that is present in a treated carpet is described in the 3M Scotchgard ™ Carpet Protector Technical Information Manual Test, published on October 1, 1998.

Examples 1-3 and comparative examples Cl-Cll This series of experiments is carried out to determine what correlation exists, if any, ben the recoil contact angle and the antifouling properties for hydrocarbon materials used as carpet treatments. The return contact angle of various hydrocarbon materials is measured using the back contact angle test. Then, using the flex application procedure- simulated narrowing, a treatment solution is applied to a Wolf-Laurel nylon 6 carpet to provide 0.25% SOF for each hydrocarbon material, 0.6% SOF for S-1 spotting material, and 1.0% SOF for MgSO4 (with pH adjusted to 1.5 using 1.5% aqueous sulfamic acid). The fouling resistance of the treated carpet samples compared to a non-dirtied, non-trafficked carpet sample is determined using two cycles of the "walking" soiling test. The "walking" fouling values and the recoil contact angle (RCA) values for the various hydrocarbon materials are presented in Table 1. Table 1 also shows the measured repellencies for the treated carpets using the test of water repellency, oil repellency test and dynamic water independence test.

Table 1 Example RCA Material Dirty Repellency Repellency Repelenc Hydrocarbon (° C) to? E Water to dynamic oil to water 1 H- l 45 11. 5 1 F 3. 7 2 H-3 45 12. 3 1 F 5. 0 3 H-10 40 14. 3 0 F 10. 4 Cl H-ll 0 13.4 1 F 3.6 C2 H-4 0 14.8 1 F 4.6 C3 H-16 0 15.0 0 F 2.8 C4 H-8 0 15.1 1 F 6.7 C5 H-19 0 15.3 0 F 5.9 C6 H-17 0 15.6 0 F 4.3 C7 H-5 0 16.0 1 F 6.2 C8 H-14 0 16.2 0 F 10.8 C9 H-18 0 16.7 0 F 4.4 CIO H-20 0 16.7 0 F 4.8 Cll H-21 0 16.8 0 F 7.4 The data in table 1 show that the hydrocarbon materials show a backlash contact angle of at least 40 ° show excellent resistance to "walking" fouling, and that the recoil contact angle surprisingly is an excellent element of Prediction for antifouling operation. Water repellency and dynamic water repellency do not correlate with the recoil contact angle, and oil repellency is poor in all cases.

Examples 4-10 and comparative examples C12-C17 A study is made to determine whether or not the fluorochemical materials show a similar correlation between the antiensuciant operation and the recoil contact angle, as shown by the hydrocarbon materials in Table 1. Reverse contact angles for the materials Fluorochemicals are measured using the backward contact angle test. Then, using the bending-narrowing application procedure, 0.25% SOF of each fluorochemical material is co-applied with 0.6% SOF of S-1 spotting material and 1.0% SOF of MgSO4 from an acidic water bath. samples of a nylon mat 6 Style M0678. In addition to the "walking" soiling test, water repellency tests, oil repellency test and dynamic water repellency test on each treated carpet sample are also carried out. The results of these evaluations are presented in table 2.

Table 2 Example Material fluo- RCA Fouling- Repellency Repellency Rochemical repellency (° C) to? E to water to dynamic oil to water 4 F-8 (Lot 30001) 11.5 12.1 5 4 2.8 5 F-8 (Lot 531) 76 11.7 5 4 1.4 6 F-10 76 12.8 4 3 2.6 7 F-5 67 12.7 3 3 1.4 8 F-11A 65 12.8 5 4 2.0 9 F-12 64 14.5 5 4 2.7 10 F-13 63 16.3 4 7 1.8 C12 F-14 54 16.2 4 1 4.1 C13 F-7 52 14.4 5 3 8.6 C14 F-6 50 15.8 5 3 5.7 C15 F -4 44 15.1 3 4 4.0 C16 F-16 43 17.0 6 7 2.3 C17 F-17 0 17.8 6 7 2.6 -all recoil contact angles are those of the fluorochemical alone, without the treatment solution.

