CN103119215A

CN103119215A - Washable carpet products with coating layers formed from vinyl ester/ethylene copolymer dispersions

Info

Publication number: CN103119215A
Application number: CN2011800392750A
Authority: CN
Inventors: H·米勒; P·S·沃莫尔德; P·巴瓦伊
Original assignee: Celanese Emulsions GmbH
Current assignee: Department Of Nutrition And Food Ingredient Novi Co ltd; Celanese Sales Germany GmbH
Priority date: 2010-08-12
Filing date: 2011-08-12
Publication date: 2013-05-22
Anticipated expiration: 2031-08-12
Also published as: BR112013003394A2; WO2012020321A3; EP2603633A2; WO2012020321A2; US20130177733A1; CN103119215B

Abstract

Disclosed are carpet products comprising at least one flexible substrate and at least one coating layer associated with the at least one flexible substrate. The coating layer is formed from an aqueous composition comprising: A) an emulsifier-stabilized vinyl acetate/ethylene (VAE) emulsion copolymer dispersion wherein the VAE copolymer therein comprises co- monomers which include at least vinyl acetate copolymerized with ethylene and optionally also with other additional functional and/or non-functional co-monomers; and B) at least one particulate filler material selected from particulate inorganic compounds and particulate plastic material. The vinyl acetate/ethylene copolymer in the copolymer dispersion has a particle size, dw, ranging from about 50 to about 500 nm as determined by Laser Aerosol Spectroscopy.; Such carpet products maintain their integrity and appearance after multiple machine washing operations. Some of these carpet products which have backing coated with certain of the coating compositions used herein also exhibit desirable non-slip properties.

Description

Has the carpet product washed by vinyl acetate/coating layer that the ethylene copolymer dispersion forms

The cross reference of related application

U.S. Provisional Application and the sequence number No. that 2011 year May 2 day submit of the sequence number No. that the application submitted to take on August 12nd, 2010 as 61/373,091 is that 61/481,445 U.S. Provisional Application be basic.According to Paris Convention and 35USC § 119 (e), require the rights and interests of the applying date of these two pieces of temporary patent applications.The disclosure of these two pieces of temporary patent applications is introduced by reference at this.

Invention field

The application's research and development relate to the carpet product that has coating layer within it, and described coating layer comprises and contain filler, and the vinyl acetate/ethene of emulsifying agent-and/or colloid-stable-base co-polymer dispersion is as the emulsion binding agent of small grain size.This carpet product demonstrates required washed feature and preferably also can especially effectively as anti-slip carpet or application therein, for example be used for bath mats or gymnasium pad.

Background technology

The carpet of most conventional comprises the main lining cloth that has the cutting or do not cut the yarn tufting of looped pile form, and described looped pile extends upward the formation pile surface from this lining cloth.For tufted carpet, by tufting needle, yarn is inserted in main lining cloth (usually weaving or nonwoven substrate), and applies precoated shet (being adhesive) thereon.

Many dwelling houses and commercial carpets also adopt the woven woven scrim (typically by the polypropylene manufacturing) that is connected with the carpet back side to make, so that size of carpet stability to be provided.These are double-layer products, and wherein wet method is added two-layer coating layer (be used for the fixing precoated shet of tufting and be used for the fixing adhesive of woven scrim), and adds afterwards woven scrim.After fixing woven scrim, solidify the carpet certain hour under 130-200 ℃.

It is important that the physical property of adhesive coating is successfully used in carpet product for it.About this point, the many important requirement that existence must be satisfied by these coatings.Must be able to use to be used for for example technology and equipment that uses routinely of the carpet industry of emulsion coating of latex, apply a coating on carpet and drying.Adhesive composition must provide the cohesiveness good to pile fiber, and they are fixed in lining cloth solidly.This coating also typically has high filler load, for example the carpet lining cloth of calcium carbonate, clay, aluminum trihydrate, barite, feldspar, cullet, flyash and/or circulation.In addition, the coating on the underlayment layer of cloth must preferably can also play the effect of anti-skidding substrate, can prepare thereby make the anti-slip material that uses in for example bathroom and rug or the application of gymnasium pad.

Usually emulsion polymer at carpet material with the adhesive in coating composition, i.e. latex dispersion, styrene-base emulsion copolymer for example, for example, styrene-butadiene latex (SBL) material or acrylic polymer latex dispersion for example.Also can use the copolymer of vinyl acetate (for example vinyl acetate) and ethene, and with rubber coating or contain cinnamic coating for example the SBL-based composition and use thereof in packaging compare, they usually can have cost and manufacturing advantage.For example, can use vinyl ester copolymers, provide required ground VOC (volatile organic compounds) content low and do not contain potential toxic material, for example the carpet product of 4-benzyl ring hexene (4-PCH) and the related compound that may find in the styryl emulsion polymer.

