EP3060716B1 - Carpet product and process for the manufacturing of a carpet product - Google Patents

Carpet product and process for the manufacturing of a carpet product Download PDF

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Publication number
EP3060716B1
EP3060716B1 EP14789761.5A EP14789761A EP3060716B1 EP 3060716 B1 EP3060716 B1 EP 3060716B1 EP 14789761 A EP14789761 A EP 14789761A EP 3060716 B1 EP3060716 B1 EP 3060716B1
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EP
European Patent Office
Prior art keywords
vinyl acetate
carpet
ethylene copolymer
comonomers
coating layer
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Application number
EP14789761.5A
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German (de)
English (en)
French (fr)
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EP3060716A1 (en
Inventor
Dennis Sagl
Ronald Joseph PANGRAZI
John M. Mcclurken
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Wacker Chemical Corp
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Wacker Chemical Corp
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Classifications

    • 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
    • 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
    • D06N7/0081—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 with at least one extra fibrous layer at the backing, e.g. stabilizing fibrous layer, fibrous secondary backing
    • 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
    • D06N2203/042—Polyolefin (co)polymers
    • 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
    • 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
    • D06N2205/02—Dispersion
    • D06N2205/023—Emulsion, aqueous dispersion, latex
    • 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
    • D06N2205/04—Foam
    • D06N2205/045—Froth
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/06—Building materials
    • D06N2211/066—Floor coverings
    • 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
    • D06N2213/00—Others characteristics
    • D06N2213/06—Characteristics of the backing in carpets, rugs, synthetic lawn
    • D06N2213/065—Two back coatings one next to the other

Definitions

  • the present invention relates to a carpet product and a process for manufacturing it.
  • Carpets typically include a primary backing material to which carpet fibers are attached to form a carpet pile on the face side, and a primary coating layer on the back side of the primary backing material to fix the carpet fibers to the primary backing.
  • a secondary backing material is often fixed to the primary backing material by means of a secondary coating layer.
  • the primary and secondary coating layers are typically formed from aqueous polymer dispersions, for example aqueous vinyl acetate ethylene copolymer dispersions and lattices of carboxylated styrene butadiene copolymers.
  • aqueous polymer dispersions for example aqueous vinyl acetate ethylene copolymer dispersions and lattices of carboxylated styrene butadiene copolymers.
  • U.S. patent 3,779,799 describes the use of an aqueous latex of carboxylated styrene butadiene copolymers, or alternatively of an aqueous dispersion of vinyl acetate ethylene copolymer, as the primary coating for the tufted primary backing material of carpets.
  • U.S. patent application 2001/0046581 discloses a carpet comprising a primary backing with a yarn attached with an adhesive, with a woven secondary backing attached to the back side of the primary backing with the same adhesive.
  • the second side of the secondary backing is coated with a thermoplastic polymer layer by melt bonding.
  • WO 2012/020321 A2 discloses carpet products with coating layers formed from vinyl ester ethylene copolymer dispersions.
  • the vinyl ester ethylene copolymer dispersions have a particle size of 50 to 500 nm, and the dispersions are used to coat the primary backing material as well as for laminating the secondary backing material.
  • Styrene-based emulsions are described as prior art binders for coating compositions for carpet materials, but these are said to be more expensive and have worse washability and are not used in the invention.
  • U.S. patent application 2008/0113146 describes a method for manufacturing carpets from recycled materials wherein EVA hotmelt, vinyl acetate ethylene emulsion, carboxylated styrene butadiene latex, styrene butadiene latex, acrylic latex, polyolefin hotmelt, polyolefin dispersion, or butadiene acrylate copolymers are described as adhesive backing materials for coating the primary backing materials.
  • WO 2010/129945 discloses a method for manufacturing carpets from recycled materials, using filler obtained from recycling of waste carpets.
  • EVA hotmelt, vinyl acetate ethylene emulsion, carboxylated styrene butadiene latex, styrene butadiene latex, acrylic latex, polyolefin hotmelt, polyolefin dispersion, or butadiene acrylate copolymers are described as coating agents for coating the primary backing materials.
