WO2012020321A2 - Washable carpet products with coating layers formed from vinyl ester/ethylene copolymer dispersions - Google Patents
Washable carpet products with coating layers formed from vinyl ester/ethylene copolymer dispersions Download PDFInfo
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- WO2012020321A2 WO2012020321A2 PCT/IB2011/002652 IB2011002652W WO2012020321A2 WO 2012020321 A2 WO2012020321 A2 WO 2012020321A2 IB 2011002652 W IB2011002652 W IB 2011002652W WO 2012020321 A2 WO2012020321 A2 WO 2012020321A2
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- carpet
- carpet product
- vinyl acetate
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Classifications
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- 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
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/042—Acrylic 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
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0006—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using woven fabrics
-
- 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
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0009—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using knitted fabrics
-
- 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
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
-
- 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
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using flocked webs or pile fabrics upon which a resin is applied; Teasing, raising web before resin application
-
- 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
- D06N2209/00—Properties of the materials
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/106—Roughness, anti-slip, abrasiveness
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/23907—Pile or nap type surface or component
- Y10T428/23979—Particular backing structure or composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/23907—Pile or nap type surface or component
- Y10T428/23986—With coating, impregnation, or bond
Definitions
- the present development relates to carpet products having coating layers therein which comprise a filler-containing, emulsifier- and/or colloid-stabilized vinyl ester/ethylene- based copolymer dispersion as a small particle size emulsion binder.
- Such carpet products exhibit desirable washability characteristics and preferably can also be especially effective for use as or in non-slip carpet applications such as for bathroom rugs or gymnasium mats.
- Most conventional carpets comprise a primary backing with yarn tufts in the form of cut or uncut loops extending upwardly from this backing to form a pile surface.
- the yarn is inserted into a primary backing (frequently a woven or nonwoven substrate) by tufting needles and a pre-coat (i.e., a binder) is applied thereto.
- the binder composition must provide excellent adhesion to the pile fibers to secure them firmly in the backing.
- the coating will also typically have a high loading of fillers such as calcium carbonate, clay, aluminum trihydrate, barite, feldspar, cullet, fly ash and/or recycled carpet backing. Further, coatings on carpet backing layers must preferably also be able to serve as non-slip substrates, thereby enabling the preparation of non-slip material for use in, for example, bathroom and rug carpet or gymnasium mat applications.
- the binders in coating compositions for carpet materials are frequently emulsion polymers, i.e., latex dispersions, such as styrene -based emulsion copolymers like styrene- butadiene latex (SBL) materials or such as acrylic polymer latex dispersions.
- emulsion polymers i.e., latex dispersions, such as styrene -based emulsion copolymers like styrene- butadiene latex (SBL) materials or such as acrylic polymer latex dispersions.
- Copolymers of vinyl esters (such as vinyl acetate) and ethylene can also be used and can frequently have cost and performance advantages over rubber coatings or styrene-containing coatings such as SBL-based compositions.
- vinyl ester copolymers can be used to provide carpet products which are desirably low in VOC (volatile organic compound) content and which do not contain potentially toxic materials such a 4-phenyl cyclohexene (4-PCH) and related compounds which can be found in styrene-based emulsion polymers.
- VOC volatile organic compound
- 4-phenyl cyclohexene (4-PCH) and related compounds which can be found in styrene-based emulsion polymers.
- Emulsion binders and carpet coating compositions based on vinyl ester/ethylene, e.g., vinyl acetate/ethylene (VAE), copolymers are disclosed, for example, in WO 2010/089142 and in U.S. Patent Nos. 4,735,986; 5,026,765; 5,849,389; 6,359,076; 7,056,847; 7,582,699; 7,649,067 and in U.S. Patent Application Publication No. 2005/0287336.
- Some of these patent documents note that such VAE binders and coating compositions are compatible with polyvinyl chloride (PVC) plastisols which are frequently used as backing layers in such carpet products.
- PVC polyvinyl chloride
- the vinyl ester/ethylene copolymers used in the binders and coating compositions described in the foregoing patent documents are prepared by polymerizing appropriate co- monomers in an aqueous emulsion.
- emulsions or dispersions can be stabilized by adding conventional surfactants (anionic, nonionic, cationic) as emulsifiers.
- surfactants anionic, nonionic, cationic
- Such emulsions or dispersions may also be stabilized by including protective colloids.
- Such carpet products can also be desirably low in VOC content.
- the carpet products described herein with their VAE-based binder coatings having a selected combination of features e.g., specific co-monomers, cross-linkers, stabilizers, relatively small polymer particle sizes, T g 's, and fillers
- the present development is directed to a carpet product comprising at least one flexible substrate and at least one coating layer associated with the at least one flexible substrate.
- a coating layer is formed from an aqueous composition comprising: A) an emulsifier-stabilized vinyl acetate/ethylene (VAE) copolymer dispersion, and B) at least one particulate filler material selected from particulate inorganic compounds and particulate plastic material.
- VAE emulsifier-stabilized vinyl acetate/ethylene
- the vinyl acetate/ethylene copolymer in the copolymer dispersion comprises main co-monomers which include vinyl acetate, which is copolymerized with ethylene and optionally also with one or more additional different non-functional main co- monomer(s) which can be vinyl esters of Ci-Cis mono-carboxylic acids or Ci-Cis esters of ethylenically unsaturated mono-carboxylic acids or Ci-Cis diesters of ethylenically unsaturated di-carboxylic acids.
- main co-monomers which include vinyl acetate, which is copolymerized with ethylene and optionally also with one or more additional different non-functional main co- monomer(s) which can be vinyl esters of Ci-Cis mono-carboxylic acids or Ci-Cis esters of ethylenically unsaturated mono-carboxylic acids or Ci-Cis diesters of ethylenically unsaturated di-carboxylic acids.
- the vinyl acetate/ethylene copolymer in the copolymer dispersion has a particle size, d w , ranging from about 50 to about 500 nm as determined by Laser Aerosol Spectroscopy.
- the vinyl acetate/ethylene copolymer in the copolymer dispersion typically comprises from about 8 wt% to about 40 wt%, based on total main co-monomers therein, of ethylene and has a glass transition temperature, T g , of from about -25 °C to about +15 °C.
- the copolymer dispersion is preferably stabilized with at least about 0.5 wt%, based on total main co-monomers in the copolymer, of one or more, preferably anionic and/or nonionic, emulsifiers and from about 0 wt% to about 3 wt%, based on total main co- monomers in the copolymer, of a protective colloid which, when used, is preferably polyvinyl alcohol.
- the vinyl acetate/ethylene copolymer in the copolymer dispersion will also preferably be substantially free of cross-linkable co-monomer moieties which generate formaldehyde upon formation of the coating or adhesive layer in the carpet product.
- the carpet products herein will generally exhibit good washability characteristics in that they maintain their integrity and appearance well after multiple washings. Preferably, the carpet products herein will exhibit less than about 4.5% weight loss and less than about 40% tuft anchorage loss after 20 wash cycles in the Washability and Tuft Anchorage Tests described herein.