For example at WO2010/089142 with in United States Patent(USP) Nos. 4,735,986; 5,026,765; 5,849,389; 6,359,076; 7,056,847; 7,582,699; 7,649,067; With disclose based on vinyl acetate/ethene in U.S. Patent Application Publication No.2005/0287336, for example emulsion binding agent and the carpet coating compositions of vinyl acetate/ethene (VAE) copolymer.Some in these patent documentations notice, this VAE adhesive and coating composition and to be commonly used for polyvinyl chloride (PVC) plastisol of lining cloth layer in this carpet product compatible.

By the suitable comonomer of polymerization in aqueous emulsion, the vinyl acetate/ethylene copolymer that uses in the adhesive that preparation is described in the aforementioned patent document and coating composition.Can by adding conventional surfactant (anion, nonionic, CATION) as emulsifying agent, stablize these emulsions or dispersion.Also can by comprising protective colloid, stablize these emulsions or dispersion.

Although can obtain the various carpet coating compositions based on stable vinyl acetate and vinyl acetate/ethene (for example VAE) latex emulsion/dispersion adhesive, advantageously identify and select the relatively soft (by the glass transition temperature (T of copolymer of particular type _g) quantize) the VAE-base, containing the eco-friendly adhesive agent emulsion/dispersion of filler, described adhesive agent emulsion/dispersion demonstrates and makes them be particularly useful for preparing for example required performance balance of carpet and carpet material of textile constructions.In case research and development of the present invention provide cyclic washing to have required especially washed feature, i.e. the carpet product of minimum weight loss and integrality, and carpet product and the carpet assembly of preferred required non-skid property.These carpet products also can have low VOC content requiredly.The carpet product of the VAE-of having based adhesive coating described herein has combination (for example, specific comonomer, crosslinking agent, stabilizing agent, relatively little polymer particle size, the T that selects feature _gAnd filler), it can provide this required performance balance, when particularly comparing with the carpet product of the SBL-Carpets coating that uses prior art.

Summary of the invention

Research and development of the present invention relate to carpet product, the coating layer of one deck at least that described carpet product comprises at least one flex substrate and is combined with at least one flex substrate.Form this coating layer by the Aquo-composition that comprises following substances: A) stable vinyl acetate/ethylene copolymer (VAE) dispersion of emulsifying agent, and B) be selected from least a particulate filler material in particulate inorganic compound and granular plastic material.Vinyl acetate/ethylene copolymer in copolymer dispersion comprises the main comonomer that comprises vinyl acetate, described main comonomer and ethene and randomly also with one or more extra main comonomer copolymerization of different non-senses, the main comonomer of described non-sense can be C ₁-C ₁₈The C of the vinyl acetate of monocarboxylic acid or ethylenic unsaturated monocarboxylic ₁-C ₁₈The C of ester or ethylenic unsaturated dicarboxylic ₁-C ₁₈Diester.

The granularity d of the vinyl acetate/ethylene copolymer in copolymer dispersion _wScope is the about about 500nm of 50-, and this measures by laser aerosol spectrum method.In addition, the vinyl acetate/ethylene copolymer in copolymer dispersion typically comprises approximately the approximately ethene of 40wt% of 8wt%-, based on whole main comonomers within it, and glass transition temperature T _gBe approximately-25 ℃ to approximately+15 ℃.

Preferably use based on one or more preferred anionic and/or the nonionic emulsifier of the whole main comonomer in copolymer at least about 0.5wt%; with based on the about about protective colloid of 3wt% (if use, it is polyvinyl alcohol preferably) the stable copolymer dispersion of 0wt%-of the whole main comonomers in copolymer.In case the vinyl acetate/ethylene copolymer in copolymer dispersion generates the crosslinkable comonomer part of formaldehyde when also preferably being substantially free of the coating layer that forms in carpet product or adhesive phase.

Carpet product herein demonstrates good washed feature usually, and after repeatedly washing, they keep their integrality and outward appearance well.Preferably, in the washability that carpet product is herein described herein and tufting fixation test, after 20 wash cycle, demonstrate less than about 4.5% the loss in weight with less than about 40% tufting dead loss.

When the carpet lining cloth of the coating in these carpets contacted with the floor, some embodiments of carpet product herein also demonstrated good non-skid property.Preferably, these carpet products can demonstrate non-skid property, in order to need to move more than or equal to about 6.0 newton's maximum drag force the sample of this carpet product, when according to TAPPI test 816om-92 test.

Describe in detail

Carpet product described herein mainly comprises at least one flex substrate and the coating layer of one deck at least or the adhesive phase of being combined with this flex substrate.Form adhesive phase or coating layer by containing the Aquo-composition of particular type vinyl acetate-base co-polymer dispersion as its coating or film-forming components and particulate filler material.Below described component and preparation, copolymer dispersion and filler component thereof in cambial Aquo-composition in detail, flexible for example textile substrate, and contain preparation and the sign of the carpet product of all these components.

Copolymer dispersion

The component that is applied to formation film in the Aquo-composition on carpet flex substrate herein or coating is to comprise ethene and the vinyl acetate-base co-polymer of one or more extra main comonomers of non-sense randomly.This vinyl acetate/ethylene copolymer is present in by in the copolymer dispersion that the emulsion polymerisation of the comonomer of selection prepares suitably.