  • U.S. patent application 2013/0209726 describes a latex coating composition comprising a blend of a vinyl ester ethylene copolymer and a styrene butadiene copolymer.
  • the blend may be used as a precoat binder, a skipcoat binder, or both.
  • U.S. patent application 2013/0149487 describes coating compositions for the scrim coat and for the skip coat which comprise an aqueous dispersion of vinyl acetate ethylene copolymers which have cross-linking silane comonomer units, or which have non-silicon multi-functional cross-linking comonomer units.
  • Japanese parent application JP 59-214633 discloses coating a polypropylene woven fabric coated with an ethylenic copolymer emulsion, e.g., a vinyl acetate ethylene copolymer emulsion (VAE), followed by drying. Pile yarns are then interwoven with the dry VAE-coated base fabric. A styrene butadiene rubber latex (SBR) is then applied to the dried VAE layer and the loops of pile yarn emerging from it.
  • an ethylenic copolymer emulsion e.g., a vinyl acetate ethylene copolymer emulsion (VAE)
  • VAE vinyl acetate ethylene copolymer emulsion
  • SBR styrene butadiene rubber latex
  • a secondary base fabric of expanded polypropylene woven cloth bearing a wet coating of an ethylenic copolymer emulsion e.g., a VAE
  • a VAE ethylenic copolymer emulsion
  • the VAE emulsion on the secondary base fabric is omitted.
  • the invention provides a carpet product comprising in sequence
  • the invention provides a process for making a carpet product, comprising in sequence
  • the primary backing material typically comprises any material recognized in the art for use as a carpet backing. Specific examples typically include woven or nonwoven fabrics made from one or more of natural or synthetic fibers or yarns including jute, wool, polypropylene, polyethylene, polyamide, polyesters, rayon, or various copolymers.
  • the primary backing has a face side and a back side.
  • Carpet fibers are attached to the primary backing, extending from the face side to form the carpet face.
  • the fibers can be made with uncut yarn loops, cut yarn loops (a pile of single yarns), or a combination of cut and uncut yarns.
  • the fibers can be made from wool, cotton, nylon, acrylic resin, polyester, polypropylene and blends thereof. As the fiber material is not critical, other fiber material would be readily apparent to one of skill in the art, i.e., any material recognized in the art for use as a carpet fiber.
  • a tufting method can be used to fix fibers to the primary backing material.
  • carpet fibers extend from the face side to form a carpet pile and pass through the primary backing material to form loops on the back side.
  • the primary backing will have a basis weight in a range from 102 to 339 g/m 2 (3 to 10 oz./yd 2 ), more typically in a range from 136 to 237 g/m 2 (4 to 7 oz./yd 2 ).
  • the combination of primary backing and carpet fibers (yarn) will typically have a basis weight in a range from 339 to 1017 g/m 2 (10 to 30 oz./yd 2 ).
  • the secondary backing side is oriented toward and attached to the back side of the primary backing, with the primary and secondary coating layers interposed.
  • the secondary backing can be made of a variety of materials. Typically, it will be made of one or more of the materials mentioned above for making the primary backing. In most cases the secondary backing will not have carpet pile fibers passing through it, and will not have carpet pile fibers directly adhered or otherwise directly attached to it. Here the term "directly" means without any intervening woven or nonwoven fabric layer(s).
  • the secondary backing will have a basis weight in a range from 33.9 to 203 g/m 2 (1 to 6 oz./yd 2 ). More typically, the range will be in a range from 102 to 170 g/m 2 (3 to 5 oz./yd 2 ).
  • the primary coating layer will typically be present at a loading level in a range from 542 to 1085 g/m 2 (16 to 32 oz./yd 2 ) on a dry solids basis. More typically, the amount will be in a range from 610 to 881 g/m 2 (18 to 26 oz./yd 2 ).
  • the secondary coating layer will typically be present at a loading level in a range from 203 to 305 g/m 2 (6 to 9 oz./yd 2 ) on a dry solids basis. More typically, the amount will be in a range from 237 to 271 g/m 2 (7 to 8 oz./yd 2 ).
