US3332797A - Textile fabric backsizing composition process for treating textile fabric therewith and the treated fabric - Google Patents

Textile fabric backsizing composition process for treating textile fabric therewith and the treated fabric Download PDF

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US3332797A
US3332797A US313750A US31375063A US3332797A US 3332797 A US3332797 A US 3332797A US 313750 A US313750 A US 313750A US 31375063 A US31375063 A US 31375063A US 3332797 A US3332797 A US 3332797A
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adduct
percent
latex
ammonia
epihalohydrin
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US313750A
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Joseph P Strasser
Melvin J Hatch
Frederick L Knochel
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Dow Chemical Co
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Dow Chemical Co
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Priority to GB3963664A priority patent/GB1032139A/en
Priority to FR990201A priority patent/FR1416604A/en
Priority to NL6411492A priority patent/NL6411492A/xx
Priority to DE19641469525 priority patent/DE1469525A1/en
Priority to BE653978A priority patent/BE653978A/xx
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/61—Polyamines polyimines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of 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
    • D06M15/227—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
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
    • D06N7/0063—Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf
    • D06N7/0071—Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf characterised by their backing, e.g. pre-coat, back coating, secondary backing, cushion backing
    • D06N7/0073—Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf characterised by their backing, e.g. pre-coat, back coating, secondary backing, cushion backing the back coating or pre-coat being applied as an aqueous dispersion or latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/045—Vinyl (co)polymers
    • D06N2203/047—Arromatic vinyl (co)polymers, e.g. styrene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2205/00—Condition, form or state of the materials
    • D06N2205/20—Cured materials, e.g. vulcanised, cross-linked

Definitions

  • the invention relates to coatings, sizes, and impregnants for textile materials and more particularly to compositions dispersed in aqueous media which are applied to rugs, carpets, and similar materials to improve the wash resistance thereof.
  • An object of this invention is to provide new compositions which are useful as coatings, sizes, and impregnants for textile fabrics.
  • a furtherobject is to provide a backsizing for rugs and carpets.
  • a still further object is to supply new coatings, sizes, and impregnants for textile fabrics which provide improved resistance to deterioration of the article from laundering or washing-in-place.
  • an aqueous dispersion comprising a water-soluble ammonia-epihalohydrin adduct, as hereinafter described, blended with a carboxyl-containing film-forming latex.
  • the latex and the water-soluble ammonia-epihalohydrin adduct must be selected so that the blend thereof is stable as an aqueous dispersion during normal working periods.
  • dispersion stability is required during blending and application to the substrate. In general, dispersion stability for a minimum of about 2 hours is desirable and for at least 8 hours is preferable.
  • Epihalohydrinammonia adducts and the carboxyl-containing latexes fulfill these and other requirements.
  • ammonia-epihalohydrin adduct The components of the ammonia-epihalohydrin adduct are used in such proportions that for each molecule of ammonia there are from about 0.5 mole to about 2.8
  • the ratio is from about 1 mole to about two moles of epihalohydrin per mole of ammonia.
  • epichlorohydrin is preferred, epibromohydrin may be used, if desired, with similar results.
  • the halogen in the epihalohydrin has an atomic number from 17 to 35.
  • the ammonia-epihalohydrin adduct ordinarily is prepared by dissolving the epihalohydrin in a dilute aqueous solution of ammonium hydroxide using mild agitation. Control of the temperature of the solution to from about 0 C. to about 40 C.
  • aqueous medium aqueous medium
  • temperatures of up to C. or higher may be used.
  • a mineral acid such as hydrochloric acid may be added to stop, or kill, the reaction to prevent the formation of an adduct having too high a viscosity.
  • ammonia-epihalohydrin adduct conveniently is prepared and used as an aqueous solution containing about 1-0 percent by weight of the adduct, calculated as the free base, although this is not a critical limitation since compositions containing higher or lower proportions of adduct may be used so long as the inherent viscosity of the adduct is less than about 0.1 as determined at 25 C. in a solution of 1 gram of the adduct per ml. of water containing 5 percent of hydrogen chloride. If water containing 5 percent of sodium chloride is used as the solvent, then the measured inherent viscosity would be less than about 0.13.
  • the term calculated as the free base is meant that any salt-forming ingredients which may be associated therewith are not included in the weight of the adduct in the calculations.
  • the latex which is used with the ammonia-epihalohydrin adduct as heretofore defined is characterized as being film-forming below about 100 C. and contains as an essential ingredient from about 0.5 percent to about 10 percent, preferably from about 1 percent to about 4 percent, by weight of units derived from monomers having pendant carboxyl groups based on the weight of the polymer in the latex.
  • Latexes containing larger proportions of units derived from carboxyl-containing monomers up to about 30 percent by Weight may be prepared and used but such materials require higher amounts of the ammonia-epihalohydrin adduct to achieve the requisite water resistance and undesirable stiffness may result. Thus, ordinarily such compositions are not preferred.
  • At least two polymerizable, ethylenically unrners copolymerizable with styrene are copolymerized in an emulsion system to form a latex copolymer which is film-forming below about 100 C. or can be made filmforming at that temperature by the addition of solvents or plasticizers.
  • At least one of the monomers polymerized to form a latex for use in the instant invention consists of those polymerizable, ethylenically unsaturated monomers which have pendant carboxyl groups or which have substituent groups which after polymerization can be converted to carboxyl groups.
  • Such carboxyl-containing monomers are represented by the a,,3-ethylenically unsaturated monocarboxylic acids, the gr-ethylenically unsaturated dicarboxylic acids, half esters of a,/8-ethylenically unsaturated dicarb-oxylic acids, and mixtures and salts thereof.
