EP0648886B1 - Agents antitâches contenant des polymères d'anhydride maléique/oléfine - Google Patents

Agents antitâches contenant des polymères d'anhydride maléique/oléfine Download PDF

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Publication number
EP0648886B1
EP0648886B1 EP94203127A EP94203127A EP0648886B1 EP 0648886 B1 EP0648886 B1 EP 0648886B1 EP 94203127 A EP94203127 A EP 94203127A EP 94203127 A EP94203127 A EP 94203127A EP 0648886 B1 EP0648886 B1 EP 0648886B1
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Prior art keywords
maleic anhydride
acid
polymer
alpha
substrate
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EP94203127A
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German (de)
English (en)
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EP0648886A3 (fr
EP0648886A2 (fr
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Engelbert Pechhold
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EIDP Inc
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EI Du Pont de Nemours and 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
    • 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
    • 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
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
    • 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
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • 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
    • D06M15/31—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles
    • 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
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • 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
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • 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
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3566—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing sulfur
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone resins
    • D06M15/412—Phenol-aldehyde or phenol-ketone resins sulfonated
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention relates to polyamide textile substrates treated with stain-resistant compositions comprising water-soluble or water-dispersible maleic anhydride/ alpha-olefin polymers, and processes for their synthesis.
  • the substrates of this invention possess stain-resistance but do not suffer from yellowing to the extent that some previously known materials do.
  • Polyamide substrates such as nylon carpeting, upholstery fabric and the like, are subject to staining by a variety of agents, e.g., foods and beverages.
  • An especially troublesome staining agent is FD&C Red Dye No. 40, commonly found in soft drink preparations.
  • Different types of treatments have been proposed to deal with staining problems.
  • One approach is to apply a highly fluorinated polymer to the substrate.
  • Another is to use a composition containing a sulfonated phenol-formaldehyde condensation product.
  • Liss et al. in U.S. Patent No. 4,963,409, disclose stain-resistant synthetic polyamide textile substrates having deposited on them sulfonated phenol-formaldehyde polymeric condensation products.
  • sulfonated phenol-formaldehyde condenation products are themselves subject to discoloration; commonly they turn yellow.
  • Yellowing problems are described by W. H. Hemmpel in a March 19, 1982 article in America's Textiles , entitled Reversible Yellowing Not Finisher's Fault. Hemmpel attributes yellowing to exposure of a phenol-based finish to nitrogen oxides and/or ultraviolet radiation. To deal with the yellowing problem, the condensation products were modified by Liss et al.
  • the modified condensation products were dissolved in a hydroxy-containing solvent, such as ethylene glycol prior to there being applied to the textile substrate.
  • Allen et al. in U.S. Patent 3,835,071, disclose rug shampoo compositions which upon drying leave very brittle, non-tacky residues which are easily removed when dry.
  • the compositions comprise water-soluble metal, ammonium or amine salt of a styrenemaleic anhydride copolymer, or its half ester, and a detergent.
  • Water-soluble metal salts of Group II and the alkali metals (particularly magnesium and sodium) are preferred and ammonium salts are most preferred by Allen et al.
  • Fitzgerald et al. in EP-A 0 329 899, disclose the usefulness of aqueous solutions of hydrolyzed vinylaromatic/maleic anhydride copolymers in the treatment of textiles to render them resistant to staining.
  • the preferred copolymer of Fitzgerald et al. is a hydrolyzed styrene/maleic anhydride copolymer.
  • Fitzgerald et al. disclose that the monoalkyl ester of their maleic anhydride/vinyl aromatic polymer was ineffective as a stain-resist.
  • maleic anhydride/alpha-olefin polymers are known.
  • EP-A 306,992 published 15 March 1989 discloses maleic anhydride/-1-alkene (C 4-30 ) polymers.
  • Florjanczyk et al. in Terpolymerization of Maleic Anhydride With Vinyl Monomers, J. Polymer SCI., Part A: Polym. Chem., 27 (12), 4099-108 disclose terpolymers of maleic anhydride with (i) 1-hexene, propylene, isobutylene, styrene, isoprene or 1,3-butadiene, and (ii) methyl methacrylate, methyl acrylate or acrylonitrile.
  • EP-A-0 177 972 discloses an aqueous fabric finishing composition containing a solubilised copolymer of a 1-alkene having at least 10 carbon atoms and maleic anhydride.
  • EP-A-0 332 342 discloses imparting stain resistance to fibrous polyamide using aqueous compositions of copolymers of methacylic acid with a monocarboxylic acid or a mono olefin.