- carpet products herein will also exhibit good non-slip properties when the coated carpet backing of such carpets is in contact with the floor.
- these carpet products can exhibit non-slip properties such that a maximum drag force of about 6.0 Newtons or more are needed to move a sample of such carpet products when tested in accordance with TAPPI test 816 om-92
- the carpet products described herein will essentially comprise at least one flexible substrate and at least one coating or adhesive layer associated with the flexible substrates(s).
- the adhesive or coating layer(s) is/are formed from an aqueous composition containing a specific type of vinyl ester-based copolymer dispersion as the coating- or film-forming component thereof, together with a particulate filler material.
- the components and preparation of the layer-forming aqueous compositions, the copolymer dispersion and filler components thereof, the flexible, e.g., textile, substrate(s) and the preparation and characteristics of carpet products comprising all of these components are described in detail below: Copolymer Dispersion
- the film- or coating-forming component of the aqueous compositions applied to carpet flexible substrates(s) herein is a vinyl acetate-based copolymer comprising ethylene and optionally one or more additional non-functional main co-monomers.
- This vinyl acetate/ethylene copolymer is present in a copolymer dispersion prepared by the emulsion polymerization of appropriately selected co-monomers.
- the primary co-monomer used in the preparation of the copolymer dispersion is vinyl acetate.
- This primary vinyl acetate co-monomer is generally present in the copolymer of the dispersion in amounts of from about 40% to about 80% by weight, more preferably from about 60% to 70% by weight, based on the total main co-monomers in the copolymer.
- the second essential co-monomer for incorporation into the copolymer of the dispersion is ethylene.
- the ethylene will generally comprise from about 8% to about 40% by weight, preferably 10% to about 32% by weight, most preferably from about 12% to about 30% by weight, based on the total main co-monomers in the copolymer.
- the vinyl acetate/ethylene copolymer of the copolymer dispersion can optionally comprise one or more additional non-functional main co-monomers besides vinyl acetate and ethylene.
- One type of such optional main non-functional co-monomer comprises vinyl ester co-monomers. Examples thereof are vinyl esters of monocarboxylic acids having one to eighteen carbon atoms (except vinyl acetate), e.g.
- Another type of optional main non-functional co-monomer which can be incorporated into the vinyl acetate/ethylene copolymer of the dispersion comprises esters of ethylenically unsaturated mono-carboxylic acids or diesters of ethylenically unsaturated di-carboxylic acids.
- Particularly advantageous co-monomers of this type are the esters of alcohols having one to eighteen carbon atoms.
- non- functional, main co-monomers include methyl methacrylate or acrylate, butyl methacrylate or acrylate, 2-ethylhexyl methacrylate or acrylate, dibutyl maleate and/or dioctyl maleate.
- non-functional main co- monomer types can be co-polymerized into the vinyl acetate/ethylene copolymer.
- non-functional main co-monomers can comprise up to about 40 wt based on total main co-monomers in the copolymer. More preferably, such non-functional main co- monomers can comprise from about 5 wt to about 20 wt , based on the total main co- monomers in the vinyl acetate/ethylene copolymer.
- the vinyl acetate/ethylene emulsion copolymer used in the coatings for the carpet products herein can also optionally contain relatively minor amounts of other types of co- monomers besides vinyl acetate, ethylene or other main co-monomer types.
- Such other optional co-monomers will frequently be those which contain one or more functional groups and can serve to provide or facilitate cross-linking between copolymer chains within the copolymer dispersion-containing aqueous composition, or upon the drying or curing of films and coatings formed from such compositions.
- Such optionally present, functional co-monomers can include ethylenically unsaturated acids, e.g. mono- or di-carboxylic acids, sulfonic acids or phosphonic acids.
- ethylenically unsaturated acids e.g. mono- or di-carboxylic acids, sulfonic acids or phosphonic acids.
- salts preferably alkali metal salts or ammonium salts.
- optional functional co-monomers of this type include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid, vinylphosphonic acid, styrenesulfonic acid, monoesters of maleic and/or fumaric acid, and of itaconic acid, with monohydric aliphatic saturated alcohols of chain length Ci-Cis, and also their alkali metal salts and ammonium salts, or (meth) acrylic esters of sulfoalkanols, an example being sodium 2-sulfoethyl methacrylate.
- Suitable optional functional co-monomers include ethylenically unsaturated co-monomers with at least one amide-, epoxy-, hydroxyl, trialkoxysilane- or carbonyl group. Particularly suitable are ethylenically unsaturated epoxide compounds, such as glycidyl methacrylate or glycidyl acrylate. Also suitable are hydroxyl compounds including methacrylic acid and acrylic acid C1-C9 hydroxyalkyl esters, such as n- hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl acrylate and methacrylate.
- Suitable functional co-monomers include compounds such as diacetone acrylamide and acetylacetoxyethyl acrylate and methacrylate; and amides of ethylenically unsaturated carboxylic acids, such as acrylamide or meth acrylamide.
- the emulsion copolymer used herein can optionally contain trialkoxysilane functional co-monomers.
- the emulsion copolymers used herein can be substantially free of silane-based co-monomers.
- One type of functional co-monomer which should not be incorporated into the vinyl acetate/ethylene copolymers used herein comprises any co-monomer which contains cross- linkable moieties that generate formaldehyde upon formation of a coating layer from compositions containing such copolymers.
- the vinyl acetate/ethylene copolymer in the copolymer dispersion should be substantially free of such co-monomers, which include, for example, common cross-linkers like N-methylolacrylamide (NMA) or even low formaldehyde versions of N-methylolacrylamide such as NMA-LF.
- co-monomers include, for example, common cross-linkers like N-methylolacrylamide (NMA) or even low formaldehyde versions of N-methylolacrylamide such as NMA-LF.
- NMA N-methylolacrylamide
- NMA-LF low formaldehyde versions of N-methylolacrylamide
- the vinyl acetate/ethylene copolymer in the copolymer dispersion should contain no halogenated co- monomers such as vinyl chloride co-monomers.
- Optional functional co-monomers can be incorporated into the vinyl acetate/ethylene emulsion copolymers used herein in amount of up to about 5 wt , based on total main co- monomers in the copolymer. More preferably, optional functional co-monomers can comprise from about 0.5 wt to about 2 wt , based on total main co-monomers in the copolymer.
- the emulsion copolymer can be formed within the copolymer dispersion using emulsion polymerization techniques described more fully hereinafter.
- the copolymer will be present in the form of relatively small particles ranging in weight average particle size, d w , of from about 50 nm to about 500 nm, measured by laser aerosol spectroscopy. More preferably, the copolymer dispersion will be present in the form of particles ranging in weight average particle size, d w , of from about 120 nm to about 350 nm. Particle size can be determined by means of laser aerosol spectroscopy techniques.
- the vinyl acetate-ethylene based copolymer can be either homogeneous or heterogeneous in monomeric configuration and make-up.
- Homogeneous copolymers will have a single discreet glass transition temperature, T g , as determined by differential scanning calorimetry techniques.
