WO1997028304A1 - Compositions et procedes pour rendre des articles resistants aux taches, et articles resistants aux taches - Google Patents

Compositions et procedes pour rendre des articles resistants aux taches, et articles resistants aux taches Download PDF

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Publication number
WO1997028304A1
WO1997028304A1 PCT/US1996/001238 US9601238W WO9728304A1 WO 1997028304 A1 WO1997028304 A1 WO 1997028304A1 US 9601238 W US9601238 W US 9601238W WO 9728304 A1 WO9728304 A1 WO 9728304A1
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WIPO (PCT)
Prior art keywords
stainblocking
ofthe
acid
monomers
complex
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PCT/US1996/001238
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English (en)
Inventor
Gail S. Boardman
Larry D. Boardman
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Minnesota Mining And Manufacturing Company
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Publication date
Application filed by Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to AU49088/96A priority Critical patent/AU4908896A/en
Priority to US08/666,518 priority patent/US5952409A/en
Priority to PCT/US1996/001238 priority patent/WO1997028304A1/fr
Priority to ZA97623A priority patent/ZA97623B/xx
Publication of WO1997028304A1 publication Critical patent/WO1997028304A1/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
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3566—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing sulfur
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • 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
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone resins
    • D06M15/412—Phenol-aldehyde or phenol-ketone resins sulfonated

Definitions

  • This invention relates generally to compositions that impart stain resistance to substrates that have been treated with the compositions.
  • the invention further relates to methods for imparting stain resistance to the substrates by treating them with these compositions, and to the articles that have been treated with the compositions. More specifically, this invention relates to the use of organoborane amine complexes to provide compositions that impart stain resistance, as well as to methods for imparting stain resistance using these complexes, and to articles (especially carpet) that have been treated with compositions that incorporate these complexes.
  • Fibrous substrates e.g., fabrics, textiles and carpets
  • compositions that provide stain resistance are often treated with compositions that provide stain resistance.
  • stainblocking compositions or stainblockers prolong the useful life of fabrics and textiles by rendering them more resistant to staining by food and other materials.
  • stainblockers One well-known use of stainblockers is for treating carpet. It has been reported that most carpet is replaced because of unsightly stains rather than physical wear.
  • nylon carpet resistant to staining is particularly important.
  • Nylon fiber is commonly used to manufacture carpet because it has many desirable qualities. It is durable, comfortable and provides warmth. It can be made into carpet having a wide variety of textures, colors and patterns.
  • nylon carpet can be readily, if not permanently, stained by various natural and artificial colorants found in foods such as coffee, mustard, wine and soft drinks.
  • An artificial colorant for food known as "Red Dye No. 40” (sometimes called FD&C Red Dye No. 40 or CT. Food Red 17) has been reported to actually dye and, therefore, permanently stain, nylon carpet fiber within minutes after a food containing this dye has been spilled on the carpet.
  • a composition comprising (a) a partially sulfonated novolak resin; and (b) polymethacrylic acid, copolymers of methacrylic acid, or combinations thereof is applied to the carpet.
  • a stain resistant composition for polyamide fibers that is prepared by polymerizing an ⁇ -substituted acrylic acid or ester in the presence ofa sulfonated aromatic formaldehyde condensation polymer is described in U.S. Pat. No. 5,061,763 (Moss, 111 et al., assigned to Peach State Labs, Inc.). Also described in this patent is a stain resistant composition prepared by (1) esterification of an acrylic acid with a sulfonated hydroxyaromatic compound followed by (2) polymerization ofthe acrylic acid.
  • U.S. Pat. No. 4,892,558 (Blyth et al., assigned to Monsanto Company) describes nylon fibers that resist staining by acid dye colorants.
  • the nylon fibers are spin finish coated with a stainblocker that can be prepared by the condensation of formaldehyde with one or more phenols.
  • U.S. Pat. No. 4,963,409 (Liss et al., assigned to E. I. du Pont de Nemours and Company) describes imparting stain resistance to polyamide substrates by using sulfonated phenol-formaldehyde products in which a portion ofthe free hydroxyl groups have been acylated or etherified.
  • U.S. Pat. No. 5,001,004 (Fitzgerald et al., also assigned to Dupont) discloses polyamide textile substrates treated with a non- sulfonated stain-resistant composition comprising hydrolyzed ethylenically unsaturated aromatic/maleic anhydride polymers.
  • a composition that is said to impart stain resistance to polyamide textile substrates and containing a sulfonated phenol-formaldehyde condensation product, and a hydrolyzed polymer of maleic anhydride and one or more ethylenically unsaturated aromatic monomers is described in U.S. Pat. No. 4,883,839 (Fitzgerald et al., also assigned to Dupont).
  • U.S. Pat. No. 4,865,885 (Herlant et al., assigned to Crompton & Knowles Corporation) describes an agent that is reportedly useful in preventing nylon fibers from being permanently stained by food colors.
  • the agent is obtained by adding a sulfonated phenol-formaldehyde or naphthol-formaldehyde to an anionic surfactant.
  • U.S. Pat. No. 5,073,442 (Knowlton et al., assigned to Trichromatic Carpet,
  • Inc. discloses a method of enhancing the soil-and/or stain-resistant characteristics of polyamide fabrics by applying a solution containing, in a variety of combinations: sulfonated phenolic resins, sulfonated aromatic compounds, compounds of sulfonated phenolics; and aldehydes, modified wax emulsions, fluorochemicals, acrylics, and organic acids of low molecular weight.
  • stainblocking compositions having even improved properties. It would be advantageous if such compositions could provide either enhanced stain resistance at concentrations of stainblocker that are equivalent to those conventionally used (as this would yield improved performance), or equivalent performance at concentrations of stainblocker that are less than conventionally used (as this could reduce manufacturing costs since less stainblocker would be needed).
  • stainblocking compositions retained their effectiveness after the carpet has been cleaned. It has been reported that steam cleaning carpets can reduce the efficacy of a previously applied stainblocking composition. Consumer-applied stainblocking treatments that are available to revitalize carpet provide only a partial solution because commercial treatments are usually applied by the carpet mill in a steaming process that is difficult for consumers to effectively duplicate. Thus, a stainblocking composition that can be easily and effectively applied by consumers would be highly desired.
  • stainblocking compositions in order to achieve maximum effectiveness, are applied at a very low pH of about 3 or less (i.e., highly acidic conditions).
  • the manufacturer ofthe stainblocking composition will often ship it to an end user (e.g., a carpet mill) at a pH of about 4 or higher so as to reduce the corrosive effects that highly acidic compositions can have on the shipping containers (e.g., drums, tank cars, etc.). This not only complicates the handling ofthe stainblocking composition, it also raises the cost of manufacturing and using it.
  • the manufacturer ofthe stainblocking composition will often add an alkaline material to raise the pH so that the stainblocking composition can be more easily shipped.
  • the user's resulting waste stream also becomes highly acidic, and frequently alkali must be added to the waste stream so that it can be discharged into a municipal sewer system.
  • stainblocking composition that could be effectively used at a higher pH. This would not only provide a more environmentally acceptable composition, it would also reduce or eliminate the need for special handling requirements before shipping, using or disposing ofthe stainblocking composition.
  • this invention relates to compositions (or systems) that impart stain resistance to substrates (for example fibrous substrates such as fabric, textiles and carpet) that have been treated with the compositions.
  • substrates for example fibrous substrates such as fabric, textiles and carpet
  • stainblocking compositions stainblocking systems or stainblockers.
  • the invention provides a stainblocking system that comprises a stainblocking material, and a complex of organoborane and amine.
  • stainblocking materials may be used in the stainblocking compositions ofthe invention.
  • sulfonated aromatic polymers polymers that are derived from at least one or more ( ⁇ -and/or ⁇ -substituted) acrylic acid monomers, and hydrolyzed copolymers of at least one or more ethylenically unsaturated monomers and maleic anhydride.
  • stainblocking materials are blends of at least two or more of these polymers, reaction products of at least two or more ofthe monomers from which these polymers may be derived, reaction products of at least one or more ofthe monomers from which the polymers may be derived and at least one or more ofthe polymers, and materials obtained by polymerizing at least one or more ofthe monomers in the presence of one or more ofthe polymers.
  • Sulfonated aromatic polymers are a preferred stainblocking material.
  • Desirable examples may comprise a condensation polymer of an aldehyde (e.g., formaldehyde or acetaldehyde) and a sulfonated aromatic compound, or a subsequently sulfonated condensation polymer of an aldehyde and an aromatic compound.
  • aldehyde e.g., formaldehyde or acetaldehyde
  • a sulfonated aromatic compound e.g., formaldehyde or acetaldehyde
  • Various sulfonated aromatic compounds are available for use in the stainblocking compositions ofthe invention.
  • hydroxyl functionality such as bis(hydroxy phenyl sulfone), hydroxy benzenesulfonic acid, hydroxynaphthalenesulfonic acid, sulfonated 4,4'-dihydroxydiphenylsulfone, and blends thereof.
  • Other useful sulfonated aromatic polymers comprise a copolymer of an ethylenically unsaturated aromatic monomer (e.g., styrene) and a sulfonated ethylenically unsaturated aromatic monomer (e.g., styrene sulfonate).
  • Particularly preferred examples of the resulting polymers are acrylic polymers; i.e., polyacryhc acid, copolymers of acrylic acid and one or more other monomers that are copolymerizable with acrylic acid, and blends of polyacrylic acid and one or more acrylic acid copolymers.
  • methacrylic polymers which includes polymethacrylic acid, copolymers of methacrylic acid and one or more other monomers that are copolymerizable with methacrylic acid, and blends of polymethacrylic acid and one or more methacrylic acid copolymers.
  • a third preferred class of stainblocking materials are hydrolyzed copolymers of at least one or more ethylenically unsaturated monomers and maleic anhydride.
  • the ethylenically unsaturated monomers can be alpha-olefin type monomers (e.g. 1- alkenes) or, more preferably, aromatic monomers such as styrene.
  • stainblocking materials may be obtained by blending together two or more polymers selected from among the different general classes of polymers described above, reacting together at least two or more monomers from which the different general classes of polymers are derived, reaction products of at least one or more ofthe monomers from which the polymers may be derived and at least one or more ofthe polymers, or by polymerizing at least one or more ofthe monomers in the presence of one or more ofthe polymers.
  • one or more ( ⁇ -and/or ⁇ -substituted) acrylic acid monomers may be polymerized together and, subsequent to the polymerization, blended with a sulfonated aromatic polymer.
  • the ( ⁇ -and/or ⁇ -substituted) acrylic acid monomers can be polymerized in the presence of a sulfonated aromatic polymer.
  • a hydrolyzed copolymer of ethylenically unsaturated monomer and maleic anhydride may be combined with a sulfonated aromatic polymer, and, optionally, a polymer derived from at least one or more ( ⁇ -and/or ⁇ - substituted) acrylic acid monomers.
  • the presence ofthe organoborane amine complex substantially improves the ability ofthe stainblocking material to impart stain resistance to a substrate that has been treated with the stainblocking material.
  • about 1 to 70 parts ofthe complex is combined with 100 parts of stainblocking material, although amounts of about 5 to 20 parts are more preferred.
  • Useful organoboranes for the complex may be represented by the general structure
  • R 1 is an alkyl group having 1 to 18 (preferably 1 to 10) carbon atoms
  • R 2 and R 3 are independently alkyl groups having 1 to 18 (preferably 1 to 10) carbon atoms or phenyl-containing groups. More preferably, R 1 , R 2 and R 3 are each independently selected from alkyl groups having 1 to 5 carbon atoms.
