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WO1992010605A1 - Agents anti-taches contenant des polymeres d'olefine/d'anhydride maleique - Google Patents

Agents anti-taches contenant des polymeres d'olefine/d'anhydride maleique Download PDF

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Publication number
WO1992010605A1
WO1992010605A1 PCT/US1991/009155 US9109155W WO9210605A1 WO 1992010605 A1 WO1992010605 A1 WO 1992010605A1 US 9109155 W US9109155 W US 9109155W WO 9210605 A1 WO9210605 A1 WO 9210605A1
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WO
WIPO (PCT)
Prior art keywords
maleic anhydride
polymer
alpha
substrate
olefin
Prior art date
Application number
PCT/US1991/009155
Other languages
English (en)
Inventor
Engelbert Pechhold
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to EP92903258A priority Critical patent/EP0562024B1/fr
Priority to DE69109694T priority patent/DE69109694T2/de
Priority to AU91573/91A priority patent/AU660639B2/en
Priority to JP4503687A priority patent/JPH06503386A/ja
Publication of WO1992010605A1 publication Critical patent/WO1992010605A1/fr

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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. For example, Liss et al., in U.S. Patent No.
  • 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 styrene- maleic 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 U.S. Patent Application Serial No. 07/502819, filed 2 April 1990, 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.
  • the present invention provides polyamide fibrous substrates treated with water-soluble or water-dispersible maleic anhydride/alpha-olefin polymers so as to impart stain-resistance to the substrates, and methods for preparing the same.
  • 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 relates to the use of 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.
  • alpha-olefins are dienes containing 4 to 18 carbon atoms, such as butadiene, chloroprene, isoprene, and 2-methyl-l,5-hexadiene; 1-alkenes containing 4 to 8 carbon atoms, preferably C -1 0 such as isobutylene, 1-butene, 1-hexene, 1-octene, and the like, with isobutylene being most preferred.
  • a part of the alpha-olefins can be replaced by other monomers, e.g.
  • maleic anhydride A part (1-75%) of the maleic anhydride can be replaced by maleimide, N-alkyl(C ⁇ -4) maleimides, N-phenyl-maleimide, fumaric acid, itaconic acid, citraconic acid, aconitic acid, crotonic acid, cinnamic acid, alkyl(C ⁇ _i 8 ) esters of the foregoing acids, cycloalkyl(C3_ 8 ) esters of the foregoing acids, sulfated castor oil, or the like.
  • maleimide N-alkyl(C ⁇ -4) maleimides, N-phenyl-maleimide, fumaric acid, itaconic acid, citraconic acid, aconitic acid, crotonic acid, cinnamic acid, alkyl(C ⁇ _i 8 ) esters of the foregoing acids, cycloalkyl(C3_ 8 ) esters of the foregoing acids, sulf
  • 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, l-hexene and 1-octene
  • polyamide substrates e.g. carpeting
  • Copolymers of maleic anhydride with butadiene or 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 ethyleen 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 can be hydrolyzed to the free acid or their salts by reaction with water or alkali, or they can also be reacted with C1-4 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 about 0.7 and 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.
  • the olefin/maleic anhydride polymers of this invention can be used as such 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: padding, spraying, foaming in conjunction with foaming agents, batch exhaust in beck dyeing equipment, or continuous exhaust during a continuous dyeing operation. They can be applied by such methods to dyed or undyed polyamide textile substrates. In addition, they can be applied to such substrates in the absence or presence of a polyfluoroorgani ⁇ oil-, water-, and/or soil- repellent materials. In the alternative, such a polyfluoroorganic material can be applied to the textile substrate before or after application of the polymers of this invention thereto.
  • the quantities of the polymers of this invention 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 of this invention 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 deg.C. The autoclave was then pressurized with propylene to 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 benzyl- triethylammonium chloride resulting after about 1 to 2 hours in a clear solution containing 10 wt% of a water-soluble maleic anhydride/propylene copolymer.
  • Example 2 A 1% aqueous solution of the resulting water-soluble maleic anhydride/isobutylene copolymer at
  • EXAMPLE 8 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

