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EP0797699B1 - Composition resistant aux taches contenant un tensioactif sulfone - Google Patents

Composition resistant aux taches contenant un tensioactif sulfone Download PDF

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Publication number
EP0797699B1
EP0797699B1 EP95940061A EP95940061A EP0797699B1 EP 0797699 B1 EP0797699 B1 EP 0797699B1 EP 95940061 A EP95940061 A EP 95940061A EP 95940061 A EP95940061 A EP 95940061A EP 0797699 B1 EP0797699 B1 EP 0797699B1
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EP
European Patent Office
Prior art keywords
composition
acid
weight
carpet
fluorochemical
Prior art date
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
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EP95940061A
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German (de)
English (en)
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EP0797699A1 (fr
Inventor
Van Giao Nguyen
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3M Co
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Minnesota Mining and Manufacturing Co
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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
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/262—Sulfated compounds thiosulfates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/425—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes
    • D06M13/428—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes containing fluorine atoms
    • 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
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • 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
    • 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
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
    • 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
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk
    • 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

  • This invention relates to a composition and process for providing stain release/resistance to fibrous materials, particularly polyamide fibrous materials such as nylon and wool carpets, nylon, wool, silk fabrics and natural and synthetic leathers.
  • the invention also relates to a direct application process for providing stain release/resistance to fibrous materials.
  • Fibrous polyamide articles such as nylon and wool carpets, nylon, wool and silk fabrics, natural leather and synthetic fibers are particularly susceptible to staining by natural and artificial acid colorants such as are commonly found in many foods and beverages. There has been a long felt need for compositions and processes for economically providing such fibrous polyamide articles with resistance to acid colorant staining.
  • US-A-4,081,383 discloses an anti-soiling treatment for carpets and carpet yarns.
  • the carpet or carpet yarns prior to carpet manufacture are coated with a polymeric material containing either (A) a blend of a methacrylic acid emulsion copolymer having an epoxy resin. or (B) a methacrylic acid emulsion copolymer having epoxy monomer units therein.
  • the copolymer in either case contains 40% to 70% by weight methacrylic acid.
  • US-A-4,669,812 discloses a method for imparting stain resistance to fibers containing free amino groups, and especially polyamide fibers by contacting the fiber with a solution of an aliphatic sulphonic acid containing 8 to 24 carbons, under acidic conditions. If the fibers are not thoroughly rinsed after application of the aliphatic sulphonic acid the product of this method after being dried has an undesirable finish due to the deposition of a filmy coating.
  • US-A-4,579,762 discloses stain resistant nylon carpet in which the nylon fibers are made from polymers modified to contain, as an integral part of its polymer chain, aromatic sulphonate units and in which the backing adhesive contains a fluorochemical.
  • US-A-4,329,391 discloses the treatment of synthetic fibers with a sulphonated polyester stain-releasing finish in an aqueous bath which includes the addition of water soluble salts to the aqueous fabric treating bath.
  • US-A-3,322,488 discloses sulphomethylated condensation products of bisphenols and aldehydes for use in treating synthetic polyamide and polyurethane fibers to render them resistant to acid and direct dyes.
  • AU-A-599427 discloses a method for imparting polyamide materials with stain resistance to natural and synthetic colorants which comprises contacting the polyamide material with a water-soluble divalent metal salt of a partially sulphonated novolak resin.
  • AU-A-632641 (hereafter the "'641 patent") describes a method for imparting stain resistance to fibrous polyamide materials in which the polyamide materials are coated with stain resistant agents comprising (a) a partially sulphonated novolak resin, and (b) polymethacrylic acid, copolymers of methacrylic acid or combinations of said polymethacrylic acid and copolymers of polymethacrylic acid, or combinations of (a) and (b).
  • compositions and processes for imparting stain resistance to fibrous materials which do not adversely effect the finish of the treated fiber, which fully treat the fibrous material avoiding "dead spaces", and which do not reduce the performance of fluorochemical treatments for oil and water repellency.
  • an aqueous treating composition for providing stain release properties to fibrous materials which comprises:
  • This invention is also directed to a process for providing fibrous material and leather with stain release properties which comprises applying directly to said material a composition which comprises:
  • the treatment composition is applied to fibrous materials using a foaming agent as a carrier.