- Heterogeneous copolymers will exhibit two or more discreet glass transition temperatures and might lead to core shell particle morphologies.
- the vinyl acetate-based copolymer used herein normally has a glass transition temperature, T g , which ranges between about -25 °C and +15 °C, more preferably between about - 20°C and about +5 °C.
- T g glass transition temperature
- the T g of the polymer can be controlled, for example, by adjusting the ethylene content, i.e., generally the more ethylene present in the copolymer relative to other co-monomers, the lower the T g .
- the copolymer dispersion used to prepare the aqueous compositions that form the carpet adhesive or coating layers is stabilized in the form of an aqueous copolymer dispersion or latex.
- the copolymer dispersion therefore will be prepared in the presence of and will contain a stabilization system which generally comprises emulsifiers, in particular nonionic emulsifiers and/or anionic emulsifiers. Mixtures of nonionic and anionic emulsifiers can also be employed.
- the amount of emulsifier employed will generally be at least 0.5 wt , based on the total quantity of main co-monomers in the copolymer dispersion. Generally emulsifiers can be used in amounts up to about 8 wt , based on the total quantity of main co-monomers in the copolymer dispersion.
- the weight ratio of emulsifiers nonionic to anionic may fluctuate within wide ranges, between 1 :1 and 50:1 for example.
- the vinyl acetate/ethylene copolymer dispersion may further comprise small amounts of polymeric stabilizers (protective colloids).
- Emulsifiers employed with preference herein are nonionic emulsifiers having alkylene oxide groups and/or anionic emulsifiers having sulfate, sulfonate, phosphate and/or phosphonate groups.
- Such emulsifiers can be used together with molecularly or dispersely water-soluble polymers, preferably together with polyvinyl alcohol.
- the emulsifiers used contain no alkylphenolethoxylates (APEO).
- nonionic emulsifiers examples include acyl, alkyl, oleyl, and alkylaryl ethoxylates. These products are commercially available, for example, under the name Genapol ® , Lutensol ® or Emulan ® .
- ethoxylated mono-, di-, and tri- alkylphenols (EO degree: 3 to 50, alkyl substituent radical: C 4 to C12) and also ethoxylated fatty alcohols (EO degree: 3 to 80; alkyl radical: Cs to C36), especially Ci2-Ci 4 fatty alcohol (3-40) ethoxylates, C13-C15 oxo-process alcohol (3-40) ethoxylates, C16-C18 fatty alcohol (11- 80) ethoxylates, C10 oxo-process alcohol (3-40) ethoxylates, C13 oxo-process alcohol (3-40) ethoxylates, polyoxyethylenesorbitan monooleate with 20 ethylene oxide groups, copolymers of ethylene oxide and propylene oxide having a minimum ethylene oxide content of 10% by weight, and the polyethylene oxide (4-40) ethers of oleyl alcohol. Particularly suitable are the polyethylene oxide (4-40) ethers of fatty alcohols (EO degree
- the amount of nonionic emulsifiers used in preparing the copolymer dispersions herein is typically about 1% to about 8% by weight, preferably about 1% to about 5% by weight, more preferably about 1 % to about 4% by weight, based on the total main monomer quantity. Mixtures of nonionic emulsifiers can also be employed.
- Suitable anionic emulsifiers include sodium, potassium, and ammonium salts of linear aliphatic carboxylic acids of chain length C12-C2 0 , sodium hydroxyoctadecanesulfonate, sodium, potassium, and ammonium salts of hydroxy fatty acids of chain length C12-C2 0 and their sulfonation and/or sulfation and/or acetylation products, alkyl sulfates, including those in the form of triethanolamine salts, alkyl(Cio-C2o) sulfonates, alkyl(Cio-C2o) arylsulfonates, dimethyl-dialkyl (Cs-Cis) ammonium chloride, and their sulfonation products, lignosulfonic acid and its calcium, magnesium, sodium, and ammonium salts, resin acids, hydrogenated and dehydrogenated resin acids, and their alkali metal salts, dodecyl
- the amount of anionic emulsifiers used can typically range from about 0.1 % to about 3.0% by weight, preferably from about 0.1% to about 2.0% by weight, more preferably from about 0.5% to about 1.5% by weight, based on the total main monomer quantity. Mixtures of anionic emulsifiers can also be employed.
- the vinyl ester/ethylene copolymer dispersions employed in accordance with the invention may comprise as part of the stabilizer system protective colloids, preferably polyvinyl alcohols and/or their modifications.
- Protective colloids if present, are generally present only in comparatively low concentrations, as for example at up to about 3% by weight, such as 0.2 to 2 % by weight, based on the total amount of the main monomers used.
- Certain vinyl acetate/ethylene copolymer dispersions employed herein can preferably contain no protective colloids or only up to about 1% by weight of protective colloids, based on the total amount of the main co-monomers employed in the vinyl acetate/ethylene copolymer.
- Suitable protective colloids include water-soluble or water-dispersible polymeric modified natural substances, such as cellulose ethers, examples being methyl- ,ethyl-, hydroxyethyl- or carboxymethylcellulose; water-soluble or water-dispersible polymeric synthetic substances, such as polyvinylpyrrolidone or polyvinyl alcohols or their copolymers (with or without residual acetyl content), and polyvinyl alcohol which is partially esterified or acetalized or etherified with saturated radicals and also with different molecular weights.
- the protective colloids can be used individually or in combination.
- the two or more colloids can each differ in their molecular weights or they can differ in their molecular weights and in their chemical composition, such as the degree of hydrolysis, for example.
- the vinyl acetate/ethylene copolymer dispersions used herein may contain subsequently added water- soluble or water-dispersible polymers as hereinafter described. Additional emulsifiers may also be added to the dispersions post-polymerization.
- copolymer dispersions comprising the vinyl acetate/ethylene copolymers described herein can be prepared using emulsion polymerization procedures which result in the preparation of polymer dispersions in aqueous latex form.
- emulsion polymerization procedures which result in the preparation of polymer dispersions in aqueous latex form.
- Such preparation of aqueous polymer dispersions of this type is well known and has already been described in numerous instances and is therefore known to the skilled artisan.
- Such procedures are described, for example, in U.S. Patent No. 5,849,389, and in the Encyclopedia of Polymer Science and Engineering, Vol. 8, p. 659 ff (1987). The disclosures of both of these publications are incorporated herein by reference in their entirety.
- the polymerization may be carried out in any manner known per se in one, two or more stages with different monomer combinations, giving polymer dispersions having particles with homogeneous or heterogeneous, e.g., core shell or hemispheres, morphology.
- Any reactor system such as batch, loop, continuous, cascade, etc, may be employed.
- the polymerization temperature generally ranges from about 20 °C to about 150 °C, more preferably from about 50 °C to about 120 °C.
- the polymerization generally takes place under pressure if appropriate, preferably from about 2 to about 150 bar, more preferably from about 5 to about 100 bar.
- the vinyl acetate, ethylene, and other co-monomers can be polymerized in an aqueous medium under pressures up to about 120 bar in the presence of one or more initiators and at least one emulsifying agent, optionally along with protective colloids like PVOH.