The data in table 2 generally show an excellent correlation between the fluorochemical backward contact angle and the "walking" dirt resistance, which means that the recoil contact angle again is an excellent predictive element for antifouling operation. The best anti-fouling performances on carpets (ie, E values of less than 13) are imparted by fluorochemical materials that show back contact angles of at least 65 °, compared to? E values of more than 14 imparted by materials Fluorochemicals that show receding contact angles of less than 65 °. Some improvement in dynamic water repellency is evident using fluorochemical materials that have higher recoil contact angles.

Examples 11-22 and comparative example C19 The level (% SOF) of fluorochemical materials (F-10) or hydrocarbon material (H-1) necessary for optimal operation was determined, using the simulated bending-narrowing co-application procedure. In this series of experiments, an aqueous acid treatment bath is adjusted to apply 0.6% SOF of an S-1 spotting material and 1.0% SOF of MgSO4 to a nylon 6 carpet of Wolf-Laurel. In comparative example C19, neither F-10 nor H-1 is used. The performance properties on the carpet measured in terms of dirt resistance, Water repellency, oil repellency, dynamic water repellency and stain resistance (the latter measured by the stain test) are presented in Table 3.

Table 3 Example Material% Fouling Repellence Repellency Repellent Stain, repellent SOF to? E water to dynamic oil? A water 11 F-10 0.169 16.0 3 4 1.9 5.1 12 F-10 0.100 17.0 2 3 3.6 13.1 13 F-10 0.068 16.5 3 3 5.4 4.1 14 F-10 0.034 18.5 2 1.5 7.4 9.5 15 F-10 0.017 20.6 0 F 12.3 3.0 16 Hl 0.169 16.7 1 F 6.8 4.0 17 Hl 0.100 17.6 1 F 6.8 5.7 28 Hl 0.068 19.7 o F 7.3 4.1 19 Hl 0.034 20.5 or F 10.7 4.5 20 Hl 0.017 22.3 or F 11.7 3.2 C19 -_ __- 20.9 FF 19.9 2.8 The data in Table 3 show that, not unexpectedly, as the level of fluorochemical or hydrocarbon material decreases, operation is reduced general. The only exception is stain resistance, which generally remains relatively constant at the constant concentration of the stain-blocking material used. The best overall results are obtained at a level of fluorochemical material of at least 0.034% SOF and at a level of hydrocarbon material of at least 0.100% SOF. Surprisingly, at high concentrations, the hydrocarbon material functions in a manner almost comparable to the fluorochemical material as an anti-fouling treatment.

Examples 21-26 and comparative example C19 The effect of the total performance of the carpet of the combination of a fluorochemical and a hydrocarbon material was determined. Fluorochemical material F-18, hydrocarbon material H-4A, and combinations thereof, are co-applied to a total level of 0.15% SOF with S-1 soil blocking material at 0.6% SOF to a nylon carpet. 6 of Wolf-Laurel. The level of MgSO4 is maintained at 1.0% SOF during the study. The results of this study are presented in table 4.

Table 4 Example F-18, H-4A, Dirty Repellence Repellency Dirty Spotting, % by weight% by weight to,? E to water to dynamic oil? A "to water 21 100 - 15.2 2 3 3.2 4.8 22 75 25 15.1 3 3 3.9 2.4 23 50 50 15.9 2 1 3.9 2.2 24 25 75 14.3 2 1 5.2 14.8 10 90 16.5 1 F 5.7 4.2 26 - 100 14.3 0 F 5.4 3.4 C19 _-- 21.6 F F 18.0 2.2 The data in table 4 show that, the higher the percentages of hydrocarbon material incorporated in the combination, the dirt resistance, the stain resistance and the dynamic water repellency all remain at a high level of operation, although the water and oil repellency is reduced as the hydrocarbon percentage approaches 90%.