  • the aqueous treating composition for providing stain release properties to fibrous materials and leather comprises three key components:
  • the treatment composition also includes a volatile organic acid.
  • composition of the invention When the composition of the invention is applied to fibrous material, particularly polyamide fibers, such as nylon and wool carpets, nylon, wool, silk fibers and fabrics, natural and synthetic leathers and the like, stain release properties are imparted without loss of product finish.
  • fibrous material particularly polyamide fibers, such as nylon and wool carpets, nylon, wool, silk fibers and fabrics, natural and synthetic leathers and the like, stain release properties are imparted without loss of product finish.
  • stain release used herein refers to the property of ready release of stains which have been absorbed by fibrous materials or leather.
  • stain resistance used herein refers to anti-wetting properties which result from treatment of fibrous materials or leather with fluorochemicals.
  • methacrylic acid copolymers of methacrylic acid. or combinations thereof are embraced in this disclosure by the term "methacrylic polymer", which is intended to include polymethacrylic acid homopolymer as well as polymers formed from methacrylic acid and one or more other monomers.
  • the monomers useful for copolymerization with the methacrylic acid are monomers having ethylenic unsaturation.
  • Such monomers include, for example, monocarboxylic acids, polycarboxylic acids, and anhydrides; substituted and unsubstituted esters and amides of carboxylic acids and anhydrides; nitriles; vinyl monomers; vinylidene monomers: monoolefinic and polyolefinic monomers: and heterocyclic monomers.
  • Representative monomers include, for example, acrylic acid, itaconic acid, citraconic acid, aconitic acid, maleic acid, maleic anhydride, fumaric acid. crotonic acid, cinnamic acid, oleic acid, palmitic acid, vinyl sulphonic acid, vinyl phosphoric acid, alkyl or cycloalkyl esters of the foregoing acids, the alkyl or cycloalkyl groups having 1 to 18 carbon atoms such as, for example, ethyl, butyl, 2-ethylhexyl, octadecyl, 2-sulphoethyl, acetoxyethyl, cyanoethyl, hydroxyethyl and hydroxypropyl acrylates and methacrylates, and amides of the foregoing acids, such as, for example, acrylamide, methacrylamide, methylolacrylamide, and 1,1-dimethylsulphoethylacrylamide,
  • Particularly useful monomers include, for example, ethyl acrylate, itaconic acid, sodium sulphostyrene, and sulphated castor oil. Mixtures of the monomers can be copolymerized with the methacrylic acid.
  • the methacrylic polymers useful in the present invention can be prepared using methods well known in the art for polymerization of ethylenically unsaturated monomers.
  • the methacrylic acid comprises about 30% to 100% by weight, more preferably 60% to 90% by weight, of the methacrylic polymer.
  • the optimum proportion of methacrylic acid in the polymer is dependent on the comonomers used, the molecular weight of the copolymer, and the pH at which the material is applied.
  • water-insoluble comonomers such as ethyl acrylate
  • they may comprise up to about 40% by weight of the methacrylic polymers.
  • the water-soluble comonomers When water-soluble monomers, such as acrylic acid or sulphoethyl acrylate are copolymerized with the methacrylic acid, the water-soluble comonomers preferably comprise no more than 30% by weight of the methacrylic polymer and preferably the methacrylic polymer also comprises up to about 50% by weight water-insoluble monomer.
  • the methacrylic polymer should be sufficiently water-soluble that uniform application and penetration of the polymer into the fiber surface can be achieved.
  • the glass transition temperature of the methacrylic acid copolymer can be as low as about 35°C although high glass transition temperatures are preferred. When polymers having high glass transition temperatures, that is, as high as 230°C or higher, are used, an additional benefit of improved soil resistance of the fibrous polyamide substrate can be obtained.
  • the weight average molecular weight and the number average molecular weight of the methacrylic polymer should be such that satisfactory stain resistance is provided by the polymer.
  • the higher 90% by weight of the polymer material preferably has a weight average molecular weight in the range of about 3000 to 100,000.
  • the lower 90% by weight of the polymer material preferably has a number average molecular weight in the range of about 500 to 20,000 more preferably in the range of about 800 to 10,000.
  • more water-soluble comonomers are preferred when the molecular weight of the polymer is high and less water-soluble or water-insoluble comonomers are preferred when the molecular weight of the polymer is low.
  • methacrylic polymers generally useful in the present invention include LeukotanTM 970, LeukotanTM 1027, LeukotanTM 1028 and LeukotanTM QR 1083 available from Rohm and Haas Company.
  • the partially sulphonated novolak resins useful in this invention include known substances such as those compositions which are condensation products of formaldehyde with bis (hydroxyphenyl) sulphone and phenylsulphonic acid.
  • formaldehyde another aldehyde such as, for example, acetaldehyde, furfuraldehyde, or benzaldehyde, can be used to make the condensation product.
  • other phenolic compounds such as, for example, bis(hydroxyphenyl)alkane, for example, 2,2-bis(hydroxyphenyl)propane, and bis(hydroxyphenyl)ether compounds can be used instead of, or in addition to, the bis(hydroxyphenyl)sulphone.
  • the sulphonated novolak resin is partially sulphonated, that is, has a sulphonic acid equivalent weight of about 300 to 1200, preferably 400 to 900.