  • the present invention is based on the finding that polyamide fibrous substrates treated with specified water-soluble or water-dispersible maleic anhydride/alpha-olefin polymers have stain-resistance.
  • prior art materials known to be useful as stain-blockers were sulfonated phenol-formaldehyde condensates (excepting those of Fitzgerald et al, supra).
  • Finding a non-sulfonated material, such as the water-soluble or water-dispersible alpha-olefin/maleic anhydride polymers of this invention, to be useful for this purpose was unexpected.
  • the present invention provides a polyamide fibrous substrate having deposited on it an amount of a composition effective to impart stain-resistance to said substrate comprising a water-soluble or water-dispersible alphaolefin/maleic anhydride polymer or a mixture of said polymers, wherein said polymer contains from 0.7 to 1.3 polymer units derived from one or more alpha-olefin monomers per polymer unit derived from maleic anhydride and has been hydrolysed to the corresponding free acid or salt thereof or converted to a C 1-4 alkyl monoester, the alpha-olefin content of said polymer comprising between (a) 100 and 80 mol percent of at least one 1-alkene containing 4 to 8 carbon atoms or terminally unsaturated diene containing 4 to 18 carbon atoms and (b) 0 to 20 mol percent of at least one 1-alkene containing 3 or 10 to 18 carbon atoms.
  • the present invention relates to the use of certain water-soluble or water-dispersible maleic anhydride/alpha-olefin polymers, or mixtures of the same, as stain-resists for fibrous polyamides.
  • a variety of linear and branched chain alpha-olefins can be used for the purposes of this invention.
  • Useful alpha-olefins are dienes containing 4 to 18 carbon atoms, such as butadiene, chloroprene, isoprene, and 2-methyl-1,5-hexadiene; 1-alkenes containing 4 to 8 carbon atoms, such as isobutylene, 1-butene, 1-hexene, 1-octene, with isobutylene being most preferred.
  • a part of the alpha-olefins can be replaced by other monomers, e.g. up to 50 wt% of vinyl acetate, vinyl chloride, vinylidine chloride, vinyl sulfides, N-vinyl pyrrolidone, acrylonitrile, acrylamide, as well as mixtures of the same.
  • a part (1-75%) of the maleic anhydride can be replaced by maleimide, N-alkyl(C 1-4 ) maleimides, N-phenyl-maleimide, fumaric acid, itaconic acid, citraconic acid, aconitic acid, crotonic acid, cinnamic acid, alkyl(C 1-18 ) esters of the foregoing acids, cycloalkyl(C 3-8 ) esters of the foregoing acids, sulfated castor oil, or the like.
  • At least 95 wt% of the maleic anhydride co- or terpolymers have a number average molecular weight of in the range between about 700 and 200,000, preferrably between about 1000 and 100,000.
  • water-soluble or water-dispersible interpolymers i.e. copolymers, terpolymers, and the like
  • maleic anhydride and one or more 1-alkenes having 4 to 8 carbon atoms particularly isobutylene, 1-hexene and 1-octene
  • polyamide substrates e.g. carpeting
  • Copolymers of maleic anhydride with propylene were found by the inventor to be less effective as stain-resists on such substrates than were interpolymers of maleic anhydride and 1-alkenes containing 4 to 8 carbon atoms.
  • copolymers of maleic anhydride and at least one olefin selected from ethylene and 1-alkenes having 10 to 24 carbon atoms impart no detectable stain-resistance to such substrates.
  • the maleic anhydride polymers useful in the present invention can be prepared according to methods well-known in the art.
  • the maleic anhydride polymers thus obtained are hydrolyzed to the free acid or their salts by reaction with water or alkali, or they are reacted with C 1-4 alkyl alcohol to provide polymeric alpha-olefin/maleic acid monoesters, which have stainblocking properties.
  • the hydrolyzed maleic anhydride polymer, or the monoester polymer should be sufficiently water-soluble that uniform application to a fibrous polyamide surface can be achieved at an appropriate acidity.
  • applications using water dispersions of the polymer mixed with a suitable surfactant may be used to impart stain-resistance.
  • stain-resists of the present invention can blend with other known stain-resists, such as phenol-formaldehyde condensation products as disclosed in U.S. Patents 4,833,009 and 4,965,325; methacrylic acid polymers disclosed in U.S. Patent No. 4,937,123; or hydrolized polymers of maleic anhydride and one or more ethylenically unsaturated aromatic compounds described by Fitzgerald et al., supra.
  • stain-resists of the present invention can blend with other known stain-resists, such as phenol-formaldehyde condensation products as disclosed in U.S. Patents 4,833,009 and 4,965,325; methacrylic acid polymers disclosed in U.S. Patent No. 4,937,123; or hydrolized polymers of maleic anhydride and one or more ethylenically unsaturated aromatic compounds described by Fitzgerald et al., supra.
  • the polymers suitable for the purposes of this invention contain between from 0.7 to 1.3 polymer units derived from one or more alpha-olefin monomers per polymer unit derived from maleic anhydride.
  • the alpha-olefin content of the polymers of this invention comprise between (a) 100 and 80 mol% of at least one 1-alkene containing 4 to 8 carbon atoms or terminally unsaturated diene containing 4 to 18 carbon atoms and (b) 0 to 20 mol% of at least one 1-alkene containing 3, or 10 to 18, carbon atoms.