The main comonomer that uses in the preparation of copolymer dispersion is vinyl acetate.Usually with the about 80wt% of about 40%-, more preferably from about the consumption of 60%-70wt% is present in dispersion copolymers this main vinyl acetate copolymerization monomer, based on the whole main comonomers in copolymer.The main comonomer of the second that is incorporated in dispersion copolymers is ethene.Ethene accounts for approximately approximately 40wt% of 8%-usually, and preferred 10%-is 32wt% approximately, and the about 30wt% of 12%-most preferably from about is based on the whole mainly comonomers in copolymer.

Vinyl acetate/ethylene copolymer in copolymer dispersion also optionally comprises the main comonomer of non-sense that one or more are extra except comprising vinyl acetate and ethene.This optional main non-sense comonomer of one class comprises the vinyl acetate comonomer.The example is the vinyl acetate (except vinyl acetate) with monocarboxylic acid of 1-18 carbon atom, vinyl formate for example, propionate, vinyl butyrate, the isobutyric acid vinyl acetate, vinyl benzoate, 2-ethyl-vinyl caproate, the vinyl acetate that has [the α]-branched carboxylic acids of 5-11 carbon atom in acid moieties, for example Versatic ^TMAcid and neopentanoic acid, 2 ethyl hexanoic acid, laurate, palmitic acid, myristic acid and stearic vinyl acetate.Preferred Versatic ^TMThe vinyl acetate of acid, more specifically VeoVa ^TM9, VeoVa ^TM10, and VeoVa ^TM11.

The comonomer that can be incorporated into the another kind of optional main non-sense in the vinyl acetate/ethylene copolymer of dispersion comprises the ester of ethylenic unsaturated monocarboxylic or the diester of ethylenic unsaturated dicarboxylic.Especially this favourable class comonomer is the ester with alcohol of 1-18 carbon atom.The example of the main comonomer of this non-sense comprises methacrylic acid or acrylic acid methyl esters, methacrylic acid or acrylic acid butyl ester, methacrylic acid or acrylic acid 2-Octyl Nitrite, dibutyl maleate and/or di-2-ethylhexyl maleate.

The combination of the main comonomer type of two or more aforementioned optional non-senses can be copolymerized in vinyl acetate/ethylene copolymer.If exist, the main comonomer of this non-sense can account for maximum approximately 40wt%, based on the whole main comonomer in copolymer.More preferably, the main comonomer of this non-sense can account for approximately approximately 20wt% of 5wt%-, based on the whole main comonomers in vinyl acetate/ethylene copolymer.

The vinyl acetate that the coating that is used for carpet product is herein used/vac emulsion copolymer beyond ethene or other main comonomer type, also optionally contains the comonomer of the other types of relative a small amount of except containing vinyl acetate.This other optional comonomers are usually that one or more functional groups and or in case dry or can play when solidifying the film that formed by this composition and coating and provide or promote to contain in the Aquo-composition of copolymer dispersion crosslinked those between copolymer chain are provided.

This sense comonomer that randomly exists can comprise the ethylenic unsaturated acids, for example list or dicarboxylic acids, sulfonic acid or phosphonic acids.Also can use their salt, preferred as alkali salt or ammonium salt substitute free acid.The example of the sense comonomer that this class is optional comprises acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, vinyl sulfonic acid, vinyl phosphonate, styrene sulfonic acid, the monoesters of maleic acid and/or fumaric acid, and the monoesters of itaconic acid (it has chain length is C ₁-C ₁₈Monobasic aliphatic series saturated alcohols), and alkali metal salt and ammonium salt, perhaps (methyl) acrylate of sulfo group alkanol, one of them example is 2-sulfoethyl Sodium methacrylate.

The suitable optional sense comonomer of other types comprises having at least one amide groups, epoxy radicals, hydroxyl, the ethylenic unsaturated comonomer of trialkoxy silane base or carbonyl.Especially suitable is ethylenic unsaturated epoxide compound, for example glycidyl methacrylate or glycidyl acrylate.Same suitable is hydroxy compounds, comprising methacrylic acid and acrylic acid C ₁-C ₉Hydroxyalkyl, for example positive hydroxy methacrylate of acrylic acid and methacrylic acid, positive hydroxy propyl ester or positive hydroxyl butyl ester.Other suitable sense comonomers comprise such as diacetone acrylamide, and the compound of the acetoacetoxy ethyl ester of acrylic acid and methacrylic acid; With the acid amides of ethylenic unsaturated carboxylic acid, for example acrylamide or Methacrylamide.

As described, emulsion copolymers as used herein optionally contains the comonomer of trialkoxy silane official energy.Perhaps, emulsion copolymers as used herein can be substantially free of the silylation comonomer.