  • Specific examples of such ethylenically unsaturated monomers having pendant carboxyl groups are acrylic acid, methacrylic acid, itaconic acid, fum-aric acid, maleic acid, ethyl acid maleate, butyl acid maleate, salts of such acids, and the like.
  • ethylenically unsaturated monomers of the class of styrene and monomers copolymerizable with styrene are the monomers having carboxyl groups described supra, the alkenyl-aromatic compounds (the styrene compounds), the derivatives of ethylenically unsaturated acids such as the acrylic esters, acrylic nitriles, maleic esters, fumaric esters, unsaturated alcohol esters, unsaturated ketones, the conjugated diolefins and other compounds containing one or more ethylenic linkages capable of addition polymerization.
  • ethylenically unsaturated compounds are styrene, a-methylstyrene, ar-methylstyrene, ar-ethylstyrene, a,ar-dimethylstyrene, ar,ar-dimethylstyrene, ar-t-butyl styrene, vinylnaphthalene, methoxystyrene, cyanostyrene, acetylstyrene, monochlorostyrene, dichlorostyrene and other halostyrenes, methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, Z-ethylhexyl acrylate, lauryl methacrylate, phenyl acrylate, acrylonitrile, methacrylonitrile, ethyl a-chloroacrylate, diethyl maleate, polyglycol maleate,
  • At least one of such ethylenically unsaturated monomers not containing a carboxyl group are required and as many as 4 or more may be used.
  • the optimum amount of the monomers, having carboxyl groups, which are copolymerized in the latex will vary somewhat according to the properties desired for the particular end use.
  • the lower amounts, in general, will be used where the pendant reactive carboxyl groups of the latex polymer are in relatively greater concentration on the surface of the particles rather than homogeneously scattered throughout the particles and where a minimum amount of cross-linking is desired.
  • the above-described monomers are copolymerized in aqueous emulsion containing surface active agents, catalysts, modifiers, etc., and under conditions of time, temperature, pressure, agitation, etc., in accordance with well known principles of emulsion polymerization.
  • the kinds of constituents employed in the aqueous phase of the emulsion polymerization are selected to be compatible with such monomers. For example, only anionic or non-ionic emulsifiers ordinarily are used.
  • the latexes may be prepared by c-opolymerization of monomers selected as heretofore described or there may be substituted for such latexes water dispersions of preformed polymers which have been modified, e.g., by grafting or by other means, to have pendant carboxyl groups or polymers which are hydrolyzable to give water dispersions of polymers having such carboxyl groups.
  • ammonia-epihalohydrin adduct in an amount to provide from about 0.1 part to about 5 parts, preferably from about 0.5 part to about 2 parts, of the adduct (calculated as the free base) per 100 parts of polymer solids in the latex.
  • the ratio is dependent somewhat on the proportion of carboxyl groups in the latex polymer.
  • the amount of adduct usually used ranges from about 0.1 part to about 2 parts whereas the range is from about 0.1 part to about 5 parts of the adduct when the polymer contains parts of acid, calculated as above.
  • the blend of a latex comprising a carboxyl-containing polymer and an ammonia-epihalohydrin adduct as heretofore described is required for the practice of this invention. It is customary, however, with the usual backsizes, impregnants and coatings of the art for textile materials, to add thickeners and especially fillers to achieve maximum economy. Such thickeners and fillers may also be used in the practice of this invention. However, the vulcanizing ingredients which ordinarily are required for the prior art materials which contain latexes are unnecessary.
  • Calcium carbonate is the most commonly used filler but other mineral pigments, such as titanium dioxide, mica, clay, lead carbonate, ochre, manganese silicate, lead chromate and other inorganic salts, e.g., sulfates, and arsenates, may be used if desired as a portion of the filler.
  • Such fillers may be used in amounts varying from about 75 parts, or lower, to about 600 parts per parts of copolymer solids in the latex of the composition.
  • the blends comprising the carboxyl-containing latex and the epihalohydrin-ammonia adduct are applied to numerous textile fabrics with advantageous results.
  • Such blends are applied by numerous types of apparatus, e.g., roll coaters, knife coaters, and spray c-oaters.
  • the composite material is then passed through an oven for removal of volatile materials, especially moisture, usually at a temperature of from about 200 F. to about 350 F., preferably from about 260 F. to about 325 F.
  • the heating which facilitates such removal also speeds the interaction of the carboxyl groups of the polymer, provided by the latex, with the reactive groups of the epihalohydrin-ammonia adduct so that the composition becomes cured or cross-linked.
  • compositions thus provide coatings, impregnants and backsizings for textile fabrics such as woven rugs and carpets, tufted rugs and carpets, flocked carpets, upholstery fabrics and non-woven fabrics.
  • textile fabrics such as woven rugs and carpets, tufted rugs and carpets, flocked carpets, upholstery fabrics and non-woven fabrics.
  • the fibers comprising such textile fabrics may be either natural or synthetic or mixtures thereof.
  • WASH RESISTANCE TEST The wash resistance test is carried out in a domestic oscillating-agitator automatic washer using water at F. and 30 g. of a commercial built-detergent of the type customarily used in a home laundry.
  • the carpet or rug sample is washed in the usual wash cycle for 15 minutes then subjected to the normal rinse and spin-dry cycle of the machine.
  • the samples of the material are then examined for visible effect resulting from treatment and rated in the following manner:
  • the backed carpet thus obtained was checked for wash resistance according to the procedure hereinbefore described and a rating of excellent (1) was obtained.