  • Polymers containing about one polymer unit derived from one or more olefin monomers per polymer unit derived from maleic anhydride are most effective in imparting stain resistance to textile substrates.
  • the molecular weight of the polymers useful in the invention does not appear to be a limitation so long as the polymers are water-soluble or water-dispersible.
  • hydrolyzed isobutylene/maleic anhydride copolymers having number average molecular weights between about 6000 and 100,000 impart good stain-resistance to polyamide substrates.
  • water-soluble isobutylene/maleic anhydride copolymers having number average molecular weights between about 6000 and 100,000 remained in solution in water at 60°C.
  • the polymers suitable for the purposes of this invention can be prepared by hydrolyzing the maleic anhydride/olefin polymers according to methods well-known in the art. For example, they can be hydrolyzed to the free acid or their salts by reaction with water or alkali.
  • the maleic anhydride polymer should be sufficiently water-soluble that uniform application to a fiber surface can be achieved at an appropiate acidity.
  • applications using dispersions of the polymers with suitable surfactants may be used to impart stain-resistance.
  • olefin/maleic anhydride polymers disclosed herein are used in treating polyamide textile substrates. They can be effectively applied to polyamide fibrous substrates by a wide variety of methods known to those skilled in the art, such as:
  • the quantities of the polymers disclosed herein which are applied to the textile substrate are amounts effective in imparting stain-resistance to the substrate. Those amounts can be varied widely; in general, one can use between 1 and 5% by weight of them based on the weight of the textile substrate, usually 2.5% by weight or less.
  • the polymers can be applied, as is common in the art, at pHs ranging between about 2 and 7. However, more effective exhaust deposition can be obtained at a pH as low as 1.5. When the latter low pH is used, the preferred level of application to the textile substrate is about 2.5% by weight, based on the weight of the textile substrate. In an embodiment, a pH between about 2 and 3 is used.
  • stainblocking is obtained if the polymers are applied to the textile substrate at either 20°C followed by heat treatment at a temperature in the range between about 50 and 150°C for about 1 to 60 minutes, or applied at temperatures in the range between about 40 and 95°C for about 1 to 60 minutes. For example, at a pH between about 2 and 3, a temperature between about 70 and 90°C is preferred. However, stain-blocking can be obtained when application is effected even at that of cold tap water (10-15°C).
  • the polymers disclosed herein can also be applied in-place to polyamide carpeting which has already been installed in a dwelling place, office or other locale. They can be applied as a simple aqueous preparation or in the form of aqueous shampoo preparation, with or without one or more polyfluoro-organic oil-, water-, and/or soil-repellent materials. They may be applied at the levels described above, at temperatures described, and at a pH between about 1 and 12, preferably between about 2 and 9.
  • a 500 ml autoclave was charged with 40 g of maleic anhydride (0.408 mole), 300 ml of ethylbenzene and 4.3 g of 70 wt% of benzoyl peroxide. It was closed, vented twice with propylene and heated under stirring to 70 °C. The autoclave was then pressurized with propylene to 1379 kPa (200 psi). After agitation for 3 hours at 70°C, a solution of 2.7 g of 70 wt% benzoyl peroxide in 10 ml of ethylbenzene was blown into the reactor and the reaction was continued at 70°C for another 14 hours. The vessel was then cooled and vented.
  • the maleic anhydride/propylene copolymer product in form of a dispersion, was discharged and filtered giving 46.7 g of a white powder having a number average molecular weight, by gel permeation chromatography (GPC), of 2150.
  • GPC gel permeation chromatography
  • a portion of the solid copolymer (10 g) was hydrolyzed at 80-95°C in the presence of 82.5 g deionized water, 6.7 g 30 wt% sodium hydroxide and 2 drops of a 1% solution of benzyltriethylammonium chloride resulting after about 1 to 2 hours in a clear solution containing 10 wt% of a water-soluble maleic anhydride/propylene copolymer.
  • An isobutylene/maleic anhydride copolymer (50 parts) having a number average molecular weight (GPC) of 32,000, commercially available from Kuraray Co. (Japan) as "Isobam”-04, was reacted under agitation with methanol (50 parts) at reflux temperature (about 65°C) for 23 hours. Excess methanol was then removed at reduced pressure (20 mm Hg) at 70-90°C to give the isobutylene/maleic acid monomethyl ester which was then dissolved at room temperature in dilute ammonium hydroxide ( 2.5 parts of ammonia in 356 parts of water) to give a 14.5 wt % solution.
  • GPC number average molecular weight
  • Nylon fiber was treated with 1.2 wt% or 2.4 wt% stain resist at a goods-to-liquor ratio of 1:32 at a pH of 2.0 or 2.35 for 45 minutes at 80 or 95°C.
  • the fiber was then washed, air-dried and exposed at room temperature to a dye solution consisting of 0.2 g of FD&C Red Dye No. 40 and 3.2 g of citric acid in 1 liter of deionized water at a goods-to-liquor ratio of 1:40. After approximately 65 hours, the dye adsorbed onto the fiber was determined at a wavelength of 498-502 nm by comparing the absorbance with that of the Control.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (5)