  • amines may be complexed with the organoborane including primary monoamines, secondary monoamines, polyamines containing a primary amine or a secondary amine, selected heterocyclic tertiary polyamines, and ammonia.
  • useful polyamines include diamines having the structure H 2 N-R-NH 2 in which R is a divalent, organic radical comprised of an alkylene, arylene or alkylenearylene group.
  • polyoxyalkylenepolyamines having either the structure Hj R 1 ⁇ — (R 2 OV- ⁇ R 3 O) ⁇ — (R 2 O) y - ⁇ 1 NH 2 or the structure rHbNR'O— (R 2 O) w ] z — 4t 4 wherein R 1 , R 2 and R 3 are each independently selected from alkylene groups having 1 to 10 carbon atoms, R 4 is the residue ofa polyol used to prepare the polyoxyalkylenepolyamine, the value of w is > 1, the value of x is > 0, the value of y is > 0, and the value of z is > 2.
  • Another useful class of polyamines are those which comprise the condensation reaction product of a diprimary amine-terminated material (i.e., a material having two terminal groups that are primary amine), and a material containing at least two groups reactive with primary amine.
  • heterocyclic diamines in which both amine groups are within the heterocyclic structure.
  • Useful examples of such materials may be represented by the general structure
  • the stainblocking compositions ofthe invention can be used to impart stain resistance to a wide variety of fibrous substrates that contain polyamide linkages, including fabrics, textiles and carpets. Nylon carpet is particularly preferred as a substrate.
  • the invention relates to a fibrous polyamide linkage-containing substrate that has been treated with a stainblocking composition according to the invention, especially where the fibrous substrate is nylon carpet, a substrate that is susceptible to permanent staining by acid colorants found in many foods.
  • the invention also provides for a method of imparting stain resistance to a fibrous substrate by applying a stainblocking composition according to the invention to the fibrous substrate.
  • a stainblocking composition according to the invention to the fibrous substrate.
  • a wide variety of application methods are available including the use of dyeing techniques conventionally used to dye fibrous substrates, immersing, padding, foaming, and spin finishing.
  • the invention provides a method for improving the ability of an existing stainblocking material to impart stain resistance to a fibrous substrate that has been treated with the stainblocking material.
  • An organoborane amine complex is added to the existing stainblocking material.
  • the presence ofthe complex also permits the use of less stainblocking material without decreasing the effectiveness ofthe stainblocking material in providing stain resistance.
  • the invention provides for a method of reducing the amount of stainblocking material that is needed to impart a desired degree of stain resistance to a substrate that is treated with the stainblocking material.
  • the presence ofthe organoborane amine complex permits the stainblocking material to be applied to a substrate at a higher pH than is typically done, while still imparting excellent stain resistance to the substrate.
  • the invention also relates to a method of raising the pH at which an aqueous stainblocking material may be applied to a substrate to impart stain resistance thereto. The method is accomplished by adding an organoborane amine complex to the aqueous stainblocking material.
  • this invention relates to compositions (or systems) that impart stain resistance to substrates that are treated with the compositions.
  • Such compositions are sometimes referred to herein as stainblocking compositions, stainblocking systems or stainblockers.
  • stainblocking compositions stainblocking systems or stainblockers.
  • substrates may be treated with the stainblocking compositions ofthe invention, although they are particularly useful on carpet (especially nylon carpet).
  • the stainblocking compositions ofthe invention are typically aqueous systems that comprise (and, more preferably, consist essentially of) one or more stainblocking materials, and a complex of organoborane and amine.
  • a stainblocking material refers to a material which, when applied to a substrate, enhances the ability ofthe substrate to resist staining, for example, by natural or artificial colorants found in food or other household items.
  • the stain resistance is accomplished without permanently and visibly changing (to the unaided eye) the color ofthe substrate, except for a slight yellowing ofthe substrate that is associated with the use of some known stainblocking materials, although it is most preferred that no permanent and visible yellowing ofthe substrate occur.
  • stainblocking composition not change the texture or the feel of the substrate to which it has been applied.
  • the stainblocking compositions ofthe invention are typically clear to slightly turbid materials having a waterlike viscosity at room temperature and possessing anionic solubilizing functionality to promote dissolution or dispersion in water.
  • stainblocking materials are useful in the stainblocking compositions ofthe invention. Included among such stainblocking materials are sulfonated aromatic polymers, polymers derived from at least one or more ( ⁇ - and/or ⁇ -substituted) acrylic acid monomers, and hydrolyzed polymers of maleic anhydride and at least one or more ethylenically unsaturated monomers.
  • stainblocking materials are blends of at least two or more ofthe foregoing polymers, reaction products of at least two or more ofthe monomers from which these polymers may be derived, reaction products of at least one or more ofthe monomers from which the polymers may be derived and at least one or more ofthe polymers, and materials obtained by polymerizing at least one or more ofthe monomers in the presence of one or more ofthe polymers.
  • monomer is meant a polymerizable single unit (typically of low molecular weight) that provides repeating units in the ultimate polymer, as well as partially reacted materials that can still participate in a polymerization reaction so as to provide repeating units in the ultimate polymer.
  • Sulfonated aromatic polymers useful in the invention may be obtained by condensation polymerizing an aldehyde with a sulfonated aromatic compound, the resulting polymer sometimes being referred to herein as either a sulfonated aromatic condensation polymer or as a condensation polymer.
  • the resulting condensation polymer should contain a significant number of sulfonate groups.
  • at least one sulfonate group is attached to at least 30% ofthe monomeric units ofthe condensation polymer, more preferably between 30% and 70% ofthe monomeric units.
  • the resulting condensation polymer be substantially soluble in water to simplify handling and application ofthe stainblocking composition to a substrate at normal temperatures (about room temperature to 100 °C, where "room temperature” refers to a temperature of about 20 to 25 °C).
  • the sulfonated aromatic polymer should have an effective sulfonic acid equivalent weight.
  • an "effective sulfonic acid equivalent weight” is meant an equivalent weight that is sufficient to impart stain resistance to a substrate treated with the stainblocking composition, while rendering the stainblocking composition sufficiently water soluble or water dispersible to permit application to a substrate at normal temperatures (typically about room temperature to 100 °C).
  • the sulfonic acid equivalent weight is preferably about 300 to 1,200, more preferably, about 400 to 900. Any aldehyde that can be condensation polymerized with a sulfonated aromatic compound may be used in the invention.
  • Suitable examples of such aldehydes include acetaldehyde, benzaldehyde, furfuraldehyde, and, most preferably, formaldehyde.
  • Suitable sulfonated aromatic compounds for forming the condensation polymer include monomers such as benzene sulfonic acid (which, in general, may contain various combinations of alkyl, hydroxy and alkoxy substituents), toluene sulfonic acid, xylene sulfonic acid (e.g., 2,4-dimethyl benzene sulfonic acid), phenyl 4-sulfonic acid, cumene sulfonic acid, dodecylbenzene sulfonic acid, sulfonated diphenyl ether, benzaldehyde sulfonic acid, aminobenzene sulfonic acid, alkoxybenzenesulfonic acid, benzophenone sulfonic acid, sulfonated
  • Including hydroxyl functionality in the sulfonated aromatic compound may enhance its solubility in water.
  • Hydroxyl functionality may be introduced into the sulfonated aromatic compound (so as to form a sulfonated hydroxyaromatic compound) by either sulfonating a phenolic compound, or by polymerizing the aldehyde and the sulfonated aromatic compound with a hydroxyaromatic material (preferably a phenolic compound).
  • Phenolic compounds useful in either approach include phenol, halogenated phenol (e.g., chlorophenol or trifluoromethylphenol), naphthol, dihydroxydiphenylsulfide, resorcinol, catechol, hydroxyarylcarboxylic acid (e.g., salicylic acid), hydroxyphenylphenyl ether, phenylphenol, alkylphenol (e.g., nonylphenol or cresol), dihydroxydiphenylsulfone, and bis(hydroxyphenyl)alkane (e.g., 2,2-bis(hydroxyphenyl)propane or 2,2,- bis(hydroxyphenyl)hexafluoropropane).
  • phenol halogenated phenol
  • naphthol e.g., dihydroxydiphenylsulfide
  • resorcinol e.g., catechol
  • hydroxyarylcarboxylic acid e.g., salicylic acid
  • Resulting materials include sulfoalkylated phenol, (e.g., sulfomethylated dihydroxydiphenyl sulfone).
  • Particularly preferred sulfonated hydroxyaromatic compounds include bis(hydroxyphenyl)sulfone, hydroxybenzenesulfonic acid, hydroxynapthalenesulfonic acid, and sulfonated 4,4'- dihydroxydiphenylsulfone.
  • Enhanced solubility in water may also be obtained by providing the sulfonated aromatic compound as a salt based on, for example, sodium, potassium, or ammonium, such as sodium xylene sulfonate, ammonium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, ammonium cumene sulfonate, potassium toluene sulfonate, potassium cumene sulfonate, and potassium xylene sulfonate.
  • sodium xylene sulfonate such as sodium xylene sulfonate, ammonium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, ammonium cumene sulfonate, potassium toluene sulfonate, potassium cumene sulfonate, and potassium xylene s
  • condensation polymers consist essentially of repeating units ofthe formula
  • R is the same or different in each unit, and is either hydrogen or a radical selected from the group consisting of -SO 3 X,
  • condensation polymers having these structures and which are water soluble, have at least 40% ofthe repeating units containing an -SO3X radial, and have at least 40% ofthe repeating units containing the group
  • Sulfonated aromatic condensation polymers useful in the invention are described in U.S. Pat. No. 4,680,212 (Blyth et al.), U.S. Pat. No. 4,875,901 (Payet et al.), U.S. Pat. No. 4,940,757 (Moss, III et al.), U.S. Pat. No. 5,061,763 (Moss, m et al.), U.S. Pat. No. 5,074,883 (Wang), and U.S. Pat. No. 5,098,774 (Chang). Sulfonated aromatic condensation polymers useful in the invention can be prepared by methods known to those skilled in the art.
  • an aromatic compound such as phenol, naphthalene or naphthol is sulfonated, for example by reacting it with a sulfonating compound such as sulfuric acid, chlorosulfonic acid or alkaline sulfite so as to form a sulfonated aromatic compound.
  • a sulfonating compound such as sulfuric acid, chlorosulfonic acid or alkaline sulfite so as to form a sulfonated aromatic compound.
  • the sulfonated aromatic compound is then condensation polymerized with formaldehyde or other aldehyde, typically under acidic conditions.
  • Mixtures of different sulfonated aromatic compounds can also be polymerized.
  • one mole of sulfonated aromatic compound is reacted with 0.3 to 0.5 mole of aldehyde.
  • the sulfonated aromatic condensation polymer can be subsequently reacted with a base (e.g., sodium hydroxide, potassium hydroxide, or ammonium hydroxide) so as to form a sulfonic acid salt.
  • a base e.g., sodium hydroxide, potassium hydroxide, or ammonium hydroxide
  • condensation polymers are typically sold as a sodium sulfonate salt.
  • a sulfonated aromatic condensation polymer may be prepared by reacting an unsulfonated hydroxy aromatic compound (e.g., a phenolic compound such as phenol, naphthol, etc.) with an aldehyde such as formaldehyde and then sulfonating the resulting condensation polymer by treatment with fuming sulfuric acid.
  • an unsulfonated hydroxy aromatic compound e.g., a phenolic compound such as phenol, naphthol, etc.
