EP0332342B1 - Procédé pour rendre des matériaux polyamidiques résistants aux taches - Google Patents

Procédé pour rendre des matériaux polyamidiques résistants aux taches Download PDF

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Publication number
EP0332342B1
EP0332342B1 EP89302085A EP89302085A EP0332342B1 EP 0332342 B1 EP0332342 B1 EP 0332342B1 EP 89302085 A EP89302085 A EP 89302085A EP 89302085 A EP89302085 A EP 89302085A EP 0332342 B1 EP0332342 B1 EP 0332342B1
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Prior art keywords
acid
methacrylic acid
polymer
methacrylic
weight
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German (de)
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EP0332342A3 (fr
EP0332342A2 (fr
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John C. Chang
Maynard H. Olson
Imelda A. Muggli
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3M Co
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Minnesota Mining and Manufacturing Co
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof

Definitions

  • This invention relates to a process for providing fibrous polyamide materials such as nylon carpet with stain resistance and to fibrous polyamide materials so treated.
  • Fibrous polyamide articles such as nylon carpets are particularly susceptible to staining by natural and artificial acid colorants such as are commonly found in many foods and beverages.
  • a need has long been felt for processes for economically providing such fibrous polyamide articles with resistance to staining by acid colorants.
  • US-A-3,961,881 discloses a process for coloring synthetic polyamide textile materials which comprises applying to the textile materials by a dyeing, padding or printing process, an aqueous dispersion of pH less than 7 of a disperse dyestuff containing at least one carboxylic acid group and in the presence of a tanning agent, whereby level colorations are obtained which have excellent wet fastness properties.
  • examples of natural agents include tannic acid and the vegetable tannins
  • synthetic agents include condensation products of naphthols, naphthalene sulphonic acids and formaldehyde, condensation products of phenol, naphthalene, formaldehyde and sulphuric acid, condensation products of dihydroxydiphenylsulphone and formaldehyde, condensation products of dihydroxydiphenylsulphone sulphonic and aliphatic aldehydes, condensation products of sulphurized phenols, naphthalene and formaldehyde.
  • US-A-2,205,883 discloses tanning agents which are the acidic polymerization products of the polymerization of methacrylic acid with itself as well as interpolymerization of methacrylic acid with other materials.
  • US-A-3,408,319 discloses tanning compositions which are made by copolymerization of a mixture of (A) methacrylic acid, acrylic acid or mixtures of such acids with (B) a sulfated unsaturated oil.
  • the unsaturated acid used is preferably 75 to 100% methacrylic acid and 25 to 0% respectively of acrylic acid, and generally the use of methacrylic acid exclusively is most practical from the standpoint of cost and effectiveness.
  • the amount of sulfonated oil is from 10 to 25% by weight of the acid monomer.
  • US-A-3,994,744 discloses aqueous cleaning compositions having a minimum film-forming temperature of at least 30°C and comprising a polymer having a glass transition temperature of at least 35°C and a metal salt, form a tacky film after being applied to a soiled substrate. Soil adheres to the tacky film which, as a result of the drying of said composition, fractures to form a removable residue.
  • the compositions contain polymers preferably derived from a carboxylic acid monomer and a soft monomer and/or a hard monomer. Preferred soft monomers are vinyl acetate and the alkyl esters of acrylic acid wherein the alkyl group contains from 1-12 carbon atoms.
  • Suitable hard monomers include lower alkyl methacrylates wherein the lower alkyl group contains 1-3 carbon atoms, cycloalkyl acrylates and methacrylates wherein the cycloalkyl group contains 5-7 carbon atoms, and hard vinyl monomers.
  • acid monomer include acrylic, methacrylic, itaconic, maleic and crotonic acids and monoalkyl esters of itaconic and maleic acids wherein the alkyl group contains 1-8 carbon atoms.
  • US-A-4,081,383 discloses an anti-soiling treatment for carpets and carpet yarns.
  • the carpets or carpet yarns prior to carpet manufacture are coated with a polymeric material containing either (A) a blend of a methacrylic acid emulsion copolymer and an epoxy resin or (B) a methacrylic acid emulsion copolymer having epoxy monomer units therein.