  • the primary backing material, the secondary backing material, the primary coating layer and the secondary coating layer are each independently coextensive with one or more of the others. Most typically, they are all mutually coextensive.
  • the vinyl acetate ethylene copolymer comprises vinyl acetate units in an amount of 70 to 98 wt%, based on the total weight of comonomers.
  • the vinyl acetate content is in the range of 75 to 95 wt%, most preferred the vinyl acetate content is in the range of 80 to 95 wt%, in each case based on the total weight of comonomers.
  • the copolymer comprises ethylene in an amount of 2 to 30 wt%, based on the total weight of comonomers.
  • the amount is preferably 5 to 15 wt%, most preferred 10 to 12 wt%, in each case based on the total weight of comonomers.
  • the monomers are preferably selected so as to give copolymers with a glass transition temperature Tg of -30°C to +30°C, preferably -5°C to 20°C, and most preferred 0°C to 18°C.
  • the glass transition temperature Tg of the copolymers may be determined in a known manner by means of differential scanning calorimetry (DSC) according to ASTM D3418-03.
  • the vinyl acetate ethylene copolymer can be prepared by an aqueous emulsion polymerization using conventional emulsion polymerization procedure. Preferably at a temperature in a range from 40°C to 150°C, more preferred 50°C to 120°C and most preferred 60°C to 100°C.
  • the polymerization pressure is generally between 40 and 100 bar absolute, preferably between 45 and 90 bar absolute, and most preferred between 45 and 85 bar absolute, depending on the ethylene feed.
  • Polymerization may be initiated using a redox initiator combination such as is customary for an aqueous emulsion polymerization.
  • suitable oxidation initiators are hydrogen peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, potassium peroxodiphosphate, tert-butyl peroxopivalate, cumene hydroperoxide, isopropylbenzene monohydroperoxide, azobisisobutyronitrile, and the sodium, potassium, and ammonium salts of peroxodisulfuric acid. Preference is given to the sodium, potassium, and ammonium salts of peroxodisulfuric acid and to hydrogen peroxide.
  • the stated initiators are used in general in an amount of 0.01 wt% to 2.0 wt%, based on the total weight of the comonomers.
  • the stated oxidizing agents may also be used on their own as thermal initiators.
  • Suitable reducing agents are ammonium or alkali metal sulfites and bisulfites, as for example sodium sulfite, the derivatives of sulfoxylic acid such as zinc sulfoxylates or alkali metal formaldehyde sulfoxylates, such as sodium hydroxymethanesulfinate (Brüggolit). It is preferred to use a non-formaldehyde generating redox initiation system.
  • suitable non-formaldehyde generating reducing agents for redox pairs include, as non-limiting examples, those based on ascorbic acid or its salts, or erythorbate (iso-ascorbic acid) or its salts, or tartaric acid or its salts, or bisulfite salts particularly sodium bisulfite, as known in the art, or disodium glycolic acid sulfonate hydrate, which is available as a commercial reducing agent known as BRUGGOLITE® FF6M manufactured by Brueggeman Chemical of Heilbronn, Germany.
  • disodium glycolic acid sulfonate hydrate or sodium sulfite, or ascorbic acid or its salts, or erythorbic acid (iso-ascorbic acid) or its salts.
  • the amount of reducing agent is preferably 0.01 wt% to 3 wt%, based on the total weight of the comonomers.
  • Regulating substances may be used during the polymerization to control the molecular weight of the copolymer. In a preferred embodiment no regulating substances are used. If regulators are used, they are employed typically in amounts between 0.01 wt% to 5.0 wt%, based on the total weight of the monomers to be polymerized, and are metered separately or else as a premix with reaction components. Examples of such substances are n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptopropionic acid, methyl mercaptopropionate, isopropanol, and acetaldehyde.
  • One or more emulsifiers and/or one or more protective colloids are used to stabilize the aqueous dispersion of the vinyl acetate ethylene copolymers.
  • Suitable emulsifiers are nonionic, anionic or cationic emulsifiers.