  1. Substrat fibreux de polyamide sur lequel est déposée une quantité d'une composition efficace pour donner une résistance aux taches audit substrat comprenant un polymère d'alpha-oléfine/anhydride maléique soluble dans l'eau ou pouvant être dispersé dans l'eau ou un mélange desdits polymères, dans lequel ledit polymère contient de 0,7 à 1,3 unités de polymères dérivées d'un ou de plusieurs monomères d'alpha-oléfine par unité de polymère dérivée de l'anhydride maléique et il a été hydrolysé en acide libre ou en sel correspondant de celui-ci ou converti en un monoester de C1-4 alkyle, le contenu en alpha-oléfine dudit polymère comprenant entre (a) 100 et 80 pour-cent en moles d'au moins un alcène-1 contenant de 4 à 8 atomes de carbone ou un diène à terminaison insaturée contenant de 4 à 18 atomes de carbone et (b) 0 et 20 pour-cent en moles d'au moins un alcène-1 contenant de 3 ou 10 à 18 atomes de carbone.
  2. Substrat suivant la revendication 1, dans lequel ledit polymère contient environ une unité de polymère dérivée de l'anhydride maléique par unité de polymère dérivée d'un ou de plusieurs monomères d'alpha-oléfine.
  3. Substrat suivant la revendication 1 ou 2, dans lequel au moins 95% en poids desdits polymères possèdent un poids moléculaire moyen en nombre d'environ 700 à 200.000.
  4. Substrat suivant l'une quelconque des revendications précédentes, dans lequel jusqu'à 50% en poids de ladite alpha-oléfine sont remplacés par un ou plusieurs composés parmi l'acétate de vinyle, le chlorure de vinyle, le chlorure de vinylidène, le sulfure de vinyle, la N-vinylpyrrolidone, l'acrylonitrile ou l'acrylamide ou des mélanges de ces derniers.
  5. Substrat suivant l'une quelconque des revendications précédentes, dans lequel jusqu'à 75% en poids dudit anhydride maléique sont remplacés par le maléimide, des maléimides de N-alkyle (C1-14), le N-phénylmaléimide, l'acide fumarique, l'acide itaconique, l'acide citraconique, l'acide aconitique, l'acide crotonique, l'acide cinnamique, des esters d'alkyle (C1-18) ou de cycloalkyle (C3-8) des acides déjà cités ou d'huile de ricin sulfatée.
EP94203127A 1990-12-13 1991-12-13 Agents antitâches contenant des polymères d'anhydride maléique/oléfine Expired - Lifetime EP0648886B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US62688590A 1990-12-13 1990-12-13
US626885 1990-12-13
EP92903258A EP0562024B1 (fr) 1990-12-13 1991-12-13 Agents anti-taches contenant des polymeres d'olefine/d'anhydride maleique