  • the copolymer in either case contains 40-75% by weight methacrylic acid and the glass transition temperature of cured coatings of the polymeric material is at least 50°C.
  • US-A-4,334,876 discloses a process for producing leather wherein leather stock is subjected to a multiple-stage tanning process involving a first treatment with an aqueous dispersion or solution of a synthetic polymeric composition made by polymerizing at least one member selected from the group consisting of acrylic acid and methacrylic acid and, optionally, one or more polymerizable compounds selected from the group of alkyl esters of acrylic acid, alkyl esters of methacrylic acid and sulfated unsaturated drying oils, followed by a second treatment with a zirconium tanning compound having a 0-45% basicity by the Schorlemmer scale.
  • US-A-4,388,372 discloses a durable antisoiling coating composition for textile filaments comprising a perfluoroalkyl ester of a citric acid urethane and fluorinated alcohols in combination with a modified epoxy resin which is the reaction product of a carboxyl-functional vinyl polymer, an epoxy resin and a tertiary amine.
  • Preferred vinyl resins for use in making the modified epoxy resin reaction product are the terpolymers of styrene/ethyl acrylate/methacrylic acid, and particularly such terpolymers wherein the monomers are in a mol ratio to one another respectively of about 1:1:2.
  • US-A-4,526,581 discloses a process for producing leather which employs a copolymer tanning agent comprising at least 60 mole percent residues of methacrylic acid and at least about 5 mole percent of residues of at least one alkyl acrylate selected from methyl, ethyl, propyl, and butyl acrylates, the copolymer having a weight average molecular weight from about 3,500 to 9,000.
  • US-A-4,699,812 discloses a method for imparting stain resistance to fibers containing free amino groups, and especially polyamide fibers, by contacting the fiber with a solution of an aliphatic sulfonic acid containing 8 to 24 carbon atoms under acidic conditions.
  • US-A-3 993 830 discloses a soil release finish to assist in removal of soils and/or oily materials employing polymers of molecular weight of 2000 to 5,000 000 with 5,000 000 to 1,000 000 being preferred. Also, any polycarboxylic polymer appears to be useful. There is no disclosure of imparting resistance to staining by acid colorants.
  • the present invention in one aspect, provides a method for imparting to fibrous polyamide materials stain resistance to acid colorants comprising contacting the fibrous polyamide materials with an agueous treating solution comprising polymethacrylic acid, copolymers of methacrylic acid, or combinations thereof, and drying said substrate, said copolymers of methacrylic acid comprise at least 30 weight percent methacrylic acid and said polymethacrylic acid, copolymers of methacrylic acid, or combinations thereof having the lower 90 weight percent having a weight average molecular weight in the range of 2500 to 250,000 and a number average molecular weight in the range of 500 to 20,000 and being provided in a sufficient amount to provide at least 0.5 weight percent based on the weight of the material.
  • Application of said method provides fibrous polyamide substrate with improved acid colorant stain resistance.
  • a rating of at least 5 is satisfactory, a rating of 7 is good, and a rating of 8 is excellent when the treated substrate is tested according to the test method set forth hereinafter, which test method challenges the substrate with an aqueous solution of FD&C Red Dye No. 40, a common stain test solution.
  • the present invention in another aspect, provides fibrous polyamide substrates treated with an aqueous treating solution comprising polymethacrylic acid, copolymers of methacrylic acid, or combinations thereof, said copolymers of methacrylic acid comprise at least 30 weight percent methacrylic acid and said polymethacrylic acid, copolymers of methacrylic acid, or combinations thereof having the lower 90 weight percent having a weight average molecular weight in the range of 2500 to 250,000 and a number average molecular weight in the range of 500 to 20,000 and being provided in a sufficient amount to provide at least 0.5 weight percent based on the weight of the material.
  • Such treated substrates have improved acid colorant stain resistance. Generally, a rating of at least 5 is satisfactory, a rating of 7 is good, and a rating of 8 is excellent.