Examples 27-30 In this study, the effect of total carpet performance on hybrid fluorochemical materials having both fluorochemical and hydrocarbon portions present in the same molecule of repellent material was determined. The hybrid fluorochemical materials FH-1, FH-2, FH-3 and FH-4 were compared in their performance with respect to their non-hybrid analogs, the fluorochemical material F-18 and the hydrocarbon material H-4A. The different repellent materials were co-applied to a total level of 0.15% SOF with a S-1 spot blocking material at 0.6% SOF to a nylon 6 carpet from Wolf-Laurel. The level of MgSO4 was maintained at 1.0% SOF during the study. Table 5 presents the results of this study. (Examples 21 and 26 representing 100% fluorochemical portions and 100% hydrocarbon portions, respectively, were included in Table 4).

Table 5 Example: Repellent material: Dirt- Repellency Repellency Dyeing, Name% (by weight)% (by weight) ment E to water to dynamic oil? 21 F-18 100 - 15.2 2 3 3.2 4.8 27 FH-1 79 21 13.9 2 3 2.6 1.5 28 FH-2 56 44 14.9 2 F 4.4 1.9 29 FH-3 30 70 16.1 1 F 5.5 5.0 30 FH-4 13 87 15.9 1 F 5.3 1.3 26 H-4A - 100 14.3 0 F 5.4 3.4 The data in Table 5 show similar trends to the data in Table 4, with dirt resistance, stain resistance and dynamic water repellency remaining all at a high level of performance and repellency (especially oil), decreasing as the percentage of hydrocarbon increases.

Examples 31-38 The level (% SOF) of magnesium sulfate necessary to provide optimum performance in the coaplication formulation applied by bending and tapering was determined. In each example, the procedure was used of simulation flexion-constriction coaplication to apply 0.15% SOF of fluorochemical material F-10 and 0.6% SOF of stain-blocking material S-1 to a carpet nylon 6 of Wolf-Laurel, with a pH-adjusted treatment solution to 2 using sulfamic acid. The results show the effect of magnesium sulfate level on water repellency in the carpet, oil repellency, dynamic water repellency and stain resistance (the latter measured by the stain test) and are presented in Table 6 Tab 6 Example M S04 Repellency Repellency Repeller Staining% SOF to water to dynamic oil? A to water 31 0.05 0 F 9.0 3.8 32 0.1 0 F 7.4 4.7 33 0.2 0 F 3.3 4.3 34 0.5 0 F 5.1 1.6 35 1.0 3 4 1.7 1.4 36 2.0 2 4 3.3 0.9 37 5.0 2 2 4.0 5.1 38 10.0 2 4 4.0 3.4 The data in Table 6 show the total operation that is reached at most with a concentration of magnesium sulfate in the intermediate range (ie, approximately 1% SOF), especially dynamic water repellency and stain resistance. Under these experimental conditions, at least 1.0% SOF of MgSO is required to provide good water and oil repellency for the carpet. Figures 2 to 5 are micrographs which illustrate the effects of the concentration of the magnesium salt in the treatment process of the present invention. Figure 2, which corresponds to Example 31, where the concentration of magnesium in the treatment method is used is too small. Consequently, there is little or no consumption of dye of the fluorochemical substance on the fiber, resulting in poor water repellency and no oil repellency. On the other hand, figure 3, which corresponds to example 38, the concentration of magnesium salt is too high, which results in coagulation of the fluorochemical substance. This causes a decrease in the dynamic water repellency and a slightly less than optimum oil repellency. In figure 4, which corresponds to example 35, the concentration of magnesium salt is optimal, which results in a uniform dye consumption of the fluorochemical substance on the surface of the fiber and optimum performance characteristics. For comparison, Figure 5 is a micrograph of a hydrocarbon (Hl) which has been consumed as a dye under conditions similar to those of Example 35. As in Example 35, a uniform coating of hydrocarbons is obtained on the surface of the fiber, and good performance characteristics are observed. Figure 6 is a micrograph of a carpet treated by a typical spray application process. When comparing Figures 4-5, it is evident that the carpet fibers treated according to the method of the present invention are coated more uniformly, and therefore show better antifouling properties, than the treated carpets by an application method. by sprinkling.