  • Preferably nonionic or anionic emulsifiers are used, or mixtures of nonionic and anionic emulsifiers.
  • the amount of emulsifier is preferably 0.5 to 10 wt%, more preferably 1 to 5 wt%, in each case based on the total amount of comonomers.
  • Suitable nonionic emulsifiers are, for example, acyl, alkyl, and oleyl ethoxylates. These products are available commercially, for example, under the name GENAPOL® or LUTENSOL®. Suitable nonionic emulsifiers also include ethoxylated branched or unbranched fatty alcohols (aliphatic alcohols), preferably having a degree of ethoxylation of 3 to 80 ethylene oxide units and C 6 to C 36 alkyl radicals.
  • nonionic emulsifiers include C 13 -C 15 oxo-process alcohol ethoxylates having a degree of ethoxylation of 3 to 30 ethylene oxide units, C 16 -C 18 fatty alcohol ethoxylates having a degree of ethoxylation of 11 to 80 ethylene oxide units, C 10 oxo-process alcohol ethoxylates having a degree of ethoxylation of 3 to 11 ethylene oxide units, C 13 oxo-process alcohol ethoxylates having a degree of ethoxylation of 3 to 20 ethylene oxide units, polyoxyethylenesorbitan monooleate having 20 ethylene oxide groups, copolymers of ethylene oxide and propylene oxide with a minimum content of at least 10 wt% of ethylene oxide, and polyethylene oxide ethers of oleyl alcohol having a degree of ethoxylation of 4 to 20 ethylene oxide units.
  • Preferred nonionic emulsifiers are also C 13 -C 15 oxo-process alcohol ethoxylates having a degree of ethoxylation of 3 to 30 ethylene oxide units, and C 16 -C 18 aliphatic alcohol ethoxylates having a degree of ethoxylation of 11 to 80 ethylene oxide units.
  • the copolymer dispersion is free of alkylphenol ethoxylates and esters thereof.
  • Suitable anionic emulsifiers are sodium, potassium, and ammonium salts of straight-chain aliphatic carboxylic acids having 12 to 20 C atoms; sodium hydroxyoctadecanesulfonate; sodium, potassium, and ammonium salts of hydroxyl-fatty acids having 12 to 20 C atoms and the sulfonation and/or acetylation products thereof; sodium, potassium, and ammonium salts of alkyl sulfates, also as triethanolamine salts, and sodium, potassium, and ammonium salts of alkylsulfonates having in each case 10 to 20 C atoms and of alkylarylsulfonates having 12 to 20 C atoms; dimethyldialkylammonium chlorides having 8 to 18 C atoms and its sulfonation products; sodium, potassium, and ammonium salts of sulfosuccinic esters with aliphatic saturated moriohydric alcohols having 4 to 16 C atoms, and
  • anionic emulsifiers are the sodium, potassium, and ammonium salts of alkyl sulfates and of alkylsulfonates having in each case 10 to 20 C atoms, and also of alkylarylsulfonates having 12 to 20 C atoms, and of sulfosuccinic esters with aliphatic saturated monohydric alcohols having 4 to 16 C atoms.
  • Suitable protective colloids include polyvinyl alcohols; polyvinyl acetals; polyvinylpyrrolidones; polysaccharides in water-soluble form such as starches (amylase and amylopectin), celluloses and their carboxymethyl, methyl, hydroxyethyl, hydroxypropyl derivatives; proteins such as casein or caseinate, soya protein, gelatine; lignosulfonates, synthetic polymers such as poly(meth)acrylic acid, copolymers of (meth)acrylates with carboxyl-functional comonomer units, poly(meth)-acrylamide, polyvinylsulfonic acids, and the water-soluble copolymers thereof; melamine-formaldehyde sulfonates, naphthalene-formaldehyde sulfonates, styrene-maleic acid copolymers, and vinyl ether-maleic acid copolymers.
  • Preferred partially hydrolyzed polyvinyl alcohols have a degree of hydrolysis of 80 to 95 mol% and a Höppler viscosity, in 4% strength aqueous solution, of 1 to 30 mPas (method of Höppler at 20°C, DIN 53015).