  • Example 2 In a 20-gallon reactor, were mixed 129 pounds of water and 8.8 pounds of an aqueous solution containing 28 percent of ammonia. To the resulting solution was added 15.6 pounds of epichlorohydrin over a period of about ten minutes. The reactor was closed and a slight positive pressure maintained to keep any ammonia from escaping. The temperature within the reactor was held at 44 C. for two hours. The reaction mixture was then cooled, filtered through glass wool and stored in 5-gallon polyethylene-lined cans. The aqueous solution thus obtained contained 8.3 percent of product, calculated as the free base. The inherent viscosity at C. of a 1 percent solution of the product in an aqueous solution containing 5 percent of sodium chloride was 0.068 whereas a one percent solution in 5 percent hydrogen chloride had an inherent viscosity of 0.054.
  • an adduct prepared substantially by the method of Example 2 of United States Letters Patent No. 2,- 844,490 according to the following procedure: Into a oneliter round-bottom flask equipped with a condenser, stirrer, heating mantle, and thermocouple was placed 642 ml. (600 g.) of 25 percent ammonia solution. Over a period of about 15 minutes, 39 ml. (46 g.) of epichlorohydrin was added thereto causing a temperature rise from 20 C. to 47 C. By use of the heating mantle, the temperature was increased to 90 C. during the next minutes. After 20.0 grams of sodium hydroxide pellets were added, the temperature of the mixture was increased to 105 C. over a period of about one-half hour. Heating was continued until 150 m1. of condensate (including that obtained during the preceding step) was collected.
  • the pro-polymer product at this point had an equivalent weight of 465 (as determined by titration with perchloric acid).
  • Portion A-1-stirred at room temperature overnight Portion Btreated with 1.25 ml. of concentrated hydrochloric acid to stop the reaction (viscosity of the solution was about 10 cen-tipoises)
  • Portion Cstirred at 60 C. overnight in the original flask When checked the following morning, portions A-1 and B appeared unchanged whereas portion C was cross-linked into an amber gel and hence was unusable.
  • Portion A-l was then heated to 60 C. After about 11 /2 hours of stirring at that temperature,'a visually observable increase in viscosity occurred. At the end of 12 hours the viscosity had increased to about 350 centipoises and 1.25 ml. of concentrated hydrochloric acid was added to stop the reaction (product A-2).
  • the inherent viscosities as determined at 25 C. in a solution of 1 gram of the adduct per ml. of water containing 5 percent sodium chloride as well as similar solutions containing 5 percent hydrogen chloride were as shown in the following table:
  • An aqueous dispersion comprising a stable blend of (A) a latex comprising a copolymer of at least 2 polymerizable ethylenically unsaturated monomers selected from the class consisting of styrene and monomers copolymerizable with styrene, from about 0.5 percent to about 10 percent by weight of said monomers having a pendant carboxyl group and (B) from about 0.1 part to about 5 parts, for each 100 parts of copolymer in the latex, of a water-soluble adduct of ammonia and an epihalohydrin, said adduct having for each mole of ammonia from about 0.5
  • adduct having an inherent viscosity of less than about 0.1 as determined at 25 C. .in a solution of 1 gram of the adduct per 100 m1. of water containing 5 percent by weight of hydrogen chloride.
  • ethylenically unsaturated monomers comprise from about 1 percent to about 4 percent by weight of monomers having a pendant carboxyl group.
  • ethylenically unsaturated monomers comprise a mixture of styrene and 1,3-butadiene.
  • a process of treating a textile comprising the steps of:
  • (A) Coating a textile fabric with an aqueous composition comprising a stable blend of (1) a latex of a carboxyl-containing polymer and (2) from about 0.1 part to about 5 parts, for each 100 parts of oarboxylcontaining polymer, of a water-soluble epihalohydrinammonia adduct, said latex comprising a copolymer of at least two polymerizable ethylenically unsaturated monomers selected from the class consisting of styrene and monomers copolymerizable with styrene from about 0.5 to about percent by weight of said monomers having a substituent carboxyl group, said adduct having for each mole of ammonia from about 0.5 mole to about 2.8 moles of epihalohydrin, and said epihalohydrin-ammonia adduct having an inherent viscosity less than about 0.1 as determined at 25 C. in a solution of 1 gram of the adduct per 100 ml. of
  • the monomer having a pendant carboxyl group comprises a mixture of a monocarboxylic acid and a dicarboxylic acid, each of said acids having a,B-ethylenic unsaturation.
  • a wash-resistant treated textile comprising a textile fabric having an adherent coating comprising an interaction product of a carboxyl-containing polymer and from about 0.1 part to about 5 parts, for each parts of carboxyl-containing polymer, of a water-soluble epihalohydrin-ammonia adduct, said carboxyl containing polymer being a copolymer of at least 2 polymerizable ethylenically unsaturated monomers selected from the class consisting of styrene and monomers copolymerizable with styrene, from about 0.5 to about 10 percent by weight of said monomers having a substituent carb-oxyl group, said adduct having for each mole of ammonia from about 0.5 mole to about 2.8 moles of epihalohydrin, and said epihalohydrin-ammonia adduct having an inherent viscosity less than about 0.1 as determined at 25 C. in a solution of 1 gram of the adduct per 100 ml. of water

Description

United States Patent 3,332,797 TEXTILE FABRIC BACKSIZING COMPOSITION PROCESS FOR TREATING TEXTILE FABRIC THEREWITH AND THE TREATED FABRIC Joseph P. Strasser, Melvin J. Hatch, and Frederick L.
Knochel, Midland, Mich, assignors to The Dow Chemical Company, Midland, Mich, a corporation of Delaware No Drawing. Filed Oct. 4, 1963, Ser. No. 313,750 21 Claims. (Cl. 117139.5)
\ The invention relates to coatings, sizes, and impregnants for textile materials and more particularly to compositions dispersed in aqueous media which are applied to rugs, carpets, and similar materials to improve the wash resistance thereof.