The one class official that should not be incorporated in vinyl acetate/ethylene copolymer as used herein can comprise any comonomer that contains the crosslinkable part by comonomer, in case when forming coating by the composition that contains these copolymers, described crosslinkable part will generate formaldehyde.Therefore, vinyl acetate/ethylene copolymer in copolymer dispersion should be substantially free of this comonomer, described comonomer comprises for example common crosslinking agent, for example even low formaldehyde variant, for example NMA-LF of N hydroxymethyl acrylamide (NMA) or N hydroxymethyl acrylamide.Also the vinyl acetate/ethylene copolymer in the preferred copolymer dispersion should not contain the halogenation comonomer, for example the chloroethylene copolymer monomer.

Can be with based on the whole main comonomers in copolymer, the optional sense comonomer of the maximum approximately 5wt% of consumption is incorporated in vinyl acetate as used herein/vac emulsion copolymer.More preferably, optional sense comonomer can account for approximately approximately 2wt% of 0.5wt%-, based on the whole mainly comonomers in copolymer.

Can use the emulsion polymerization technology of hereinafter describing more fully, form emulsion copolymers in copolymer dispersion.In this copolymer dispersion, copolymer is with average particle size d _wScope is the approximately approximately relatively little particle form existence of 500nm of 50nm-, and this measures by laser aerosol spectrum method.More preferably, this copolymer dispersion is with average particle size d _wScope is the approximately approximately particle form existence of 350nm of 120nm-.Can measure granularity by laser aerosol spectrum law technology.

The type that depends on the comonomer that uses, solubility, and monomer feed technology, vinyl acetate-ethylenic copolymer at monomer structure with in forming, can be homogeneous phase or heterogeneous.Homogeneous copolymers has single discrete glass transition temperature T _g, this is by the means of differential scanning calorimetry commercial measurement.Non-homogeneous copolymer demonstrates two or more discrete glass transition temperatures and can cause the nucleocapsid particles pattern.No matter homogeneous phase or heterogeneous, the glass transition temperature T of vinyl acetate-base co-polymer as used herein _gScope is approximately-25 ℃ to+15 ℃, more preferably from about-20 ℃ to+5 ℃.Just as is known, can for example control the T of polymer by regulating ethylene contents _g, namely be present in copolymer with respect to the common more ethene of other comonomers, T _gLower.

The stabilizing agent that is used for polymeric dispersions

After the polymerization process neutralization, form the copolymer dispersion that Aquo-composition was used of carpet adhesive phase or coating layer with moisture copolymer dispersion or the stable preparation of latex form.Therefore prepare copolymer dispersion under stabilising system exists, described stabilising system generally includes emulsifying agent, especially nonionic emulsifier and/or anion emulsifier.Also can use the mixture of nonionic and anion emulsifier.

The consumption of the emulsifying agent that uses is 0.5wt% at least normally, based on the total amount of the main comonomer that exists in copolymer dispersion.Usually can use the emulsifying agent of the maximum approximately 8wt% of consumption, based on the total amount of main comonomer in copolymer dispersion.In emulsifying agent, the weight ratio of nonionic and anion can fluctuate in wide scope, for example 1:1-50:1.The vinyl acetate/ethylene copolymer dispersion can further comprise polymer stabilizer (protective colloid) in a small amount.

The preferred emulsifying agent that uses is have the nonionic emulsifier of epoxy alkyl and have sulfate, sulfonic group, the anion emulsifier of phosphate and phosphonate group herein.Optionally, these emulsifying agents can with the water-soluble polymer of molecule or dispersion, preferably use together with polyvinyl alcohol.Also preferred described emulsifying agent does not contain alkylphenol b-oxide (APEO).

The example of suitable nonionic emulsifier comprises acyl group, alkyl, oil base and alkaryl b-oxide.These products are for example with title ,

Or

Be purchased.These for example comprise the ethoxyquin list-, two-and three-alkylphenol (EO degree: 3-50, alkyl substituent: C ₄-C ₁₂), and B oxidation fat alcohol (EO degree: 3-80; Alkyl: C ₈-C ₃₆), C particularly ₁₂-C ₁₄Fatty alcohol (3-40) b-oxide, C ₁₃-C ₁₅Carbonylation alcohol (3-40) b-oxide, C ₁₆-C ₁₈Fatty alcohol (11-80) b-oxide, C ₁₀Carbonylation alcohol (3-40) b-oxide, C ₁₃Carbonylation alcohol (3-40) b-oxide has the polyoxyethylene sorbitol monooleate of 20 Oxyranyles, and minimum ethylene oxide content is the oxirane of 10wt% and the copolymer of expoxy propane, and the poly(ethylene oxide) of oleyl alcohol (4-40) ether.Especially suitable is poly(ethylene oxide) (4-40) ether of fatty alcohol, oleyl alcohol more specifically, stearyl alcohol, or C ₁₁Alkylol.

The consumption of the nonionic emulsifier that uses in herein copolymer dispersion of preparation typically is approximately approximately 8wt% of 1%-, and preferred approximately 1%-is 5wt% approximately, and the about 4wt% of 1%-more preferably from about is based on the consumption of whole principal monomers.Also can use the mixture of nonionic emulsifier.

