WO1994018376A1 - Composition anti-tache a base de polymere anhydride maleique hydrolyse et durable - Google Patents

Composition anti-tache a base de polymere anhydride maleique hydrolyse et durable Download PDF

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Publication number
WO1994018376A1
WO1994018376A1 PCT/US1994/000438 US9400438W WO9418376A1 WO 1994018376 A1 WO1994018376 A1 WO 1994018376A1 US 9400438 W US9400438 W US 9400438W WO 9418376 A1 WO9418376 A1 WO 9418376A1
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WO
WIPO (PCT)
Prior art keywords
stain
maleic anhydride
resistance
resist
ethylenically unsaturated
Prior art date
Application number
PCT/US1994/000438
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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
Priority claimed from US08/012,792 external-priority patent/US5358769A/en
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to AU60269/94A priority Critical patent/AU6026994A/en
Publication of WO1994018376A1 publication Critical patent/WO1994018376A1/fr

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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
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • 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
    • D06M15/55—Epoxy resins

Definitions

  • the present invention relates to novel compositions and processes for imparting more durable stain-resistance to polyamide fiber substrates.
  • compositions which impart resistance to staining by an acid dye such as FD&C Red Dye No. 40.
  • Such compositions are commonly referred to as stain-resists or stain-resist agents.
  • one class of known stain-resist agents comprises one or more sulfonated hydroxyaromatic-formaldehyde condensation products, for example, phenol-formaldehyde condensation products or formaldehyde-naphthol condensates.
  • stain-resist agents based on such condensation products are applied to polyamide substrates, they provide acid dye stain-resistance which resists removal by shampooing. But such treated substrates are prone to yellowing on exposure to ultraviolet light (UV) or to nitrogen oxides (NOx), or to combinations of UV and NOx exposure.
  • stain-resists involves the use of hydrolyzed copolymers derived from maleic anhydride and ethylenically unsaturated compounds. Examples include hydrolyzed copolymers of maleic anhydride and one or more of the following comonomers: ethylenically unsaturated aromatics, alpha-olefins, alkyl vinyl ethers, and alkyl allyl ethers. Due to the ionic character of stain-resist agents based on hydrolyzed maleic anhydride copolymers, polyamide fiber substrates treated with such stain-resists tend to be sensitive to high pH values, such as those that may often be encountered in commercial rug shampoos.
  • Epoxy resins can be cured with carboxylic or polycarboxylic acids, and epoxy resins in combination with carboxylic acid-containing polymers can be applied to fiber substrates. For example, combinations of epoxy resins and copolymers of methacrylic acid have been applied to carpets and carpet yarns as anti-soilants for carpets and carpet yarns.
  • the present invention provides compositions and processes of using them which at the same time impart resistance to staining of polyamide substrates caused by acid dyes and improved durability to shampooing and resistance to yellowing caused by exposure to UV and/or NO x . It has been found in accordance with the present invention that the stain-resist performance of hydrolyzed maleic anhydride copolymers can be dramatically improved either by co-applying the stain-resist with a water- dispersed epoxy resin or by post-treatment of the stain-resist-treated polyamide fiber substrate with a water-dispersed epoxy resin.
  • the current invention provides a means to render the stain-resist agents less soluble by crosslinking the stain-resist agent so that the stain-resist properties of a stain-resist-treated polyamide substrate are retained to a greater extent after the treated substrate has been shampooed.
  • the present invention provides a method of combining epoxy resins with polymeric stain-resists based on hydrolyzed copolymers of maleic anhydride with either ethylenically unsaturated aromatics, alpha-olefins, alkyl vinyl ethers or alkyl allyl ethers, which greatly improves shampoo resistance without introducing yellowing instability to UV and NOx exposures.
  • the present invention relates to novel compositions for imparting more durable stain-resistance to polyamide fiber substrates comprising blends of epoxy resins with polymeric stain-resists consisting essentially of hydrolyzed copolymers of maleic anhydride with ethylenically 5 unsaturated aromatics, alpha-olefins, alkyl vinyl ethers or alkyl allyl ethers.
  • This invention relates also to processes for imparting resistance to staining of polyamide substrates caused by acid dyes which consists essentially of
  • the present invention relates 5 also to resulting polyamide substrates having the epoxy resins and the hydrolyzed maleic anhydride copolymers reacted on them at said elevated temperatures.
  • the hydrolyzed maleic anhydride copolymer and the epoxy resin are applied to the polyamide substrate as an o aqueous blend.