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP92903258.9 Division 1991-12-13
EP92903258A Division EP0562024B1 (fr) 1990-12-13 1991-12-13 Agents anti-taches contenant des polymeres d'olefine/d'anhydride maleique

Publications (3)

Publication Number Publication Date
EP0648886A2 EP0648886A2 (fr) 1995-04-19
EP0648886A3 EP0648886A3 (fr) 1996-05-15
EP0648886B1 true EP0648886B1 (fr) 2001-04-25

Family

ID=24512269

Family Applications (2)

Application Number Title Priority Date Filing Date
EP92903258A Expired - Lifetime EP0562024B1 (fr) 1990-12-13 1991-12-13 Agents anti-taches contenant des polymeres d'olefine/d'anhydride maleique
EP94203127A Expired - Lifetime EP0648886B1 (fr) 1990-12-13 1991-12-13 Agents antitâches contenant des polymères d'anhydride maléique/oléfine

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP92903258A Expired - Lifetime EP0562024B1 (fr) 1990-12-13 1991-12-13 Agents anti-taches contenant des polymeres d'olefine/d'anhydride maleique

Country Status (9)

Country Link
EP (2) EP0562024B1 (fr)
JP (1) JPH06503386A (fr)
AU (1) AU660639B2 (fr)
CA (1) CA2098120A1 (fr)
DE (2) DE69132592T2 (fr)
IE (1) IE914340A1 (fr)
MX (1) MX9102558A (fr)
WO (1) WO1992010605A1 (fr)
ZA (1) ZA919847B (fr)