The example of suitable anion emulsifier comprises that chain length is C ₁₂-C ₂₀The sodium of linear aliphatic carboxylic acid, potassium and ammonium salt, the hydroxyl Sodium sterylsulfonate, chain length is C ₁₂-C ₂₀Sodium, potassium and the ammonium salt of hydroxy fatty acid, and sulfonation and/or sulphation and/or acetylate, alkyl sulfate, comprising the form of triethanolamine salt, alkyl (C ₁₀-C ₂₀) sulfonate, alkyl (C ₁₀-C ₂₀) arylsulphonate, dimethyl-dialkyl group (C ₈-C ₁₈) ammonium chloride, and sulfonated products, lignin sulfonic acid and calcium thereof, magnesium, sodium and ammonium salt, resin acid, hydrogenation and dehydrogenation resin acid, and alkali metal salt, dodecyl diphenyl ether sodium disulfonate, NaLS, EO degree are the sulphation alkyl or aryl b-oxide of 1-10, the salt of ethoxyquin sodium laureth sulfate (EO degree 3) or diester for example, preferred two-C ₄-C ₁₈The salt of alkane ester has the salt of the sulfonation dicarboxylic acids of 4-8 carbon atom, or the mixture of these salt, the sulfonated salts of preferred succinate, more preferably sulfosuccinate two-C ₄-C ₁₈The salt of alkane ester, for example alkali metal salt, or the phosphate of poly-ethoxyquin alkanol.

The amount ranges of the anion emulsifier that uses can be typically the about about 3.0wt% of 0.1%-, and preferred approximately 0.1%-is 2.0wt% approximately, and the about 1.5wt% of 0.5%-more preferably from about is based on the consumption of whole principal monomers.Also can use the mixture of anion emulsifier.

Together with emulsifying agent, vinyl acetate used according to the invention/ethylene copolymer dispersion can comprise protective colloid as the part of stabiliser system, preferably polyethylene alcohol and/or its modifier.If protective colloid exists, mostly just exist with relatively low concentration, maximum approximately 3wt% for example, 0.2-2wt% for example is based on the total amount of the principal monomer that uses.Vinyl acetate/ethylene copolymer dispersions more as used herein can preferably not contain protective colloid or contain the only protective colloid of maximum approximately 1wt%, based on the total amount of the main comonomer that uses in vinyl acetate/ethylene copolymer.

The example of suitable protective colloid comprises the natural materials water-soluble or modification of water dispersible polymers, cellulose ether for example, the example be methyl-, ethyl-, ethoxy-or carboxymethyl cellulose; Water-soluble or water dispersible polymers synthetic; for example polyvinylpyrrolidone or polyvinyl alcohol or its copolymer (having or do not have residual acetyl content), and have saturated group and also have the partial esterification of different molecular weight or the polyvinyl alcohol of acetylation or etherificate.

Can separately or be combined with protective colloid.In the situation that combination, two or more colloids are can be aspect its molecular weight different, and perhaps they can be at its molecular weight and for example different on degree of hydrolysis in its chemical composition.

The emulsifying agent and protective colloid optionally that uses in the emulsion polymerization process of herein copolymer; same possible situation is that vinyl acetate/ethylene copolymer dispersion as used herein contains the water-soluble or water dispersible polymers that adds subsequently described below.Also can add extra emulsifying agent in the rear polymerization of dispersion.

The preparation of copolymer dispersion

Can use the emulsion polymerisation operation, preparation contains the copolymer dispersion of vinyl acetate/ethylene copolymer described herein, and described emulsion polymerisation operation causes the preparation of the polymeric dispersions of aqueous latex form.This preparation method of this class aqueous polymer dispersion is well-known, and has been disclosed in many examples, is therefore well known by persons skilled in the art.These operations for example are disclosed in U.S. Patent No. 5,849, and 389 and Encyclopedia of Polymer Scienceand Engineering, Vol.8 is p.659ff in (1987).The disclosure of these publications is introduced by reference in its entirety at this.

Can at one, in two or more sections, adopt different combination of monomers according to known mode itself, carry out polymerization, thereby obtain having homogeneous phase or non-homogeneous particle, for example the polymeric dispersions of nucleocapsid or hemispherical pattern.Can use any reactor system, for example intermittently, endless tube, continuously, cascade etc.

The polymerization temperature scope is generally approximately 20 ℃-Yue 150 ℃, more preferably from about 50 ℃-Yue 120 ℃.Usually under pressure, polymerization occurs, preferred approximately 2-is 150bar approximately, more preferably from about the about 100bar of 5-.

In involving the typical polymerization operation of vinyl acetate/ethylene copolymer dispersion for example; can be in water-bearing media; under the pressure of maximum approximately 120bar; at one or more initators and at least a emulsifying agent; randomly together with protective colloid for example PVOH exist down; polymerization vinyl acetate, ethene and other comonomers.Can pass through suitable buffer, keep aqueous reaction mixture in aggregation container at about 2-approximately under 7 pH.

In conjunction with several polymerization compositions, i.e. emulsifying agent, comonomer, the mode of catalyst system component etc. can vary widely.Usually, can form the water-bearing media that contains at least some emulsifying agents at first in aggregation container, and after various other polymerization compositions are joined this container.

