EP0632856B1 - Fleckabweisende zusammensetzung fuer polyamidsubstrate - Google Patents

Fleckabweisende zusammensetzung fuer polyamidsubstrate Download PDF

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Publication number
EP0632856B1
EP0632856B1 EP93908582A EP93908582A EP0632856B1 EP 0632856 B1 EP0632856 B1 EP 0632856B1 EP 93908582 A EP93908582 A EP 93908582A EP 93908582 A EP93908582 A EP 93908582A EP 0632856 B1 EP0632856 B1 EP 0632856B1
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EP
European Patent Office
Prior art keywords
composition
maleic anhydride
stain
alpha
acid
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Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
EP93908582A
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English (en)
French (fr)
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EP0632856A1 (de
Inventor
Engelbert Pechhold
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of EP0632856A1 publication Critical patent/EP0632856A1/de
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Anticipated expiration legal-status Critical
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M15/263—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
    • D06M15/37—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

Definitions

  • the present invention relates to polymeric stain-resist compositions.
  • 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 composition containing a sulfonated phenol-formaldehyde condensation product to the substrate.
  • sulfonated phenolformaldehyde condensation products are themselves subject to discoloration; commonly they turn yellow. Yellowing problems are described by W. H. Hemmpel in a March 19, 1932 article in America's Textiles , entitled "Reversible Yellowing Not Finisher's Fault".
  • WO-A-92 10605 discloses and claims polyamide fibrous substrates treated with water-soluble or water-dispersible maleic anhydride/alpha-olefin polymers to make them stain resistant and methods for preparing them.
  • the present invention provides a composition useful for imparting stain resistance to a polyamide fibrous substrate comprising
  • compositions of the present invention show enhanced durability to shampoo washing of polyamide substrates treated with the compositions.
  • the invention provides stain resists which are more resistant to yellowing when exposed to UV light or NO x gases than are the sulfonated phenol/formaldehyde condensates.
  • At least some embodiments of the invention seek to provide a stain-resistant composition capable of imparting good stain resistance together with a low propensity to yellowing and having good substantive properties.
  • a further problem associated with prior art compositions is that they have low solubility in water at the low pH preferably used to treat textile articles unless surfactant is used.
  • At least some embodiments of the invention seek to provide a stain-resistant composition having a good water-solubility.
  • the two components may be blended together in a wide range of relative proportions.
  • the weight ratio of maleic anhydride copolymer to resin may lie in the range of between about 95:5 and 5:95, preferably between about 90:10 and about 10:90, more preferably between about 60:40 40:60.
  • the pH of the blend is adjusted to the required pH preferably in the range about 1 to 3 more preferably 1.5 to 2.5 with acid.
  • the stain-resistant compostion of the present invention remains clear at such low pH. This finding is advantageous since the stain-resistant compostion of this invention need not contain any surfactant to solubilize the active ingredient. If desired however, the composition may contain a surfactant. Higher pH in the range up to about pH 7 to 9 may be used as well.
  • copolymers useful for the purposes of this invention comprise one or more water-soluble or water-dispersible hydrolyzed maleic anhydride polymers.
  • alpha-olefins A variety of linear and branched chain alpha-olefins can be used for the purposes of this invention.
  • the used 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, and the like, with isobutylene being most preferred.
  • alpha-olefins can be replaced by other monomers, e.g., up to 50 wt% of alkyl (C1 ⁇ 4) acrylates, alkyl (C1 ⁇ 4) methacrylates, vinyl sulfides, N-vinyl pyrrolidone, acrylonitrile, acrylamide, as well as mixture of the same.
  • a part (preferably 1-75% by weight) of the maleic anhydride can be replaced by maleimide.
  • 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, preferably between about 1,000 and 100,000.
  • the maleic anhydride copolymers 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 aqueous 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 copolymers suitable for the purposes of this invention contain between about 0.7 and 1.3 polymer units derived from one ore more alpha-olefin monomers per polymer unit derived from maleic anhydride.
  • the alpha-olefin content of the copolymers 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.
  • Copolymers 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 copolymers useful in the invention does not appear to be a limitation so long as the copolymers are water-soluble or water-dispersible.
  • hydrolyzed isobutylene/maleic anhydride copolymer having number average molecular weights between about 6,000 and 100,000 impart good stain-resistance to polyamide substrates.
  • Even at a pH as low as 1.5 water-soluble isobutylene/maleic anhydride copolymers having number average molecular weights between about 6,000 and 100,000 remained in solution in water at 60°C.
  • copolymers suitable for the purposes of this invention can be prepared by hydrolyzing the maleic anhydride/olefin copolymers 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.
  • Suitable maleic anhydride copolymers can conveniently obtained by hydrolysis of "Isobam”-01, an isobutylene maleic anhydride copolymer of molecular weight around 10,000, "Isobam”-04 a similar polymer having a molecular weight of around 40,000 or "Isobam”-10 a similar polymer having a molecular weight of around 100,000 with sodium hydroxide.