- the aqueous reaction mixture in the polymerization vessel can be maintained by a suitable buffering agent at a pH of about 2 to about 7.
- emulsifiers emulsifiers
- co- monomers emulsifiers
- catalyst system components emulsifiers
- an aqueous medium containing at least some of the emulsifier(s) can be initially formed in the polymerization vessel with the various other polymerization ingredients being added to the vessel thereafter.
- Co-monomers can be added to the polymerization vessel continuously, incrementally or as a single charge addition of the entire amounts of co-monomers to be used.
- Co- monomers can be employed as pure monomers or can be used in the form of a pre-mixed emulsion.
- Ethylene as a co-monomer can be pumped into the polymerization vessel and maintained under appropriate pressure therein.
- the polymerization of the ethylenically unsaturated monomers will generally take place in the presence of at least one initiator for the free-radical polymerization of these co-monomers.
- Suitable initiators for the free-radical polymerization include all known initiators which are capable of initiating a free -radical, aqueous polymerization in heterophase systems. These initiators may be peroxides, such as alkali metal and/or ammonium peroxodisulfates, or azo compounds, more particularly water-soluble azo compounds.
- redox initiators it is also possible to use what are called redox initiators.
- redox initiators examples thereof are tert-butyl hydroperoxide and/or hydrogen peroxide in combination with reducing agents, such as with sulfur compounds, an example being the sodium salt of hydroxymethanesulfinic acid, Briiggolit FF6 and FF7, Rongalit C, sodium sulfite, sodium disulfite, sodium thiosulfate, and acetone -bisulfite adduct, or with ascorbic acid, sodium erythobate, or with reducing sugars.
- reducing agents such as with sulfur compounds, an example being the sodium salt of hydroxymethanesulfinic acid, Briiggolit FF6 and FF7, Rongalit C, sodium sulfite, sodium disulfite, sodium thiosulfate, and acetone -bisulfite adduct, or with ascorbic acid, sodium erythobate
- the amount of the initiators or initiator combinations used in the process varies within what is usual for aqueous polymerizations in heterophase systems. In general the amount of initiator used will not exceed 5% by weight, based on the total amount of the co-monomers to be polymerized. The amount of initiators used, based on the total amount of the co- monomers to be polymerized, is preferably 0.05% to 2.0% by weight. [0048] In this context, it is possible for the total amount of initiator to be included in the initial charge to the reactor at the beginning of the polymerization.
- a portion of the initiator is included in the initial charge at the beginning, and the remainder is added after the polymerization has been initiated, in one or more steps or continuously.
- the addition may be made separately or together with other components, such as emulsifiers or monomer emulsions. It is also possible to start the emulsion polymerization using a seed latex, for example with about 0.5 to about 15% by weight of the dispersion.
- the copolymer dispersions used herein can additionally contain copolymers formed from Ci-Cis esters of (meth) acrylic acids, Ci-Cis esters of other ethylenically unsaturated mono- carboxylic acids, or Ci-Cis diesters of ethylenically unsaturated di-carboxylic acids.
- Such additional copolymers can comprise, for example, from about 0.5 to about 20 parts by weight based on total copolymers in the copolymer dispersion and can include copolymers formed from ethyl acrylate, butyl acrylate (BuA), 2-ethylhexyl acrylate (2-EHA), dibutyl maleate, dioctyl maleate or combinations of these esters.
- BuA butyl acrylate
- 2-EHA 2-ethylhexyl acrylate
- dibutyl maleate dioctyl maleate or combinations of these esters.
- the molecular weight of the various copolymers in the copolymer dispersions herein can be adjusted by adding small amounts of one or more molecular weight regulator substances.
- These regulators as they are known, are generally used in an amount of up to 2% by weight, based on the total co-monomers to be polymerized.
- As regulators it is possible to use all of the substances known to the skilled artisan. Preference is given, for example, to organic thio compounds, silanes, allyl alcohols, and aldehydes.
- the copolymer dispersions as prepared herein will generally have a viscosity which ranges from about 100 mPas to about 5000 mPas at 45 - 55 % solids, more preferably from about 200 mPas to about 4000 mPas, most preferably 400 - 3000 mPas measured with a Brookfield viscometer at 25 °C, 20 rpm, with appropriate spindle. Viscosity may be adjusted by the addition of thickeners and/or water to the copolymer dispersion. Suitable thickeners can include polyacrylates or polyure thanes, such as Borchigel L75 ® and Tafigel PUR 60 ® . Alternatively, the copolymer dispersion may be substantially free of thickeners.
- the solids content of the resulting aqueous copolymer dispersions can be adjusted to the level desired by the addition of water or by the removal of water by distillation.
- the desired level of polymeric solids content after polymerization is from about 40 weight percent to about 70 weight percent based on the total weight of the polymer dispersion, more preferably from about 45 weight percent to about 55 weight percent.
- the aqueous copolymer dispersions used to form the coating layer-forming compositions herein can be desirably low in Total Volatile Organic Compound (TVOC) content.
- TVOC Total Volatile Organic Compound
- a volatile organic compound is defined herein as a carbon containing compound that has a boiling point below 250° C (according to the ISO 11890-2 method for polymer dispersions TVOC content determination) at atmospheric pressure. Compounds such as water and ammonia are excluded from VOCs.
- the aqueous copolymer dispersions used herein will generally contain less than 0.5% TVOC by weight based on the total weight of the aqueous copolymer dispersion.
- the aqueous copolymer dispersion will contain less than 0.3% TVOC by weight based on the total weight of the aqueous copolymer dispersion.
- the aqueous copolymer dispersions used herein will generally also emit a relatively small amount of its TVOC content when exposed to the atmosphere.
- the copolymer dispersions herein will emit TVOC materials to the extent of no more than about 15 times the Toluene D8 standard, when films formed from such dispersions are tested in accordance with the procedures of ISO 16000-9, described hereinafter in the Test Methods section. More preferably, the copolymer dispersions herein will emit TVOC materials to the extent of no more than about 10 times the Toluene D8 standard.
- the vinyl acetate/ethylene copolymer dispersions used herein can also optionally comprise a wide variety of conventional additives which are typically used in the formulation of binders and/or adhesives.
- Such optional additives may be present in the copolymer dispersion from the beginning of or during polymerization, may be added to the dispersion post-polymerization or, such as in the case of fillers, may be used in connection with preparation of the aqueous coating compositions from the copolymer dispersions as hereinafter described.
- Typical conventional optional additives for the copolymer dispersions herein can include, for example, film-forming assistants, such as white spirit, Texanol ® , TxiB ® , butyl glycol, butyl diglycol, butyl dipropylene glycol, and butyl tripropylene glycol; wetting agents, such as AMP 90 ® , TegoWet.280 ® , Fluowet PE ® ; defoamers, such as mineral oil defoamers or silicone defoamers; UV protectants, such as Tinuvin 1130 ® ; agents for adjusting the pH; preservatives; plasticizers, such as dimethyl phthalate, diisobutyl phthalate, diisobutyl adipate, Coasol B , Plastilit 3060 , and Triazetin ; subsequently added stabilizing polymers, such as polyvinyl alcohol or cellulose ethers; and other additives and auxiliaries
- the copolymer dispersions as hereinbefore described are combined with filler material and additional water to form aqueous coating compositions for the carpet products herein.