  • partially sulphonated novolak resins which may be used in place of or in addition to the aforementioned novolak resins include those resins described in AU-A-599427, that is, a water-soluble divalent metal salt of a partially sulphonated novolak resin, wherein the salt contains less than 1% sulphonic acid moieties.
  • AU-A-599427 is incorporated herein by reference in their entirety.
  • the surfactant used in preparing the aqueous treating compositions of this invention comprises a mono-, di- or tri-ethanolamine lauryl sulphate.
  • ethanolamine lauryl sulphate is diethanolamine lauryl sulphate, a commercially available surfactant which is sold under the trade mark Empicol DA by Albright & Wilson, Victoria, Australia
  • Diethanolamine lauryl sulphate has the following formula: C 11 H 23 OSO 3 .NH 2 (CH 2 CH 2 OH) 2
  • ethanolamine lauryl sulphates can be applied in the form of a foam given their detergent properties. This is an advantage, as will be hereinafter described in further detail.
  • the respective amounts of the methacrylate, novolak resin and surfactant used in the compositions of the invention are those which provide the desired degree of stain release from the fibrous materials, without adversely effecting the finish of the fibrous materials or reducing the effects of fluorochemical treatments for water repellency. It has surprisingly been found that ethanolamin lauryl sulphates can replace to a significant extent the methacrylate polymer and novolak resin previously thought to be necessary in significant quantity.
  • substitution enhances the effects of the treating composition in a number of unexpected ways. Firstly, the substitution provides a greater penetration into the fibrous materials, thereby ensuring that the totality of fibers are treated. Secondly, the gluing effect which results from the direct application of high concentrations of methacrylate polymer in the order of 15% to 90% in association with a novolak resin is avoided giving a soft handling finish to polyamide fibers. This is particularly significant in the carpet industry where a high texture bloom (opening of the yarn ends to give softer feel or hand) is demanded by carpet customers, particularly in respect of nylon carpets. As treated fibers according to this invention are not washed to remove non-fixed material, significant economic and environmental benefits apply. Thirdly, methacrylate polymers and novolak resins reduce the effects of fluorochemical treatment due to their strong hydrophilic properties and hence the ability to reduce the amounts of these materials without diminishing stain release properties is an important advantage.
  • compositions of the invention contain from 20% to 90% by weight of surfactant, preferably 30% to 80% by weight and more preferably 30% to 60% by weight.
  • the methacrylate polymer and novolak resin are generally provided in approximately the same weight percentage in the composition, in amounts from about 5% by weight to 30% by weight, preferably 10% to 20% by weight.
  • the treating compositions according to the invention may contain other ingredients which increase effectiveness, stability of the composition, miscibility, foaming properties and the like.
  • these compositions may contain ingredients which make the composition more suitable for use and less susceptible to degradation.
  • wetting agents improve migration of compositions along fiber tips and improve stability of the compositions.
  • wetting agent NFTM from Hoechst AG which is a modified diestersulphosuccinate acid surfactant.
  • Minor amounts of de-aerating and stabilizing additives may be used in an amount from 1% to 10% by weight.
  • An example of such an ingredient is LeonilTM GP-Z from Hoechst AG, which composition is a nonylphenylethoxylate surfactant.
  • Divalent metal salts may be used in the treating compositions.
  • Suitable divalent metal salts include water-soluble inorganic and organic salts of metals, such as magnesium, calcium and zinc.
  • Organic metal salts include, for example, acetates and formates of the aforementioned metals.
  • Preferred divalent metal salts are magnesium sulphate, magnesium chloride and calcium chloride. Mixtures of two or more divalent metal salts may be used.
  • divalent metal salts are added to the treating composition, they are preferably used in an amount of at least 0.5% by weight of solids, based on the weight of the fabric ("owf"), more preferably at least I % by weight of solid owf, most preferably at least 2% by weight of solid owf.
  • an organic acid more preferably a volatile aliphatic carboxylic acid
  • volatile carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid and valeric acid, with formic acid and acetic acid being particularly preferred.
  • Acids are believed to assist in fixation of stain release reagents to polyamide fibers. Conventional methods in the art use strong mineral acids and non-volatile acids for fixation of novolak resins and methacrylate polymers. These acids must be removed by washing of the fibers. Volatile acids, in contrast, are simply removed from polyamide fibers during conventional drying procedures, which for carpets is above 120°C.
  • Acids may be used in an amount from 0.1% to 5% by weight of the composition at a pH of about 2.0 to 4.0. Without wishing to be limited to any reaction mechanisms, it is believed that at low pH the affinity of the stain release reagents and the polyamide fiber is greater, allowing chemical bonding by dipolar attraction as well as covalent bonding to amine groups on the fiber (the sites of dye binding).
  • Foaming agents as are well known in the art may be incorporated into the composition of the invention in order to assist application as a foam.
  • the composition itself may form a foam on agitation due to the properties of the sulphonated surfactant or other components.