The application of synthetic latexes to textile fabrics is well known. It is also known to prepare tufted rugs and carpets by mechanically punching (forcing) yarns and/ or fibers through loosely-woven fabrics such as burlap and subsequently securing the yarns and fibers by applying a formulated natural or synthetic latex to the back of such articles followed by drying. The resistance of such fabricated articles to deterioration during laundering and washing-in-place is dependent to a large extent upon the water resistance of the adherent backing supplied by the dried latex formulation. To provide the necessary water resistance, earlier prior art developed vulcanized adhesives using compounding formulations based on the known art of vulcanization of rubber. Such systems, however, are complex and relatively expensive. They have been replaced in many applications by non-vulcanized latexes commonly referred to as self-curing with which a degree of water resistance is obtained from carboxyl-containing latexes through cross-linking by the application of heat. The water resistance provided by the latter system is minimal for many applications and insuflicient for other uses. It would be very desirable to have a composition which is stable at least for normal working periods and which contributes water resistance equal to or better than that provided by vulcanized latexes while retaining the simplicity of handling and the economy provided by the self-cure carboxylated late'xes.
An object of this invention is to provide new compositions which are useful as coatings, sizes, and impregnants for textile fabrics. A furtherobject is to provide a backsizing for rugs and carpets. A still further object is to supply new coatings, sizes, and impregnants for textile fabrics which provide improved resistance to deterioration of the article from laundering or washing-in-place.
These and other objects are obtained in an aqueous dispersion comprising a water-soluble ammonia-epihalohydrin adduct, as hereinafter described, blended with a carboxyl-containing film-forming latex. The application of such a composition (including fillers and thickneners) to a tufted rug, for example, followed by drying and subsequent curing by heating provides a backing which is resistant to deterioration resulting from repetitive laundering or washing-in-place.
The latex and the water-soluble ammonia-epihalohydrin adduct must be selected so that the blend thereof is stable as an aqueous dispersion during normal working periods. Thus dispersion stability is required during blending and application to the substrate. In general, dispersion stability for a minimum of about 2 hours is desirable and for at least 8 hours is preferable. Epihalohydrinammonia adducts and the carboxyl-containing latexes according to the following description fulfill these and other requirements.
The components of the ammonia-epihalohydrin adduct are used in such proportions that for each molecule of ammonia there are from about 0.5 mole to about 2.8
3,332,707 Patented July 25, 1967 ice moles of epihalohydrin. Preferably, however, the ratio is from about 1 mole to about two moles of epihalohydrin per mole of ammonia. While epichlorohydrin is preferred, epibromohydrin may be used, if desired, with similar results. Thus the halogen in the epihalohydrin has an atomic number from 17 to 35. The ammonia-epihalohydrin adduct ordinarily is prepared by dissolving the epihalohydrin in a dilute aqueous solution of ammonium hydroxide using mild agitation. Control of the temperature of the solution to from about 0 C. to about 40 C. and a low percent solids in the aqueous medium are conducive to formation of an adduct of a molecular weight range which is advantageous in the practice of the invention. However, temperatures of up to C. or higher, may be used. Additionally, a mineral acid such as hydrochloric acid may be added to stop, or kill, the reaction to prevent the formation of an adduct having too high a viscosity.
The ammonia-epihalohydrin adduct conveniently is prepared and used as an aqueous solution containing about 1-0 percent by weight of the adduct, calculated as the free base, although this is not a critical limitation since compositions containing higher or lower proportions of adduct may be used so long as the inherent viscosity of the adduct is less than about 0.1 as determined at 25 C. in a solution of 1 gram of the adduct per ml. of water containing 5 percent of hydrogen chloride. If water containing 5 percent of sodium chloride is used as the solvent, then the measured inherent viscosity would be less than about 0.13. Throughout this specification, by the term calculated as the free base is meant that any salt-forming ingredients which may be associated therewith are not included in the weight of the adduct in the calculations.
The latex which is used with the ammonia-epihalohydrin adduct as heretofore defined is characterized as being film-forming below about 100 C. and contains as an essential ingredient from about 0.5 percent to about 10 percent, preferably from about 1 percent to about 4 percent, by weight of units derived from monomers having pendant carboxyl groups based on the weight of the polymer in the latex. Latexes containing larger proportions of units derived from carboxyl-containing monomers up to about 30 percent by Weight may be prepared and used but such materials require higher amounts of the ammonia-epihalohydrin adduct to achieve the requisite water resistance and undesirable stiffness may result. Thus, ordinarily such compositions are not preferred.
To prepare the latexes applicable to the practice of the invention, at least two polymerizable, ethylenically unrners copolymerizable with styrene, are copolymerized in an emulsion system to form a latex copolymer which is film-forming below about 100 C. or can be made filmforming at that temperature by the addition of solvents or plasticizers. At least one of the monomers polymerized to form a latex for use in the instant invention consists of those polymerizable, ethylenically unsaturated monomers which have pendant carboxyl groups or which have substituent groups which after polymerization can be converted to carboxyl groups. Such carboxyl-containing monomers are represented by the a,,3-ethylenically unsaturated monocarboxylic acids, the gr-ethylenically unsaturated dicarboxylic acids, half esters of a,/8-ethylenically unsaturated dicarb-oxylic acids, and mixtures and salts thereof. Specific examples of such ethylenically unsaturated monomers having pendant carboxyl groups are acrylic acid, methacrylic acid, itaconic acid, fum-aric acid, maleic acid, ethyl acid maleate, butyl acid maleate, salts of such acids, and the like. Mixtures of a monocarboxylic acid and a dicarboxylic acid, each having a,13-lhyl6l1ic unsaturation often are used. Sometimes as many as 3 or more diiferent e,,6-ethylenically unsaturated carboxylic acids are combined in the recipe.