- a coating composition can then be applied to the textile substrate(s) which form the carpet products herein.
- the applied aqueous coating compositions then provide the coating layer(s) within the carpet products.
- the carpet product can comprise only one or more than one coating layer.
- the carpet products herein will always contain a binder coating layer to secure the carpet fibers to a primary backing substrate.
- the carpet products herein can then optionally also comprise a second or additional layer which may be an adhesive layer to secure a secondary backing substrate to the coated primary backing.
- the carpet product can comprise both a coating and an adhesive layer which are formed from the same type of aqueous coating compositions as described herein.
- the carpet products herein can comprise both a coating layer as described herein and a different type of adhesive layer which may also be formed from the same type of compositions as the coating compositions herein or may be formed from a completely different conventional adhesive coating composition.
- the aqueous coating compositions used herein will also contain a particulate filler material selected from particulate inorganic compounds and particulate plastic materials.
- the filler employed can be essentially any filler suitable for use in carpet manufacture. Such fillers are widely commercially available.
- Filler examples include inorganic, e.g., mineral, fillers or pigments such as fly ash and ground glass and those known in the art, such as calcium carbonate, clay, kaolin, talc, barites, feldspar, titanium dioxide, calcium aluminum pigments, satin white, zinc oxide, barium sulphate, gypsum, silica, mica, and diatomaceous earth.
- Particulate plastic material such as synthetic polymer pigments, hollow polymer pigments and recycled carpet backing may also be employed, as can mixtures of any of the foregoing filler types.
- the preferred filler material is particulate calcium carbonate.
- the particulate filler material can generally range in average particle size between about 200 nm and ⁇ , more preferably between about 1 ⁇ and 500 ⁇ , most preferably 10 ⁇ - 300 ⁇ .
- Preferred coating compositions used to prepare carpet products in accordance with the present invention are loaded with filler to yield an aqueous coating composition comprising from about 10 to about 70 weight percent, more preferably from about 20 to about 60 weight percent, and more preferably from about 20 to about 50 weight percent of dry copolymer and from about 30 to about 90 weight percent, preferably about 40 to about 80 weight percent, and most preferably 50 to 80 weight percent of filler based on total weight of solids in the aqueous composition, depending in part on the type and form of the carpet being constructed.
- Such coating compositions can contain in addition to the copolymer dispersions and filler materials hereinbefore described, a variety of additional conventional additives in order to modify the properties thereof.
- additional conventional additives may be included thickeners, rheology modifiers, dispersants, flame retardants, colorants, biocides, anti-foaming agents, etc.
- These optional additives are largely the same as those hereinbefore described with respect to the copolymer dispersions herein
- the coating compositions hereinbefore described form the coating, i.e., binder, layer(s) in the carpet products herein which will also comprise at least one flexible substrate.
- Such flexible substrates can, for example, be selected from nonwovens, wovens, unidirectional weaves, knitted fabrics and pile fabrics.
- the carpet products herein can be conventional tufted carpet, non-tufted carpet or needle-punched carpet.
- Such carpet products can be prepared by applying and drying the emulsion copolymer-containing aqueous compositions using equipment which is readily available in most carpet mills.
- Pile carpet products comprise a primary backing with pile yarns extending from the primary backing substrate to form pile tufts.
- Pile or tufted carpet can be prepared by a) tufting or needling yarn into a woven or non-woven backing substrate; b) applying the aqueous carpet coating composition as described herein to the rear of the backing such that the yarn is embedded in the carpet coating composition; and c) drying the resultant carpet construction.
- the primary backing substrate can be non-woven polypropylene, polyethylene or polyester or woven jute, polypropylene or poly amide (synthetic and natural).
- the carpet products herein can also be non-tufted carpets wherein the fibers are embedded into a coating or binder composition which has been coated onto a woven or non- woven substrate.
- Non-tufted carpets also may be prepared by a) coating an aqueous composition such as hereinbefore described onto a substrate; b) embedding the carpet fibers in the substrate; and c) drying the resultant carpet construction.
- the carpet coating can be thickened and applied to a scrim surface.
- the fibers then are directly embedded into the wet coating using conventional techniques and then dried.
- These non-tufted carpets also may be advantageously prepared utilizing a secondary backing that can provide additional dimensional stability.
- the aqueous composition is applied in a manner such that it penetrates the fibers of the carpet yarns to yield better adhesion, fiber bundle integrity, anti-fuzzing properties and suitable tuft-bind values.
- Suitable carpet performance properties can be achieved by applying an amount of the aqueous coating/binder composition ranging from about 100 g/m 2 to about 3000 g/m 2 , more preferably from about 200 g/m 2 to about 2000 g/m 2 , most preferably from about 400 g/m 2 to about 1500 g/m 2 (dry basis).
- the carpet product will comprise a textile fabric stricture treated with a selected type of vinyl acetate/ethylene (VAE) copolymer dispersion.
- the textile fabric structure in such a carpet product can be in the form of a fabric selected from wovens, nonwovens, unidirectional weaves, knitted fabrics or pile fabrics.
- the carpet product can comprise a pile fabric which is coated with a coating composition based on the selected type of VAE copolymer dispersion with the coating being on the far side of the pile (tread side).
- the carpet product can be in the form of a carpet wherein a secondary backing layer is bonded to the pile fabric layer on the far side of the tread side.
- the bonding between the two layers is effected through the VAE copolymer dispersion-based coating.
- Such textile fabric structures can have a weight per unit area of from about 1000 to about 3000 g/m 2 .
- the selected VAE copolymer dispersions used to treat the textile fabric structure in order to form such a carpet product embodiment can comprise from about 70 to about 80 pphm (parts per hundred of monomers) of vinyl acetate and from about 20 to about 30 pphm, more preferably from about 20 to 24 pphm, of ethylene.
- This copolymer will have a glass transition temperature, T g , of from about 0 °C to about -10 °C, more preferably between about -3 °C and -6 °C, and a mean particle diameter, d w , within the dispersion of about 150 to 200 nm.
- Such a selected VAE copolymer can also comprise up to about 10 pphm of further co- monomers which are copolymerizable with the vinyl acetate and ethylene co-monomers.
- Such further co-monomers can include ethylenically unsaturated acids, or the salts thereof, ethylenically unsaturated monomers having at least one amide, epoxy, hydroxyl, N-methylol, trialkoxysilane or carbonyl group, and combinations of two or several monomers from any of these further monomer types.
- such further co-monomers can include vinyl esters which are not vinyl acetate, alpha-olefins which are not ethylene, vinyl aromatics, esters of ethylenically unsaturated monocarboxylic acids, and diesters of ethylenically unsaturated dicarboxylic acids.