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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)

Abstract

L'invention concerne un substrat fibreux en polyamide sur lequel est déposée une quantité d'une composition efficace pour conférer audit substrat une résistance aux taches, ladite composition comprenant un polymère soluble dans l'eau ou dispersible dans l'eau à base d'alpha-oléfine/d'anhydride maléique ou un mélange desdits polymères. L'invention concerne également des procédés de préparation desdits substrats. Le polymère d'anhydride maléique est utilisé soit sous sa forme hydrolysée soit sous sa forme résultant de sa réaction avec un alcool d'alkyle inférieur, de façon à produire un polymère d'alpha-oléfine/ester de monoalkyle d'acide maléique.
PCT/US1991/009155 1990-12-13 1991-12-13 Agents anti-taches contenant des polymeres d'olefine/d'anhydride maleique WO1992010605A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP92903258A EP0562024B1 (fr) 1990-12-13 1991-12-13 Agents anti-taches contenant des polymeres d'olefine/d'anhydride maleique
DE69109694T DE69109694T2 (de) 1990-12-13 1991-12-13 Fleckabweiser aus maleinsäureanhydrid/olefin-polymeren.
AU91573/91A AU660639B2 (en) 1990-12-13 1991-12-13 Maleic anhydride/olefin polymer stain-resists
JP4503687A JPH06503386A (ja) 1990-12-13 1991-12-13 マレイン酸無水物／オレフィンポリマーステインレジスト

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US626,885 1984-07-02
US62688590A 1990-12-13 1990-12-13

Publications (1)

Publication Number Publication Date
WO1992010605A1 true WO1992010605A1 (fr) 1992-06-25

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Application Number Title Priority Date Filing Date
PCT/US1991/009155 WO1992010605A1 (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) EP0648886B1 (fr)
JP (1) JPH06503386A (fr)
AU (1) AU660639B2 (fr)
CA (1) CA2098120A1 (fr)
DE (2) DE69109694T2 (fr)
IE (1) IE914340A1 (fr)
MX (1) MX9102558A (fr)
WO (1) WO1992010605A1 (fr)
ZA (1) ZA919847B (fr)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993019238A1 (fr) * 1992-03-25 1993-09-30 E.I. Du Pont De Nemours And Company Revetements antitaches pour substrats de polyamide
WO1994018376A1 (fr) * 1993-02-02 1994-08-18 E.I. Du Pont De Nemours And Company Composition anti-tache a base de polymere anhydride maleique hydrolyse et durable
US5708087A (en) * 1996-02-23 1998-01-13 E. I. Du Pont De Nemours And Company Carboxylic acid-containing polymer/resole stain-resists
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
EP0758928A4 (fr) * 1995-02-13 1998-12-02 Shaw Ind Inc Procede de traitement de fil pour tapis et de tapis
WO1999049124A3 (fr) * 1998-03-24 1999-12-09 Avantgarb Llc Tissus et autres matieres modifiees, procedes d'obtention
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
US6077468A (en) * 1999-01-11 2000-06-20 3M Innovative Properties Company Process of drawing fibers
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
US6120695A (en) * 1999-01-11 2000-09-19 3M Innovative Properties Company High solids, shelf-stable spin finish composition
US6197378B1 (en) 1997-05-05 2001-03-06 3M Innovative Properties Company Treatment of fibrous substrates to impart repellency, stain resistance, and soil resistance
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
US6380336B1 (en) 1998-03-24 2002-04-30 Nano-Tex, Llc Copolymers and oil-and water-repellent compositions containing them
US6537662B1 (en) 1999-01-11 2003-03-25 3M Innovative Properties Company Soil-resistant spin finish compositions
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
US7772290B2 (en) 2005-03-21 2010-08-10 Ho Cheong Poon Method to prepare a nanosized-structure film of multi-phobic effects and its application
US7914890B2 (en) 2007-12-19 2011-03-29 E.I. Dupont De Nemours And Company Cyclic olefin-maleic acid copolymers for stain resists
US9353335B2 (en) 2013-11-11 2016-05-31 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion

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WO1993019238A1 (fr) * 1992-03-25 1993-09-30 E.I. Du Pont De Nemours And Company Revetements antitaches pour substrats de polyamide
WO1994018376A1 (fr) * 1993-02-02 1994-08-18 E.I. Du Pont De Nemours And Company Composition anti-tache a base de polymere anhydride maleique hydrolyse et durable
EP0758928A4 (fr) * 1995-02-13 1998-12-02 Shaw Ind Inc Procede de traitement de fil pour tapis et de tapis
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
US5708087A (en) * 1996-02-23 1998-01-13 E. I. Du Pont De Nemours And Company Carboxylic acid-containing polymer/resole stain-resists
US6197378B1 (en) 1997-05-05 2001-03-06 3M Innovative Properties Company Treatment of fibrous substrates to impart repellency, stain resistance, and soil resistance
US6379753B1 (en) 1998-03-24 2002-04-30 Nano-Tex, Llc Modified textile and other materials and methods for their preparation
WO1999049124A3 (fr) * 1998-03-24 1999-12-09 Avantgarb Llc Tissus et autres matieres modifiees, procedes d'obtention
US6617267B2 (en) 1998-03-24 2003-09-09 Nano-Tex, Llc Modified textile and other materials and methods for their preparation
US6380336B1 (en) 1998-03-24 2002-04-30 Nano-Tex, Llc Copolymers and oil-and water-repellent compositions containing them
US6613862B2 (en) 1998-04-30 2003-09-02 3M Innovative Properties Company Treatment of fibrous substrates to impart repellency, stain resistance, and soil resistance
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
US6120695A (en) * 1999-01-11 2000-09-19 3M Innovative Properties Company High solids, shelf-stable spin finish composition
US6468452B1 (en) 1999-01-11 2002-10-22 3M Innovative Properties Company Process of drawing fibers
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
US6536804B1 (en) 1999-01-11 2003-03-25 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
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
US6472476B1 (en) 2000-01-18 2002-10-29 Nano-Tex, Llc Oil- and water-repellent finishes for textiles
US7772290B2 (en) 2005-03-21 2010-08-10 Ho Cheong Poon Method to prepare a nanosized-structure film of multi-phobic effects and its application
US7579420B2 (en) 2006-04-04 2009-08-25 E. I. Du Pont De Nemours And Company Hyperbranched maleic anhydride-diene polymers
US7579403B2 (en) 2006-04-04 2009-08-25 E. I. Du Pont De Nemours And Company Stain resist comprising hyperbranched maleic anhydride-diene polymers
US7790822B2 (en) 2006-04-04 2010-09-07 E.I. Du Pont De Nemours And Company Hyperbranched maleic anhydride-diene polymers
US7833585B2 (en) 2006-04-04 2010-11-16 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
US9353335B2 (en) 2013-11-11 2016-05-31 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
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Also Published As

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EP0648886A2 (fr) 1995-04-19
IE914340A1 (en) 1992-06-17
DE69109694D1 (de) 1995-06-14
DE69109694T2 (de) 1996-01-11
DE69132592D1 (de) 2001-05-31
AU9157391A (en) 1992-07-08
DE69132592T2 (de) 2001-10-18
ZA919847B (en) 1993-06-14
EP0648886B1 (fr) 2001-04-25
EP0562024A1 (fr) 1993-09-29
EP0562024B1 (fr) 1995-05-10
CA2098120A1 (fr) 1992-06-14
JPH06503386A (ja) 1994-04-14
AU660639B2 (en) 1995-07-06
MX9102558A (es) 1992-06-01
EP0648886A3 (fr) 1996-05-15

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