  • an aldehyde such as formaldehyde
  • sulfonated aromatic condensation polymers examples include ErionalTM NW (Ciba-Geigy Limited; containing a naphthalene sulfonic acid polymer with formaldehyde and 4,4'- dihydroxydiphenylsulfbne), ErionalTM PA (polymer of phenol sulfonic acid, formaldehyde, and 4,4' dihydroxydiphenyl sulfone from Ciba-Geigy), 3MTM brand stain release concentrate FX-369TM (3M Co.), TamolTM SN (Rohm & Haas Co.),
  • sulfonated aromatic polymers are typically purchased commercially as a 30 to 40% solids aqueous solution that can contain other compounds, including aromatic sulfonic acids and glycols.
  • the effectiveness of a sulfonated aromatic condensation polymer in imparting stain resistance to a substrate may be improved by providing the condensation polymer in the form ofa divalent metal salt.
  • These salts are water soluble and are substantially free of sulfonic acid moieties (i.e., — SO 3 H groups); that is, they typically contain less than 1 mole percent sulfonic acid moieties.
  • the salt form ofthe polymer may be obtained by reacting the condensation polymer with a divalent metal oxide or hydroxide, or the divalent metal salt of a weak acid (e.g., carbonic acid, boric acid, or a carboxylic acid) so as to form an aqueous solution having a pH of at least 3.
  • a weak acid e.g., carbonic acid, boric acid, or a carboxylic acid
  • a sulfonated aromatic compound that is used to prepare the condensation polymer may first be converted to a salt (by using a divalent metal oxide or hydroxide, or a divalent metal salt ofa weak acid) before reaction with an aldehyde to yield the salt form of the polymer.
  • Suitable divalent metal oxides or hydroxides include oxides and hydroxides of calcium, magnesium and zinc.
  • Divalent metal salts of weak acids include carbonates, bicarbonates, acetates, formates and borates of calcium, magnesium and zinc.
  • Silicates are another useful additive for obtaining improved stain resistance.
  • Silicates that may be used in the invention have the formula M O m (SiO 2 ), where M is an alkali metal such as sodium or potassium, and the value of m is about 0.5 to 2.0.
  • M is an alkali metal such as sodium or potassium
  • m is about 0.5 to 2.0.
  • the silicate is a sodium silicate and most preferably sodium metasilicate (i.e. where M is sodium and m is 1.0).
  • the silicate may contain water of hydration, for example, Na 2 O SiO 2 9H 2 O (Na 2 SiO 3 9H 2 O).
  • Sulfonated aromatic condensation polymers may discolor with time and assume a yellow tint that can be undesirable, especially depending on the color of the substrate to which the stainblocking composition is applied.
  • a blue substrate may acquire a greenish cast.
  • One technique for reducing the tendency to change color is to remove color formers inherent in the stainblocking material. This can be accomplished by dissolving the condensation polymer in aqueous base so as to form a solution having a pH of about 8-12, acidifying the aqueous solution to a pH of about 2 to 7.5, heating the acidified material to a temperature of about 50 to 65 °C so as to cause phase separation, removing materials which remain water- soluble after acidification and heating (e.g., by filtering, centrifuging or decanting), and dissolving the resultant water-insoluble material in aqueous base to a final pH of at least about 8, using heat as necessary to effect dissolution.
  • Strong bases e.g., sodium hydroxide, potassium hydroxide, lithium hydroxide
  • Virtually any acid is suitable, e.g. glacial acetic acid, dilute acetic acid, hydrochloric acid, sulfuric acid, oxalic acid, citric acid, or sulfamic acid.
  • glacial acetic acid dilute acetic acid, hydrochloric acid, sulfuric acid, oxalic acid, citric acid, or sulfamic acid.
  • Another technique for reducing the tendency to change color is to acylate or etherify a portion ofthe free hydroxyl groups in the condensation polymer.
  • acylating or etherifying the free hydroxyl groups can reduce the stainblocking characteristics ofthe condensation polymer.
  • Useful acylating agents include acetic anhydride and ethylchloroformate (conversion of about 50% to 80% ofthe phenolic hydroxyl groups).
  • Chloroacetic acid is a useful etherifying agent (conversion of about 40% .to 60% ofthe phenolic hydroxyl groups).
  • the acylated and etherified products can be prepared by dissolving the condensation polymer in an aqueous medium having a pH of 7 or above, preferably about 10 or 11 to 13 or 14 (the actual pH depending on the acylating or etherifying agent), and at a temperature that favors acylation or etherification.
  • the water-insoluble phase can be separated from the unwanted water solution by filtering, centrifuging, decanting, etc., and then redissolved in a hydroxyl-functional material, such as ethylene glycol, 1,3-propylene glycol, or 1,3-butylene glycol.
  • a hydroxyl-functional material such as ethylene glycol, 1,3-propylene glycol, or 1,3-butylene glycol.
  • sulfonated aromatic polymers useful in the invention as stainblocking materials may comprise a copolymer of: (a) one or more ethylenically unsaturated aromatic monomers; and (b) one or more sulfonated ethylenically unsaturated aromatic monomers.
  • ethylenically unsaturated aromatic monomers (a) include styrene, ⁇ -methylstyrene, 4-methyl styrene, stilbene, 4-acetoxystilbene, eugenol, isoeugenol, 4-allylphenol, safrole, and mixtures of these materials.
  • the sulfonated monomers are water soluble, which can be facilitated by providing the monomer in the form ofa salt, for example, salts of alkali metals (e.g., sodium) and ammonium salts.
  • a salt for example, salts of alkali metals (e.g., sodium) and ammonium salts.
  • alkali metals e.g., sodium
  • ammonium salts e.g., sodium
  • sulfonated monomers (b) may be used including those which result from sulfonating the ortho and or para positions ofthe monomers used to provide ethylenically unsaturated aromatic monomer (a).
  • Particular examples include sodium p-styrene sulfonate, sodium vinyl p-toluene sulfonate, ammonium p-styrene sulfonate.
  • the ratio of units derived from monomer (a) to the units derived from monomer (b) is preferably about 0.1 to 10: 1, more preferably about 0.9: 1.
  • Materials of this type are described in International Patent Publication No. WO 92/07131 (E.I. du Pont de Nemours and Company).
  • the sulfonated aromatic copolymers can be conveniently prepared by a variety of free radical-initiated polymerization reactions using, for example benzoyl peroxide or 2,2'-azobis (2-methylbutyronitrile).
  • a second class of stainblocking materials useful in the invention are polymers of at least one or more ( ⁇ -and/or ⁇ -substituted) acrylic acid monomers, these materials sometimes being referred to herein as ( ⁇ -and/or ⁇ -substituted) acrylic acid polymers.
  • the use ofthe parenthetical expression " ⁇ -and/or ⁇ - substituted" indicates that substitution ofthe ⁇ and ⁇ positions ofthe acrylic acid monomer is independently optional. That is, both positions may be substituted, neither position may be substituted, or either one ofthe two positions may be substituted without the other position being substituted.
  • ( ⁇ -and/or ⁇ - substituted) acrylic acid monomers that are useful in preparing the polymers have the general structure HR'C ⁇ COOX, wherein R and R 1 are independently selected (i.e., they may be the same or they may be different) from hydrogen, organic radicals or halogen, and X is hydrogen, an organic radical, or a cation.
  • Organic radicals that may be used to provide R and R 1 include aliphatic hydrocarbons (more preferably, alkyl moieties having about 1 to 20, most preferably about 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl), which, optionally, may be sulfonated or halogenated (for example, by chlorine or fluorine); and aromatic hydrocarbons (more preferably, a phenyl group), which, optionally, may be sulfonated, halogenated (for example, by chlorine or fluorine), hydroxylated (e.g., phenol or naphthol), or combinations thereof (e.g., sulfonated phenol or sulfonated naphthol).
  • Halogens that may be used for R and R 1 include chlorine and fluorine.
  • Organic radicals that may be used to provide the X group include both aliphatic moieties (which may be linear, branched or cyclic, and preferably containing about 1 to 10 carbon atoms), or aromatic moieties, any of which may, optionally, be halogenated, sulfonated, carboxylated, hydroxylated or ethoxylated, including cationic (e.g., sodium, potassium, ammonium, and quaternary amine) salts of these materials.
  • Cations that may be used to provide X include sodium, potassium, ammonium, and quaternary amine.
  • Preferred monomers are defined by structures in which R 1 is hydrogen, R is an alkyl group having 1 to 4 carbon atoms, phenyl, phenol, sulfonated phenol, naphthol, chlorine, or fluorine, and X is hydrogen, an alkyl group of 1 to 10 carbon atoms, sodium, potassium or ammonium.
  • the most preferred monomer is methacrylic acid (R 1 and X are hydrogen, R is methyl).
  • the ( ⁇ -and/or ⁇ -substituted) acrylic acid polymers are preferably sufficiently water-soluble or water dispersible that uniform application and penetration ofthe polymer into the substrate surface can be achieved at normal application temperatures (about room temperature to 100 °C). However, excessive water solubility may reduce the treated substrate's. resistance to staining by acid colorants, as well as the effectiveness ofthe stainblocking compositions after cleaning the substrate.
  • the glass transition temperature ofthe ( ⁇ -and/or ⁇ -substituted) acrylic acid polymers can be as low as about 35 °C although higher glass transition temperatures are preferred. When polymers having high glass transition temperatures (e.g., about 90 °C or higher) are used, an additional benefit of improved soil resistance may be obtained.
  • the weight average molecular weight and the number average molecular weight ofthe ( ⁇ -and/or ⁇ -substituted) acrylic acid polymers should be selected so as to provide satisfactory stain resistance, water solubility, viscosity, and ability to be handled in conventional stainblocking material manufacturing and application processes.
  • the lower 90 weight percent ofthe polymer has a weight average molecular weight of about 3,000 to 100,000, and a number average molecular weight of about 500 to 20,000, more preferably about 800 to 10,000.
  • a larger proportion of water-soluble comonomer is preferred for high molecular weight polymers- and a larger proportion of water-insoluble comonomer is preferred for low molecular weight polymers.
  • a water soluble copolymer of acrylic acid and methacrylic acid may have a weight average molecular weight of about 80,000 to 350,000, more preferably about 100,000 to 250,000, and most preferably about 130,000 to 200,000.
  • the acrylic acid preferably comprises about 1 to 20 weight percent, more preferably about 5 to 15 weight percent, while the methacrylic acid correspondingly provides about 99 to 80 weight percent, more preferably, about 95 to 85 weight percent, the sum ofthe acrylic acid and methacrylic acid equaling 100 weight percent.
  • acrylic acid polymers Included within the class of ( ⁇ -and/or ⁇ -substituted) acrylic acid polymers are acrylic polymers; i.e., polyacryhc acid, copolymers of acrylic acid and one or more other monomers that are copolymerizable with acrylic acid, and blends of polyacryhc acid and one or more acrylic acid copolymers. These can be produced using well-known techniques for polymerizing ethylenically unsaturated monomers.
  • methacrylic polymers i.e., polymethacrylic acid, copolymers of methacrylic acid and one or more other monomers that are copolymerizable with methacrylic acid, and blends of polymethacrylic acid and one or more methacrylic acid copolymers.
  • the methacrylic polymers useful in the invention can also be prepared using methods well-known in the art for polymerization of ethylenically unsaturated monomers.
  • Monomers useful for copolymerization with either the acrylic acid or the methacrylic acid have ethylenic unsaturation.
  • Such monomers include monocarboxylic acids, polycarboxylic acids, and anhydrides ofthe mono- and polycarboxylic acids; substituted and unsubstituted esters and amides of carboxylic acids and anhydrides; nitriles; vinyl monomers; vinylidene monomers; monoolefinic and polyolefinic monomers; and heterocyclic monomers.