  • the aforementioned ingredients may be simply added to the composition of the invention prior to treating fibrous material.
  • composition of the invention may be coapplied with a fluorochemical composition in order to provide oil, water and soil repellency (that is, stain resistance) in addition to stain release properties.
  • the fluorochemical composition is added in an appropriate amount to the treating solution.
  • the resultant compositions may be referred to as stain release/resistant compositions.
  • the fluorochemicals which may be used in the present invention for providing oil and water repellency include anionic, cationic, or nonionic fluorochemicals which are usually provided as aqueous emulsions, such as the fluorochemical allophanates disclosed in US-A-4,606,737 (Stern); fluorochemical polyacrylates disclosed in US-A-3,574,791 (Sherman et al.) and 4,147,851 (Raynolds); fluorochemicals urethanes disclosed in US-A-3,398,182 (Guenthner et al.); fluorochemical carbodiimides disclosed in US-A-4,024,178 (Landucci); fluorochemical guanidines disclosed in US-A-4,540,497 (Chang et al.); and fluorochemical potassium salts (which are self curing or cross-link under ambient temperatures).
  • anionic, cationic, or nonionic fluorochemicals which are usually provided as aqueous
  • the fluorochemical when included in the treating solution, is preferably present in an amount that is sufficient to retain on the fiber of the finished article about 200 to 1000 ppm fluorine based on the weight of the fiber. This can generally be achieved by using at least about 0.4% product owf, more preferably at least 0.7% product owf, most preferably 0.8% product owf. Generally, amounts of the fluorochemical in excess of 2% product do not appreciably improve the oil and water repellency.
  • the respective components of the treating composition are admixed utilizing standard procedures. Heat and agitation may be applied as necessary.
  • the pH of the treating solutions depends on the fiber being treated. Generally, the pH is acidic in the range of 2.0 to 4.0, more preferably 2.5 to 4.5. The pH may be adjusted with acid or base reagents.
  • the treatment composition according to the invention can be conveniently applied directly to a fibrous substrate by spraying, dipping, coating, padding, foaming or roller coating application, or by a combination of two or more of these methods.
  • Application by way of foaming is particularly preferred as the amount of composition applied is much decreased compared to other applications, wastage of treating solution is minimized and processing is streamlined. As no washing is required to remove non-fixed reagents, overall processing is streamlined and waste products minimized.
  • the interaction between the components of the treatment composition of the invention may be regarded as synergistic. Alternatively, the result of the combination may be regarded as unexpected. These considerations arise from a number of perspectives. Sulphonated surfactants have not hitherto been proposed as stain release agents. When applied directly to fibrous materials such as carpets at high levels, excess sulphonated surfactants have the disadvantage that they leave a filmy residue after drying and actually attract dry soil, (such problems are associated with the processes of US-A-4,699,812 (Munk et al.) described earlier in this document). However, when a sulphonated surfactant is used in combination with a methacrylate polymer and a novolak resin (that is. to substitute a proportion of these components), these problems are overcome, particularly in the situation where the sulphonated surfactant is used to an appreciable extent, such as 15% to 80% by weight of the treatment composition.
  • an ethanolamine lauryl sulphate in the treatment composition of the invention does not adversely effect the actions of the methacrylate polymer and novolak resin and removes disadvantages associated with these agents.
  • methacrylate polymers when applied directly (that is, without washing after application) to fibrous materials may cause aggregation or a gluing effect which adversely effects the finished product, giving a hard texture due to the aggregated fibers as well as a poor texture bloom. This is a particular problem in nylon carpets where the weight of the carpet determines costs.
  • Fibrous material which may be treated according to this invention includes polyamide fibrous materials such as nylon and wool carpets, nylon, wool, silk fabrics and natural and synthetic leathers.
  • the oil repellency of treated carpet and textile samples is measured by the American Association of Textile Chemists and Colorists (AATCC) Standard Test Method No. 118-1983, which test is based on the resistance of treated fabric to penetration by oils of varying surface tensions. Treated fabrics resistant only to KaydolTM, a brand of mineral oil and the least penetrating of the test oils, are given a rating of 1, whereas treated fabrics resistant to heptane (the most penetrating of the test oils) are given a value of 8.
  • test sample In the test procedure the test sample is placed on a flat surface. A dropper pipette is used to gently place five drops of the selected oil onto the sample at 5 cm intervals. After ten seconds, if four out of five drops are still visible, the sample passes the test. A rating of "2" is generally considered a minimum requirement.
  • the aqueous stain or water repellency of treated samples is measured using a water/isopropyl alcohol test, and the result is expressed in terms of a water repellency rating of the treated fabric.
  • Treated fabrics which are resistant to a 100% water/0% isopropyl alcohol mixture (the least penetrating of the test mixtures) are given a rating of W; resistance to a 90% water/10% isopropyl alcohol mixture is given a rating of 1, whereas treated fabrics resistant to 0% water/100% isopropyl alcohol mixture (the most penetrating of the test mixtures) are given a rating of 10.