Examples 39-44 and Comparative Examples C20-C22 The pH required to provide optimum performance in fluorochemical substances that are applied by bending-narrowing or co-application formulations containing hydrocarbon material, in the absence of a salt, is determined. In each example, the simulated bending-taper co-application procedure is used to co-apply 0.15% SOF of fluorochemical material F-10 or 0.15% SOF of H-1 hydrocarbon material, with 0.6% SOF of S-l stain-blocking material to a nylon-6 carpet Wolf-Laurel. In Comparative Example C22, only stain blocking material is applied. The treatment solution is adjusted to various pH values using sulfamic acid. The results show the effect of pH on the carpet water repellency, oil repellency, dynamic water repellency and stain resistance, and are presented in table 7.

Table 7 Example Material pH Repellency Repellency Repellent Stain, water repellent to dynamic oil? A al asua C20 F-10 2.12 FF 17.9 18.5 39 F-10 1.87 FF 9.1 21.5 40 F-10 1.69 2 1 5.2 6.5 41 F-10 1.49 2 3 3.1 11.3 C21 Hl 2.18 FF 20.0 17.3 42 Hl 1.88 FF 16.9 14.1 43 Hl 1.69 0 F 10.5 6.6 44 Hl 1.56 0 F 4.2 12.1 C22 2.0 FF 20.0 2.5 The data in Table 7 show that water repellency, oil repellency and dynamic water repellency values are optimized when the pH is adjusted to about 1.7 or less, especially at about 1.5 or less. Poor repellency is observed when the pH is greater than 2. The operation of stain blocking in the presence of a repellent material reaches a maximum at a pH of about 1.7.

Examples 49-70 The necessary pH is determined to provide optimum performance in coaplication formulations containing fluorochemical or hydrocarbon material applied by bending and tapering. In each example, the simulated bending-taper co-application method was used to co-apply 0.15% SOF of fluorochemical material F-10 or 0.15% SOF of hydrocarbon material Hl with 0.6% SOF of stain blocking material S- 1 and 1.0% SOF of MgSO4 to a carpet nylon 6 of Wolf-Laurel. The treatment solution is adjusted to various pH values using sulfamic acid. The results show the effect of pH on water repellency, oil repellency and dynamic water repellency of a carpet, and are presented in table 8. Table 8 also shows examples 49-59 that they constitute parts per million of fluorine detected in each of the treated carpets determined using the combustion test of fluorine analysis.

Table 8 The data in Table 8 show that, when magnesium sulfate is present, optimum values of water repellency, oil repellency and dynamic water repellency are presented for both F-10 and Hl when the pH of the treatment solution is set to about 3 or less, preferably to about 2.7 or less. For F-10, this corresponds to higher fluorine levels measured on carpet samples treated at a pH of 2.7 or lower (Examples 53-59).

The dynamic behavior of the repellency of Examples 39-66 is shown graphically in Figure 1. Here, one observes that dynamic repellency, which is a measure of the instantaneous absorption of water by the substrate, increases more slowly as a function of the descending pH when a salt is used (MgSO4) in comparison to the case in which such salt is not used. Therefore, the pH has a minor effect on the dynamic repellency in the process of the present invention when salt is used. The data also indicate that, at a given pH, the presence of salt improves dynamic repellency across the board. For materials with good repellency properties, the improved dynamic repellency is indicative of an improved (ie, more uniform) application of the fluorochemical or hydrocarbon substance to the substrate. Therefore, at a given pH, the presence of a salt improves the application of a fluorochemical substance or a hydrocarbon to the substrate. For fluorochemical substances or hydrocarbons that have good antifouling properties, the improvement in application to the substrate can be expected to better impart antifouling properties.