  • FIG. is a copy of a colour photograph of carpet samples tested for stain resistance according to the test method set forth hereinafter.
  • the polymethacrylic acid, copolymers of methacrylic acid, or combinations thereof useful in the present invention are preferably hydrophilic.
  • the term "methacrylic polymer” is intended to include the polymethacrylic acid homopolymer as well as polymers formed from methacrylic acid and one or more other monomers.
  • the monomers useful for copolymerization with the methacrylic acid are monomers having ethylenic unsaturation.
  • Such monomers include, for example, monocarboxylic acids, polycarboxylic acids, and anhydrides; substituted and unsubstituted esters and amides of carboxylic acids and anhydrides; nitriles; vinyl monomers; vinylidene monomers; monoolefinic and polyolefinic monomers; and heterocyclic monomers.
  • Representative monomers include, for example, acrylic acid, itaconic acid, citraconic acid, aconitic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, cinnamic acid, oleic acid, palmitic acid, vinyl sulfonic acid, vinyl phosphonic acid, alkyl or cycloalkyl esters of the foregoing acids, the alkyl or cycloalkyl groups having 1 to 18 carbon atoms such as, for example, ethyl, butyl, 2-ethylhexyl, octadecyl, 2-sulfoethyl, acetoxyethyl, cyanoethyl, hydroxyethyl and hydroxypropyl acrylates and methacrylates, and amides of the foregoing acids, such as, for example, acrylamide, methacrylamide, methylolacrylamide, and 1,1-dimethylsulfoethyl
  • Particularly useful monomers include, for example, alkyl acrylates having 1-4 carbon atoms, itaconic acid, sodium sulfostyrene, and sulfated castor oil.
  • monomers such as, for example, sodium sulfostyrene and styrene, and sulfated castor oil and acrylic acid, can be copolymerized with the methacrylic acid.
  • the methacrylic polymers useful in the present invention can be prepared using methods well-known in the art for polymerization of ethylenically unsaturated monomers.
  • the methacrylic acid comprises 30 to 100 weight percent, preferably 60 to 90 weight percent, of the methacrylic polymer.
  • the optimum proportion of methacrylic acid in the polymer is dependent on the comonomer used, the molecular weight of the polymer, and the pH at which the material is applied.
  • water-insoluble comonomers such as ethyl acrylate are copolymerized with the methacrylic acid, they may comprise up to about 40 weight percent of the methacrylic polymers.
  • the water-soluble comonomers When water-soluble monomers, such as acrylic acid or sulfoethyl acrylate are copolymerized with the methacrylic acid, the water-soluble comonomers preferably comprise no more than 30 weight percent of the methacrylic polymer and preferably the methacrylic polymer also comprises up to 50 weight percent water-insoluble monomer.
  • the methacrylic polymer should be sufficiently water-soluble that uniform application and penetration of the polymer into the fiber surface can be achieved. However, when the polymer is excessively water soluble, acid colorant stain resistance and durability to cleaning may be reduced.
  • the glass transition temperature of the polymer can be as low as about 35°C, although higher glass transition temperatures are preferred. When polymer having high glass transition temperatures, i.e., as high as 230°C or higher, are used, an additional benefit of improved soil resistance of the fibrous polyamide substrate can be obtained.
  • the weight average molecular weight and the number average molecular weight of the methacrylic polymer are such that satisfactory stain resistance is provided by the polymer.
  • the lower 90 weight percent of the polymer material preferably has a weight average molecular weight in the range of 2500 to 250,000, more preferably in the range of 3000 to 100,000.
  • the lower 90 weight percent of the polymer material preferably has a number average molecular weight in the range of 500 to 20,000, preferably in the range of 800 to 10,000. Generally, more water-soluble comonomers are preferred when the molecular weight of the polymer is high and less water-soluble or water-insoluble comonomers are preferred when the molecular weight of the polymer is low.
  • methacrylic polymers generally useful in the present invention include LeukotanTM 970, LeukotanTM 1027, LeukotanTM 1028, and LeukotanTM QR 1083, available from Rohm and Haas Co.