Among the ethylenically unsaturated monomers of the class of styrene and monomers copolymerizable with styrene are the monomers having carboxyl groups described supra, the alkenyl-aromatic compounds (the styrene compounds), the derivatives of ethylenically unsaturated acids such as the acrylic esters, acrylic nitriles, maleic esters, fumaric esters, unsaturated alcohol esters, unsaturated ketones, the conjugated diolefins and other compounds containing one or more ethylenic linkages capable of addition polymerization.
Specific examples of such ethylenically unsaturated compounds are styrene, a-methylstyrene, ar-methylstyrene, ar-ethylstyrene, a,ar-dimethylstyrene, ar,ar-dimethylstyrene, ar-t-butyl styrene, vinylnaphthalene, methoxystyrene, cyanostyrene, acetylstyrene, monochlorostyrene, dichlorostyrene and other halostyrenes, methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, Z-ethylhexyl acrylate, lauryl methacrylate, phenyl acrylate, acrylonitrile, methacrylonitrile, ethyl a-chloroacrylate, diethyl maleate, polyglycol maleate, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide, vinyl methyl ketone, methyl isopropenyl ketone, vinyl ethyl ether, 1,3-butadiene, isoprene and the like.
At least one of such ethylenically unsaturated monomers not containing a carboxyl group are required and as many as 4 or more may be used.
The optimum amount of the monomers, having carboxyl groups, which are copolymerized in the latex will vary somewhat according to the properties desired for the particular end use. The lower amounts, in general, will be used where the pendant reactive carboxyl groups of the latex polymer are in relatively greater concentration on the surface of the particles rather than homogeneously scattered throughout the particles and where a minimum amount of cross-linking is desired.
The above-described monomers are copolymerized in aqueous emulsion containing surface active agents, catalysts, modifiers, etc., and under conditions of time, temperature, pressure, agitation, etc., in accordance with well known principles of emulsion polymerization. However, because of the effects provided by the carboxyl-containing monomers, the kinds of constituents employed in the aqueous phase of the emulsion polymerization are selected to be compatible with such monomers. For example, only anionic or non-ionic emulsifiers ordinarily are used. More over, since the carboxylic substituents (particularly in the salt form) confer surface active properties to the monomer and to the resulting copolymer in the latex, the amount of conventional surface active agent can often be markedly reduced or even eliminated in the emulsion polymerization step. The latexes may be prepared by c-opolymerization of monomers selected as heretofore described or there may be substituted for such latexes water dispersions of preformed polymers which have been modified, e.g., by grafting or by other means, to have pendant carboxyl groups or polymers which are hydrolyzable to give water dispersions of polymers having such carboxyl groups.
To the latex there is added the ammonia-epihalohydrin adduct in an amount to provide from about 0.1 part to about 5 parts, preferably from about 0.5 part to about 2 parts, of the adduct (calculated as the free base) per 100 parts of polymer solids in the latex. As suggested hereinabove, the ratio is dependent somewhat on the proportion of carboxyl groups in the latex polymer. For example, when the latex polymer contains 1 part of copolymerized carbox'yl-con-taining monomer per 100 parts total weight of polymer then the amount of adduct usually used ranges from about 0.1 part to about 2 parts whereas the range is from about 0.1 part to about 5 parts of the adduct when the polymer contains parts of acid, calculated as above.
The blend of a latex comprising a carboxyl-containing polymer and an ammonia-epihalohydrin adduct as heretofore described is required for the practice of this invention. It is customary, however, with the usual backsizes, impregnants and coatings of the art for textile materials, to add thickeners and especially fillers to achieve maximum economy. Such thickeners and fillers may also be used in the practice of this invention. However, the vulcanizing ingredients which ordinarily are required for the prior art materials which contain latexes are unnecessary. Calcium carbonate is the most commonly used filler but other mineral pigments, such as titanium dioxide, mica, clay, lead carbonate, ochre, manganese silicate, lead chromate and other inorganic salts, e.g., sulfates, and arsenates, may be used if desired as a portion of the filler. Such fillers may be used in amounts varying from about 75 parts, or lower, to about 600 parts per parts of copolymer solids in the latex of the composition. The blends comprising the carboxyl-containing latex and the epihalohydrin-ammonia adduct are applied to numerous textile fabrics with advantageous results. Such blends are applied by numerous types of apparatus, e.g., roll coaters, knife coaters, and spray c-oaters. The composite material is then passed through an oven for removal of volatile materials, especially moisture, usually at a temperature of from about 200 F. to about 350 F., preferably from about 260 F. to about 325 F. Concurrently with the removal of the volatile materials in the oven, the heating which facilitates such removal also speeds the interaction of the carboxyl groups of the polymer, provided by the latex, with the reactive groups of the epihalohydrin-ammonia adduct so that the composition becomes cured or cross-linked. The compositions thus provide coatings, impregnants and backsizings for textile fabrics such as woven rugs and carpets, tufted rugs and carpets, flocked carpets, upholstery fabrics and non-woven fabrics. The fibers comprising such textile fabrics may be either natural or synthetic or mixtures thereof.
The advantageous water resistance of the products of this invention are illustrated by the wash resistance test.
WASH RESISTANCE TEST The wash resistance test is carried out in a domestic oscillating-agitator automatic washer using water at F. and 30 g. of a commercial built-detergent of the type customarily used in a home laundry. The carpet or rug sample is washed in the usual wash cycle for 15 minutes then subjected to the normal rinse and spin-dry cycle of the machine. The samples of the material are then examined for visible effect resulting from treatment and rated in the following manner:
observable Effect Numerical Rating Verbal Rating N0 visible effect Very slight edge fraying Holds in body of material t tears on edg N0 protection Excellent. Good. Fair. Poor.