Examples 67-72 The level (% SOF) of soil blocking material was determined to provide an operation optimum in a coaplication formulation applied by bending-narrowing. In each example, the simulated flexion-constriction co-application method was used to apply the% SOF designated soil-blocking material S-1, 0.15% "SOF of fluorochemical material F-10 and 1.0% SOF of MgSO4 to a nylon 6 carpet from Wolf-Laurel, with a treatment solution adjusting the pH to 2 using sulfamic acid.The results show the effect of the level of soil blocking material on water repellency, oil repellency, dynamic repellency water and the resistance to stains of the carpet, on the carpet presented in table 9.

Table 9 The data in Table 9 show that, as expected, stain resistance is improved by using higher concentrations of soil blocking material. The repellency performance is basically not affected by the level of stain blocker used within the concentration range studied.

Examples 73 and 74, and comparative examples C23-C26 A study is carried out comparing the total performance of the coaplication systems containing fluorochemical materials and hydrocarbon materials both inside (F-10 and Hl) and outside (F-7, F-11A, F-19 and H- 19) of this invention. In each example, the simulated flex-constriction co-application procedure is used to apply 0.15% SOF of the designated fluorochemical material and 0.68% d SOF of S-1 spot blocking material to a Wolf-Laurel nylon 6 carpet from an aqueous treatment solution that has a pH adjusted to approximately 1.5 with sulfamic acid. The results show the effect of the level of repellent material on carpet dirt, water repellency, oil repellency, dynamic water repellence and staining, and are presented in table 10.

Table 10 The data in Table 10 show that, of the fluorochemical materials, F-10 and F-llA show the best antisuciedad combination, water repellency, oil repellency, dynamic water repellency and stain resistance. However, F-10 is clearly superior to F-llA in its antifouling operation as predicted by its greater recoil contact angle, and it is also superior in most other categories. Similarly, the hydrocarbon material H-1, which has a higher recoil contact angle compared to the hydrocarbon material H-19, which also shows superior antifouling characteristics, as compared to H-19.

Examples 75-118 and comparative example C27 Using the simulated flexion-constriction coaplication procedure, numerous salts were evaluated. in coaplication systems containing the fluorochemical material F-10 at 0.25% SOF and the material S-1 of blocking material at 0.6% SOF on a nylon carpet UpbeatHR. The monovalent cationic salts were examined in Examples 75-100. The divalent cationic salts were evaluated in Examples 101-115, and the trivalent cationic salts were evaluated in Examples 116-118; no salts were used in comparative example C27. The concentrations of salts used are expressed as% SOF in the carpet. The results show the effect of the selection of salt and the level of water repellency of the carpet, oil repellency, dynamic water repellency and resistance to stains, and is presented in table 11.

Table 11 The data in Table 11 show that divalent and monovalent cationic metal salts improve all physical properties of treated carpets compared to the case where no salts are used (comparative example C27). The monovalent cationic metal salts work well at concentrations ranging from about 0.25 to about 2.5% SOF, while the divalent cationic metal salts function even more efficiently, working at levels ranging from -0.1% to 1.27%. SOF (the highest concentration or level that was evaluated).

Examples 119-123 and comparative examples C28-C44 Using the spray application and curing procedure, 0.25% SOF from each of the various hydrocarbon materials was applied by spraying samples of a Style M0678 nylon carpet previously treated with 0.84% SOF of stain-blocking material. S-1 and 0.5% SOF of MgSO4, using the simulated bending-narrowing co-application procedure, with a pH adjusted 1.5 using 1.5% aqueous sulfamic acid. The resistance to soiling of the samples of treated carpet was compared with carpet samples not subjected to traffic, not soiled, determined using two "walked" test cycles. Table 13 presents a tabulation comparing the contact angle of fouling and backstrokes of the "walked" (RCA) for the various hydrocarbon materials.