  • an application technique which uses the least amount of water e.g. by padding, Kuster/knife roll, or print roll application. While use of the foregoing application technique involving the use of the least amount of water is preferred, in the alternative, one can use a technique in which the blend is applied at a 5 higher liquor-to-goods ratio, e.g. by flex-nip application.
  • the polymeric stain-resist and the epoxy resin are usually applied at o temperatures in the range between 20° and 60°C.
  • the treated polyamide fiber substrate can then be dried and cured with dry heat, or steam-cured and dried, at elevated temperatures in the range between 50° and 200°C for periods of one minute to one hour, thereby providing a polyamide fiber substrate on which the epoxy resins and the hydrolized maleic anhydride 5 copolymer have been reacted at said elevated temperatures.
  • the amounts of the hydrolyzed maleic anhydride polymeric stain-resists and the epoxy resins to be applied to the polyamide substrates can be determined by observation. Thus the minimum amounts of each are those which are sufficient provide the polyamide substrates with durable resistance to straining by acid dyes. Obviously, amounts in excess of those needed to effect optimum stain-resistance are uneconomical, but Lhey are undesirable for yet another reason. Excessive amounts will stiffen the substrates; indeed, such amounts will adversely affect the "hand" of a polyamide fibous substrate.
  • the hydrolyzed maleic anhydride copolymer stain-resist agents of this invention show poor resistance to high pH values, specifically the pH values of about 10 found in commercial shampoo formulations. To be effective, the stain-resist agents should be applied at pH values below 4.0, preferably between 2.0 to 2.5.
  • the carboxylic acid-containing stain-resist agents of this invention can be applied in combination with sulfonated phenol/formaldehyde condensates, such as those described in U.S. Patent Nos. 4,948,650, 4,879,180, 4,865,885, 4,839212, 4,822,373. 4,789,099, and 4,592,940.
  • the epoxy resins useful for the purposes of this invention are subtantially diverse in nature.
  • the water-dispersible epoxy resins useful for the purposes of this invention include any water-soluble or emulsifiable epoxy compounds containing two or more epoxy groups.
  • these resins are resins of up to about 800 epoxy equivalent weight, preferably up to about 200, which may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic.
  • Such resins include epoxidized triglycerides, epoxy polyethers of polyhydric alcohols and phenols, glycidyl ethers of resins obtained by condensing an aldehyde with a polyhydric phenol, reaction products of polyhydric alcohols or phenols with a polyepoxide, polymers and copolymers of epoxy-containing monomers having at least one polymerizable ethylenic linkage, and epoxy esters of polybasic acids, including aliphatic diglycidyl ethers within the scope of Formula I below, such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and trimethylene glycol diglycidyl ether.
  • water-soluble or readily water-dispersible glycidyl ethers that may be used are the polyglycidyl ethers of polyhydric alcohols having two to four carbon atoms, such as of ethylene glycol, glycerol, trimethylene glycol, propylene glycol, butylene glycols, their dimers, trimers, and higher polymers and especially the water-soluble or water-dispersible glycidyl ethers having the structure of one of Formulas I, II and III.
  • R is an alkylene group of from two to six carbon atoms
  • x is a number having an average value of one to three
  • m is an integer having a value of two to four
  • x is a number having an average value of one to five.
  • All of these polyepoxides contain at least two vic-epoxy groups in which the epoxy oxygen atom is attached to o adjacent carbon atoms and have molecular weights of about 160-1000.
  • the glycidyl ethers may preferably have molecular weights of about 180 to 400.
  • Other examples of epoxy resins are described in the article on epoxy resins, Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Vol. 8, pages 294-312, John Wiley and Sons, Inc. New York (1965).
  • Epoxy resins based on Bisphenol A and epichlorohydrin are preferred, with "Custom Solution 287” water- dispersible Bisphenol A/epichlorohydrin-based epoxy resin being most preferred.
  • a dispersing agent such as polyvinylalcohol, a polyoxyethylene sorbitan monolaurate, or an octylphenoxypolyethoxyethanol may be employed to aid in the dispersion of those epoxy compounds which are not readily water-soluble.
  • Their solubility in aqueous systems may also be improved by the addition of a lower alcohol, such as ethanol, isopropanol, and the like. Such methods of improving dispersibility are well known.
  • aromatic compounds can be used for the purpose of preparing the hydrolyzed polymers of this invention.
  • aromatic compounds can be represented by the formula:
  • R 2 is H- or CH 3 - ;
  • R3 is H- or CH3O- ;
  • R 4 is H-, CH3-, or CH3CO-, and
  • R 3 plus R 4 is -0-CH 2 -0-.
  • ethylenically unsaturated aromatic compounds suitable for the purposes of this invention include styrene, alpha-methylstyrene, 4- methyl styrene, stilbene, 4-acetoxystilbene (used to prepare a hydrolyzed polymer from maleic anhydride and 4-hydroxy-stilbene), eugenol acetate, isoeugenol acetate,