  • the procedure involves placing five small drops of water/alcohol mixture onto the carpet face. After ten seconds, if four out of five drops are still visible, the sample passes the test.
  • a rating of "1" (90/10 water/isopropanol mixture) is generally considered as a minimum requirement.
  • This test is intended to measure the tendency of a carpet to resist dry soil during the use.
  • the soil contains clay, carbon black, silica and mineral oil. It is deposited on to the carpet via a soil capsule in a tumbler containing seventy steel balls. The tumbler rotates for ten minutes and the carpet samples are removed and the excess soil is blown off by an air nozzle at 345 kPa (50 psi).
  • the degree of soiling resistance is measured by comparing the soiled area to a standard rating board. A 5.0 rating is the absolute standard of soil repellency and 3.0 is an acceptable soiling degree.
  • This test is designed to evaluate the effectiveness of stain resistant treatments on carpet against acid staining medium (artificial colourings in food and drink).
  • a stock solution using 80 mg of FD8C Red 40 is dissolved in one liter of water containing citric acid to pH 3.0 ⁇ 0.2; a 15 ml aliquot of the staining medium is deposited on carpet sample via a bottomless staining ring of approximately 50 mm internal diameter.
  • the stained sample was left untouched for 24 ⁇ four hours in room temperature, on a flat and non-absorbing surface.
  • This test determines the colour fastness of textiles to light, using an artificial light source.
  • a test specimen of the textile, together with blue light fastness standards, is exposed to the light from a 500 W mercury vapour, tungsten filament lamp. Fading/colour change is rated against the blue scale standards - while 8.0 as an absolute rating and 5.0 as a minimum industry requirement.
  • a carpet with an open bloom has the appearance of an expansion or spread of the carpet fibers, giving a greater apparent bulk. For a given weight carpet, it is advantageous to provide the appearance of increased bulk.
  • stain release and other test properties outlined above were compared using sulphonated surfactants only, a combination of novolak resin and polymethacrylate polymer, and the combination of sulphonated surfactant, novolak resin and polymethacrylate polymer according to this invention.
  • the treatment composition of the invention contained the following components: 1. methacrylate polymer F-7867 15% 2. novolak resin FX-369 14% 3. sulphonated surfactant Empicol DA 50% 4. wetting agent NF 1% 5. de-aerator Leonil GP-Z 7% 6. formic acid 3% 7. water 10% The treatment composition was applied at 1.6% product owf.
  • Components (1) and (2) are commercially available products of Minnesota Mining and Manufacturing Company, St. Paul, Minnesota, U.S.A.
  • Component (1) is a polymethacrylic acid polymer formed from methacrylic acid and one or more monomers having ethylenic unsaturation.
  • the molecular weight of the polymer is preferably in the range of 800 to 10,000 daltons.
  • the partially sulphonated novolak resin (2) has a sulphonic equivalent weight of preferably 400 to 900.
  • Component (3) is from Albright & Wilson Australia Ltd., St. Marys, New South Wales, Australia, and comprises diethanolamine lauryl sulphate.
  • Component (4) is a non-flammable (NF) wetting agent from Hoechst AG, Frankfurt, Germany which comprises a modified diester sulphosuccinic acid surfactant, which component improves stability of the composition at low temperature (below 5°C).
  • Component (5) is from Hoechst AG and comprises a nonyl phenol ethoxylate and alkane sulphonate surfactants in isopropanol, and is used as a de-aerator as well as to assist in solubilization and stabilization of F-7867 and FX-369.
  • the combination according to the invention of methacrylate polymer, novolak resin and sulphonated surfactant gave a treated product with excellent properties. Particularly notable is the open bloom of the treated material, soft texture, excellent stain release properties and no effect on the oil and water repellency of the fluorochemical treatment.
  • the treatment composition showed excellent penetration into the carpet pile.
  • Nylon 6,6 carpet was treated on a commercial scale using the combination of the invention particularized in Example 1, namely containing 50% sulphonated surfactant, 14% methacrylate polymer and 15% sulphonated novolak resin.
  • the product was applied by foam via a Texicon Autofoamer with a 1 mm applicator slot.
  • the composition of the invention was dosed at 1.6% product on carpet in conjunction with an anionic aliphatic fluorochemical at 0.7%.
  • the following parameters were recorded: Stain release composition 108 g/L Fluorochemical 47 g/L Magnesium sulphate dihydrate 4 g/L Wet pick-up 15% add-on based on dry carpet weight Blow ratio 60:1 Gap setting 1 Liquor back pressure 315 kPa (45 psi) Foam back pressure 345 kPa (50 psi) Foam quality continuous fine lather
  • composition of the invention can be applied in conjunction with a fluorochemical directly to installed carpets to give similar properties of stain release and stain resistance to carpets treated commercially during the manufacturing stage.
  • the compound and fluorochemical were applied via an airless sprayer at 175 kPa (25 psi) pressure, 7 m/minute speed, at 15% wet add-on to a wet/precleaned nylon 6,6 carpet of 680 g (19 oz/yd 2 ).
  • the solution contained the following ingredients per liter:
  • composition of the invention is therefore also suitable for application to installed carpet and other polyamide fabrics. Heat treatment is unnecessary when fluorochemicals which self-cure or cross-link under ambient conditions are used.