Can comonomer is continuous, incremental is perhaps introduced the form of adding whole amounts comonomer to be used with single comonomer is joined in aggregation container.Can use comonomer with the pure monomer form, perhaps can use with the premix emulsion form.Ethene as comonomer can be pumped in aggregation container, and maintains within it under suitable pressure.

As described, the polymerization of ethylenically unsaturated monomers under existing, at least a initator that the radical polymerization of these comonomers share occurs usually.Cause in the preparation process of dispersion and continue the initiator appropriate that is used for radical polymerization that polymerization uses and comprise and to cause all known initators of free radical aqueous polymerization at heterogeneous system.These initators can be peroxide, for example alkali metal of peroxy-disulfuric acid and/or ammonium salt, or azo-compound, more specifically water-soluble azo compounds.

As polymerization initiator, also can use so-called redox initiator.The example is that for example (example is the sodium salt of hydroxyl methyl-sulfinic acid with sulphur compound with reductant, Br ü ggolit FF6 and FF7, Rongalit C, sodium sulfite, sodium hydrogensulfite, sodium thiosulfate, and acetone-bisulfite adduct), or and ascorbic acid, sodium isoascorbate, or the t-butyl hydroperoxide of being combined with reducing sugar and/or hydrogen peroxide.

Change in the common scope of consumption aqueous polymerization in heterogeneous system of the initator that uses in the method or initator combination.Usually, the consumption of the initator that uses is no more than 5wt%, based on the total amount of the comonomer for the treatment of polymerization.Based on the total amount of the comonomer for the treatment of polymerization, the preferred 0.05%-2.0wt% of the consumption of the initator that uses.

In the context of the present invention, all the initator of consumption can be included in when polymerization begins in the initial charge that arrives reactor.Preferably, perhaps, a part of initator is included in when beginning in initial charge, and all the other after polymerization causes in one or more steps or interpolation continuously.Can be independently or for example add together with emulsifying agent or monomer emulsions with other components.Also can use seed latex, the about seed latex of 15wt% of the approximately 0.5-of dispersion for example, beginning emulsion polymerisation.

Except the vinyl acetate/ethylene copolymer of emulsion polymerisation, copolymer dispersion as used herein can contain in addition by (methyl) acrylic acid C ₁-C ₁₈Ester, the C of other ethylenic unsaturated monocarboxylics ₁-C ₁₈The C of ester or ethylenic unsaturated dicarboxylic ₁-C ₁₈The copolymer that diester forms.This extra copolymer for example can comprise approximately approximately 20 weight portions of 0.5-, based on the whole copolymers in copolymer dispersion, and can comprise by ethyl acrylate, butyl acrylate (BuA), 2-EHA (2-EHA), dibutyl maleate, the copolymer that is combined to form of di-2-ethylhexyl maleate or these esters.

Can by adding one or more molecular weight regulator materials in a small amount, be adjusted in the molecular weight of various copolymers in copolymer dispersion herein.These conditioning agents are known, and they use with the consumption of maximum 2wt% usually, based on whole comonomers for the treatment of polymerization.As conditioning agent, can use all substances well known by persons skilled in the art.Preference such as organic thio-compounds, silanes, allyl alcohol, and aldehydes.

The range of viscosities of copolymer dispersion under the solid of 45-55% of the preparation about about 5000mPas of 100mPas-normally herein, more preferably from about approximately 4000mPas, most preferably 400-3000mPas of 200mPas-, this adopts the Brookfield viscosimeter, at 25 ℃, under 20rpm, adopt suitable spindle to measure.Can be by adding thickener and/or water in copolymer dispersion, adjusting viscosity.Suitable thickener can comprise polyacrylate or polyurethane, for example Borchigel

And Tafigel PUR

Perhaps, this copolymer dispersion can be substantially free of thickener.

After polymerization, can be by adding water or passing through dephlegmate, the solids content of regulating in the moisture copolymer dispersion of gained arrives required level.Usually, the desired level of the solids content of polymer is the about about 70wt% of 40wt%-after the polymerization, based on the gross weight of polymeric dispersions, and the about 55wt% of 45wt%-more preferably from about.

The moisture copolymer dispersion that coating-the formation composition uses that forms herein can have low TOVC (TVOC) content requiredly." volatile organic compounds " be defined as herein boiling point under atmospheric pressure lower than 250 ℃ contain carbon compound (the ISO11890-2 method of using according to the TVOC assay of polymeric dispersions).Compound such as water and ammonia is not included in VOCs.

Moisture copolymer dispersion as used herein contains usually less than 0.5wt%TVOC, based on the gross weight of moisture copolymer dispersion.Preferred moisture copolymer dispersion contains less than 0.3wt%TVOC, based on the gross weight of moisture copolymer dispersion.Can according to hereinafter at the ISO11890-2 described in the test method part, measure these numerical value.