Table 13 The data in table 13 show an excellent correlation between the hydrocarbon retreat contact angle and the "walking" fouling resistance similar to that observed with the hydrocarbon material applied by immersion included in table 1. With the Except for hydrocarbon material H-2, hydrocarbon materials show the highest recoil contact angles with a better antifouling performance in the carpet (that is, they show the lowest E values when compared to a non-dirtied, untreated carpet). In general, very few hydrocarbon materials show good recoil contact angles and a good resulting antifouling operation.

Examples 123-128 and comparative examples C52-C55 Using the simulated flex-constriction co-application procedure, the fluorochemical materials F-10 and F-19, the S-1 stain-blocking material and the magnesium sulfate were co-applied to Chesapeake Bay ™ polypropylene (PP) and Venus polyester mats. 8 (PE) using a pH treatment solution adjusted to approximately 2 with sulfamic acid For each fluorochemical, a theoretical level of 500 ppm fluorine was applied to the carpet In some examples, S-1 or MgS04 A very low level of S-1 (0.073% SOF) is used since the carpets inherently exhibit good stain resistance, although low levels of S-1 serve to stabilize the emulsion in water. of treated carpets are tested to determine water repellency, oil repellency, dynamic water repellency, with the results presented in table 14.

Table 14 'fifteen The data in table 14 show that, in all cases, the repellency values are better with fluorochemical material F-10 (receding contact angle of 76 °) than with the fluorochemical material F-19 (backward contact angle of 12 °). For polypropylene carpets, the best results are obtained using a combination of F-10, stain-blocking material and magnesium sulfate. For polyester carpet, only magnesium sulfate with F-10 is required to provide good results.

Comparative example C56 and examples 129-134 This series of experiments is carried out to illustrate the antifouling synergy shown between the hydrocarbon material applied by immersion and a fluorochemical material applied by spraying subsequently. For Examples 129-134, the simulated Flex-Nip Coaplication procedure is used to co-apply to a 6 UPBEATMR nylon carpet a 1.0 or 5.0% SOF hydrocarbon mixture, S-1 spot blocking material at 0.6% SOF and magnesium sulfate at 1% SOF from a treatment solution with pH adjusted to approximately 2 with sulfamic acid. Subsequently, by using the spray application and the curing process, the fluorochemical material F-8 is applied by spray to the carpet treated with hydrocarbon material at a theoretical fluorine level of 250 or 500 ppm.

And then the treated carpet undergoes a cycle of the "walking" soiled test In Comparative Example C56, the carpet is not treated In comparative example C57, fluorochemical material is not applied to the carpet by sprinkling. carpet samples are subjected to a cycle of a 'walking' dirt test and are also tested using the dynamic water repellency test, with results shown in table 15.

Table 15 * N / R means not performed ** F-8 used at 325 ppm By comparing the fouling value in Table 15 for Example 134 against the fouling values for Example 129 and Comparative Example C57, a synergistic antifouling effect between the hydrocarbon material H-1 and the fluorochemical F-8 is evident. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or products to which it refers.

Claims (56)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. A method for treating a fibrous substrate, characterized in that it comprises the steps of: providing a fibrous substrate; applying to the substrate a composition comprising: (a) a salt, and (b) a material that is selected from the group consisting of (i) fluorochemical substances having a back-contact angle to n-hexadecane of at least 65 °, and (ii) free compositions of fluorine, having at least a portion of hydrocarbon and having a back-contact angle to n-hexadecane of at least about 35 °.

2. The method according to claim 1, characterized in that the composition further comprises a spot blocker.

3. The method according to claim 1, characterized in that the composition is an aqueous solution.

4. The method according to claim 3, characterized in that the solution has a pH in the range from about 2 to about 5.

5. The method according to claim 2, characterized in that it further comprises the step of adjusting the pH of the solution within the range from about 2 to about 5.

6. The method according to claim 2, characterized in that it further comprises the step of adjusting the pH of the solution within the range from about 2 to about 5 by the addition of sulfuric acid and sulfamic acid.