  • Specific representative monomers include acrylic acid, itaconic acid, citraconic acid, aconitic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, cinnamic acid, oleic acid, palmitic acid, vinyl sulfonic acid, vinyl phosphonic acid, and substituted or unsubstituted alkyl and cycloalkyl esters of these acids, the alkyl or cycloalkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, butyl, 2-ethylhexyl, octadecyl, 2-sulfoethyl, acetoxyethyl, cyanoethyl, hydroxyethyl, ⁇ -carboxyethyl and hydroxypropyl groups.
  • amides ofthe foregoing acids such as acrylamide, methacrylamide, methylolacrylamide, 1,1-dimethylsulfoethylacrylamide, acrylonitrile, and methacrylonitrile.
  • Various substituted and unsubstituted aromatic and aliphatic vinyl monomers may also be used; for example, styrene, ⁇ - methylstyrene, p-hydroxystyrene, chlorostyrene, sulfostyrene, vinyl alcohol, N-vinyl pyrrolidone, vinyl acetate, vinyl chloride, vinyl ethers, vinyl sulfides, vinyl toluene, butadiene, isoprene, chloroprene, ethylene, isobutylene, and vinylidene chloride.
  • sulfated natural oils such as sulfated castor oil, sulfated sperm oil, sulfated soybean oil, and sulfonated dehydrated castor oil.
  • Particularly useful monomers include ethyl acrylate, butyl acrylate, itaconic acid, styrene, sodium sulfostyrene, and sulfated castor oil, either alone or in combination.
  • the methacrylic acid preferably provides about 30 to 100 weight percent, more preferably about 60 to 90 weight percent, ofthe polymer.
  • the optimum proportion of methacrylic acid in the polymer depends on the comonomer(s) used, the molecular weight ofthe copolymer, and the pH at which the material is applied.
  • water-insoluble comonomers such as ethyl acrylate are copolymerized with methacrylic acid, they may comprise up to about 40 weight percent ofthe methacrylic polymer.
  • the water soluble comonomers When water-soluble comonomers such as acrylic acid or sulfoethyl acrylate are copolymerized with methacrylic acid, the water soluble comonomers preferably comprise no more than 30 weight percent of the methacrylic polymer and preferably the methacrylic polymer also comprises up to about 50 weight percent water-insoluble monomer.
  • acrylic polymers useful as stainblocking materials include AcrysolTM (available from Rohm and Haas Company) and CarbopolTM from B.F. Goodrich.
  • methacrylic polymers generally useful in the present invention include the LeukotanTM family of materials such as Leukotan TM 970, Leukotan TM 1027, Leukotan TM 1028, and Leukotan TM QR 1083, available from Rohm and Haas Company.
  • a third class of stainblocking materials useful in the invention are hydrolyzed polymers of maleic anhydride and at least one or more ethylenically unsaturated monomers.
  • the unsaturated monomer may be an alpha-olefin monomer or an aromatic monomer, although the latter is preferred.
  • a variety of linear and branched chain alpha-olefins may be used including alkyl vinyl ethers.
  • alpha-olefins are 1-alkenes containing 4 to 12 carbon atoms, such as isobutylene, 1-butene, 1-hexene, 1-octene, 1-decene, and 1-dodecene, with isobutylene and 1-octene being preferred, and with 1-octene being most preferred.
  • a portion ofthe alpha-olefins can be replaced by one or more other monomers, e.g., up to 50 wt. % of alkyl (C1-4) acrylates, alkyl (CM) methacrylates, vinyl sulfides, N-vinyl pyrrolidone, acrylonitrile, acrylamide, as well as mixture ofthe same.
  • ethylenically unsaturated aromatic monomers may be used to prepare the hydrolyzed polymers.
  • the ethylenically unsaturated aromatic monomers may be represented by the general formula: wherein R is ;
  • R l is H- CH 3 - or ;
  • R 2 is H- or CH 3 -;
  • R 3 is H- or CH 3 O-
  • R 4 is H-, CH 3 - , or CH3CO- ; and R 3 plus R 4 is -CH 2 -O-CH 2 -O-CH 2 - .
  • ethylenically unsaturated aromatic monomers include free radically polymerizable materials such as styrene, ⁇ -methylstyrene, 4-methyl styrene, stilbene, 4-acetoxystilbene (used to prepare a hydrolyzed polymer from maleic anhydride and 4-hydroxy-stilbene), eugenol, isoeugenol, 4-allylphenol, safrole, mixtures of these materials, and the like. Styrene is most preferred. The utility of some of these materials may be improved by increasing the amount of polymerization initiator or acylating or etherifying the phenolic hydroxy groups.
  • the ratio of units derived from ethylenically unsaturated monomer to units derived from maleic anhydride is about 0.4:1 to 1.3: 1 when the unsaturated monomer is an alpha-olefin, and is about 1 : 1 to 2: 1 when using an unsaturated aromatic monomer. In any event, a ratio of about 1:1 is most preferred.
  • Hydrolyzed polymers suitable for use in the invention may be prepared by hydrolyzing ethylenically unsaturated maleic anhydride polymers.
  • Alkali metal hydroxides such as potassium hydroxide, lithium hydroxide and, most often, sodium hydroxide, as well as blends of these
  • Hydrolysis can be effected in the presence of more than or less than a molar amount ofthe alkali metal hydroxide. The presence of an alcohol in the hydrolysis mixture should be avoided.
  • Hydrolyzed polymers of at least one or more alpha-olefin monomers and maleic anhydride useful in the stainblocking compositions ofthe invention are described in U.S. Patent No. 5,460,887 (Pechhold). Hydrolyzed polymers of at least one or more ethylenically unsaturated aromatic monomers and maleic anhydride useful in the stainblocking compositions ofthe invention are described in U.S. Pat. No. 5,001,004 (Fitzgerald et al.).
  • stainblocking materials may be obtained: (1) by blending together at least two or more polymers selected from among the different general classes of polymers described above; (2) by reacting together at least two or more monomers from which the different general classes of polymers are derived; (3) as the reaction product of at least one or more ofthe monomers from which the polymers may be derived and at least one or more ofthe polymers; or (4) by polymerizing at least one or more ofthe monomers in the presence of one or more ofthe polymers.
  • one or more ( ⁇ -and/or ⁇ -substituted) acrylic acid monomers may be polymerized together and, subsequent to the polymerization, blended with a sulfonated aromatic polymer. This permits both the carboxyl functionality from the ( ⁇ -and/or ⁇ -substituted) acrylic acid polymer and the sulfonate functionality from the sulfonated aromatic polymer to contribute to the stainblocking properties ofthe composition.
  • Such blends comprise a sulfonated aromatic condensation polymer (e.g., the condensation polymerization product of an aldehyde such as formaldehyde or acetaldehyde, a hydroxyaromatic compound such as bis(hydroxyphenyl)sulfone, phenol or napthol, and phenylsulfonic acid), and methacrylic polymer (e.g., polymethacrylic acid or a copolymer of methacrylic acid and or more ofthe following monomers: ethyl acrylate, butyl acrylate, itaconic acid, styrene, sodium sulfostyrene, sulfated castor oil, and acrylic acid).
  • a sulfonated aromatic condensation polymer e.g., the condensation polymerization product of an aldehyde such as formaldehyde or acetaldehyde, a hydroxyaromatic compound such as bis(hydroxyphenyl)sulfone
  • the amounts ofthe sulfonated aromatic polymer and the ( ⁇ - and/or ⁇ - substituted) acrylic acid polymer used should be sufficient to provide the desired degree of stain resistance to the substrate.
  • the substrate is nylon 6,6
  • lower application levels can be used than when the substrate is nylon 6 or wool.
  • the substrate is yarn heat-set under moist conditions (e.g., in an autoclave)
  • generally higher application levels are required than when the yarn is heat-set under substantially dry conditions.
  • the amount of sulfonated aromatic polymer is at least about 0.1 % SOF, more preferably at least about 0.2 % SOF, most preferably at least about 0.4% SOF when treating nylon 6,6 carpet fiber.
  • amounts of sulfonated aromatic polymer in excess of about 2 % SOF provide little added benefit.
  • the amount of ( ⁇ - and/or ⁇ - substituted) acrylic acid polymer is at least about 0.1 % SOF, more preferably at least about 0.2 % SOF, most preferably at least about 0.4 % SOF when treating nylon 6,6 carpet fiber.
  • amounts of ( ⁇ - and/or ⁇ - substituted) acrylic acid polymer in excess of 2 % SOF provide little added benefit.
  • the amount of sulfonated aromatic polymer used is at least about 0.2 % SOF, more preferably at least about 0.4 % SOF, based on the weight ofthe fiber when treating nylon 6 carpet fiber.
  • the amount of ( ⁇ - and/or ⁇ - substituted) acrylic acid polymer is at least about 0.2 more, % SOF, preferably at least about 0.4 % SOF when treating nylon 6 carpet fiber.
  • the ( ⁇ -and/or ⁇ -substituted) acrylic acid monomer may be polymerized in the presence ofthe sulfonated aromatic polymer.
  • a sulfonated aromatic condensation polymer e.g., the condensation polymerization product of an aldehyde such as
  • a free radical polymerization initiator is added to initiate polymerization of the ( ⁇ -and/or ⁇ -substituted) acrylic acid monomer in the presence ofthe sulfonated aromatic polymer.
  • Useful initiators include persulfates (e.g., potassium persulfate, ammonium persulfate, or sodium persulfate), peroxides (e.g., sodium peroxide, hydrogen peroxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, cumyl peroxide, t-butyl peroxide, or t-butyl hydroperoxide), azo compounds (e.g., azo- bis-isobutryonitrile), and hydrochloride salts of azo compounds.
  • persulfates e.g., potassium persulfate, ammonium persulfate, or sodium persulfate
  • peroxides e.g., sodium peroxide, hydrogen
  • a stainblocking material may be prepared by reacting a sulfonated hydroxy aromatic compound with isocyanate, carboxylic acid, carboxylic acid anhydride, carboxylic acid chloride, or other carboxylic acid precursor, any of which may be saturated or unsaturated.
  • the ester formed by this reaction may then be reacted by itself or with an ( ⁇ -and/or ⁇ -substituted) acrylic acid, and a free radical polymerization initiator, either in the presence of or in the absence of another sulfonated aromatic polymer.
  • the ester formed from the first reaction may be homopolymerized or copolymerized with an aromatic compound in an aldehyde condensation reaction.
  • the resulting product can be further reacted, either by itself or with an ( ⁇ -and/or ⁇ -substituted) acrylic acid in the presence of a free radical polymerization initiator.
  • free-radical polymerization initiators include persulfates (e.g., ammonium persulfate, sodium persulfate, or potassium persulfate), peroxides (e.g., sodium peroxide, hydrogen peroxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, cumyl peroxide, t- butyl peroxide, or t-butyl hydroperoxide), an azo compound (e.g., azo-bis- isobutyronitrile), and peracetate (e.g., t-butyl peracetate).
  • persulfates e.g., ammonium persulfate, sodium persulfate, or potassium persulfate
  • peroxides
  • a part ofthe maleic anhydride (up to 30 weight %) can be replaced by acrylic or methacrylic acid.
  • a part (preferably 1-75% by weight) of the maleic anhydride can be replaced by maleimide, N-alkyl (C M ) maleimides, N- phenyl-maleimide, fumaric acid, itaconic acid, citraconic acid, aconitic acid, crotonic acid, cinnamic acid, alkyl (C M S) esters ofthe foregoing acids, cycloalkyl (C 2 ⁇ ) esters ofthe foregoing acids, sulfated castor oil, or the like.