Landscapes

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

Claims (8)

  1. Composition de traitement aqueuse fournissant des propriétés de libération des taches aux matières fibreuses qui comprend :
    (a) un polymère acrylique choisi parmi l'acide polyméthacrylique, les copolymères d'acide méthacrylique et leurs combinaisons,
    (b) une résine novolaque partiellement sulfonée,
    (c) un tensioactif comprenant un laurylsulfate de mono, di ou tri éthanolamine
    (d) de l'eau.
  2. Composition selon la revendication 1, qui comprend :
    (a) 5 à 3% en poids d'un polymère méthacrylate,
    (b) 5 à 30% en poids d'une résine novolaque partiellement sulfonée et
    (c) 10 à 90% en poids d'un tensioactif.
  3. Composition selon la revendication 1, qui comporte de plus un produit fluorochimique pour assurer l'imperméabilité à l'huile et à l'eau.
  4. Composition selon la revendication 1, qui comporte de plus un acide organique acide qu'on peut enlever après application de la composition à un substrat par séchage à des températures au dessus de 120°C.
  5. Procédé fournissant à un substrat choisi parmi une matière fibreuse et le cuir une libération des taches, qui consiste à appliquer à ladite matière une composition selon la revendication 1 et ensuite à sécher la matière.
  6. Procédé selon la revendication 5, dans lequel la matière fibreuse est un tapis, un textile ou un cuir synthétique.
  7. Procédé selon la revendication 5, dans lequel on applique conjointement ou on applique séparément le produit fluorochimique à la composition selon la revendication 1 afin de fournir l'imperméabilité à l'huile et à l'eau.
  8. Procédé selon la revendication 7, dans lequel le séchage de la matière traitée a lieu dans des conditions ambiantes en présence d'un produit fluorochimique qui auto-durcit ou opère une réticulation dans des conditions ambiantes.
EP95940061A 1994-12-15 1995-11-17 Composition resistant aux taches contenant un tensioactif sulfone Expired - Lifetime EP0797699B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AUPN0088A AUPN008894A0 (en) 1994-12-15 1994-12-15 Stain resistance to fibrous material
AUPN0088/94 1994-12-15
PCT/US1995/015112 WO1996018765A1 (fr) 1994-12-15 1995-11-17 Composition resistant aux taches contenant un tensioactif sulfone