  • polyvinyl alcohols having a degree of hydrolysis of 85 to 94 mol% and a Höppler viscosity, in 4% strength aqueous solution, of 3 to 25 mPas (method of Höppler at 20°C, DIN 53015).
  • degree of hydrolysis of a polyvinyl alcohol means the degree to which vinyl acetate monomer units have been hydrolyzed to alcohols.
  • Preferred fully hydrolyzed polyvinyl alcohols have a degree of hydrolysis of 98 to 99.95 mol% and a Hoeppler viscosity of 13 to 30 mPa•s (method of Höppler at 20°C, DIN 53015).
  • Both partially hydrolyzed and fully hydrolyzed polyvinyl alcohols may be hydrophobically modified, e.g., they may comprise hydrophobic comonomers, one example of which is ethylene.
  • the total amount of the protective colloid is preferably 1 to 5 wt%, based on the total weight of comonomers.
  • emulsifiers and protective colloids discussed above are all commercially available or obtainable by processes known to the skilled person.
  • all of the protective colloid or all of the emulsifier may form an initial charge, or all of the protective colloid or all of the emulsifier may form a feed, or portions of the protective colloid or of the emulsifier may form an initial charge and the remainder may form a feed after the polymerization has been initiated.
  • the feeds may be separate (spatially and chronologically), or all or some of the components may be fed after pre-emulsification.
  • all of the protective colloid and optionally all of the emulsifier are charged initially to the reactor.
  • All of the monomers may form an initial charge, or all of the monomers may form a feed, or portions of the monomers may form an initial charge and the remainder may form a feed after the polymerization has been initiated.
  • the feeds may be separate (spatially and chronologically), or all or some of the components may be fed after pre-emulsification.
  • post-polymerization may be carried out using known methods to remove residual monomer, for example using post-polymerization initiated by a redox catalyst.
  • Volatile residual monomers may also be removed by distillation, preferably at subatmospheric pressure, and, where appropriate, by passing inert entraining gases, such as air, nitrogen, or water vapor, through or over the material.
  • the solids content of suitable aqueous vinyl acetate ethylene copolymer dispersions is typically in a range from 45 wt% to 75 wt%.
  • the particle size distribution may be monomodal or multimodal, and the mean particle diameter may range in size from 0.15 ⁇ m to 10 ⁇ m as measured by laser diffraction.
  • the styrene butadiene copolymers comprise 20 to 79.9 wt%, preferably 50 to 65 wt% styrene and 20 to 79.9 wt%, preferably 35 to 50 wt% butadiene, based on the total amount of comonomers.
  • 0.1 to 15 wt% of further auxiliary comonomers may be present, in each case based on the total weight of comonomers.
  • Preferred auxiliary comonomers are ethylenically unsaturated mono-carboxylic acids, and/or di-carboxylic acids, their anhydrides, and their salts, and mixtures thereof, particularly acrylic acid, methacrylic acid, itaconic acid and/or maleic acid and/or fumaric acid.
  • auxiliary comonomers are for example, alkyl esters of (meth)acrylic acid, such as, for example, methyl methacrylate, ethylenically unsaturated carboxamides and carbonitriles, such as, for example, (meth)acrylonitrile; diesters of fumaric acid or maleic acid; hydroxy alkyl (meth)acrylates; sulfur acid monomers, phosphorus acid monomers, crosslinking comonomers, such as, for example, divinyl benzene or divinyl adipates; postcrosslinking comonomers, such as acrylamidoglycolic acid (AGA), allyl methacrylates or allyl N-methylol carbamates; epoxy-functional comonomers, such as glycidyl (meth)acrylates; and silicon-functional comonomers, such as alkoxysilane containing (meth)acrylates or vinyl monomers.
  • While some applications may favor the inclusion of additional monomers in the styrene butadiene copolymer, for example such as those listed above, it may nonetheless in some cases be advantageous to exclude certain monomers, depending on the specific needs of a given application. In other cases, these monomers may be included up to a limit of 1.0 wt% of the styrene butadiene copolymer.