  • maleimide N-alkyl (C M ) maleimides, N- phenyl-maleimide, fumaric acid, itaconic acid, citraconic acid, aconitic acid, crotonic acid, cinnamic acid, alkyl (C M S) esters ofthe foregoing acids, cycloalkyl (C 2 ⁇ ) esters ofthe foregoing acids, sulfated castor oil, or
  • Particularly preferred blends comprise about 95 to 30 weight % of hydrolyzed polymer of ethylenically unsaturated aromatic monomer and maleic anhydride (more preferably, about 85 to 40 weight %), and about 5 to 70 weight % ofa sulfonated aromatic condensation polymer, e.g., a sulfonated phenol- formaldehyde condensation polymer (more preferably, about 15 to 60 weight %), wherein the sum of these two components is 100 weight %.
  • a sulfonated aromatic condensation polymer e.g., a sulfonated phenol- formaldehyde condensation polymer (more preferably, about 15 to 60 weight %)
  • the various stainblocking materials may also be polymerized with a halogenated compound, which can be especially useful in enhancing the stain resistance ofthe treated substrate and/or imparting oil and water repellency thereto.
  • Semihalogenated or perhalogenated acrylic acid and acrylate monomers are preferred; the preferred halogen being fluorine.
  • the halogenated monomers are preferably fluorinated esters of methacrylic acid, having about 3 to 20 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably, 4 to 10 carbon atoms in the (usually terminal) fluoroalkyl group. It is recommended to copolymerize the fluorinated (meth)acrylate ester with some free methacrylic acid.
  • the fluorinated esters may have low water solubility it can be helpful to include an emulsifying agent such as nonyl phenol, an ethoxylated oleic ester, or sorbitan monooleate in the stainblocking composition.
  • the emulsifying agent is used in an amount sufficient to provide a stable emulsion, typically about 0.1 to 8 %.
  • Typical fluorochemicals are produced by condensation ofa fluorinated alcohol or fluorinated primary amine with a suitable anhydride or isocyanate, for example, N-ethyl perfluorooctyl-sulfonamidoethanol and toluene diisocyanate reacted in a 2: 1 molar ratio.
  • Organoborane Amine Complexes Organoborane amine complexes useful in the invention preferably have the following general structure:
  • R 1 is an alkyl group having 1 to 18 (preferably 1 to 10) carbon atoms
  • R' and R 3 are independently selected from alkyl groups having 1 to 18 (preferably 1 to 10) carbon atoms and phenyl-containing groups. More preferably, R 1 , R 2 and R 3 are alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, iso ⁇ propyl, n-butyl, iso-butyl, and pentyl.
  • independently selected it is meant that R 2 and R 3 may be the same or that they may be different.
  • R 1 may be the same as R 2 or R 3 , or it may be different.
  • Preferably R 1 , R 2 and R 3 are the same. Most preferred are complexes in which R 1 , R 2 and R 3 are each butyl groups.
  • the value of v is selected so as to provide an effective ratio of nitrogen atoms to boron atoms in the complex.
  • the nitrogen atom to boron atom ratio in the complex is broadly about 0.5: 1 to 4: 1, preferably about 1 : 1 to 4: 1. More preferably, however, the ratio is about 1 : 1 to 2: 1, even more preferably about 1 : 1 to 1.5:1, and most preferably about 1:1.
  • a nitrogen atom to boron atom ratio of less than 1 : 1 could leave free organoborane, a material that tends to be pyrophoric.
  • the practical utility ofthe complex in, for example, a stainblocking composition diminishes as the amount of complex that must be employed to generate a useful stainblocking composition becomes larger.
  • Am represents the amine portion ofthe complex and may be provided by a wide variety of materials having at least one amine group, including blends of different amines.
  • the amine may be any primary or secondary monoamine, a polyamine containing a primary or secondary amine, or ammonia.
  • Useful monoamines may be represented by the following general formula:
  • R 4 and R 5 are hydrogen or alkyl groups having 1 to 18 carbon atoms, more preferably 1 to 10 carbon atoms, most preferably 1 to 4 carbon atoms (so as to provide, for example, n-octylamine, diethylamine, and dibutylamine), and
  • n 1 or 2. More preferably, however, "Am” represents a polyamine (i.e., having more than one amine group), including blends of different polyamines. Even more preferably, the polyamine has two to four amine groups, although polyamines with two amine groups (i.e., diamines) are most preferred. In one embodiment, the polyamine may be described by the structure
  • R 6 is a divalent, organic radical comprised of an alkylene, arylene or alkylenearylene group.
  • R 6 is a divalent, organic radical comprised of an alkylene, arylene or alkylenearylene group.
  • alkane diamines which may be branched or linear, and having the general structure
  • alkane diamines include 1,2-ethanediamine, 1,3-propanediamine, 1,5- pentanediamine, 1,6-hexanediamine, 1,12-dodecanediamine, 2-methyl-l,5-pentane diamine, 3-methyl-l,5-pentane diamine, and isomers of these materials. While alkane diamines are preferred, other alkylene polyamines may be used such as triethylene tetraamine and diethylene triamine.
  • the polyamine may also be provided by a polyoxyalkylenepolyamine.
  • Polyoxyalkylenepolyamines useful in making complexes are preferably selected from the following structures:
  • R 8 , R 9 and R 10 are alkylene groups having 1 to 10 carbon atoms and may be the same or may be different.
  • R* is an alkylene group having 2 to 4 carbon atoms such as ethylene, n-propylene, iso-propylene, n-butylene or iso-butylene.
  • R 9 and R 10 are alkylene groups having 2 or 3 carbon atoms such as ethylene, n-propylene or iso-propylene.
  • R ⁇ is the residue ofa polyol used to prepare the polyoxyalkylenepolyamine (i.e., the organic structure that remains if the hydroxyl groups are removed).
  • R 11 may be branched or linear, and substituted or unsubstituted (although substituents should not interfere with oxyalkylation reactions).
  • the value of w is ⁇ 1, more preferably about 1 to 150, and most preferably about 1 to 20. Structures in which w is 2, 3 or 4 are particularly useful too.
  • the values of x and y are both ⁇ 0.
  • the value of z is > 2, more preferably 3 or 4 (so as to provide, respectively, polyoxyalkylene triamines and tetraamines). It is preferred that the values of w, x, y and z be chosen such that the resulting complex is a liquid at room temperature, as this simplifies the handling and mixing thereof.
  • the polyoxyalkylenepolyamine is itself a liquid.
  • molecular weights of less than about 5,000 may be used, although molecular weights of about 1,000 or less are more preferred, and molecular weights of about 250 to 1,000 are most preferred.
  • Examples of particularly preferred polyoxyalkylenepolyamines include polyethyleneoxidediamine, polypropyleneoxidediamine, polypropyleneoxidetriamine, diethyleneglycolpropylenediamine, triethyleneglycolpropylenediamine, polytetramethyleneoxidediamine, polyethyleneoxide-co-polypropyleneoxidediamine, and polyethyleneoxide-co- polypropyleneoxidetriamine.
  • suitable commercially available polyoxyalkylenepolyamines include various JeffaminesTM from Huntsman Chemical Company such as the D, ED, and EDR series diamines (e.g., D-400, D-2000, D-5000, ED-600, ED-900, ED-2001, and EDR-148), and the T series triamines (e.g., T-403), as well as H221 from Union Carbide Company.
  • the polyamine may also comprise the condensation reaction product of diprimary amine-terminated material (i.e., the two terminal groups are primary amine), and one or more materials containing at least two groups reactive with primary amine (referred to herein at times as "difunctional primary amine-reactive material").
  • diprimary amine-terminated material i.e., the two terminal groups are primary amine
  • materials containing at least two groups reactive with primary amine referred to herein at times as "difunctional primary amine-reactive material”
  • Such materials are preferably substantially linear so as to have the general structure E-(L-E) travers-L-E in which each E is the residue ofthe diprimary arnine-terminated material and each L is a linking group that is the residue ofthe difunctional primary amine-reactive material.
  • Residue is meant those portions ofthe diprimary amine-terminated material and the difunctional primary amine- reactive material that remain after reaction to form the polyamine adduct.
  • each E group may be the same or may be different, as may each L group, although it is preferred that each E group be the same and that each L group be the same.
  • the majority (more than 50%) ofthe terminal groups in the polyamine should be primary amine.
  • the value of u is selected so as to provide both a polyamine and a complex of useful viscosity.
  • both the polyamine and the complex are liquid at room temperature. Consequently, the value of u may be greater than or equal to zero, although a value of about 0 to 5 is more preferred, and a value of 0 or 1 is most preferred.
  • the diprimary amine-terminated material may be alkylene diprimary amine, arylene diprimary amine, alkylenearylene diprimary amine, a polyoxyalkylenediamine (such as those described above), or mixtures thereof.
  • Useful alkylene diprimary amines include those having the structure NH 2 -R 12 -NH 2 wherein R 12 is a linear or branched alkylene group having about 1 to 12 carbon atoms such as 1,3 -propane diamine, 1,6-hexanediamine, and 1,12-dodecanediamine.
  • Other useful alkylene diprimary amines include triethylene tetraamine and diethylene triamine.
  • useful arylene diprimary amines include 1,3- and 1,4- phenylene diamine as well as the various isomers of diaminonaphthalene.
  • An example of a useful alkylenearylene diprimary amine is m-tetramethylxylylene diamine.
  • Difunctional primary amine-reactive materials contain at least two groups reactive with primary amine.
  • the reactive groups may be different, but it is preferred that they be the same.
  • Difunctional primary amine-reactive materials having a functionality of 2 are preferred.
  • Useful difunctional primary amine-reactive materials may be generally represented by the formula Y-R 13 -Z wherein R 13 is a divalent organic radical such as an alkylene, arylene or alkylenearylene group or combination thereof, and Y and Z are groups reactive with primary amine and which may be the same or may be different. Examples of useful Y and Z groups reactive with primary amine include carboxylic acid (-COOH), carboxylic acid halide (-COX, where X is a halogen, for
  • Suitable carboxylic acid-functional materials are preferably those which are use l in forming polyamides, for example, cyclohexane-l,4-dicarboxylic acid and dicarboxyUc acids having the structure HOOC-R 14 -COOH in which R 14 is a linear alkylene group having about 2 to 21 carbon atoms.
  • Aromatic dicarboxyUc acids having the structure HOOC-R 14 -COOH in which R 14 is a linear alkylene group having about 2 to 21 carbon atoms.
  • alkylenearylene dicarboxylic acids e.g., terephthalic and isophthalic acids
  • carboxylic halide acid-functional materials and ester-functional materials include those which are obtained by derivatizing the above-described carboxylic acid-functional materials.
  • Suitable aldehyde-functional materials include alkylene, arylene and alkylenearylene dialdehydes such as oxalaldehyde, malonaldehyde, succinaldehyde, adipaldehyde, 2-hydroxyhexanedial, phthalaldehyde, l,4,benzenediacetaldehyde, 4,4-(ethylenedioxy) dibenzaldehyde, and 2,6-naphthalene dicarbaldehyde. Most preferred are gtutaraldehyde and adipaldehyde.
  • Suitable epoxide-functional materials include aliphatic, cycloaliphatic and glycidyl ether diepoxides. Most preferred are the diepoxides based upon bis-phenol
  • acrylic-functional materials are preferably diacrylates and a wide variety of such materials may be successfully employed in the invention.
  • heterocyclic diamines in which both amine groups are within the heterocyclic structure.
  • Useful examples of such materials may be represented by the general structure in which R 15 and R 16 are alkylene groups which may be the same or which may be different.
  • R 1J and R 16 cooperate to form, with the two nitrogen atoms, a 5 to 8-membered ring.
  • R 15 and R 16 are each -CH 2 -CH 2 - radicals so as to yield piperazine.
  • heterocyclic tertiary polyamines such as triethylenediamine.