  • Other suitable maleic anhydride copolymers include BM-30 available from Kuraray Co. (Japan). BM-30 is an isobutylene/maleic anhydride/N-phenylmaleimide terpolymer having a molecular weight of around 40,000.
  • a commercially available product usable without further treating is "Lindron" 10 (ex Lindau Chemical), a butadiene/maleic anhydride copolymer having a molecular weight of about 5,000 to 10,000.
  • Other suitable copolymers include monoesters of C4 ⁇ 8 alpha-olefin/maleic anhydride copolymers. The monoesters can be obtained by a range of reactions well known to those skilled in the art.
  • a preferred method is by reaction with an alcohol by heating under reflux with the alcohol and then removing excess alcohol.
  • Preferred alcohols are C1 ⁇ 6 alcohols especially methanol and ethanol.
  • the sulfonated phenol-formaldehyde condensation products which can be used for the purposes of this invention include any sulfonated hydroxy aromatic-formaldehyde condensation products which have been described in the prior art as being useful as dye-resist agents or dye-fixing agents, in other words, dye-reserving agents or agents which improve wetfastness or dyeings on polyamide fibers. See for example US-A-4,592,940, US-A-4,591,591, US-A-3,790,344 and GB-A-1,291,784, the disclosure of which is specifically incorporated herein by reference.
  • condensation products suitable for the invention are MESITOL NBS, product of Bayer AG (a condensation product prepared from bis(4-hydroxyphenyl)-sulfone, formaldehyde, and phenol sulfonic acid; US-A-3,790,344), as well as "Erional” NW, a product of Ciba-Geigy Corp., (formed by condensing a mixture of naphthalene monosulfonic acid, bis(hydroxyphenyl) sulfone and formaldehyde; US-A-3,716,393) and "Erional" LY.
  • the sulfonated hydroxyaromatic formaldehyde products sold as "Stainfree” by Cybron Chemicals and "Algard” NS by Allied Colloid Co. are also suitable.
  • the stain-resistant composition 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.
  • the stain-resist components of the present invention can be applied to the substrate separately or together as a blend.
  • stain-resistance of polyamide substrates is slightly better if the maleic anhydride/olefin polymer is applied to the polyamide substrate followed by the sulfonated phenol/formaldehyde condensate.
  • carpet mills in general prefer to apply components of a stain-resist mixture together, and such would be expected with the composition of this invention.
  • the stain resistant compositions of this invention can be applied by the foregoing methods to dyed or undyed polyamide textile substrates.
  • they can be applied to such substrates in the absence or presence of a polyfluoroorganic oil-, water-, and/or soil-repellent materials.
  • a polyfluoroorganic material can be applied to the textile substrate before or after application of the compositions of this invention thereto.
  • stain-resistant compositions are applied to the textile substrate at either 20°C followed by heat treatment at a temperature in the range between about 50 to 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.
  • a temperature between about 70 and 90°C is preferred.
  • stain-blocking can be obtained when application is effected even at that of cold tap water (10-15°C).
  • the stain-resistant compositions of this invention can also be applied in situ 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 polyfluoroorganic oil-, water-, and/or soil- repellent materials. They may be applied at the levels described above, at temperature described, and at a pH between about 1 and 9, preferably between about 2 and 7.
  • a light blue dyed cut-pile carpet constructed from 70 oz/sq yd 102 ⁇ 2.8 ⁇ 10 ⁇ 2 kg yd ⁇ 0.9144 m inch ⁇ 2.54 cm superba-set BCF nylon 66 is treated in a laboratory Beck apparatus for 20 minutes at 80°C (176°F) at a 20:1 liquor-to-goods ratio with a solution of a stain resist agent described in one of the examples of pH of 2.0 and in the presence of 2.0 g per liter of magnesium sulfate to give an application load of 0.8% owf. Based on active ingredients.
  • the carpet was then rinsed under tap water, partially de-watered by squeezing and dried in an forced-air oven for about 20 minutes at 121°C (250°F).
  • a commercially available latex composition (Textile Rubber Co. Calhoun, GA) was applied as to carpet backing adhesive, with a secondary polypropylene backing under the trade name Actionbac (AMOCO, Atlanta, GA).
  • a carpet specimen (3x5 inch) 102 ⁇ 2.8 ⁇ 10 ⁇ 2 kg yd ⁇ 0.9144 m inch ⁇ 2.54 cm was placed on a flat non-absorbent surface.
  • 20 ml of a solution made from 45 g of cherry-flavored, sugar sweetened, commercially available dilutable soft drink containing FD&C Red Dye No. 40 and 500 ml of water was poured into a 2-inch 102 ⁇ 2.8 ⁇ 10 ⁇ 2 kg yd ⁇ 0.9144 m inch ⁇ 2.54 cm diameter cylinder which was tightly placed over the specimen. The cylinder was removed after all the liquid had been absorbed.
  • a stain rating of 5 is excellent, showing outstanding stain resistance, whereas 1 is the worst rating comparable to an untreated control sample.
  • a 3x5 inch carpet specimen was submerged for 5 minutes at room temperature in a detergent solution consisting of Duponol WAQE (1.5 g per liter) and adjusted with dilute sodium carbonate to a pH of 10 ⁇ 0.1. The specimen was then removed, rinsed thoroughly under tap water, de-watered by squeezing and air-dried. The dry carpet specimen was then tested according to the stain test described above.
  • Example 3 To 364.8 g of the polymer used in Example 3 was added under agitation at room temperature 50 g of a sulfonated hydroxyaromatic formaldehyde condensate available from Allied Colloid Co. as "Algard" NS (30% active ingredients) to give a clear brownish liquid having an active ingredient content of about 24.1%. This material remained clear at a pH of 2.0 at any desired concentration.