- the VAE copolymer dispersion used to make this carpet embodiment are stabilized with at least about 1 wt of emulsifiers and about 0 wt to about 2 wt of a protective colloid based on polyvinyl alcohol.
- the emulsifiers used are selected from anionic and nonionic surfactants but contain no alkylphenylethoxylates (APEs).
- APEs alkylphenylethoxylates
- These VAE copolymer dispersions can have a viscosity of from about 400 to about 1600 mPa.s measured with a Brookfield viscometer at 25 °C. Such dispersions can also have a solids content of from about 45 wt to about 55 wt .
- the carpet products herein have especially desirable washability and, in some instances, especially desirable non-slip characteristics as well.
- Washability refers to the ability of a movable carpet product such as one, for example, in the form of an area rug, a throw rug, a runner, a carpet tile, a tapestry or wall hanging, a door mat, an automobile floor mat or a gymnasium mat to maintain its integrity upon being washed in a machine washing operation.
- Maintenance of carpet integrity includes the propensity of the carpet product not to lose weight upon being subjected to one or multiple machine washings.
- Carpet integrity after one or more washings further involves the propensity of the carpet to maintain its original appearance, its hand feel, the integrity of it backing and its anchorage of tufted yarn and fibers (pile) within the carpet backing.
- Carpet washability can be determined by test procedures which involve weighing of carpet product test samples before and after washing operations. A suitable test procedure for determining carpet weight loss upon washing is set forth in the Test Methods section hereinafter. Generally, the carpet products herein will exhibit a weight loss of less than about 4.5% after 20 washings in this washability test. More preferably, the carpet products herein will exhibit a weight loss of less than about 3.6% after 20 washings.
- Carpet washability can also be quantified by making tuft anchorage measurements both before and after carpet washing operations.
- Carpet tuft anchorage is a conventionally determined parameter in the carpet industry.
- a procedure for determining the extent of tuft anchorage is also set forth hereinafter in the Test Methods section.
- the carpet products herein will exhibit a loss of tuft anchorage of less than about 40% after 20 washings in this tuft anchorage test. More preferably, the carpet products herein will exhibit a tuft anchorage loss of less than about 25% after 20 washings.
- the resistance of carpet products to deterioration upon washing can also, of course, be determined by simple visual observation of the effect of one or more washing operations on samples of the carpet product. Suitable procedures for visual grading of carpet products on a scale of 1 to 4 for their appearance and integrity before and after washing are also set forth hereinafter in the Test Methods section. Preferred carpet products herein will have a washability grade of 3 or less after 20 washing operations.
- Non-slip performance refers to the propensity of a movable, weight-bearing carpet product to resist movement along or across the surface, e.g., the floor, which it covers when the carpet is subjected to a lateral force parallel to its plane. Resistance to this kind of lateral movement, i.e., slippage, is provided by the frictional drag which the weighted coated backing exerts on the surface which the carpet product covers.
- Non-slip propensity can be determined objectively by measuring the maximum force needed to drag a weighted carpet sample across a test surface. A procedure for making these kinds of measurements to determine carpet non- slip performance is also set forth in the Test Methods section hereinafter.
- Non-slip carpet embodiments herein will generally exhibit a maximum drag force in this test of at least about 6.0 Newtons, even after washing. More preferably, non-slip carpet embodiments herein will exhibit a maximum drag force of at least about 7.0 Newtons in this test.
- the carpet products herein with the specific type of vinyl acetate/ethylene-based copolymer dispersions used in forming coating layers, also have especially desirable, environmentally friendly characteristics.
- the copolymer dispersions used by virtue of containing no cross-linking groups which generate formaldehyde (e.g. no NMA or NMA- LF), and by virtue of their low TVOC content and TVOC emission, do not cause potentially problematic materials of this type to be emitted from the carpet products herein.
- the carpet products herein are furthermore preferably substantially free of halogenated co-monomers, polyvinyl chloride and bitumen, which are types of materials which typically have been used in commercial carpet products.
- the carpet product since the carpet products herein do not utilize SBL coatings or binders, the carpet product will also be substantially free of potentially toxic components such as 4-phenylcyclohexene (4-PCH), 4-vinylcyclohexene (4-VCH), styrene, and ethylbenzene.
- 4-phenylcyclohexene (4-PCH)
- 4-vinylcyclohexene (4-VCH)
- styrene styrene
- ethylbenzene ethylbenzene
- the carpet products which contain the coating layers formed from aqueous compositions containing the copolymer dispersions and fillers herein can have a weight per unit area of from about 100 g/m 2 to about 3000 g/m 2 , more preferably from about 200 g/m 2 to about 2000 g/m 2 , most preferably from about 400 g/m 2 to about 1500 g/m 2 (dry basis).
- the carpet products herein can be in the form of rugs or mats which can be used as area floor coverings.
- the carpet products herein can be in the form of carpet tiles or even in the form of wall-to-wall carpeting.
- the size of solid particles within the copolymer dispersions used herein can be determined by laser aerosol spectroscopy (LAS).
- This LAS method is described in the publication Kunststoffharz horren 28; "Characterization and Quality Assurance of Polymer Dispersions”; Rush 1992, Dr. J. Paul Fischer.
- the method uses a Nd:YV04 Laser (Millenia II) supplied by Spectra Physics with a laser power of 2 W and a wave length of 532 nm.
- the detector is a Bialkali Photocathode Typ 4517 supplied by Burle (formerly RCA).
- the scattered light of the spray dried single particles will be detected at 40 °.
- the evaluation of the data is done with a multi channel analyser by TMCA with 1024 channels.
- 0.2 ml of a dispersion sample is diluted in 100 ml of deionized and filtered water (conductivity of 18.2 ⁇ 8/ ⁇ ).
- the sample is spray dried over a Beckmann-nozzle and dried with nitrogen gas.
- the single particles are neutralized with beta radiation (Kr-85) and then investigated by single particle laser scattering. After evaluation the number and mass mean values within the range of 80 nm to 550 nm and mean particle size values d n , d w , d z and d w /d n are obtained.
- the glass transition temperature, T g can be obtained by using a commercial differential scanning calorimeter Mettler DSC 820 at 10 K/min. For evaluation, the second heating curve is used and the DIN mid point calculated.
- the extent of emission of the Total Volatile Organic Compound (TVOC) content of a copolymer dispersion sample is determined using the general procedures of ISO-16000-9, which test method is incorporated herein by reference. In such a procedure, 2 grams of the copolymer dispersion are weighed into an alumina dish with a diameter of 4.2 cm. The dispersion is dried at room temperature (23 CI 50% humidity) overnight to form a film which is then tested in a micro chamber having a diameter of 4.5 cm and a volume of 40 ml. A continuous air flow (100 ml/minute of clean dry air not reconditioned for humidity) is passed through the chamber and the film sample therein is allowed to equilibrate for a period of 20 min to chamber conditions (25 °C).
- the air flow is directed to an absorption device which is a Tenax tube spiked with 111 ng of Toluene D8 which is used as an absorption standard.