  • the amount of the methacrylic polymer used should be sufficient to provide the desired degree of stain resistance to the polyamide substrate. Generally, when the substrate is nylon 66, lower application levels can be used than when the substrate is nylon 6 or wool. When the polyamide material is heat-set carpet yarn, yarn heat-set under moist conditions, e.g., in an autoclave, generally requires higher application levels than yarn heat-set under substantially dry conditions.
  • the amount of methacrylic polymer used is at least about 0.5 weight percent, most preferably at least about 1 weight percent, based on the weight of the fiber when the fiber is nylon 66 carpet fiber.
  • the amount of methacrylic polymer used is at least 0.5, more preferably at least 1 weight percent, based on the weight of the fiber when treating nylon 6 carpet fiber.
  • the methacrylic polymer is applied from an aqueous solution.
  • the pH of the solution is preferably below 7, more preferably below 5.
  • amounts of methacrylic polymer in excess of 3 weight percent owf provide little added benefit and may cause the fiber to have a harsh hand.
  • the methacrylic polymer can be applied from an aqueous exhaust bath such as is used in beck dyeing of carpet.
  • the methacrylic polymer can be added to the aqueous dye bath solution and exhausted concurrently with the dye.
  • the dye bath is maintained at a temperature at or near the boiling point for a period of 10 to 90 minutes or more to effect exhaustion of the dye and the methacrylic polymer.
  • the methacrylic polymer can be added to the aqueous dye bath after exhaustion of the dye or the dye bath can be drained and fresh water added prior to the addition of the methacrylic polymer.
  • the bath is maintained at a temperature at or near boiling for a period of time sufficient to exhaust the methacrylic polymer, usually 10 to 90 minutes.
  • the methacrylic polymer can be applied during continuous dyeing, such as with KusterTM or OttingTM carpet dyeing equipment.
  • the methacrylic polymer can be added directly to the aqueous dye solution and the solution is conventionally applied to the polyamide carpet.
  • the methacrylic polymer can be applied during a wetting out step prior to application of the dye.
  • the methacrylic polymer can also be applied to polyamide material by a padding operation. This can be done as a separate step or in conjunction with the application of various convention finishes such as wetting agents, softeners, and leveling agents. After application of the solution, the polyamide material is conventionally dried.
  • the methacrylic polymer can also be applied by foam techniques which are well-known in the art. Generally, the methacrylic polymer is applied from an aqueous solution which may further contain a foaming agent.
  • the foaming agents used are those typically used in foam dyeing.
  • the methacrylic polymer can also be applied to polyamide fabrics by other methods well known to those skilled in the art.
  • Other suitable methods include application by padding, low-pressure padding such as can be accomplished with Kuster FlexnipTM equipment, spray applicators such as those available from Otting International, or dip boxes which need not be equipped with moisture reduction apparatus such as squeeze rolls.
  • the methacrylic polymer is generally applied in these methods from an aqueous solution at ambient conditions followed by steaming for from 15 to 180 seconds, then drying or from an aqueous solution at elevated temperatures, e.g., 60°C to 90°C, followed by skying for 15 to 180 seconds, then drying.
  • the methacrylic polymer can also be applied to nylon carpet during carpet shampooing.
  • Useful techniques include the use of scrubbing machines and steam or hot water cleaning machines.
  • Fluorochemical compositions for providing oil and water repellency can also be applied in conjunction with the methacrylic polymer.
  • the fluorochemical composition can be added in an appropriate amount to the treating solution.
  • the following staining test was used: A 6.5 g test sample of carpet, which has been dyed using a blue disperse dye with a 45 minute beck dyeing cycle, is immersed in 40 g of an aqueous solution containing 0.008 weight percent FD&C Red Dye No. 40 and 0.04 weight percent citric acid. The solution is allowed to remain on the test sample for eight hours at room temperature, i.e., about 22°C. The sample is rinsed under running tap water, dried and then evaluated for staining using a graduated rating scale which ranges from 1 to 8, as shown in the drawing where 1 represents no discernible removal of the red dye stain and 8 represents complete removal of the red dye stain. In general, an eight-hour stain resistance of at least 5 is satisfactory, at least 7 is good, and 8 is excellent.