When the TVOC content that is exposed to atmosphere moisture copolymer dispersion as used herein of lower time and usually also discharges relative a small amount of.Especially, copolymer dispersion herein discharges the TVOC material to the approximately degree of 15 times that is not more than Toluene D8 reference material, when the film that is formed by these dispersions is tested according to the operation of the ISO16000-9 that hereinafter describes in the test method part.More preferably herein copolymer dispersion discharges the TVOC material to the approximately degree of 10 times that is not more than the TolueneD8 reference material.

Optionally, vinyl acetate/ethylene copolymer dispersion as used herein also optionally is included in the wide in range various conventional additives that typically use in preparation binding agent and/or adhesive.This optional additive can or be present in copolymer dispersion polymerization process from beginning, can join in the rear polymerization of dispersion, perhaps for example the situation with filler is the same, can be combined with described below the preparation in aqueous coating composition by copolymer dispersion.

The optional additives that is used for the typical routine of copolymer dispersion herein can comprise for example film forming assistant, white spirit for example,

Butanediol, butyldiglycol, butyl dipropylene glycol, and butyl tripropylene glycol; Humectant, for example

Defoamer, for example mineral oil antifoam agent or silicone defoamer; The UV protective agent, for example

Regulate the reagent of pH; Preservative agent; Plasticizer, repefral for example, diisobutyl phthalate, diisobutyl adipate,

With

The stabilization of polymer that adds subsequently, for example polyvinyl alcohol or cellulose ether; With preparation binding agent and typical other additives of adhesive and auxiliary agent kind.The consumption of these additives that use in vae copolymer thing dispersion herein can change in wide region, and can be selected in view of required Application Areas by the expert.

Aqueous coating composition

In conjunction with foregoing copolymer dispersion and filler material and extra water, form the aqueous coating composition that is used for carpet product herein.Then apply this coating composition on the textile substrate that forms carpet product herein.In case dry, then the aqueous coating composition that applies provides coating layer in carpet product.Carpet product can comprise only a kind of or greater than a kind of coating layer.

Usually, carpet product herein always contains the adhesive-coated layer, with fixing carpet fiber to main lining cloth substrate.Carpet product herein therefore also optionally comprise second or extra layer, described second or extra layer can be adhesive phase, in order to the lining cloth substrate of assisting is fixed on the main lining cloth of coating.

In one embodiment, carpet product can comprise coating layer that the Aquo-composition of described same type from here forms and adhesive phase both.Perhaps, carpet product herein can comprise coating layer described herein and dissimilar adhesive phase, and described adhesive phase also can be formed or can be formed by diverse conventional adhesive coating composition by the composition with herein coating composition same type.

Aqueous coating composition herein also contains the particulate filler material that is selected from particulate inorganic compound and granular plastic material.Therefore, the filler that uses can be any filler that basically is suitable for use in carpet is made.This filler is commercially available widely.

The example of filler comprises inorganic, mineral for example, filler or pigment, for example flyash and cullet, with known in the art those, calcium carbonate for example, clay, kaolin, talcum, barite, feldspar, titanium dioxide, calcium aluminium pigment, satin light stone, zinc oxide, barium sulfate, gypsum, silica, mica and diatomite.Also can use granular plastic material, synthetic polymer pigment for example, the carpet lining cloth of hollow polymer pigment and recovery, they can be the mixtures of any aforementioned filler type.Preferred filler material is granular calcium carbonate.

The mean particle size range of particulate filler material can be approximately 200nm-1000 μ m, more preferably 1 μ m-500 μ m, most preferably 10 μ m-300 μ m usually.The preferred coating composition load that carpet product produced according to the present invention uses has filler to contain approximately approximately 70wt% of 10-to obtain gross weight based on solid in Aquo-composition, the about 60wt% of 20-more preferably from about, the approximately dry copolymer of 50wt% and the about about 90wt% of 30-of 20-more preferably from about, preferred approximately 40-is 80wt% approximately, the aqueous coating composition of 50-80wt% filler most preferably from about, this part depends on type and the form of carpet to be constructed.

Except previously described copolymer dispersion and filler material herein, this coating composition also can contain various extra conventional additives, so that its performance of modification.In the middle of these additives, can comprise thickener, rheology modifier, dispersant, fire retardant, colouring agent, pesticide, defoamer etc.Described those are identical with respect to copolymer dispersion herein with the front to a great extent for these optional additives.

Carpet product

Form coating layer in previously described coating composition carpet product herein herein, i.e. adhesive layer, described carpet product also comprises at least one flex substrate.This flex substrate can for example be selected from supatex fabric, Woven fabric, unidirectional braided fabric, knit goods and fleece.Therefore, carpet product herein can be conventional tufted carpet, non--tufted carpet or needle punched carpet.Can use in most of carpet weaving mills the equipment that easily obtains, by applying the Aquo-composition that contains emulsion copolymers, and dry, prepare this carpet product.

The pile carpet product comprises the main lining cloth with pile yarns, and described pile yarns extend from main lining cloth substrate, forms the pile tufting.Can pass through a) tufting or hosiery yarns to weave or non-woven lining cloth substrate in; B) apply moisture carpet coating compositions described herein to the lining cloth back, so that yarn is embedded in carpet coating compositions; And c) dry gained carpet backing and installation system, preparation pile or tufted carpet.In producing this tufted carpet, also can, but not necessary, before or after dry carpet coating, apply auxiliary lining cloth to main lining cloth, this depends on the lining cloth type of using.For tufted carpet, main lining cloth substrate can the woven polypropylene of right and wrong, polyethylene or polyester or weave tossa, polypropylene or polyamide (synthetic and natural).