  • the styrene butadiene copolymers can be prepared by aqueous emulsion or suspension polymerization, preferably emulsion polymerization, in conventional manner, employing conventional polymerization temperatures, preferably from 40°C to 120°C, and pressures, preferably with diene comonomer pressures up to 10 bar absolute.
  • the polymerization may be initiated using conventional amounts of one or more conventional water-soluble initiators such as sodium persulphate, or oil (monomer) soluble initiator, such as tert-butyl peroxide and cumene hydroperoxide, or a redox initiator combination, using a reducing agent such as sulfites and bisulfites.
  • conventional regulator substances or chain transfer agents such as mercaptans, alkanols, and dimeric alpha methylstyrene can be used during the polymerization in conventional manner in conventional amounts of from 0.01 to 5.0 percent by weight, or, preferably, up to 3 percent by weight, based on the comonomer to be polymerized.
  • the polymerization process preferably takes place in known manner in the presence of conventional amounts of one or more conventional emulsifier and/or protective colloid. Suitable emulsifiers and protective colloids are the same as described for preparing the vinyl acetate ethylene dispersion.
  • the solids content of the styrene butadiene copolymer dispersion is typically in a range from 45 wt% to 75 wt%.
  • the vinyl acetate ethylene copolymer dispersion or the styrene butadiene copolymer dispersion is combined with one or more fillers and one or more thickeners, and optionally further additives.
  • filler suitable for use in carpet manufacture may be used.
  • mineral fillers or pigments including those known in the art, such as calcium carbonate, ground glass, clay, kaolin, talc, barites, feldspar, titanium dioxide, calcium aluminum pigments, satin white, synthetic polymer pigment, zinc oxide, barium sulphate, gypsum, silica, alumina trihydrate, mica, hollow polymer pigments, and diatomaceous earth. Mixtures of fillers can also be employed.
  • the amount of filler in the composition can vary depending upon the density of the filler and the coating properties desired. Typically, it will be from about 50 to about 800 dry weight parts filler, more typically from about 100 to about 600 dry weight parts, and most typically from about 250 to about 600 dry weight parts, in each case per 100 dry weight parts of copolymer solids.
  • One or more polymeric thickeners is typically included in the composition to provide sufficient viscosity for application according to conventional methods.
  • Any polymeric thickener known in the carpet coating art may be used, for example hydroxyethyl cellulose and sodium polyacrylate.
  • any amount of polymeric thickener may be used, the inventors have found that typically no more than 6 wt% of thickener is needed, relative to the amount of aqueous dispersion of the copolymer, and thus in some embodiments of the invention no more than 6 wt% is used, relative to the amount of aqueous dispersion of the copolymer.
  • At most 5 wt% or at most 4 wt% is used, relative to the amount of aqueous dispersion of the copolymer.
  • at least 1 wt% of thickener, or at least 2 wt% is used, relative to the amount of aqueous dispersion of the copolymer.
  • the Brookfield RV viscosity of the resulting coating composition should be in a range from 7000 to 15000 mPas, measured with a Brookfield RV viscometer using spindle No. 5 at 25°C and 20 rpm.
  • blowing agents can be added to the coating compositions.
  • the primary and secondary aqueous coating compositions can be applied in various ways.
  • the coating compositions can be applied directly, such as with a roll over roll applicator, or with a doctor blade.
  • they can be applied indirectly, such as with a pan applicator.
  • a roll over roller applicator is used.
  • the primary coating coats at least the loops on the back side of the primary backing, and may also coat some or all of the back side of the backing itself.
  • the primary and secondary backing materials are brought together to bring the still-wet primary and secondary coating compositions into contact, typically with application of pressure, and heat is then applied to evaporate the water from the coatings. This may be done by passing the product through an oven, typically set at a temperature between about 100°C and 150°C. Upon cooling, the final product is obtained.
  • a significant advantage of carpet products obtained according to the invention is better delamination resistance compared with carpet products according to the state of the art.