To illustrate more fully to those skilled in the art the practice of this invention, the following examples are given, without any limitation being intended thereby. In the examples all parts and percentages are by weight unless otherwise specified.
cent styrene, 58 percent butadiene, 1.75 percent of acrylic acid and 0.25 percent fumaric acid, based on the copolymer weight. Then 300 parts of calcium carbonate and sufficient sodium polyacrylate thickener to adjust the viscosity to about 4000 centipoises parts of a 10 percent solution, or 1 part of solids) were blended therein. The resulting formulation in the proportion of ounces dry weight per square yard was applied to a loop-pile tufted wool carpet prepared from 30 ounces of wool yarn tufted into 10-ounce burlap (per square yard) and cured for 12 minutes at 300 F. in a forced air oven.
The backed carpet thus obtained was checked for wash resistance according to the procedure hereinbefore described and a rating of excellent (1) was obtained.
Example 2 In a 20-gallon reactor, were mixed 129 pounds of water and 8.8 pounds of an aqueous solution containing 28 percent of ammonia. To the resulting solution was added 15.6 pounds of epichlorohydrin over a period of about ten minutes. The reactor was closed and a slight positive pressure maintained to keep any ammonia from escaping. The temperature within the reactor was held at 44 C. for two hours. The reaction mixture was then cooled, filtered through glass wool and stored in 5-gallon polyethylene-lined cans. The aqueous solution thus obtained contained 8.3 percent of product, calculated as the free base. The inherent viscosity at C. of a 1 percent solution of the product in an aqueous solution containing 5 percent of sodium chloride was 0.068 whereas a one percent solution in 5 percent hydrogen chloride had an inherent viscosity of 0.054.
When the ammonia-epichlorohydrin adduct was blended with the latex described in Example 1 together with the filler and thickener of that example and the resulting blend was applied to tufted carpet and tested for Wash resistance by the same method as used in Example 1, a rating of excellent (2) was obtained.
When epibromohydrin is substituted on an equimolar basis for the epichlorohydrin in the adducts of Examples 1 and 2, similar advantageous results are obtained. Likewise, similarly advantageous results are obtained when there are substituted for the latexes in the above examples of this invention other carboxyl-containing latexes such as latexes comprising copolymers of:
(a) Styrene, 1,3-butadiene and acrylic acid (b) Ethyl acrylate, n-butyl acrylate and acrylic acid (0) Styrene, 1,3-butadiene, acrylic acid and methacrylic acid I (d) Ethyl acrylate, methyl methacrylate and acrylic acid (e) Styrene, n-butyl acrylate, acrylonitrile and acrylic acid (f) Other latexes which are film-forming below about 100 C. and which comprise polymers containing from about 0.5 percent to about 10 percent of copolymerized carboxyl-containing monomer, based on the total copolymer weight.
For comparison with the above examples of this invention there was prepared an adduct, not an example of this invention, prepared substantially by the method of Example 2 of United States Letters Patent No. 2,- 844,490 according to the following procedure: Into a oneliter round-bottom flask equipped with a condenser, stirrer, heating mantle, and thermocouple was placed 642 ml. (600 g.) of 25 percent ammonia solution. Over a period of about 15 minutes, 39 ml. (46 g.) of epichlorohydrin was added thereto causing a temperature rise from 20 C. to 47 C. By use of the heating mantle, the temperature was increased to 90 C. during the next minutes. After 20.0 grams of sodium hydroxide pellets were added, the temperature of the mixture was increased to 105 C. over a period of about one-half hour. Heating was continued until 150 m1. of condensate (including that obtained during the preceding step) was collected.
The pro-polymer product at this point had an equivalent weight of 465 (as determined by titration with perchloric acid). Into a reactor was placed 350 grams (0.75 mole) of the above pre-polymer and 69.0 grams (0.7 5 mole) of epichlorohydrin then was added. The temperature of the reactants spontaneously rose to 78 C. in 15 minutes, then gradually cooled, to 25 C. (in 5 /2 hours). The resulting solution was divided into three equal parts (A, B, C) and the portions were treated in the following manner:
Portion A-1-stirred at room temperature overnight Portion Btreated with 1.25 ml. of concentrated hydrochloric acid to stop the reaction (viscosity of the solution was about 10 cen-tipoises) Portion Cstirred at 60 C. overnight in the original flask When checked the following morning, portions A-1 and B appeared unchanged whereas portion C was cross-linked into an amber gel and hence was unusable. Portion A-l was then heated to 60 C. After about 11 /2 hours of stirring at that temperature,'a visually observable increase in viscosity occurred. At the end of 12 hours the viscosity had increased to about 350 centipoises and 1.25 ml. of concentrated hydrochloric acid was added to stop the reaction (product A-2). The inherent viscosities as determined at 25 C. in a solution of 1 gram of the adduct per ml. of water containing 5 percent sodium chloride as well as similar solutions containing 5 percent hydrogen chloride were as shown in the following table:
Inherent Viscosity Products A-2 and B were mixed with other portions of the latex described in Example 1 in the same proporti-ons. Both products, A-2 and 13, caused coagulation of the latex and thus could not be used in the combination of this invention.
In further comparisons with the products of this invention the epichlorohydrin-ammonia adducts of Examples 1 and 2 when blended with conventional commercial latexes, such as Dow Latex 512K, containing copolymers of styrene and 1,3-butadiene, but having no carboxyl-containing monomers copolymerized therein caused such instability of the latex that a homogeneous blend could not be prepared. By adding considerable extra surfactant, a minimum amount of stability barely sufiicient to allow mixing of the latex and adduct and immediate application to a tufted-carpet was obtained. However, such coatings showed no appreciable improvement over similar coatings prepared from the latex but having no epichlorohydrinammonia adduct blended therewith.