  • a copolymer prepared from s yrene and maleic anhydride at a 1:1 molar ratio is preferred.
  • the hydrolyzed polymers can have molecular weights (number average) in the range between about 500 and 4000, preferably between about 800 and 2000. They are readily soluble, even at high concentrations, in water at neutral to alkaline pH; increasing dilution is needed at a pH below 6.
  • Such copolymers and their preparation are disclosed in U.S. Patent No. 5,001,004, the contents of which are incorporated herein by reference.
  • allyl ethers and vinyl ethers can be used for the purposes of this invention.
  • R is hydrogen or an alkyl radical containing 4 to 8 carbon atoms, or 2,3-epoxypropyl, or an alicyclic hydrocarbon radical containing 6 to 12 carbon atoms, or an aromatic hydrocarbon radical containing 6 to 12 carbon atoms, or a perfluoroalkyl radical containing 3 to 16 carbon atoms, preferably 6 to 12, and which may contain a terminal -
  • A is a divalent radical -S02R 1 - or -CONR 1 - in which R is hydrogen or an alkyl radical containing 1 to 6 carbon atoms; k is O or l; m is 0 or 2; and n is 0 or 1.
  • Particular examples include n-butyl vinyl ether, isobutyl vinyl ether, iso-octyl vinyl ether, 2-perfluorohexylethyl vinyl ether, allyl n-butyl ether, allyl phenyl ether, allyl glycidyl ether, and the like.
  • alpha-olefins include dienes containing 4 to 18 carbon atoms, such as butadiene, chloroprene, isoprene, and 2-methyl-l,5-hexadiene; preferably 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.
  • a part of the alpha-olefins can be replaced by other monomers, e.g.
  • 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, acontic acid, crotonic acid, cinnamic acid, alkyl(C ⁇ _ ⁇ g) esters of the foregoing acids, cycloalkyl(C3_g) 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, preferably between about 1000 and 100,000.
  • a nylon polyamide carpet specimen (3x5 inch) is placed on a flat non-absorbent surface. Twenty ml of a red dye solution consisting of 0.2 g FD&C Red 40 and 3.2 g citric acid in 1 liter of deionized water is poured into a 2-inch diameter cylinder which is placed tightly over the specimen.
  • the cylinder is removed after all the red dye solution has been absorbed.
  • the stained carpet specimen is left undisturbed for 24 hours, after which it is rinsed thoroughly under cold tap water and squeezed dry.
  • the specimens are visually inspected and the amount of color remaining in the stained area rated according to the following stain rating scale:
  • a 3x5 inch nylon carpet specimen is submerged for 5 minutes at room temperature in a detergent solution consisting of sodium lauryl sulfate (dodecyl sodium sulfate) such as "Duponol WAQE" (1.5 g per liter) and adjusted with dilute sodium carbonate to a pH of 10.
  • the specimen is then removed, rinsed thoroughly under tap water, de-watered by squeezing, and air-dried.
  • the dry carpet specimen is then tested according to the Stain Test described above. 3.
  • the colorfastness to UV light was measured according to AATCC Test Method 16E-1987. Nylon carpet specimens were rated in accordance with the Grey Scale for color change after exposure to 40 5 AATCC Fading Units (AFU).
  • Example 1 5 A 1/1 molar styrene/maleic anhydride copolymer having a number average molecular weight of 1600 (Atochem Inc. "SMA-1000" resin) was hydrolyzed with aqueous sodium hydroxide to a 25% concentration based on polymer.
  • One thousand parts of the resulting solution were blended with 150 parts of a commercial alkylated disulfonated diphenyl o oxide (Dow Chemical's "Dowfax 2A-4"), adjusted to a pH of 2.1 - 2.2 with sulfamic acid and diluted to a concentration of 0.72% based on "SMA-1000" resin.
  • Three hundred and thirty four parts of the 0.72% "SMA-1000” solution were mixed at 50 - 60°C with 16 parts of an epoxide resin emulsion of any desired concentration.
  • the test solutions were 5 applied by padding onto 6x8 inch pieces of white level loop carpet.
  • An isobutylene/maleic anhydride copolymer commercially available from Kuraray Co.(Japan) as Tsobam-01" and a low molecular 0 copolymer of n-butyl vinyl ether with maleic anhydride were hydrolyzed with aqueous sodium hydroxide and adjusted to a 25% concentration based on polymer.
  • One thousand parts of each of these solutions were adjusted to a pH of 2.1-2.2 with sulfamic acid and diluted to a concentration of 0.72% based on the maleic anhydride copolymer.
  • Addition of 150 parts of 5 "Dowfax 2A-4" was necessary as in Example 1 for the n-butyl vinyl ether /maleic acid copolymer before pH adjustment.
  • Example 2 the styrene-maleic acid based stain resist described in Example 1 was applied by exhaust at pH 2.15 in a Launder-O-Meter. A part of the thus treated carpet was padded with Shell's "Custom Solution 287" epoxide resin, dried and tested against the control as shown in Table III.
  • Blends of styrene-maleic acid stain-resist "SMA-1000” with Shell's epoxide "Custom Solution 287” were vertical pad applied at pH 2.1 - 2.2 onto blue cut pile carpet using semi-commercial equipment. The thus treated carpet was then steamed, washed, extracted, and finally dried. After latexing the carpet was tested for stain-resistance before and after shampooing as shown below in Table IV.