- the volatile organic compounds (VOCs) in the air flow from the film sample are absorbed onto the Tenax tube for a period of 60 minutes.
- the Tenax tube is then analyzed via GC-MS for the amount of VOCs absorbed onto it.
- the "washability" of carpet samples can be determined by measuring the weight loss of test samples after washing them in a commercial washing machine. Two carpet samples (22 x 26.5 cm / sutured with cotton web; approximately 20 + 3 g per sample) for each tested copolymer dispersion are washed together. The samples are packed separately in washing bags (40 x 50 cm with zipper) to avoid the contact between the backings during the wash cycles. All samples are washed twenty times and after each cycle the weights of the samples are measured.
- the washing machine used is a Siemens Vario Perfect E14-32. For each cycle, 15 g of washing powder are used.
- the washing powder used is Professional Clean and Cleaver (15 - 30 % phosphates, 5 - 15 % oxygen bleach, ⁇ 5 % nonionic tensides, ⁇ 5 % soap, fragrance, enzymes, and brightener).
- the following conditions are applied for every wash cycle: washing program: "Pflegeschreib", tumbling speed 600 rpm and temperature 40°C. After each washing cycle, the samples are dried overnight at 23 °C and 50 % humidity.
- the samples are weighed after each wash cycle.
- the results are the average of the total weight loss in gram [g] after every 5 th wash cycle, for the two samples washed for each applied copolymer dispersion tested. Results can be reported as the percentage of weight lost from each sample tested after every 5 washing cycles. Additionally the non-slip properties of the carpet samples are also determined in connection with this washability testing. The test method for determining non-slip properties of the washed carpet samples is described hereinafter.
- the non-slip properties of carpet samples can be determined by using a modified version of the TAPPI 816 om-92 test method, which test method is incorporated herein by reference. This test method determines the maximum force in Newtons [N] needed to drag a weighted carpet sample over a glass plate. The non-slip properties are measured initially and after every 5 th wash cycle in the Washability test described above.
- the testing machine used is made by Lloyd Instruments and is called LF Plus universal testing machine.
- the test program works with preloaded settings of 0.5 N force and a testing speed of 100 mm / min.
- the carpet sample is clamped to a mounting which is a stainless steel tray of 10 x 10 cm / hole 0 5 cm) horizontal.
- a hook is attached to one tuft and this hook is used to pull the tuft until it separates from the carpet sample.
- the maximum break force of the tufts is measured. The breakpoint should be reached within 2 to 10 seconds. For each carpet sample, 20 tufts are tested to give the average for the maximum break force. The break force is measured in Newtons (N).
- Carpet samples can also be visually evaluated for their backing appearance and hand feel.
- the unwashed carpet samples are compared with these same samples which are then washed 20 times.
- Important criteria for evaluation include the integrity of the backing, the visible weight loss of the carpet sample combined with the embedding of the fibers as well as the softness of the backed carpet samples both initially and after 20 washes.
- the results of these visible evaluations are expressed on a scale of 1 to 4.
- the reactor is purged with nitrogen to eliminate oxygen. Out of a total amount of (25316 g of vinyl acetate + 325 g Glycidyl methacrylate), 5.0% of the (vinyl acetate + Glycidyl methacrylate) is added to the water phase in the reactor.
- the ethylene valve is opened, and the reactor is pressurized to 15 bar at ambient temperature (ca. 1000 g of ethylene) and is then closed again (total amount of ethylene: 7140 g). The reactor temperature is ramped up to 65 °C. At 35 °C, a First Initiator which is sodium peroxo disulfate (145 g in 575 g of deionized water) is added quickly (over ca. 8 minutes) into the reactor.
- the (vinyl acetate + Glycidyl methacrylate) feed is started and is the remaining 95% of the vinyl acetate + Glycidyl methacrylate is introduced into the reactor in 300 minutes.
- the ethylene valve is opened again until the rest of the ethylene is fed into the reactor.
- a Second Initiator feed 35 g of sodium peroxodisulfate in 575 g of deionized water is started for approximately 30 minutes.
- the reactor temperature is ramped up to 85 °C within 30 minutes.
- Example 2 VAE copolymer dispersion has the following characteristics:
- Viscosity Brookfield (25 °C, Spindel 3, 20 rpm): 600 mPas
- the polyvinyl alcohol is dissolved 15% / 29% in deionized water at 90 °C for 2 hours.
- the reactor is purged with nitrogen to eliminate oxygen.
- Out of a total amount of (28753 g of vinyl acetate, 5% of the vinyl acetate is added to the water phase in the reactor.
- the ethylene valve is opened and the reactor is pressurized to 15 bar at ambient temperature (ca. 1000 g of ethylene) and is then closed again (total amount of ethylene: 3828 g).
- the reactor temperature is ramped up to 65 °C.
- a First Initiator (reducing agent), which is sodium metabisulfite (44 g in 1043 g of deionized water), is added quickly (over ca. 1-2 minutes) into the reactor.
- a Second Initiator (oxidizing agent), which is Trigonox AW-70, (29 g of i-butyl hydroperoxide in 2196 g of deionized water), is added quickly (over ca. 1-2 minutes) into the reactor.
- the vinyl acetate feed is started and is introduced into the reactor according to the following profile: 55% in 120 minutes and the remaining 40% in an additional 150 minutes.
- the ethylene valve is opened again until the rest of the ethylene is fed into the reactor.
- all initiator feeds are introduced according to the following profile: 51% of the First Initiator and 55% of the Second Initiator in 120 minutes and the remaining 40 % of each initiator in an additional 150 minutes.
- the reactor temperature is ramped up over 50 minutes to 85 °C.
- a Third Initiator 33 g of sodium peroxodisulfate in 763 g of deionized water
- the reactor temperature of 85 °C is maintained for 1 hour.
- the reactor is then cooled down to approximately 40 °C.
- a final redox treatment can be made at this point by introducing Briiggolit FF 6 (a sodium salt of a sulfinic acid derivative, obtained from L. Bruggemann KG) (33 g in 489 g of deionized water) and afterwards Trigonox AW 70 (95 g).
- Example 1 VAE copolymer dispersion has the following characteristics:
- Viscosity Brookfield 25 °C, Spindel 4, 20 rpm: 5400 mPas
- Litex® T 5260 is a commercial product of Polymer Latex and is a styrene-butadiene latex.
- Viscosity Brookfield (25 °C, Spindel 3, 20 rpm): 398 mPas
- Carpet samples are prepared in the lab by using a foam box to coat a base substrate having fibrous tufts inserted therein and by then curing the applied coating to embed the tufts in the base substrate.
- the base substrate is a woven polypropylene tufting base. Tufts are made of polypropylene yarn inserted into the tufting base such that the amount of tufts plus base material comprises 500 g/m 2 .