  • Polymers B through K were prepared using a procedure similar to that used in the preparation of Polymer A using the monomers and reactant ratios set forth in Table 1.
  • Table 1 Polymer Reactant(s) Reactant ratio A methacrylic acid 68 sulfonated castor oil 15 acrylic acid 17 B methacrylic acid 100 C methacrylic acid 80 ethyl acrylate 20 D methacrylic acid 65 ethyl acrylate 35 E methacrylic acid 80 ethyl acrylate 20 F methacrylic acid 84 sulfated castor oil 16 G methacrylic acid 80 sodium sulfostyrene 10 styrene 10 H methacrylic acid 81 sulfated castor oil 10 ethyl acrylate 9 I methacrylic acid 68 sulfated castor oil 15 acrylic acid 17 J acrylic acid 100 K acrylic acid 70 ethyl acrylate 30
  • Polymer L was prepared by placing in a bottle 46 g water, 8 g methacrylic acid, 2 g sodium sulfostyrene, 0.3 g mercapto propionic acid, without regard to order, and finally 0.3 g potassium persulfate.
  • the bottle was evacuated and purged three times with nitrogen.
  • the bottle cap was tightened and the bottle placed in a water bath having a temperature of 72°C under agitation for a period of 16 hours.
  • the resulting polymer solution was clear and fluid with a polymer solids content of 19 weight percent.
  • Polymers M through Q were prepared using a procedure similar to that used in the preparation of Polymer L using the monomers and reactant ratios set forth in Table 2.
  • Table 2 Methacrylic Polymer Reactants Reactant ratio L methacrylic acid 80 sodium sulfostyrene 20 M methacrylic acid 50 sodium sulfostyrene 50 N methacrylic acid 80 itaconic acid 20 O methacrylic acid 80 vinyl acetate 20
  • Q methacrylic acid 80 hydroxyethyl acrylate 20
  • Polymer R was prepared using the procedure used to prepare Polymer M except that the following ingredients were used: 92 g water, 16 g methacrylic acid, 2 g sodium sulfostyrene, 2 g styrene, 0.6 g mercapto propionic acid, 0.6 g sodium dodecyl benzene sulfonate, without regard to order, and finally 0.6 g ammonium persulfate.
  • Polymer S was prepared according to the procedure set forth in Example 1 of US-A-4,081,383
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the lower 90 weight percent of various of the thus-prepared polymers were determined using a column bank having four Ultrahydrogel columns, i.e., linear, 1000, 500, and 250, available from Waters Assoc. and polyacrylic acid standards available from American Polymer Standards Company. The results are set forth in Table 3.
  • Example 1 a treating solution was prepared containing 0.35 g Polymer A solids in 92 g water with the pH adjusted to 4.0 using 20% aqueous formic acid. To simulate a continuous treatment process, the treating solution was poured into a dye press and heated to 80°C. A 23 g sample of dyed carpet prepared using nylon 6 fiber, available from BASF, which had been heat set under moist conditions was steamed for 2 minutes and then immersed in the treating solution for 1 minute with pressure being applied to ensure thorough penetration of the treating solution. The treated sample was put through squeeze rollers at 20 ⁇ 104 N/m2 (30 psi) to remove excess liquid and then dried at 70°C for 45 minutes and 130°C for 10 minutes.
  • nylon 6 carpet samples were prepared and treated as in Example 1 except the polymers used were as set forth in Table 5.
  • Examples 1-14 provide satisfactory to excellent stain resistance to the moist heat-set nylon 6 carpet samples.
  • Comparative Example C1 which was treated with a high molecular weight methacrylic acid-based copolymer
  • Comparative Examples C2 and C3 which were treated with polyacrylic acid and an acrylic acid copolymer, respectively exhibit particularly poor stain resistance.
  • Example 15 - LeukotanTM 970 a methacrylic acid based polymer, available from Rohm and Haas Co.
  • Comparative Example C5 - LeukotanTM LP 1042 an acrylic acid-based polymer, available from Rohm and Haas Co.
  • Comparative Example C6 - AcrysolTM RM-5 an acrylic acid-based monomer, available from Rohm and Haas Company.
  • Each sample was tested for stain resistance. The results are set forth in Table 6.
  • Table 6 Example Stain resistance 15 7 C5 3 C6 2
  • Example C7 a polymer of methacrylic acid, styrene, and methyl methacrylate was prepared substantially following the teachings of U.S. Patent No. 4,081,383 (Warburton, Jr. et al.), Example 1.