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

Claims (12)

  1. Zusammensetzung, die geeignet ist, um einem faserigen Polyamidsubstrat Fleckenechtheit zu verleihen, umfassend:
    (A) ein wasserlösliches oder wasserdispergierbares α-Olefinl/Maleinsäureanhydrid-Copolymer oder ein Gemisch von Copolymeren, worin das Copolymer pro Polymereinheit, die von Maleinsäureanhydrid stammt, zwischen etwa 0,7 und 1,3 Polymereinheiten, die von einem oder mehreren α-Olefin-Monomeren stammen, enthält, wobei der α-Olefin-Gehalt des Copolymeren zwischen (i) 100 und 80 Mol-% von wenigstens einem 1-Alken, das 4 bis 8 Kohlenstoffatome enthält, oder einem endständig ungesättigten Dien, das 4 bis 18 Kohlenstoffatome enthält, und (ii) 0 bis 20 Mol-% von wenigstens einem 1-Alken, das 3 oder 10 bis 18 Kohlenstoffatome enthält, umfaßt, und
    (B) ein sulfoniertes Phenol-Formaldehyd-Kondensationsprodukt, wobei das Gewichtsverhältnis von A:B im Bereich zwischen 5:95 und 95:5 liegt.
  2. Zusammensetzung nach Anspruch 1, worin das Gewichtsverhältnis im Bereich zwischen 90:10 und 10:90 liegt.
  3. Zusammensetzung nach Anspruch 1, worin das Gewichtsverhältnis im Bereich zwischen 60:40 und 40:60 liegt.
  4. Zusammensetzung nach Anspruch 1, worin wenigstens 95 Gew.-% der Maleinsäureanhydrid-Copolymeren ein Zahlenmittelmolekulargewicht von 700 bis 200 000 besitzen.
  5. Zusammensetzung nach Anspruch 4, worin wenigstens 95 Gew.-% der Maleinsäureanhydrid-Copolymeren ein Zahlenmittelmolekulargewicht von 1 000 bis 100 000 besitzen.
  6. Zusammensetzung nach einem der Ansprüche 1 bis 5, worin das Copolymer etwa eine Polymereinheit, die von Maleinsäureanhydrid stammt, pro Polymereinheit, die von einem oder mehreren α-Olefin-Monomeren stammt, enthält.
  7. Zusammensetzung nach Anspruch 6, worin wenigstens eines der 1-Alkene Isobutylen ist.
  8. Zusammensetzung nach Anspruch 1, worin bis zu 50 Gew.-% des genannten α-Olefins durch ein oder mehrere von C₁- bis C₄-Alkylacrylat oder -methacrylat, Vinylacetat, Vinylchlorid, Vinylidenchlorid, Vinylsulfid, N-Vinylpyrrolidon, Acrylnitril oder Acrylamid oder durch Gemische derselben ersetzt sind.
  9. Zusammensetzung nach Anspruch 1, worin bis zu 75 Gew.-% des genannten Maleinsäureanhydrids durch Maleinid, N-Alkyl-(C₁₋₄)-Maleimide, N-Phenylmaleimid, Fumarsäure, Itaconsäure, Citraconsäure, Aconitinsäure, Crotonsäure, Zimtsäure, Alkyl-(C₁₋₁₈)- oder Cycloalkyl-(C₃₋₈)-Ester der vorgenannten Säuren oder durch sulfatiertes Rizinusöl ersetzt sind.
  10. Zusammensetzung nach Anspruch 1, worin bis zu 30 Gew.-% des Maleinsäureanhydrids durch Acryl- oder Methacrylsäure ersetzt sind.
  11. Faseriges Polyamidsubstrat, das darauf abgelagert die Zusammensetzung nach einem der Ansprüche 1 bis 10 in einer Menge, die wirksam ist, um dem Substrat Fleckenechtheit zu verleihen, aufweist.
  12. Verfahren, um einem textilen Polyamidsubstrat Fleckenechtheit zu verleihen, das umfaßt Auftragen auf das Substrat, zusammen oder getrennt, der Komponenten A und B mit den Zusammensetzungen nach einem der Ansprüche 1 bis 10 in Mengen, die wirksam sind, um dem genannten Substrat Fleckenechtheit zu verleihen.
EP93908582A 1992-03-25 1993-03-25 Fleckabweisende zusammensetzung fuer polyamidsubstrate Expired - Lifetime EP0632856B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US85717992A 1992-03-25 1992-03-25
US85717892A 1992-03-25 1992-03-25
US857179 1992-03-25
US857178 1992-03-25
PCT/US1993/002805 WO1993019238A1 (en) 1992-03-25 1993-03-25 Stain-resists for polyamide substrates