7. The method according to claim 1, characterized in that the element (b) comprises a fluorochemical urethane.

8. The method in accordance with the claim 1, characterized in that element (b) comprises a fluorochemical carbodiimide.

9. The method according to claim 1, characterized in that the element (b) comprises a fluorochemical acrylate.

10. The method in accordance with the claim 1, characterized in that the element (b) comprises a fluorochemical ester.

11. The method according to claim 1, characterized in that the element (b) is a urethane having at least one portion of hydrocarbon.

12. The method according to claim 1, characterized in that the element (b) is an amide having at least a portion of hydrocarbon.

13. The method according to claim 1, characterized in that the element (b) is a hydrocarbon wax.

14. The method according to claim 1, characterized in that the element (b) comprises the reaction product of a polyisocyanate with a fluorochemical alcohol and a second alcohol having at least a portion of hydrocarbon.

15. The method according to claim 14, characterized in that the second alcohol is stearyl alcohol.

16. The method in accordance with the claim 1, characterized in that the composition is applied by means of a bending and narrowing process.

17. The method according to claim 1, characterized in that the composition is a solution having a pH of less than about 1.7.

18. The method according to claim 1, characterized in that it further comprises the step of exposing the substrate to steam after it is treated with the composition.

19. The method according to claim 18, characterized in that the steam is heated to a temperature within the range from about 90 ° C to about 100 ° C.

20. A method for treating a fibrous substrate, characterized in that it comprises the steps of: providing a fibrous substrate; applying to the substrate a composition comprising: (a) a stain-blocking material, and (b) a material that is selected from the group consisting of (i) fluorochemical substances having a receding contact angle to n-hexadecane plus 65 °, and (ii) fluorine-free compositions, having at least one portion of hydrocarbon and having a back-contact angle to n-hexadecane of greater than about 40 °; adjusting the pH of the composition to less than about 2.

21. The method according to claim 20, characterized in that the composition is applied such that the% solid in the fiber of the blocker is less than about 7%.

22. The method according to claim 20, characterized in that the composition further comprises a polyvalent metal salt selected from the group consisting of sodium sulfate, lithium sulfate, magnesium sulfate, calcium chloride, barium chloride, sodium sulfate, zinc, copper sulfate, aluminum sulfate and chromium sulfate.

23. The method according to claim 20, characterized in that the composition further comprises a monovalent salt which is selected from the group consisting of NaCl and KCl, and wherein the monovalent salt is deposited on the substrate at% solids on the fiber inside. of the range from about 0.1% to about 2.0%.

24. The method according to claim 23, characterized in that the monovalent salt is deposited on the substrate at% solids on the fiber of between about 30% and about 90%.

25. The method according to claim 20, characterized in that the composition comprises a fluorochemical urethane, the product of a condensation reaction between an alcohol and a biuret isocyanate trimer, and a stain blocker comprising sulfonated resins and phenolic resins.

26. The method in accordance with the claim 25, characterized in that the alcohol is octadecanol.

27. A method for treating a fibrous substrate, characterized in that it comprises the steps of: providing a fibrous substrate; submerge the substrate in water; exposing the substrate to steam at a temperature in the range of about 90 ° C to about 100 ° C; and submerging the substrate in a treatment solution comprising: (a) a spot blocker; (b) a salt, and (c) a material that is selected from the group consisting of (i) fluorochemical substances having a backward contact angle to n-hexadecane of at least about 65 °, and (ii) compositions fluorine-free, having at least a portion of hydrocarbon and having a back-contact angle to n-hexadecane of at least about 35 °.

28. The method of compliance 'with the claim 27, characterized in that the treatment solution has a pH of about 2 to about 5.

29. The method according to claim 27, characterized in that the substrate has a wet pick up of about 350% to about 400% of the treatment solution.

30. The method according to claim 27, characterized in that the substrate has an uptake in wet of approximately less than about 30% of the treatment solution.

31. The method according to claim 27, characterized in that the substrate is exposed to vapor both before and after it is immersed in the treatment solution.