  • the organoborane amine complex may be readily prepared using known techniques. Typically, the amine is combined with the organoborane in an inert atmosphere with slow stirring. The amine and the organoborane may be combined neat or in the presence of an inert organic solvent (e.g., an aprotic ether such as tetrahydrofuran or diethyl ether). An exotherm is often observed and cooling ofthe mixture is, therefore, recommended. The use of an inert organic solvent may be helpful in moderating the exotherm. If the ingredients have a high vapor pressure, it is desirable to keep the reaction temperature below about 70 to 80° C. Once the materials have been well mixed the complex is permitted to cool to room temperature. No special storage conditions are required although it is preferred that the complex be kept in a capped vessel in a cool, dark location.
  • an inert organic solvent e.g., an aprotic ether such as
  • the organoborane amine complex is included in the stainblocking composition in an effective amount, by which is meant an amount sufficient to increase the stain resistance of a substrate treated with the stainblocking composition (as compared to a substrate that has been treated with the same stainblocking composition but which does not contain the organoborane amine complex), but without leaving insolubles that could cause undesirable spot staining.
  • Small amounts of complex may not result in a sufficient increase in stain resistance, while large amounts may be more difficult to solubilize and could cause undesirable spot staining.
  • the actual stain resistance effective amount of complex will be influenced by a variety of factors including the type of substrate, the type of stainblocking material, the concentration at which the stainblocking material is applied (% SOF), and the pH at which the stainblocking composition is applied to the substrate.
  • a stain resistance effective amount of organoborane complex is about 1 to 70 parts per 100 parts of stainblocking material, more preferably about 5 to 20 parts.
  • a wide variety of additives may be usefully inco ⁇ orated into the stainblocking compositions ofthe invention for the purpose of achieving a desired effect.
  • a water soluble, divalent metal salt in the stainblocking composition may improve its effectiveness in imparting stain resistance to a substrate.
  • the water soluble, divalent metal salt also can reduce the amount of stainblocking material that needs to be included in the stainblocking composition, as well as broaden the pH range at which a substrate may be treated.
  • Useful divalent metal salts include water soluble inorganic and organic salts of metals such as magnesium, barium, calcium and zinc. Inorganic salts include chlorides, sulfates and nitrates of these metals.
  • Organic salts include acetates and formates of these metals. Preferred are magnesium sulfate, magnesium chloride and magnesium acetate. Mixtures of two or more salts can also be used.
  • the divalent metal salts are preferably used in an amount of at least 1% SOF, more preferably at least 1.5% SOF, most preferably at least 2% SOF. However, metal salt amounts in excess of 5% SOF generaUy do not provide any appreciable increase in stain resistance. Such techniques are described in U.S. Pat. No.
  • Surfactants and/or hydrotropes may be included to improve the solubility of the various stainblocking composition ingredients in each other, to promote better wetting ofa substrate that is to be treated with the stainblocking composition, or for other benefits.
  • Useful surfactants may be ionic or nonionic while useful hydrotropes are usually anionic.
  • Common ionic surfactant families include sodium and potassium salts of straight chain fatty acids (soaps), sodium and potassium salts of coconut oil fatty acids, sodium and potassium salts of tall oil acids, amine salts, acylated polypeptides, linear alkylbenzene sulfonates, higher alkyl benzene sulfonates, aromatic sulfonates, petroleum sulfonates, paraffin sulfonates (secondary n- alkanesulfonates), olefin sulfonates, sulfosuccinate esters, alkylnaphthylsulfonates, isothioates, sulfuric acid ester salts, including sulfated linear primary alcohols, sulfonated phenols, sulfated polyoxyethylenated alkyl phenols, sulfated polyoxyethylenated straight chain alcohols, sulfated triglyceride
  • N-alkyl- ⁇ -iminodipropionic acids imidazoline carboxylates, N-alkylbetaines, amine oxides, sulfobetaines and sultaines.
  • Common nonionic surfactants include polyoxyethylenated alkylphenols (such as the polyoxyethylenated derivatives of nonylphenol, octylphenol, and dodecylphenol), alcohol ethoxylates, polyoxyethylenated polypropylene glycol, polyoxyethylenated mercaptans, long chain carboxylic acid esters, glycerol, polyglycerol esters of natural fatty acids, polyoxyethylenated sorbitol esters, polyoxyethylenated fatty acid esters, alkanolamides, alkanolamine fatty acid condensates, tertiary acetylenic glycols, polyoxyethylenated silicones and alkylpolyglycosides.
  • polyoxyethylenated alkylphenols such as the polyoxyethylenated derivatives of nonylphenol, octylphenol, and dode
  • Useful hydrotropes include sodium benzene sulfonate, sodium xylene sulfonate, sodium naphthalene sulfonate, and sodium cumene sulfonate.
  • an ( ⁇ -and/or ⁇ -substituted) acrylic acid monomer may be polymerized in the presence of an aromatic sulfonic compound.
  • Possible monomers include aromatic sulfonic acids (e.g., those described above such as toluene sulfonic acid, benzene sulfonic acid, dodecylbenzene sulfonic acid, cumene sulfonic acid and xylene sulfonic acid) or a salt (e g, potassium, sodium or ammonium) of these acids.
  • aromatic sulfonic acids e.g., those described above such as toluene sulfonic acid, benzene sulfonic acid, dodecylbenzene sulfonic acid, cumene sulfonic acid and xylene sulfonic acid
  • a salt e g, potassium, sodium or ammonium
  • halogenated materials described earlier for polymerizing with the stainblocking materials can, alternatively, be physically blended with the stainblocking composition to provide oil and water repellency to a treated substrate.
  • the stainblocking compositions ofthe invention are useful in imparting stain resistance to a wide variety of fibrous substrates that contain polyamide linkages, including fabrics, textiles and, especially, carpet.
  • Polyamide linkages are found in a wide variety of fibers such as wool, silk, natural leather, synthetic leather and nylon.
  • Nylon is particularly preferred and comprises a synthetic polyamide prepared by the polycondensation ofa dicarboxylic acid and a diamine, such as adipic acid and hexamethylene diamine (nylon 6,6).
  • Nylon can also be produced from a cyclic amide such as caprolactam (nylon 6).
  • the stainblocking compositions ofthe invention are easily prepared by physically blending the stainblocking material and the organoborane amine complex. Typically they are prepared in the form of an aqueous solution.
  • the stainblocking material and the organoborane amine complex may be combined before using the stainblocking composition and then shipped or stored in this manner until needed, or they may be retained in separate containers and combined shortly before the stainblocking composition is applied to a substrate.
  • the latter case may be regarded as a two-part stainblocking composition or system comprising the stainblocking material in one part and the organoborane amine complex in the second part.
  • a stainblocking composition refers to both two-part systems and one- part systems (i.e., the stainblocking material and the organoborane amine complex having already been combined).
  • the pH ofthe aqueous stainblocking composition is preferably below 7, more preferably below about 5, and most preferably below about 3.
  • One ofthe advantages afforded by the present invention is the ability ofthe stainblocking composition to impart stain resistance even when the stainblocking composition is applied at a relatively high pH (i.e., about 4.5).
  • the need for special handling requirements before shipping, using or disposing ofthe stainblocking composition can be reduced or eliminated.
  • the stainblocking composition may be applied to the fibrous substrate in a variety of ways including the use of dyeing techniques conventionally used to dye fibrous substrates, immersing, padding, foaming, or spin finishing. Best results are usually achieved when the stainblocking compositions are appUed under hot (e.g., near boiling) conditions to promote good absorption by the substrate, foUowed by drying the substrate.
  • the stainblocking compositions are particularly useful in conjunction with wool and nylon carpet, and many ofthe application techniques have been specifically developed for use in such environments, though they can be adapted for use with fibrous substrates other than carpet.
  • the stainblocking composition can be applied from an aqueous exhaust bath such as is used in beck dyeing of carpet.
  • the stainblocking composition can be added to the aqueous dye bath solution and exhausted concurrently with the dye.
  • the dye bath is maintained at a temperature at or near the boiling point for a period of 10 to 90 minutes or more to effect co- exhaustion ofthe dye and stainblocking composition.
  • the substrate is then dried.
  • the stainblocking composition can be added to the aqueous dye bath after exhaustion ofthe dye, or the dye bath can be drained and fresh water added prior to the addition ofthe stainblocking composition.
  • the bath is maintained at a temperature at or near boiling for a period of time sufficient to exhaust the stainblocking composition, usually 10 to 90 minutes.
  • the substrate is then dried.
  • the stainblocking composition can be applied during continuous dyeing, such as with KusterTM or OttingTM carpet dyeing equipment.
  • the stainblocking composition can be added directly to the aqueous dye solution and the solution is conventionally applied to the substrate.
  • the stainblocking composition can be applied during a wetting out step prior to application ofthe dye.
  • the substrate is then dried.
  • the stainblocking composition can also be applied to a fibrous substrate by a padding operation. This can be done as a separate step or in conjunction with the appUcation of various conventional finishes such as wetting agents, softeners, and leveling agents.
  • the fibrous substrate is dried.
  • suitable methods include application by low-pressure padding such as can be accomplished with Kuster FlexnipTM equipment, spray applicators such as those available from Otting International, or dip boxes which need not be equipped with moisture reduction apparatus such as squeeze rolls.
  • the stainblocking composition is generally applied from an aqueous solution at ambient or elevated (e.g., about 60 to 90° C) conditions, followed by steaming from 15 to 180 seconds, then drying.
  • the stainblocking composition can also be applied by foam techniques which are well-known in the carpet industry. Generally, the stainblocking composition is applied from an aqueous solution which further can contain a foaming agent, such as those typically used in foam dyeing. The stainblocking composition can also be applied to carpet during shampooing operations that use, for example, scrubbing machines and steam or hot water cleaning machines.
  • the stainblocking composition can be applied by spin finishing during the melt spinning process used to prepare polyamide fibers.
  • the stainblocking composition is applied to a fibrous substrate by a kiss-roll or other metered applicator and then the substrate is heat-set.
  • the stainblocking composition typically includes lubricating oils for the fibers as well as dispersants for the oUs.
  • subsequent processing ofthe fibers e.g., heat-setting or steaming
  • results in a slight reduction in stainblocking performance such loss can be restored to the fiber by including a small amount (about 0.1 to 3% SOF) in the dye liquor (i.e., the liquid containing the dye for dyeing the fiber).
  • the stainblocking compositions ofthe invention can be usefully applied at room temperature without using steam or heat.
  • the amount of stainblocking composition that is applied to the fibrous substrate is effective to impart stain resistance to the treated substrate.
  • the actual amount will vary depending on the type of substrate, the conditions under which it is applied, the level of stain resistance desired, the type of stainblocking material, and the type and amount of organoborane amine complex.
  • the stainblocking composition is typically applied at a level of at least about 0.1 % SOF, although amounts in excess of about 3 % SOF are generally not used for cost reasons. More preferred stainblocking composition amounts are applied at about 0.2 to 2 % SOF, with about 0.5 to 1 % SOF being most preferred.
  • the plastic bag application procedure is a convenient laboratory technique for applying a measured amount of stainblocking composition to a small sample by immersion.
  • a carpet sample measuring approximately 5 inches x 4 inches (13 cm x 10 cm) was treated by immersion for a period of time specified in the examples by placing the sample in a resealable plastic bag containing an aqueous stainblocking composition.
  • the amount of stainblocking material used in the aqueous stainblocking composition was that which gave the desired theoretical percent by weight of total solids that were to be applied to the fibrous carpet sample (% SOF), with the assumption that 100% ofthe stainblocking material would be retained on the carpet.