Publications (2)

Publication Number Publication Date
EP0632856A1 EP0632856A1 (de) 1995-01-11
EP0632856B1 true EP0632856B1 (de) 1995-10-11

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EP93908582A Expired - Lifetime EP0632856B1 (de) 1992-03-25 1993-03-25 Fleckabweisende zusammensetzung fuer polyamidsubstrate

Country Status (7)

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EP (1) EP0632856B1 (de)
JP (1) JP3271766B2 (de)
AU (1) AU664268B2 (de)
CA (1) CA2132731C (de)
DE (1) DE69300635T2 (de)
MX (1) MX9301644A (de)
WO (1) WO1993019238A1 (de)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994018376A1 (en) * 1993-02-02 1994-08-18 E.I. Du Pont De Nemours And Company Durable hydrolized maleic anhydride polymer stain-resists
US5436049A (en) * 1993-12-21 1995-07-25 Basf Corporation Process for the manufacture of a stain resistant carpet
US5520962A (en) * 1995-02-13 1996-05-28 Shaw Industries, Inc. Method and composition for increasing repellency on carpet and carpet yarn
US5670246A (en) * 1995-09-22 1997-09-23 E. I. Du Pont De Nemours And Company Treatment of polyamide materials with partial fluoroesters or fluorothioesters of maleic acid polymers and sulfonated aromatic condensates
AU4908896A (en) * 1996-01-31 1997-08-22 Minnesota Mining And Manufacturing Company Compositions and methods for imparting stain resistance and stain resistant articles
CN1141439C (zh) * 1997-05-05 2004-03-10 美国3M公司 赋予防护性、抗着色性和抗污性的纤维基质的处理
US6197378B1 (en) * 1997-05-05 2001-03-06 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
US6120695A (en) * 1999-01-11 2000-09-19 3M Innovative Properties Company High solids, shelf-stable spin finish composition
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
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
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
US7914890B2 (en) 2007-12-19 2011-03-29 E.I. Dupont De Nemours And Company Cyclic olefin-maleic acid copolymers for stain resists

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5057121A (en) * 1989-08-04 1991-10-15 E. I. Du Pont De Nemours And Company Process for imparting stain-resist agent
EP0562024B1 (de) * 1990-12-13 1995-05-10 E.I. Du Pont De Nemours And Company Fleckabweiser aus maleinsäureanhydrid/olefin-polymeren

Also Published As

Publication number Publication date
DE69300635D1 (de) 1995-11-16
JPH07505450A (ja) 1995-06-15
MX9301644A (es) 1993-09-01
AU3935393A (en) 1993-10-21
CA2132731C (en) 2006-06-20
EP0632856A1 (de) 1995-01-11
WO1993019238A1 (en) 1993-09-30
JP3271766B2 (ja) 2002-04-08
AU664268B2 (en) 1995-11-09
CA2132731A1 (en) 1993-09-30
DE69300635T2 (de) 1996-05-15

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