  • Vinyl acetate-ethylene copolymer dispersion An aqueous dispersion of a vinyl acetate ethylene copolymer with a solids content of about 60 wt% was used. The dispersion was costabilized with a protective colloid and a non-ionic surfactant. The copolymer composition was about 85 wt% vinyl acetate and about 15 wt% ethylene, with a glass transition temperature Tg of about 2°C.
  • SBR Styrene butadiene copolymer dispersion
  • aqueous dispersion of a styrene butadiene copolymer with a solids content of about 55 wt% was used.
  • the dispersion was stabilized with an anionic surfactant.
  • the copolymer composition was about 65 wt% of styrene and about 35 wt% of butadiene, with a glass transition temperature Tg of about 11°C.
  • Froth aid used was ammonium lauryl sulphate (STANFAX® 238 manufactured by Royal Adhesives, Dalton, Georgia).
  • Thickener used was a sodium polyacrylate (PARAGUM® 277 manufactured by Royal Adhesives, Dalton, Georgia).
  • the uncoated backing materials used in the test were: A nylon carpet greige goods (i.e., a backing with pile yarn tufted in but without a binder) with a 678 g/m 2 (20 oz./yd 2 ) face weight level loop nylon with a straight stitch commercial style tufting construction was used as primary backing.
  • the primary and secondary coating compositions were admixed according to the general recipe with a Lighting mixer. Thickener and water were admixed in an amount necessary for obtaining a total solids content of about 81.5 wt% and a Brookfield viscosity (spindle No. 5, 20 rpm) of 6000 to 7000 cps.
  • the primary coating composition was applied with a spatula having a 25.4 cm (10 in) blade to the backside of the nylon carpet material at a rate of 949 g/m 2 (28 oz./yd 2 ) of primary coating solids.
  • the secondary backing was coated with the secondary coating composition with a draw-down bar at a 762 ⁇ m (30 mil) wet film thickness, resulting in about 237 g/m 2 (7 oz./yd 2 ) of secondary coating solids.
  • the wet coated secondary backing was pressed against the wet coating layer on the primary backing with a large stainless steel roller.
  • the assembly was dried at 132°C (270°F) in a convection air oven for 20 minutes, and the resulting carpet product was allowed to stand at ambient temperature and humidity for at least two hours before testing.
  • Carpet Tuft Bind values were determined according to ASTM D1335-05. This procedure is a method to calculate the force required to pull a loop or cut pile from a piece of carpet.
  • Instron Model 2519-105 1000 N capacity equipped with 7.62 cm (3 inch) jaw clamps, desiccator for conditioning carpet samples, 3.8 mm cylindrical specimen holder and loop hook.
  • Samples for wet tuft bind are prepared one at a time according to the following procedure: After dry tuft binds are determined, the 17.15 x 17.15 cm (6.75 x 6.75 in) square is placed into a one gallon (3.8 liter) container that has been filled with cold tap water. The carpet sample is submerged into the water and allowed to soak for 10 minutes. After 10 minutes the sample is removed and placed on a paper towel for 30 seconds to soak up excess water. The carpet is then taken to be tested for tuft bind values as previously described.
  • the loop hook was inserted in the loop to be pulled. By visual inspection it was insured that only one loop was hooked for testing.
  • the tuft was pulled at a speed of 304.8 cm (12 in) per minute. The pull was continued until the tuft was separated from the primary backing.
  • Carpet Delamination resistance was determined according to ASTM D3936-05. This procedure is a method to calculate the force required to separate the secondary backing material from the primary backing material.
  • Samples for wet delamination were prepared one at a time according to the following procedure: An untested strip of the dimensions described above was placed in a 3.8 liter (one gallon) container that had been filled with cold tap water. The carpet sample was submerged into the water and allowed to soak for 10 minutes. After 10 minutes the sample was removed and placed on a paper towel for 30 seconds to soak up excess water. The sample was then tested for delamination values as described below.
  • the secondary backing was separated from the primary backing approximately 3.8 cm (11 ⁇ 2 in) in the long (machine) direction on each sample.