  • This amount of stainblocking material was dissolved or dispersed in deionized water (along with any organoborane amine complex) to form the aqueous stainblocking composition, the pH of which was adjusted to a level reported in the examples using 10% aqueous sulfamic acid (10 g of soUd acid in 90 g of water).
  • the weight ofthe aqueous stainblocking composition in the resealable plastic bag was approximately 4.5 times the weight ofthe carpet sample. After immersion, the carpet sample was rinsed twice with 1 liter aUquots of deionized water to remove excess stainblocking composition, spun to dampness using a Bock Centrifugal Extractor, and air-dried overnight at room temperature.
  • This procedure simulated the flex-nip operations used by commercial carpet mills to apply stainblocking composition to carpet.
  • a carpet sample measuring approximately 5 inches x 4 inches (13 cm x 10 cm) was immersed in deionized water at room temperature until dripping wet. Water was extracted from the sample by spinning in a Bock Centrifugal Extractor until the sample was damp. The damp carpet sample was then steamed for 2 minutes at atmospheric pressure, 90-100 °C, and 100% relative humidity in an enclosed steam chamber. After steaming, the carpet sample was allowed to cool to near room temperature, and the aqueous stainblocking composition was applied by placing the sample, carpet fiber side down, into a glass tray containing the stainblocking composition.
  • the stainblocking composition contained sufficient stainblocking material to give the desired theoretical % SOF and was prepared by dissolving or dispersing the stainblocking material (and any organoborane amine complex) in deionized water and adjusting the pH to the level reported in the examples using 10% aqueous sulfamic acid, as described in the plastic bag application procedure.
  • the weight ofthe aqueous stainblocking composition in the glass tray was approximately 4.5 times the weight ofthe carpet sample.
  • the carpet sample absorbed the entire volume of stainblocking composition over about 1 to 2 minutes.
  • the wet, stainblocking composition-treated carpet sample was steamed a second time for 2 minutes (using the conditions and equipment described above), immersed briefly in a 5 -gallon bucket half full with deionized water, rinsed thoroughly under a deionized water stream to remove residual, excess stainblocking composition, spun to dampness using the centrifugal extractor, rerinsed with deionized water, spun to dampness again, and allowed to air-dry overnight at room temperature.
  • a dry carpet sample that had been first treated with a stainblocking composition was stained for 2 minutes by immersing the carpet sample in an excess amount (about 800 ml to 1 liter) ofa solution of 0.007% (wt) of Red Dye FD&C #40 in deionized water with pH adjusted to 2.8 with 10% aqueous sulfamic acid.
  • the dye solution was warmed to a temperature specified in the examples, usually about 55-70 °C.
  • the treated and stained carpet sample was then immersed briefly in a 5-gallon bucket half full with deionized water, followed by rinsing under a stream of deionized water until the water ran clear.
  • the wet carpet sample was then extracted to dampness using a Bock Centrifugal Extractor and was air-dried overnight at room temperature.
  • the degree of staining was determined numerically using a Minolta Chroma MeterTM compact tristimulus color analyzer.
  • the color analyzer measured the reflected red stain color autochromatically on the red-green coordinate as a "delta a" ( ⁇ a) value as compared to the color of an unstained and untreated carpet sample. Measurements reported in the tables below are given to one place following the decimal point and represent the average of 3 measurements, unless stated otherwise. A greater ⁇ a reading indicates a greater amount of staining from the red dye.
  • organoborane amine complex is expressed in parts (reported to two significant digits), which refers to parts per 100 parts of stainblocking material.
  • Example 1 and Comparative Example Cl iUustrate the ability of nylon 6,6 carpet treated with a stainblocking composition that comprised a blend of sulfonated aromatic condensation polymer and ( ⁇ -and/or ⁇ -substituted) acryUc polymer, with and without an organoborane amine complex, to resist staining by aqueous acid red dye under a variety of time and temperature exposure conditions.
  • a stainblocking composition was prepared by blending in a jar 1.7 g (0.5 g solids) of FX-661, 25 g of deionized water, and 40 mg of neat TBB-HMDA complex.
  • the TBB-HMDA complex for example 1 and for the following examples was prepared by combining the organoborane and the amine in an inert atmosphere with slow stirring. The mixture was cooled as needed to moderate any exotherm, and when the reaction was complete was cooled to room temperature.
  • Transition IIITM carpet was cut into approximately 5.5 cm x 4.0 cm samples. The samples were soaked in the stainblocking composition for 16 hours at room temperature, rinsed with 1 liter of deionized water for approximately one minute, pressed to dampness by hand between paper towels, and allowed to air-dry overnight at room temperature.
  • the dried carpet samples were stained by immersion in an aqueous solution of 0.007% (wt) Red Dye FD&C #40 adjusted to a pH of 2 with 10% (wt) aqueous sulfamic acid for 3 minutes at temperatures of 22°C, 50°C or 80°C.
  • Carpet sample dye immersion tests were also conducted for 2.5 hours at room temperature (about 25°C). The degree of staining was visually and qualitatively estimated based on single samples (no repetitions) and with the results presented in Table 1.
  • Example 1 was repeated except that the stainblocking composition did not include TBB-HMDA complex. The degree of staining was visually and qualitatively estimated with the results presented in Table 1.
  • Examples 2-7 and Comparative Example 2 illustrate how the stain resistance of nylon 6,6 carpet is affected by the amount of organoborane amine complex in the stainblocking composition.
  • the plastic bag application procedure was used to treat Transition IDTM nylon 6,6 carpet at 1.1% SOF with a 2.5 pH stainblocking composition that comprised FX-661TM stainblocking material and varying amounts (parts) of TBB-HMDA complex as specified in Table 2 below.
  • the immersion time was approximately 22 hours.
  • the complex was added to the FX-661TM as an acetone solution having a complex concentration of 40 mg/ml.
  • the carpet samples were allowed to air-dry overnight at room temperature before the second staining and rinsing cycle. ⁇ a values were measured after each cycle using the procedure described above and with the results reported below in Table 2.
  • Table 2 shows that the ability ofthe treated carpet sample to resist staining increases with larger amounts of organoborane amine complex, but that even relatively small amounts significantly improve the stain resistance ofthe ca ⁇ et.
  • Examples 8-15 and Comparative Examples C3-C6 illustrate the durability of the stainblocking compositions ofthe invention to repeated staining cycles.
  • Transition UITM nylon 6,6 ca ⁇ et was treated at 1.1% SOF with a stainblocking composition that comprised a blend of FX-661TM and TBB-HMDA complex.
  • a stainblocking composition that comprised a blend of FX-661TM and TBB-HMDA complex.
  • the stainblocking composition pH, and amount (parts) of organoborane amine complex in the composition were varied as specified in Table 3 below.
  • the simulated flex-nip application procedure was used to apply a stainblocking composition comprising FX-369TM and TBB-HMDA complex to Transition mTM nylon 6,6 ca ⁇ et.
  • concentration at which the stainblocking composition was appUed, the amount (parts) of organoborane amine complex in the composition, and the pH ofthe stainblocking composition were varied as shown below in Table 4.
  • An "unadjusted" pH means that no aqueous sulfamic acid was used. The pH was about 6.
  • Staining was done at 65 ⁇ 3 °C and the ⁇ a color values ofthe ca ⁇ et samples were measured using the procedure described earlier (Cycle 1). After allowing each ca ⁇ et sample to air-dry overnight at room temperature, the staining procedure was repeated at 65 ⁇ 3°C and a second set of ⁇ a values was measured (Cycle 2). The results are presented in Table 4.
  • the plastic bag application procedure was used to apply a stainblocking composition comprising FX-661TM and various organoborane amine complexes to Transition 111TM nylon 6,6 ca ⁇ et, as shown below in Table 5 along with the amount (parts) ofthe complex solids that was employed.
  • No organoborane amine complex was added to the stainblocking material in Comparative Example Cl l.
  • the organoborane amine complexes were dissolved in acetone to a concentration of 40 mg/ml to facilitate addition to the stainblocking material.
  • the stainblocking composition was appUed at a concentration of 0.55 % SOF, and at a pH of 2.5, with a ca ⁇ et sample immersion time in the aqueous composition of 15 hours. Staining was done at room temperature (about 20 - 25 °C) for 3 hours and the ⁇ a color values ofthe ca ⁇ et samples were measured using the procedure described earlier. The results are presented in Table 5.
  • Table 5 show the efficacy ofthree different organoborane amine complexes in enhancing the properties of FX-661TM stainblocking material.
  • Trialkylboranes in which the three alkyl groups are the same and have from 1 to 5 carbon atoms are preferred.
  • Various amines may be used to complex the organoborane including linear alkyl diamines, heterocyclic diamines, and polyoxyalkylenediamines. Larger amounts of complex gave better performance.
  • the simulated flex-nip application procedure was used to apply stainblocking compositions at a pH of 2.5 to different types of nylon ca ⁇ et.
  • Examples 32-39 and Comparative Examples C12-C15 Transition mTM nylon 6,6 ca ⁇ et was used (identified in the examples as N6,6).
  • the stainblocking material that was used, the concentration at which the stainblocking composition was applied, and the amount (parts) of organoborane amine complex in the composition were varied as shown below in Table 6.
  • the organoborane amine complex was TBB-HMDA. Staining was done at 64 ⁇ 1 °C and the ⁇ a color values ofthe ca ⁇ et samples were measured using the procedure described earUer. The results are presented in
  • Example 37 shows that except for Example 37 which showed some spot staining, the use of organoborane amine complex in combination with either StainkleerTM GX-1 or FX-661TM stainblocking material, significantly improved the stain resistance of both nylon 6 and nylon 6,6 ca ⁇ et.
  • Stainblocking compositions using StainkleerTM GX-1 and either 21 or 64 parts organoborane amine complex, even when applied at 0.55% SOF (Examples 32 and 33), showed far superior stain resistance to stainblocking compositions that included 1.1% SOF StainkleerTM GX- 1 but no organoborane amine complex (Comparative Example C13). The best overall ⁇ a values were achieved with FX-661TM stainblocking material and the organoborane amine complex. Examples 44-47 and Comparative Examples C18-C19
  • the simulated flex-nip application procedure was used to apply stainblocking compositions at a concentration of 1.1% SOF and at a pH of 2.5 to both Transition IIITM nylon 6,6 ca ⁇ et and the off-white style #51699 nylon 6 ca ⁇ et from Examples 40-43 and Comparative Examples C16-C17.
  • the stainblocking composition comprised SR-300TM styrene/maleic anhydride stainblocking material and TBB-HMDA organoborane amine complex.
  • the amount (parts) of organoborane amine complex in the composition was varied as shown below in Table 7. Staining was done at 65 ⁇ 1 °C and the ⁇ a color values ofthe ca ⁇ et samples were measured using the procedure described earlier. The results are presented in Table 7.
  • Examples 48-65 and Comparative Examples C20-C37 illustrate the stain resistance of nylon 6,6 ca ⁇ et treated with various stainblocking compositions after simulated shampooing under mild or strong alkalinity conditions (pH of 8 or 10, respectively).
  • the simulated flex-nip appUcation procedure was used to apply a stainblocking composition comprising different stainblocking materials and TBB- HMDA complex to Transition IHTM ca ⁇ et.
  • the type of stainblocking material, the amount (parts) of organoborane amine complex in the composition, and the pH of the stainblocking composition were varied as shown below in Table 8.
  • the stainblocking compositions were appUed at 0.55% SOF.
  • test A The ca ⁇ et samples were then stained and evaluated using one ofthree test methods: Test A, Test B or Test C.
  • Test A Staining Without Prior Shampoo Exposure
  • a 0.007% (wt) solution of Red Dye FD&C #40 in deionized water was made, adjusting the solution pH to 2.8 with aqueous sulfamic acid.