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MX9301644A (es) * 1992-03-25 1993-09-01 Du Pont Substrato fibroso de poliamida, composicion y proceso para impartir resistencia a la decoloracion a tal substrato.
AU6026994A (en) * 1993-02-02 1994-08-29 E.I. Du Pont De Nemours And Company Durable hydrolized maleic anhydride polymer stain-resists
US5520962A (en) * 1995-02-13 1996-05-28 Shaw Industries, Inc. Method and composition for increasing repellency on carpet and carpet yarn
US5770656A (en) * 1995-09-22 1998-06-23 E.I. Du Pont De Nemours And Company Partial fluoroesters or thioesters of maleic acid polymers and their use as soil and stain resists
DE69724765T2 (de) * 1996-02-23 2004-07-15 E.I. Du Pont De Nemours And Co., Wilmington Schmutzabweisende mischungen aus polymeren mit carboxylgruppen und resol-harzen
US6197378B1 (en) 1997-05-05 2001-03-06 3M Innovative Properties Company Treatment of fibrous substrates to impart repellency, stain resistance, and soil resistance
CA2324949A1 (fr) 1998-03-24 1999-09-30 Avantgarb, Llc Tissu et autres matieres modifiees, procedes d'obtention
US6380336B1 (en) 1998-03-24 2002-04-30 Nano-Tex, Llc Copolymers and oil-and water-repellent compositions containing them
US6117353A (en) * 1999-01-11 2000-09-12 3M Innovative Properties Company High solids spin finish composition comprising a hydrocarbon surfactant and a fluorochemical emulsion
US6077468A (en) * 1999-01-11 2000-06-20 3M Innovative Properties Company Process of drawing fibers
US6120695A (en) * 1999-01-11 2000-09-19 3M Innovative Properties Company High solids, shelf-stable spin finish composition
US6068805A (en) * 1999-01-11 2000-05-30 3M Innovative Properties Company Method for making a fiber containing a fluorochemical polymer melt additive and having a low melting, high solids spin finish
US6537662B1 (en) 1999-01-11 2003-03-25 3M Innovative Properties Company Soil-resistant spin finish compositions
US6207088B1 (en) 1999-01-11 2001-03-27 3M Innovative Properties Company Process of drawing fibers through the use of a spin finish composition having a hydrocarbon sufactant, a repellent fluorochemical, and a fluorochemical compatibilizer
CN100506927C (zh) 2005-03-21 2009-07-01 刘景春 多质离散效应纳米结构液膜及其制备方法和应用
US7579403B2 (en) 2006-04-04 2009-08-25 E. I. Du Pont De Nemours And Company Stain resist comprising hyperbranched maleic anhydride-diene polymers
US7579420B2 (en) 2006-04-04 2009-08-25 E. I. Du Pont De Nemours And Company Hyperbranched maleic anhydride-diene polymers
US7914890B2 (en) 2007-12-19 2011-03-29 E.I. Dupont De Nemours And Company Cyclic olefin-maleic acid copolymers for stain resists
CA2929570C (fr) 2013-11-11 2021-11-30 Ecolab Usa Inc. Detergent de lavage fortement alcalin offrant un meilleur controle du tartre et une meilleure dispersion des salissures

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Publication number Priority date Publication date Assignee Title
US4623683A (en) 1984-10-12 1986-11-18 S.C. Johnson & Son, Inc. Fabric finish with alpha olefin resins and process
US4871823A (en) * 1987-09-11 1989-10-03 S. C. Johnson & Son, Inc. 1-Alkene/excess maleic anhydride polymers
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
AU627711B2 (en) 1988-03-11 1992-09-03 Minnesota Mining And Manufacturing Company Process for providing polyamide materials with stain resistance

Also Published As

Publication number Publication date
CA2098120A1 (fr) 1992-06-14
DE69109694T2 (de) 1996-01-11
DE69132592T2 (de) 2001-10-18
DE69132592D1 (de) 2001-05-31
AU660639B2 (en) 1995-07-06
EP0648886A3 (fr) 1996-05-15
JPH06503386A (ja) 1994-04-14
DE69109694D1 (de) 1995-06-14
AU9157391A (en) 1992-07-08
EP0562024B1 (fr) 1995-05-10
MX9102558A (es) 1992-06-01
EP0562024A1 (fr) 1993-09-29
ZA919847B (en) 1993-06-14
EP0648886A2 (fr) 1995-04-19
WO1992010605A1 (fr) 1992-06-25
IE914340A1 (en) 1992-06-17

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