Publications (2)

Publication Number Publication Date
EP0797699A1 EP0797699A1 (fr) 1997-10-01
EP0797699B1 true EP0797699B1 (fr) 1999-02-03

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EP95940061A Expired - Lifetime EP0797699B1 (fr) 1994-12-15 1995-11-17 Composition resistant aux taches contenant un tensioactif sulfone

Country Status (7)

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EP (1) EP0797699B1 (fr)
JP (1) JPH10511434A (fr)
AU (2) AUPN008894A0 (fr)
CA (1) CA2205357A1 (fr)
DE (1) DE69507719T2 (fr)
NZ (1) NZ296923A (fr)
WO (1) WO1996018765A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6197378B1 (en) 1997-05-05 2001-03-06 3M Innovative Properties Company Treatment of fibrous substrates to impart repellency, stain resistance, and soil resistance
AU3194197A (en) * 1997-06-25 1999-01-04 Implico B.V. Stainblocking agent
WO2006108240A1 (fr) * 2005-04-14 2006-10-19 Feltex Australia Pty Ltd Procédé de traitement de tapis
US7901589B2 (en) 2009-06-29 2011-03-08 E.I. Du Pont De Nemours And Company Propanediol soil resist compositions
US8357621B2 (en) 2009-06-29 2013-01-22 E.I. Du Pont De Nemours And Company Soil resist method
WO2012064848A2 (fr) * 2010-11-12 2012-05-18 Invista Technologies S.Ar.L. Formulations antisalissures à pulvériser destinées aux fibres, tapis et tissus
US20130101782A1 (en) * 2011-10-19 2013-04-25 E I Du Pont De Nemours And Company Nonfluorinated soil and stain resist compositions
JP6252951B2 (ja) * 2015-03-13 2017-12-27 千代田商事株式会社 獣毛製品の製造方法、及びその製造方法により処理された獣毛製品

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4865885A (en) * 1987-06-19 1989-09-12 Crompton & Knowles Corporation Food color stain blocking fiber agents
US4822373A (en) * 1988-03-11 1989-04-18 Minnesota Mining And Manufacturing Company Process for providing polyamide materials with stain resistance with sulfonated novolak resin and polymethacrylic acd
US4940757A (en) * 1989-04-20 1990-07-10 Peach State Labs, Inc. Stain resistant polymeric composition
US5057121A (en) * 1989-08-04 1991-10-15 E. I. Du Pont De Nemours And Company Process for imparting stain-resist agent
US5074883A (en) * 1989-12-11 1991-12-24 Minnesota Mining And Manufacturing Company Process for providing polyamide materials with stain resistance
WO1991019849A1 (fr) * 1990-06-12 1991-12-26 E.I. Du Pont De Nemours And Company Tissus resistant aux taches
AU6703994A (en) * 1993-04-26 1994-11-21 E.I. Du Pont De Nemours And Company Durable methacrylic acid polymer stain-resists

Also Published As

Publication number Publication date
AU4031595A (en) 1996-06-20
AUPN008894A0 (en) 1995-01-19
DE69507719T2 (de) 1999-09-02
NZ296923A (en) 1998-01-26
AU708303B2 (en) 1999-07-29
EP0797699A1 (fr) 1997-10-01
DE69507719D1 (de) 1999-03-18
CA2205357A1 (fr) 1996-06-20
WO1996018765A1 (fr) 1996-06-20
JPH10511434A (ja) 1998-11-04

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