  • a 400 ml plastic beaker with the bottom cut out was placed bottom side down in the middle ofa dry ca ⁇ et sample to which a stainblocking composition had been previously applied. 25-30 ml ofthe dye solution was then poured at room temperature inside the beaker and onto the ca ⁇ et, forming a circular stain.
  • Test B Staining After Simulated Shampoo Exposure at a pH of 8 Ca ⁇ et samples previously treated with a stainblocking composition were immersed for 5 minutes in a simulated shampoo solution containing 57 g of DuponolTM WAQE surfactant (available from Witco Co ⁇ .) in 3,800 g of deionized water, with pH adjusted to 8 using an aqueous solution of trisodium phosphate. The samples were then thoroughly rinsed under a stream of deionized water, extracted to dampness using a Bock Centrifugal Extractor, air-dried overnight at room temperature, and subjected to the two staining cycles described in Test A.
  • DuponolTM WAQE surfactant available from Witco Co ⁇ .
  • Test C Staining After Simulated Shampoo Exposure at a pH of 10 Test C used the procedure described in Test B except that the pH ofthe simulated shampoo solution was adjusted to 10.
  • stainblocking composition pH was evaluated in Examples 66-81 and Comparative Examples C38-C45.
  • the simulated flex-nip application procedure was used to apply a stainblocking composition comprising SR-300TM stainblocking material and TBB-HMDA complex to Transition IIITM nylon 6,6 ca ⁇ et.
  • the amount (parts) of organoborane amine complex in the composition, the concentration at which the stainblocking composition was appUed, and the pH of the stainblocking composition were varied as shown below in Table 9. Staining was done at 72 ⁇ 1 °C and the ⁇ a color values ofthe ca ⁇ et samples were measured using the procedure described earUer. The results are presented in Table 9.
  • Examples 82-89 and Comparative Examples C46-C53 illustrate that the stainblocking composition ofthe invention can impart improved stain resistance to wool carpet.
  • the simulated flex-nip application procedure was used to apply a stainblocking composition comprising various stainblocking materials and TBB- HMDA complex to level loop, off-white/light beige color wool ca ⁇ et (Cobblestone style CM0190, 44-50 oz./yd 2 , manufactured by Shaw Industries).
  • the weight of the stainblocking composition that was applied to the ca ⁇ et sample was about 5 times the weight ofthe ca ⁇ et sample.
  • the stainblocking material that was used, the concentration at which the stainblocking composition was applied, the amount (parts) of organoborane amine complex in the composition, and the pH ofthe stainblocking composition were varied as shown below in Table 10. Staining was done at room temperature (about 25 °C) for at least 8 hours and the ⁇ a color values ofthe ca ⁇ et samples were measured using the procedure described earlier. The results are presented in Table 10.
  • Examples 90-94 and Comparative Examples C54-C58 illustrate the durability ofthe stainblocking compositions ofthe invention to repeated staining cycles under conditions of varying stainblocking composition pH.
  • Transition IIF M nylon 6,6 ca ⁇ et was treated at 0.55% SOF with a stainblocking composition that comprised a blend of FX-661TM and either 21 parts or 0.0 parts TBB-HMDA complex.
  • a stainblocking composition that comprised a blend of FX-661TM and either 21 parts or 0.0 parts TBB-HMDA complex.
  • For each treated ca ⁇ et sample there were two cycles of dye staining and rinsing. The first staining cycle was for 5 hours at room temperature (about 25 °C). The second staining cycle was for 21 hours at room temperature.
  • ⁇ a values were measured after each cycle using the procedure described earlier and with the results reported below in Table 11. The ca ⁇ et samples were allowed to air-dry overnight at room temperature before each staining and rinsing cycle. Table 11
  • stainblocking compositions that include an organoborane amine complex consistently outperform stainblocking compositions that do not include an organoborane amine complex, across a wide range of stainblocking composition pHs.
  • stainblocking compositions with a lower pH provide better stain resistance than stainblocking compositions at a higher pH.
  • Comparative Examples C59-C64 were prepared to evaluate the inherent stainblocking characteristics ofthe organoborane amine complex. Comparative Examples C59-C62 were prepared following the plastic bag application procedure except that the plastic bag did not include any stainblocking material.
  • the plastic bag contained TBB-HMDA complex dispersed in 76.5 g deionized water, the amount of complex being specified in Table 12 below in milUgrams.
  • the pH ofthe dispersion is also shown in Table 12 where the "unadjusted" pH (i.e., no addition of sulfamic acid) was about 6. Also shown in Table 12 is the immersion time for the Transition ITJTM nylon 6,6 ca ⁇ et sample in the dispersion ofthe complex.
  • Comparative Example C63 the ca ⁇ et sample was not treated with organoborane amine complex but was stained.
  • Comparative Example C64 the ca ⁇ et sample was not treated with organoborane amine complex and was not stained. It was used as the reference for determining ⁇ a values and is given a ⁇ a value of "0" in Table 12. Staining of all samples was done at 60 ⁇ 3 °C and the ⁇ a color values were measured using the procedure described above and with the results presented in Table 12. The values reported for examples C59-C64 are an average of six measurements.
  • Table 12 shows that the organoborane amine complexes do not independently impart stain resistance to fibrous substrates treated therewith.
  • 1 pint bottle were added 25 g of methacrylic acid, 75 g of deionized water, and 1.25 g of ammonium persulfate.
  • the bottle was purged with nitrogen and placed in a Launder-o-meterTM at 65 °C for at least 12 hours (i.e., overnight).
  • the polymerized sample was then removed and placed in ajar for use in the stainblocking composition.
  • Stainblocking compositions comprising the polymethacrylic acid and varying amounts (parts) of TBB-HMDA complex (as specified below in Table 13) were appUed at pH 2.5 to Transition 111TM nylon 6,6 ca ⁇ et at varying % SOF levels using the simulated flex-nip application procedure. The ca ⁇ et samples were then stained at room temperature (about 25 °C) for at least 8 hours and the ⁇ a values were measured using the procedure described previously and with the results shown below in Table 13.
  • methacryUc polymers can be successfully used as stainblocking materials in accordance with the invention.
  • Examples in which the stainblocking composition included an organoborane amine complex gave improved stain resistance over corresponding examples that did not include the complex. Higher treatment levels also gave improved performance.
  • Examples 97 - 98 and Comparative Examples C67 - C68 illustrate how the stain resistance of nylon 6,6 ca ⁇ et is affected by the level of ( ⁇ -and/or ⁇ - substituted) acryUc polymer stainblocking material and organoborane amine complex in the stainblocking composition.
  • the stainblocking composition was prepared as follows. To a 1 liter reaction vessel equipped with a reflux condenser, a mechanical stirrer, and a thermometer, were charged 3.2 parts (i.e., parts by weight) sulfated castor oil and 71.7 parts deionized water. This solution was heated to 95° C and to this solution were added simultaneously dropwise 16.5 parts methacrylic acid and 1.7 parts ammonium persulfate in 6.9 parts water over a period of about 2 hours. The reaction mixture was further stirred for 3 hours at 90 °C and then cooled to 50 °C.
  • the resultant copolymer solution was partially neutralized to pH 4.3 by the addition of 20% aqueous sodium hydroxide.
  • the resultant product contained 21.4% copolymer solids.
  • the amount (parts) of TBB-HMDA complex was varied as shown below in Table 14 as is the % SOF level.
  • the pH ofthe stainblocking composition was 2.5. Staining was done at room temperature (about 25 °C) for at least 8 hours and the ⁇ a color values were measured using the procedure described above and with the results presented in Table 14.
  • stainblocking compositions based on an ( ⁇ -and/or ⁇ - substituted) acrylic polymer and an organoborane amine complex gave better performance than stainblocking compositions that did not include a complex. Higher treatment levels also gave improved performance.

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

Abstract

Une composition anti-taches comprend un matériau anti-taches et un complexe d'organoborane et d'amine. Cette composition est particulièrement utile pour rendre résistants aux taches des substrats fibreux contenant des liaisons polyamides, notamment les moquettes en nylon.
PCT/US1996/001238 1996-01-31 1996-01-31 Compositions et procedes pour rendre des articles resistants aux taches, et articles resistants aux taches WO1997028304A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU49088/96A AU4908896A (en) 1996-01-31 1996-01-31 Compositions and methods for imparting stain resistance and stain resistant articles
US08/666,518 US5952409A (en) 1996-01-31 1996-01-31 Compositions and methods for imparting stain resistance and stain resistant articles
PCT/US1996/001238 WO1997028304A1 (fr) 1996-01-31 1996-01-31 Compositions et procedes pour rendre des articles resistants aux taches, et articles resistants aux taches
ZA97623A ZA97623B (en) 1996-01-31 1997-01-24 Compositions and methods for imparting stain resistance and stain resistant articles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1996/001238 WO1997028304A1 (fr) 1996-01-31 1996-01-31 Compositions et procedes pour rendre des articles resistants aux taches, et articles resistants aux taches

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006108240A1 (fr) * 2005-04-14 2006-10-19 Feltex Australia Pty Ltd Procédé de traitement de tapis

Citations (9)

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Publication number Priority date Publication date Assignee Title
GB413624A (en) * 1932-10-12 1934-07-19 Ig Farbenindustrie Ag Manufacture of highly viscous products
US3019114A (en) * 1959-11-24 1962-01-30 Callery Chemical Co Gas evolving protective coating
US3405001A (en) * 1962-11-13 1968-10-08 Du Pont Solid material rendered antistatic
US4680212A (en) * 1986-03-06 1987-07-14 Monsanto Company Stain resistant nylon fibers
EP0328822A2 (fr) * 1987-12-21 1989-08-23 E.I. Du Pont De Nemours And Company Agents antisalissures pour textiles
US4883839A (en) * 1987-12-21 1989-11-28 E. I. Du Pont De Nemours And Company Stain-resistant agents for textiles
US4940757A (en) * 1989-04-20 1990-07-10 Peach State Labs, Inc. Stain resistant polymeric composition
WO1993019238A1 (fr) * 1992-03-25 1993-09-30 E.I. Du Pont De Nemours And Company Revetements antitaches pour substrats de polyamide
US5460887A (en) * 1990-12-13 1995-10-24 E. I. Du Pont De Nemours And Company Stain-resistant polyamide substrates

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB413624A (en) * 1932-10-12 1934-07-19 Ig Farbenindustrie Ag Manufacture of highly viscous products
US3019114A (en) * 1959-11-24 1962-01-30 Callery Chemical Co Gas evolving protective coating
US3405001A (en) * 1962-11-13 1968-10-08 Du Pont Solid material rendered antistatic
US4680212A (en) * 1986-03-06 1987-07-14 Monsanto Company Stain resistant nylon fibers
EP0328822A2 (fr) * 1987-12-21 1989-08-23 E.I. Du Pont De Nemours And Company Agents antisalissures pour textiles
US4883839A (en) * 1987-12-21 1989-11-28 E. I. Du Pont De Nemours And Company Stain-resistant agents for textiles
US4940757A (en) * 1989-04-20 1990-07-10 Peach State Labs, Inc. Stain resistant polymeric composition
US5460887A (en) * 1990-12-13 1995-10-24 E. I. Du Pont De Nemours And Company Stain-resistant polyamide substrates
WO1993019238A1 (fr) * 1992-03-25 1993-09-30 E.I. Du Pont De Nemours And Company Revetements antitaches pour substrats de polyamide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006108240A1 (fr) * 2005-04-14 2006-10-19 Feltex Australia Pty Ltd Procédé de traitement de tapis

Also Published As

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AU4908896A (en) 1997-08-22
ZA97623B (en) 1998-07-24

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