  • the primary backing/pile was placed in the bottom jaw as straight as possible, and the secondary backing was placed in the top jaw for a 180° peel configuration as straight as possible.
  • the two layers were pulled apart at a speed of 30.5 cm (12 in) per minute for a total of 17.8 cm (7 in) of jaw travel.
  • the combination of VAE on the primary backing and SBR on the secondary backing according to the invention provided a 26% increase in Dry Delamination strength and a 27% increase in Wet Delamination strength, compared with the use of VAE on both backings.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP14789761.5A 2013-10-24 2014-10-22 Carpet product and process for the manufacturing of a carpet product Active EP3060716B1 (en)

Applications Claiming Priority (2)

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US201361895149P 2013-10-24 2013-10-24
PCT/US2014/061697 WO2015061399A1 (en) 2013-10-24 2014-10-22 Carpet product and process for the manufacturing of a carpet product

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EP3060716B1 true EP3060716B1 (en) 2018-06-27

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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3122791B1 (en) * 2014-03-27 2018-05-02 Wacker Chemical Corporation Binder for paper coating compositions
CN108183233B (zh) 2016-12-08 2021-09-03 三星Sdi株式会社 用于锂二次电池的基于镍的活性材料、其制备方法和包括含其的正极的锂二次电池
US20180250910A1 (en) * 2017-03-06 2018-09-06 Celanese International Corporation Carpet tiles and methods of their manufacture

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3779799A (en) 1970-06-12 1973-12-18 Thiokol Chemical Corp Coated woven textile product and process therefor
JPS59214633A (ja) 1983-05-20 1984-12-04 Mitsubishi Petrochem Co Ltd パイルを有するカ−ペツトの製造方法
US5084503A (en) 1985-08-02 1992-01-28 Air Products And Chemicals, Inc. Vinyl acetate-ethylene copolymer emulsions useful as carpet adhesives
US4735986A (en) 1985-08-02 1988-04-05 Air Products And Chemicals, Inc. Vinyl acetate/ethylene copolymer emulsions useful as carpet adhesives
US5560972A (en) * 1988-07-25 1996-10-01 Interface, Inc. Latex fusion bonded pile carpets and carpet tile
US20010046581A1 (en) 2000-01-14 2001-11-29 Shaw Industries, Inc. Carpet with a polymer layer
DE10148497A1 (de) * 2001-10-01 2003-04-17 Basf Ag Verfahren zur Herstellung wässriger Styrol-Butadien-Polymerdispersionen-I
US6463963B1 (en) * 2002-05-10 2002-10-15 Shaw Industries, Inc. Acaracidal carpet and method of making the same
CN101472510A (zh) * 2006-04-27 2009-07-01 莫赫地毯公司 热熔块状地毯及其制备方法
WO2008064012A2 (en) 2006-11-13 2008-05-29 Shaw Industries Group, Inc. Methods and systems for recycling carpet and carpets manufactured from recycled material
US20100330288A1 (en) 2009-05-08 2010-12-30 Jeffery Segars Methods for reclamation of inorganic filler from waste carpet and carpet manufactured from same
US10301772B2 (en) * 2010-05-03 2019-05-28 Celanese International Corporation Carpets with surfactant-stabilized emulsion polymer carpet binders for improved processability
WO2011139267A1 (en) * 2010-05-03 2011-11-10 Celanese International Corporation Carpets with surfactant-stabilized emulsion polymer carpet binders for improved processability
EP2603633A2 (en) 2010-08-12 2013-06-19 Celanese Emulsions GmbH Washable carpet products with coating layers formed from vinyl ester/ethylene copolymer dispersions
WO2013123210A1 (en) 2012-02-15 2013-08-22 Celanese International Corporation Carpet products and processes for making same using latex coating compositions
US20140162018A1 (en) * 2012-12-07 2014-06-12 Celanese Emulsions Gmbh Carpet Products and Methods for Making Same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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WO2015061399A1 (en) 2015-04-30
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EP3060716A1 (en) 2016-08-31
US20160251801A1 (en) 2016-09-01

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