- the coating compositions which are used are prepared from the Copolymer Dispersions of Examples 1, 2 and 3. These coating compositions contain, in addition to the Example 1 , 2 or 3 copolymer dispersion, a filler material which is calcium carbonate. These aqueous coating compositions all have the following formulation based on the dry copolymer amount: 40% Copolymer Dispersion (dry) formulated with 60 % calcium carbonate (Manufacturer Omnia, tradename Omniacarp 5 GU) [0108] The copolymer dispersion and calcium carbonate filler are premixed with IKA RE 166 stirrer to form a smooth and homogenous mixture.
- This mixture is foamed up using a Moulinex Supermix 170 device to a volume of 350 + 50 ml.
- the foam density 500 + 100 g/1) is measured with a pycnometer (Erichson Pycnometer Typ 290).
- a foam box (stainless steel / adjustable gap 0 - 15 mm / 25 x 5.4 x 5 cm) is put on the carpet weighed base and is then filled with the mixture. The foam box is dragged slowly and continuously over the back of the carpet sample to form an even film. After coating, the carpet sample is dried for 30 minutes at 110 °C (Gallencamp Oven 300 Plus).
- the carpet samples are stored in a climate room for a minimum of 24 hours at 23 °C and 50 % humidity. The samples are weighed to determine that the coating add-on is 550 + 100 g/m 2 .
- the carpet samples are cut to a size of 22 x 26.5 cm (edges sutured with a cotton web to prevent decomposition) and used in the washability, non-slip, tuft anchorage and visual evaluation testing as hereinafter described.
- the Table 2 data show that the carpet sample with a coating based on the VAE copolymer of Example 1 exhibits comparable weight loss to the carpet sample with a coating based on SBL copolymer of Example 3.
- the carpet sample with a coating based on the VAE copolymer of Example 2 shows slightly better washability compared to the carpet with a coating based on the SBL coating of Example 3.
- Example 1 VAE-based coating shows better non-slip properties after 5, 10, 15 and 20 washes compared to carpet with Example 3 SBL-based coating.
- Carpet with Example 2 VAE-based coating shows comparable non-slip properties after 5, 10, 15 and 20 washes to carpet with Example 3 SBL-based coating.
- Example 1 -based coatings After 20 washes, Example 1 -based coatings still have the same smooth hand feel as they do initially.
- Example 3-based coatings have lost their initial stiffness after 20 washings and then have the same soft touch as Example 1 -based coatings.
- the hand feel of the Example 2 based coating is the same after 20 washes.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP11804780.2A EP2603633A2 (en) | 2010-08-12 | 2011-08-12 | Washable carpet products with coating layers formed from vinyl ester/ethylene copolymer dispersions |
US13/811,962 US20130177733A1 (en) | 2010-08-12 | 2011-08-12 | Washable Carpet Products With Coating Layers Formed From Vinyl Ester/Ethylene Copolymer Dispersions |
BR112013003394A BR112013003394A2 (pt) | 2010-08-12 | 2011-08-12 | produtos para tapete laváveis com camadas de revestimento formadas de dispersões de copolímeros de éster vinílico/etileno |
CN201180039275.0A CN103119215B (zh) | 2010-08-12 | 2011-08-12 | 具有由乙烯酯/乙烯共聚物分散体形成的涂布层的可洗地毯产品 |
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US37309110P | 2010-08-12 | 2010-08-12 | |
US61/373,091 | 2010-08-12 | ||
US201161481445P | 2011-05-02 | 2011-05-02 | |
US61/481,445 | 2011-05-02 |
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US (1) | US20130177733A1 (pt) |
EP (1) | EP2603633A2 (pt) |
CN (1) | CN103119215B (pt) |
BR (1) | BR112013003394A2 (pt) |
WO (1) | WO2012020321A2 (pt) |
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CN102627726A (zh) * | 2012-04-20 | 2012-08-08 | 北京化工大学 | 一种甲醛捕捉剂的制备方法及在脲醛树脂中的应用 |
WO2014089473A1 (en) * | 2012-12-07 | 2014-06-12 | Celanese Emulsions Gmbh | Carpet products and methods for making same |
WO2014165388A1 (en) * | 2013-04-02 | 2014-10-09 | Celanese International Corporation | Carpet products and processes for making same using latex coating compositions |
WO2015061399A1 (en) | 2013-10-24 | 2015-04-30 | Wacker Chemical Corporation | Carpet product and process for the manufacturing of a carpet product |
DE102014214472A1 (de) | 2014-07-24 | 2016-01-28 | Wacker Chemie Ag | Wässerige, Polyvinylalkohol-stabilisierte Vinylacetat-Ethylen-Copolymer-Dispersion mit hoher Füllstoff-Verträglichkeit für Teppichbeschichtungs-Zusammensetzungen |
WO2016092047A1 (de) | 2014-12-12 | 2016-06-16 | Wacker Chemie Ag | Wasser redispergierbare polymere-pulver für teppichbeschichtungs-zusammensetzungen |
US9382341B2 (en) | 2012-09-27 | 2016-07-05 | Wacker Chemical Corporation | Carpet coating composition |
WO2016166037A1 (de) | 2015-04-17 | 2016-10-20 | Wacker Chemie Ag | Teppichbeschichtungs-zusammensetzungen |
US9624622B2 (en) | 2010-08-12 | 2017-04-18 | Celanese Sales Germany Gmbh | Flame retardant carpet products with coating and/or adhesive layers formed from vinyl acetate/ethylene copolymer dispersions |
WO2018213904A1 (pt) * | 2017-05-24 | 2018-11-29 | Bretas Fontes De Resende Marcio | Revestimento têxtil autoadesivo para decoração em paredes, pisos, fachadas e outros |
CN116063611A (zh) * | 2022-12-29 | 2023-05-05 | 广东银洋环保新材料有限公司 | 一种耐水洗牛仔布涂层乳液及其制备方法 |
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WO2013093547A1 (en) * | 2011-12-20 | 2013-06-27 | Celanese Emulsions Gmbh | Carpet coating compositions of improved stability formed from vinyl acetate/ ethylene copolymer dispersions |
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US9624622B2 (en) | 2010-08-12 | 2017-04-18 | Celanese Sales Germany Gmbh | Flame retardant carpet products with coating and/or adhesive layers formed from vinyl acetate/ethylene copolymer dispersions |
CN102627726B (zh) * | 2012-04-20 | 2014-12-03 | 北京化工大学 | 一种甲醛捕捉剂的制备方法及在脲醛树脂中的应用 |
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CN116063611A (zh) * | 2022-12-29 | 2023-05-05 | 广东银洋环保新材料有限公司 | 一种耐水洗牛仔布涂层乳液及其制备方法 |
CN116063611B (zh) * | 2022-12-29 | 2024-05-14 | 广东银洋环保新材料有限公司 | 一种耐水洗牛仔布涂层乳液及其制备方法 |
Also Published As
Publication number | Publication date |
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CN103119215A (zh) | 2013-05-22 |
BR112013003394A2 (pt) | 2019-09-24 |
US20130177733A1 (en) | 2013-07-11 |
CN103119215B (zh) | 2015-09-23 |
EP2603633A2 (en) | 2013-06-19 |
WO2012020321A3 (en) | 2012-04-26 |
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