What is claimed is:
1. An aqueous dispersion comprising a stable blend of (A) a latex comprising a copolymer of at least 2 polymerizable ethylenically unsaturated monomers selected from the class consisting of styrene and monomers copolymerizable with styrene, from about 0.5 percent to about 10 percent by weight of said monomers having a pendant carboxyl group and (B) from about 0.1 part to about 5 parts, for each 100 parts of copolymer in the latex, of a water-soluble adduct of ammonia and an epihalohydrin, said adduct having for each mole of ammonia from about 0.5
mole to about 2.8 moles of epihalohydrin, and said adduct having an inherent viscosity of less than about 0.1 as determined at 25 C. .in a solution of 1 gram of the adduct per 100 m1. of water containing 5 percent by weight of hydrogen chloride.
2. The aqueous dispersion of claim 1 in which the ethylenically unsaturated monomers comprise from about 1 percent to about 4 percent by weight of monomers having a pendant carboxyl group.
3. The aqueous dispersion of claim 1 in which the monomer having a pendant carboxyl group comprises acrylic acid.
4. The aqueous dispersion of claim 1 in which the monomer having a pendant carboxyl group comprises fumaric acid.
5. The aqueous dispersion of claim 1 in which the ethylenically unsaturated monomers comprise styrene.
6. The aqueous dispersion of claim 1 in which the ethylenically unsaturated monomers comprise 1,3-butadiene.
7. The aqueous dispersion of claim 1 in which the ethylenically unsaturated monomers comprise a mixture of styrene and 1,3-butadiene.
8. The aqueous dispersion of claim 1 in which the epihalohydrin-ammonia adduct has for each mole of ammonia in the adduct from about 1 mole to about 2 moles of epihalohydrin.
9. The aqueous dispersion of claim 1 in which the epihalohydrin-ammonia adduct is an epichlorohydrinammonia adduct.
10. A process of treating a textile comprising the steps of:
(A) Coating a textile fabric with an aqueous composition comprising a stable blend of (1) a latex of a carboxyl-containing polymer and (2) from about 0.1 part to about 5 parts, for each 100 parts of oarboxylcontaining polymer, of a water-soluble epihalohydrinammonia adduct, said latex comprising a copolymer of at least two polymerizable ethylenically unsaturated monomers selected from the class consisting of styrene and monomers copolymerizable with styrene from about 0.5 to about percent by weight of said monomers having a substituent carboxyl group, said adduct having for each mole of ammonia from about 0.5 mole to about 2.8 moles of epihalohydrin, and said epihalohydrin-ammonia adduct having an inherent viscosity less than about 0.1 as determined at 25 C. in a solution of 1 gram of the adduct per 100 ml. of water containing 5 percent by weight of hydrogen chloride,
(B) drying and curing the resulting coating on the textile fabric by heating at temperatures from about 200 F. to about 350 F.
11. The process of claim 10 in which the ethylenically unsaturated monomers comprise from about 1 percent to about 4 percent by weight of monomers having a pendant carboxyl group.
12. The process of claim 10 in which the monomer having a pendant carboxyl group comprises acrylic acid.
13. The process of claim 10 in which the monomer having a pendant carboxyl group comprises fumaric acid.
14. The process of claim 10 in which the monomer having a pendant carboxyl group comprises a mixture of a monocarboxylic acid and a dicarboxylic acid, each of said acids having a,B-ethylenic unsaturation.
15. The process of claim 10 in which the ethylenically unsaturated monomers comprise styrene.
16. The process of claim 10 in which the ethylenically unsaturated monomers comprise 1,3-butadiene.
17. The process of claim 10 in which the ethylenically unsaturated monomers comprise a mixture of styrene and 1,3-butadiene.
18. The process of claim 10 in which the epihalohydrinammonia adduct is an epichlorohydrin-ammonia adduct.
19. A wash-resistant treated textile comprising a textile fabric having an adherent coating comprising an interaction product of a carboxyl-containing polymer and from about 0.1 part to about 5 parts, for each parts of carboxyl-containing polymer, of a water-soluble epihalohydrin-ammonia adduct, said carboxyl containing polymer being a copolymer of at least 2 polymerizable ethylenically unsaturated monomers selected from the class consisting of styrene and monomers copolymerizable with styrene, from about 0.5 to about 10 percent by weight of said monomers having a substituent carb-oxyl group, said adduct having for each mole of ammonia from about 0.5 mole to about 2.8 moles of epihalohydrin, and said epihalohydrin-ammonia adduct having an inherent viscosity less than about 0.1 as determined at 25 C. in a solution of 1 gram of the adduct per 100 ml. of water containing 5 percent by weight of hydrogen chloride.
20. The wash-resistant treated textile of claim 19 on which the textile fabric is tufted.
21. The wash-resistant treated textile of claim 19 in which the textile fabric is a carpet.
References Cited UNITED STATES PATENTS 2,748,446 6/1956 Mason 28--74 2,844,490 7/1958 Lehmann et a1. 11738 3,062,686 11/1962 Graulich et al 1l7l61 3,113,038 12/1963 Lattorulo et al. 117l40 WILLIAM B. MARTIN, Primary Examiner. T. G. DAVIS, Assistant Examiner.