  • a mixture of 69 parts methacrylic acid, 27 parts styrene and 5 parts methyl methacrylate was added to 80 parts of water containing 0.07 parts of 80% active isopropylbenzenehydroperoxide, 1.13 parts sodium dodecylbenzenesolfonate, 0.0375 parts of the sodium salt of ethylene diamine tetraacetic acid, and 0.0135 parts if FeSO4.7H2O.
  • the resulting emulsion was degassed by stirring under nitrogen for 30 minutes. Then, 0.0104 parts of sodium sulfoxylate formaldehyde in 1.15 parts of water was added. The temperature rose from 24°C to 50°C over 18 minutes.
  • a carpet sample was prepared as in Example 1 using carpet prepared from the moist heat-set nylon 6 fiber except that the sample was treated with the above-prepared Warburton, Jr. et al. polymer. The sample was tested for stain resistance and received a rating of only 2, showing poor stain resistance.
  • Comparative Example C8 200 parts of the above-prepared polymer as a 20% solids aqueous solution were added to a WaringTM blender and agitated. Epoxy resin (DERTM 736, available from Dow Chemical Company) was then added (8 parts) slowly over several minutes. The blend was diluted to 23% solids.
  • Epoxy resin DERTM 736, available from Dow Chemical Company
  • a carpet sample was prepared as in Example 1 using carpet prepared from the moist heat-set nylon 6 fiber except that the sample was treated with the above-prepared copolymer/epoxy resin. The sample was tested for stain resistance and received a rating of only 2, showing poor stain resistance.
  • Example 16 a solution containing 75 g/l LeukotanTM 970, and 10 g/l Alkafoam D, a foaming agent available from Alkaril Chemicals, Inc., was prepared and foamed onto a sample of carpet prepared from nylon 66 yarn heat set under moist conditions using a Gaston County laboratory FFT model foam finishing machine, available from Gaston County Dyeing Machine Company, using a 60:1 blow ratio and a wet pickup rate of 20% to provide an application rate of 0.5% LeukotanTM 970 based on the weight of the carpet. The sample was dried at 120°C for 20 minutes.
  • the polymers of the invention provide adequate to good stain resistance to nylon carpet prepared from moist heat-set nylon 66 carpet fiber.
  • Example 19 a treating bath was prepared containing 0.69 g Polymer B solids in 690 g water with the pH adjusted to 3.5 using 20% aqueous formic acid.
  • a 23 g sample of dyed carpet prepared using nylon 6 fiber, available from BASF, which had been heat set under moist conditions was steamed for 2 minutes and then placed in the treating bath. Under agitation, the temperature was raised to 70°C over 30 minutes and held at 70°C for 15 minutes. The sample was removed from the bath, put through squeeze rolls at 30 psi, and then dried at 70°C for 45 minutes and 130°C for 10 minutes.
  • the methacrylic polymers provide excellent stain resistance.
  • the polymer/epoxy resin blend of Warburton, Jr. et al. and the acrylic acid-based polymers provide little stain resistance.
  • Example 23-25 carpet samples were treated as in Example 1 except that LeukotanTM 1027, LeukotanTM 1028, and LeukotanTM QR 1083, respectively, each a methacrylic acid-based polymer available from Rhom and Haas Co., were substituted for Polymer A.
  • the treated samples were tested for stain resistance. The results are set forth in Table 9.
  • Table 9 Example SR 23 7 24 7 25 6
  • the LeukotanTM QR 1083 provided better than satisfactory stain resistance, while the LeukotanTM 1027 and the LeukotanTM 1028 provided good stain resistance.
  • Example 26 a treating bath was prepared containing 0.2 g Polymer B in 80 g water with pH adjusted to 3.5 using 20% aqueous formic acid.
  • a 20 g sample of dyed carpet prepared using nylon 66 fiber which had been heat set under dry conditions was steamed for 2 minutes and then placed in the treating bath. Under agitation, the temperature was raised to 70°C over 30 minutes and held at 70°C for 15 minutes. The sample was removed from the bath, rinsed, put through squeeze rolls at 30 psi, and then dried at 70°C for 45 minutes and 130°C for 10 minutes.
  • methacrylic polymers of the invention provide greater stain resistance than do acrylic acid-based polymers (Comparative Examples C13 and C14) when applied on nylon 66 carpet fiber. Further, the methacrylic acid copolymer used in Comparative Example C12 performs unsatisfactorily due to its high molecular weight.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (6)