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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)

Abstract

L'invention concerne des compositions et des procédés qui confèrent simultanément des propriétés de résistance aux taches provoquées par des colorants acides sur des substrats en polyamide ainsi qu'une durabilité améliorée au shampoing et une résistance au jaunissement dû à l'exposition aux ultra-violets et/ou à NOx, les caractéristiques anti-tache des copolymères d'anhydride maléique hydrolysés pouvant être considérablement améliorées soit par co-application sur la tache d'une résine époxyde dispersée dans l'eau, soit par post-traitement avec une résine époxyde dispersée dans l'eau du substrat en fibre polyamide traité anti-tache.
PCT/US1994/000438 1993-02-02 1994-01-26 Composition anti-tache a base de polymere anhydride maleique hydrolyse et durable WO1994018376A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU60269/94A AU6026994A (en) 1993-02-02 1994-01-26 Durable hydrolized maleic anhydride polymer stain-resists

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US1279393A 1993-02-02 1993-02-02
US08/012,792 1993-02-02
US08/012,792 US5358769A (en) 1993-02-02 1993-02-02 Process providing durable stain-resistance by use of maleic anhydride polymers
US08/012,793 1993-02-02

Publications (1)

Publication Number Publication Date
WO1994018376A1 true WO1994018376A1 (fr) 1994-08-18

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2739665A1 (de) * 1976-09-02 1978-03-09 Rohm & Haas Zubereitung fuer die behandlung von teppichen und teppichgarnen
EP0328822A2 (fr) * 1987-12-21 1989-08-23 E.I. Du Pont De Nemours And Company Agents antisalissures pour textiles
EP0329899A2 (fr) * 1987-12-21 1989-08-30 E.I. Du Pont De Nemours And Company Polymères aromatique/anhydride maléique résistant aux salissures
US4948650A (en) * 1987-12-21 1990-08-14 E. I. Du Pont De Nemours And Company Stain-resistant textile substrates
US5001004A (en) * 1987-12-21 1991-03-19 E. I. Du Pont De Nemours And Company Stain-resistant aromatic/maleic anhydride polymers
WO1992010605A1 (fr) * 1990-12-13 1992-06-25 E.I. Du Pont De Nemours And Company Agents anti-taches contenant des polymeres d'olefine/d'anhydride maleique
WO1992012286A1 (fr) * 1990-12-27 1992-07-23 E.I. Du Pont De Nemours And Company Matieres resistant aux taches a base de polymeres d'allylether ou de vinylether/d'anhydride maleique
WO1992013989A1 (fr) * 1991-02-01 1992-08-20 Allied-Signal Inc. Procede et composition ameliorant la resistance de polyamides aux taches de colorant acide
WO1993019238A1 (fr) * 1992-03-25 1993-09-30 E.I. Du Pont De Nemours And Company Revetements antitaches pour substrats de polyamide

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2739665A1 (de) * 1976-09-02 1978-03-09 Rohm & Haas Zubereitung fuer die behandlung von teppichen und teppichgarnen
EP0328822A2 (fr) * 1987-12-21 1989-08-23 E.I. Du Pont De Nemours And Company Agents antisalissures pour textiles
EP0329899A2 (fr) * 1987-12-21 1989-08-30 E.I. Du Pont De Nemours And Company Polymères aromatique/anhydride maléique résistant aux salissures
US4948650A (en) * 1987-12-21 1990-08-14 E. I. Du Pont De Nemours And Company Stain-resistant textile substrates
US5001004A (en) * 1987-12-21 1991-03-19 E. I. Du Pont De Nemours And Company Stain-resistant aromatic/maleic anhydride polymers
WO1992010605A1 (fr) * 1990-12-13 1992-06-25 E.I. Du Pont De Nemours And Company Agents anti-taches contenant des polymeres d'olefine/d'anhydride maleique
WO1992012286A1 (fr) * 1990-12-27 1992-07-23 E.I. Du Pont De Nemours And Company Matieres resistant aux taches a base de polymeres d'allylether ou de vinylether/d'anhydride maleique
WO1992013989A1 (fr) * 1991-02-01 1992-08-20 Allied-Signal Inc. Procede et composition ameliorant la resistance de polyamides aux taches de colorant acide
WO1993019238A1 (fr) * 1992-03-25 1993-09-30 E.I. Du Pont De Nemours And Company Revetements antitaches pour substrats de polyamide

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Publication number Publication date
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