32. The method according to claim 27, characterized in that the substrate is immersed in water after the second exposure to steam.

33. The method according to claim 27, characterized in that the salt is an alkaline earth divalent metal salt.

34. The method according to claim 27, characterized in that the treatment solution comprises a protic acid.

35. The method according to claim 34, characterized in that the protic acid is selected from the group consisting of sulfamic acid and sulfuric acid.

36. The method according to claim 27, characterized in that the component (c) of the treatment solution is a material having at least a portion of hydrocarbon and showing a back contact angle of at least about 40 °.

37. The method according to claim 27, characterized in that the component (c) of the treatment solution is a material having at least a portion of hydrocarbon and exhibiting a receding contact angle of at least about 45 °.

38. The method according to claim 27, characterized in that the substrate is a carpet.

39. The method according to claim 37, characterized in that the carpet comprises nylon.

40. The method according to claim 37, characterized in that the carpet comprises polypropylene.

41. The method in accordance with the claim 27, characterized in that component (c) of the treatment solution is a fluorochemical having a recoil contact angle of at least approximately 65 °.

42. The method according to claim 27, characterized in that the component (c) of the treatment solution is a fluorochemical having a receding contact angle of at least about 70 °.

43. The method according to claim 27, characterized in that the component (c) of the treatment solution is a fluorochemical having a receding contact angle of at least about 75 °.

44. The method according to claim 27, characterized in that at least about 0.6% solids in the stain-blocking fiber is applied to the substrate.

45. The method according to claim 27, characterized in that the component (c) of the treatment solution is a combination of a fluorochemical substance and a hydrocarbon.

46. The method according to claim 44, characterized in that the ratio of the fluorochemical to the hydrocarbon is at least 1: 3.

47. The method according to claim 27, characterized in that the treatment solution comprises a compound that contains at least one fluoroaliphatic portion.

48. The method according to claim 27, characterized in that the treatment solution comprises a condensation product of a fluorochemical urethane and an aliphatic alcohol.

49. A method for treating a fibrous substrate, characterized in that it comprises the steps of: providing a fibrous substrate; and submerging the substrate in a treatment solution comprising a mixture of: (i) a fluorochemical having a backward contact angle to n-hexadecane of at least 65 °, and (ii) a fluorine-free composition which has at least a portion of hydrocarbon and has a back-contact angle to n-hexadecane of at least about 35 °.

50. A method for treating a fibrous substrate, characterized in that it comprises the steps of: providing a fibrous substrate; and submerging the substrate in a treatment solution comprising a compound having at least one fluoroaliphatic group and at least one free fluorine aliphatic group.

51. A method for treating a fibrous substrate, characterized in that it comprises the steps of: providing a fibrous substrate; and submerging the substrate in a treatment solution comprising a compound having at least one fluoroaliphatic group and at least one free fluorine aliphatic group.

52. A method for treating a fibrous substrate, characterized in that it comprises the steps of: providing a fibrous substrate, - and immersing the substrate in a treatment solution comprising: (i) a blocker, and (ii) a compound having at least one aliphatic group free of fluorine.

53. A method for treating a fibrous substrate, characterized in that it comprises the steps of: providing a fibrous substrate; and submerging the substrate in a treatment solution comprising: (i) a spot blocker, and (ii) a fluorochemical having a backward contact angle to n-hexadecane of at least 65 °.

54. The method in accordance with the claim 52, characterized in that the fluorochemical is a reaction product of a triisocyanate and an alcohol having the formula RfS02N (R1) AOH, wherein Rf is a prefluoroalkyl group Rx is H or an alkyl group and A is an alkylene-linking group .

55. The method in accordance with the claim 53, characterized in that the fluorochemical substance is (C8F17S02N (CH3) C2H40H).

56. The method in accordance with the claim 53, characterized in that the triisocyanate is a trimer of biuret isocyanate which is derived from hexamethylene triisocyanate.