  1. Procédé pour communiquer une résistance aux taches par des colorants acides à des matières de polyamide fibreuses comprenant la mise en contact des matières de polyamide fibreuses avec une solution de traitement aqueuse comprenant de l'acide polyméthacrylique, des copolymères d'acide méthacrylique ou leurs combinaisons, et le séchage dudit substrat, les copolymères d'acide méthacrylique comprenant au moins 30 % en poids d'acide méthacrylique et l'acide polyméthacrylique, les copolymères d'acide méthacrylique ou leurs combinaison ayant les 90 % en poids inférieurs correspondant à un poids moléculaire moyen pondéral dans la gamme de 2.500 à 250.000 et un poids moléculaire moyen numérique dans la gamme de 500 à 20.000 et étant prévus en une quantité suffisante pour constituer au moins 0,5 % en poids par rapport au poids de la matière.
  2. Procédé suivant la revendication 1, dans lequel la solution de traitement aqueuse comprend de l'acide polyméthacrylique.
  3. Procédé suivant la revendication 1, dans lequel le copolymère est un copolymère d'acide méthacrylique et d'un comonomère qui est un acide monocarboxylique, un acide polycarboxylique ou un anhydride, un ester ou amide substitué ou non substitué d'un acide ou anhydride carboxylique, un nitrile, un monomère vinylique, un monomère de vinylidène, un monomère monooléfinique ou polyoléfinique, un monomère hétérocyclique ou leurs combinaisons.
  4. Procédé suivant la revendication 3, dans lequel le comonomère est un acrylate d'alkyle comportant 1 à 4 atomes de carbone d'alkyle, de l'acide itaconique, du sulfostyrène de sodium ou de l'huile de ricin sulfatée.
  5. Procédé suivant la revendication 3, dans lequel le copolymère est un terpolymère d'acide méthacrylique, de sulfostyrène de sodium et de styrène, d'acide méthacrylique, d'huile de ricin sulfatée et d'acide acrylique ou d'acide méthacrylique, d'acrylate d'éthyle et d'huile de ricin sulfatée.
  6. Substrats de polyamide fibreux traités par une solution de traitement aqueuse comprenant de l'acide polyméthacrylique, des copolymères d'acide méthacrylique ou leurs combinaisons, les copolymères d'acide méthacrylique comprenant au moins 30 % en poids d'acide méthacrylique et l'acide polyméthacrylique, les copolymères d'acide méthacrylique ou leurs combinaison ayant les 90 % en poids inférieurs correspondant à un poids moléculaire moyen pondéral dans la gamme de 2.500 à 250.000 et un poids moléculaire moyen numérique dans la gamme de 500 à 20.000 et étant prévus en une quantité suffisante pour constituer au moins 0,5 % en poids par rapport au poids de la matière.
EP89302085A 1988-03-11 1989-03-02 Procédé pour rendre des matériaux polyamidiques résistants aux taches Expired - Lifetime EP0332342B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16688488A 1988-03-11 1988-03-11
US166884 1988-03-11