Claims (2)

1. AN AQUEOUS DISPERSION COMPRISING A STABLE BLEND OF (A) A LATEX COMPRISING A COPOLYMER OF AT LEAST 2 POLYMERIZABLE ETHYLENICALLY UNSATURATED MONOMERS SELECTED FROM THE CLASS CONSISTING OF STYRENE AND MONOMERS COPOLYMERIZABLE WITH STYRENE, FROM ABOUT 0.5 PERCENT TO ABOUT 10 PERCENT BY WEIGHT OF SAID MONOMERS HAVING A PENDANT CARBOXYL GROUP AND (B) FROM ABOUT 0.1 PART TO ABOUT 5 PARTS, FOR EACH 100 PARTS OF COPOLYMER IN THE LATEX, OF A WATER-SOLUBLE ADDUCT OF AMMONIA AND AN EPIHALOHYDRIN, SAID ADDUCT HAVING FOR EACH MOLE OF AMMONIA FROM ABOUT 0.5 MOLE TO ABOUT 2.8 MOLES OF EPIHALOHYDRIN, AND SAID ADDUCT HAVING AN INHERENT VISCOSITY OF LESS THAN ABOUT 0.1 AS DETERMINED AT 25*C. IN A SOLUTION OF 1 GRAM OF THE ADDUCT PER 100 ML. OF WATER CONTAINING 5 PERCENT BY WEIGHT OF HYDROGEN CHLORIDE.
10. A PROCESS OF TREATING A TEXTILE COMPRISING THE STEPS OF: (A) COATING A TEXTILE FABRIC WITH AN ACQUEOUS COMPOSITION COMPRISING A STABLE BLEND OF (1) A LATEX OF A CARBOXYL-CONTAINING POLYMER AND (2) FROM ABOUT 0.1 PART TO ABOUT 5 PARTS, FOR EACH 100 PARTS OF CARBOXYLCONTAINING POLYMER OF A WATER-SOLUBLE EPIHALOHYDRINAMMONIA ADDUCT, SAID LATEX COMPRISING A COPOLYMER OF AT LEAST TWO POLYMERIZABLE ETHYLENICALLY UNSATURATED MONOMERS SELECTED FROM THE CLASS CONSISTING OF STYRENE AND MONOMERS COMPOLYMERIZABLE WITH STYRENE FROM ABOUT 0.5 TO ABOUT 10 PERCENT BY WEIGHT OF SAID MONOMERS HAVING A SUBSTITUENT CARBOXYL GROUP, SAID ADDUCT HAVING FOR EACH MOLE OF AMMONIA FROM ABOUT 0.5 TO ABOUT 2.8 MOLES OF EPIHALOHYDRIN, AND SAID EPIHALOHYDRIN-AMMONIA ADDUCT HAVING AN INHERENT VISCOSITY LESS THAN ABOUT 0.1 AS DETERMINED AT 25*C. IN A SOLUTION OF 1 GRAM OF THE ADDUCT PER 100 ML. OF WATER CONTAINING 5 PERCENT BY WEIGHT OF HYDROGEN CHLORIDE, (B) DRYING AND CURING THE RESULTING COATING ON THE TEXTILE FABRIC BY HEATING AT TEMPERATURES FROM ABOUT 200*F. TO ABOUT 350*F.
US313750A 1963-10-04 1963-10-04 Textile fabric backsizing composition process for treating textile fabric therewith and the treated fabric Expired - Lifetime US3332797A (en)

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US313750A US3332797A (en) 1963-10-04 1963-10-04 Textile fabric backsizing composition process for treating textile fabric therewith and the treated fabric
GB3963664A GB1032139A (en) 1963-10-04 1964-09-29 Textile adhesive or coating compositions
FR990201A FR1416604A (en) 1963-10-04 1964-10-02 Reverse primers for fabrics
NL6411492A NL6411492A (en) 1963-10-04 1964-10-02
DE19641469525 DE1469525A1 (en) 1963-10-04 1964-10-02 Method for treating textiles
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3385728A (en) * 1964-06-22 1968-05-28 Uniroyal Inc Method of coating a base with a carboxylated latex containing hydroxylamine hydrochloride
US3467563A (en) * 1966-04-09 1969-09-16 Polymer Corp Method of preparing a composition comprising an adherend and an adhesive latex mixture
US3494775A (en) * 1966-06-10 1970-02-10 American Cyanamid Co Protein adhesive compositions containing an amine-epichlorohydrin condensate latent insolubilizing agent
US5324789A (en) * 1991-12-30 1994-06-28 Ppg Industries, Inc. Azetidinol reaction products

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US2748446A (en) * 1952-11-25 1956-06-05 Gen Latex & Chemical Corp Tufted rug and method of making same
US2844490A (en) * 1952-10-20 1958-07-22 Bayer Ag Textile decorating and textile printing paste
US3062686A (en) * 1955-04-30 1962-11-06 Bayer Ag Process of treating textile with a copolymer and a cross-linking agent
US3113038A (en) * 1961-01-19 1963-12-03 Interchem Corp Nonwoven fabric coating containing propylenimine-cross linking agent for carboxyl containing acrylic polymer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2844490A (en) * 1952-10-20 1958-07-22 Bayer Ag Textile decorating and textile printing paste
US2748446A (en) * 1952-11-25 1956-06-05 Gen Latex & Chemical Corp Tufted rug and method of making same
US3062686A (en) * 1955-04-30 1962-11-06 Bayer Ag Process of treating textile with a copolymer and a cross-linking agent
US3113038A (en) * 1961-01-19 1963-12-03 Interchem Corp Nonwoven fabric coating containing propylenimine-cross linking agent for carboxyl containing acrylic polymer

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3385728A (en) * 1964-06-22 1968-05-28 Uniroyal Inc Method of coating a base with a carboxylated latex containing hydroxylamine hydrochloride
US3467563A (en) * 1966-04-09 1969-09-16 Polymer Corp Method of preparing a composition comprising an adherend and an adhesive latex mixture
US3494775A (en) * 1966-06-10 1970-02-10 American Cyanamid Co Protein adhesive compositions containing an amine-epichlorohydrin condensate latent insolubilizing agent
US5324789A (en) * 1991-12-30 1994-06-28 Ppg Industries, Inc. Azetidinol reaction products
US5349006A (en) * 1991-12-30 1994-09-20 Ppg Industries, Inc. Azetidinol reaction products used as pigment grind and film forming vehicles

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