Publications (3)

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EP0332342A2 EP0332342A2 (fr) 1989-09-13
EP0332342A3 EP0332342A3 (fr) 1991-09-18
EP0332342B1 true EP0332342B1 (fr) 1994-05-11

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EP89302085A Expired - Lifetime EP0332342B1 (fr) 1988-03-11 1989-03-02 Procédé pour rendre des matériaux polyamidiques résistants aux taches

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EP (1) EP0332342B1 (fr)
JP (1) JP2744053B2 (fr)
KR (1) KR970001083B1 (fr)
AU (1) AU627711B2 (fr)
CA (1) CA1286555C (fr)
DE (1) DE68915189T2 (fr)
DK (1) DK117789A (fr)
ZA (1) ZA891862B (fr)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
US6524492B2 (en) 2000-12-28 2003-02-25 Peach State Labs, Inc. Composition and method for increasing water and oil repellency of textiles and carpet

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JPH01292178A (ja) * 1988-05-13 1989-11-24 Kanebo Ltd ポリアミド繊維の黄変防止処理方法
US5310828A (en) * 1989-04-20 1994-05-10 Peach State Labs, Inc. Superior stain resistant compositions
US5061763A (en) * 1989-04-20 1991-10-29 Peach State Labs, Inc. Stain resistant treatment for polyamide fibers
US5015259A (en) * 1989-04-20 1991-05-14 Peach State Labs, Inc. Stain resistant polymeric composition
US5223340A (en) * 1989-04-20 1993-06-29 Peach State Labs, Inc. Stain resistant polyamide fibers
CA2024600A1 (fr) * 1989-09-15 1991-03-16 Robert M. Blankenship Traitement anti-taches par compose acrylique a poids moleculaire eleve pour moquettes en nylon
CA2098120A1 (fr) 1990-12-13 1992-06-14 Engelbert Pechhold Agents antitache a base de polymere d'anhydride maleique/olefine
US20010027581A1 (en) * 2000-03-10 2001-10-11 Yanhui Sun Dyeable and stain resistant nylon carpet treatment
JP2002227075A (ja) 2001-01-31 2002-08-14 Daikin Ind Ltd 繊維製品のステインブロック処理
JP2002266245A (ja) 2001-03-13 2002-09-18 Daikin Ind Ltd 繊維製品の撥水撥油処理

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US3782898A (en) * 1971-08-12 1974-01-01 Pennwalt Corp Temporary soil release resins applied to fabrics in laundering
US3993830A (en) * 1972-04-28 1976-11-23 Colgate-Palmolive Company Soil-release finish
US3994744A (en) * 1973-10-01 1976-11-30 S. C. Johnson & Son, Inc. No-scrub cleaning method
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US4203859A (en) * 1977-06-27 1980-05-20 Rohm And Haas Company Solubilized acrylic polymers and carpet shampoos containing the same
US4388372A (en) * 1980-05-13 1983-06-14 E. I. Du Pont De Nemours And Company Durable antisoiling coatings for textile filaments
JPS6072930A (ja) * 1983-09-30 1985-04-25 Bridgestone Corp ゴム補強用芳香族ポリアミド類繊維材料
JPH0689509B2 (ja) * 1986-01-16 1994-11-09 東レ株式会社 皮革様シ−トの製造方法
CA1264505A (fr) * 1986-02-14 1990-01-23 E.I. Du Pont De Nemours And Company Procede de fabrication de polyamides resistant aux taches
KR920006476B1 (ko) * 1987-12-21 1992-08-07 이 아이 듀우판 디 네모아 앤드 캄파니 방오성 폴리아미드 직물 지지체 및 직물 지지체에 방오성을 제공하는 방법

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6524492B2 (en) 2000-12-28 2003-02-25 Peach State Labs, Inc. Composition and method for increasing water and oil repellency of textiles and carpet

Also Published As

Publication number Publication date
CA1286555C (fr) 1991-07-23
DK117789A (da) 1989-09-12
EP0332342A3 (fr) 1991-09-18
AU2966389A (en) 1989-09-14
DK117789D0 (da) 1989-03-10
KR890014830A (ko) 1989-10-25
JPH01280076A (ja) 1989-11-10
AU627711B2 (en) 1992-09-03
JP2744053B2 (ja) 1998-04-28
EP0332342A2 (fr) 1989-09-13
DE68915189D1 (de) 1994-06-16
ZA891862B (en) 1990-11-28
DE68915189T2 (de) 1994-11-10
KR970001083B1 (ko) 1997-01-25

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