Carpet product herein can be also the carpet of non-tufting, and wherein fiber is embedded in coating or adhesive composition, described coating or adhesive composition be coated on weave or nonwoven substrate on.Also can pass through a) to be coated with Aquo-composition, for example previously described Aquo-composition in substrate; B) embedding carpet fiber in substrate; And c) dry gained carpet backing and installation system, thus prepare the carpet of non-tufting.In forming the carpet of non-tufting, the carpet coating can thicken and be applied on the woven scrim surface.Then use routine techniques, fiber directly is embedded in the wet coating layer, then dry.Also can advantageously utilize the auxiliary lining cloth of the DIMENSIONAL STABILITY that can provide extra, prepare the carpet of these non-tuftings.

In preparation carpet product herein, apply Aquo-composition, its mode makes the fiber of its infiltration carpet yarn, obtains cohesiveness preferably, fibre bundle integrality, picking resistance energy and suitable tufting-cementing value.Can be about 100g/m by applying amount ranges ²-3000g/m Yue ², 200g/m more preferably from about ²-2000g/m Yue ², and 400g/m most preferably from about ²-1500g/m Yue ²Aqueous coating/the adhesive composition of (dry basis) is realized suitable carpet performance.

The carpet product embodiment that some substitute

In a concrete carpet product embodiment, carpet product will comprise the textile fabric structure of processing with vinyl acetate/ethene (VAE) copolymer dispersion of Selective type.In this carpet product, the textile fabric structure can be to be selected to weave, and is non-woven, the form of fabric in unidirectional braided fabric, knit goods or fleece.Particularly, carpet product can comprise coating composition coating and the fleece of coating on the distally of pile (trampling side) of using based on the vae copolymer thing dispersion of Selective type.Perhaps carpet product can be following carpet form: wherein auxiliary lining cloth layer is bonded on fleece layer on the distally of trampling side.By vae copolymer thing dispersion-Ji coating, carry out the bonding between two-layer.This textile fabric structure can have approximately approximately 3000g/m of 1000- ²Weight per unit area.

In order to form this carpet product embodiment, process selection vae copolymer thing dispersion that the textile fabric structure uses and can comprise approximately 70-approximately 80pphm (umber/100 part monomer) vinyl acetate and about approximately 30pphm, more preferably from about 20-24pphm ethene of 20-.The glass transition temperature T of this copolymer _gBe approximately 0 ℃ to approximately-10 ℃, more preferably from about-3 ℃ to-6 ℃, and the average grain diameter d in dispersion _wBe about 150-200nm.

The vae copolymer thing of this selection also can comprise the further comonomer of maximum approximately 10pphm, described further comonomer can with vinyl acetate and ethylene comonomer copolymerization.This further comonomer can comprise the ethylenic unsaturated acids, or its salt, ethylenically unsaturated monomers with at least one amide groups, epoxy radicals, hydroxyl, N-methylol, trialkoxy silane or carbonyl, and two kinds or the combination of several monomers of any these further monomer types.Perhaps, this further comonomer can comprise vinyl acetate (it is not vinyl acetate), alpha-olefin (it is not ethene), vinyl-arene, the ester of ethylenic unsaturated monocarboxylic, and the diester of ethylenic unsaturated dicarboxylic.

Employing is at least about the 1wt% emulsifying agent, and approximately 0wt%-approximately 2wt% based on the protective colloid of polyvinyl alcohol, stablely make the vae copolymer thing dispersion that this carpet embodiment is used.Preferably, the emulsifying agent that uses is selected from anion and non-ionic surface active agent, but does not contain alkyl phenyl b-oxide (APEs).The viscosity of these vae copolymer thing dispersions can be the about about 1600mPa.s of 400-, and this adopts the Brookfield viscosimeter to measure under 25 ℃.This dispersion also can have approximately the approximately solids content of 55wt% of 45wt%-.

The washability of carpet and non-slip feature

Carpet product herein has required especially washability, and in some cases, required equally especially non-slip feature.Washability refers in case when washing in machine-washing operation, movably carpet product, for example rug, the twisted filament carpet, runner, carpet square, tapestry or wall hanging, doormat, the movably carpet product of motor vehicle foot pad or gymnasium mat form is kept the ability of its integrality.In case keeping of carpet integrality comprises that when carrying out the one or many machine-washing, carpet product tends to not bodies lost weight.Carpet integrality after the one or many washing further involves carpet and tends to keep its initial outward appearance, its feel, and its lining cloth integrality and its fixed tuft hair yarn and fiber (pile) are in the carpet lining cloth.

Can measure the washability of carpet by following the test procedure, described the test procedure involves similar washing operation and takes before and afterwards the carpet product sample.In a single day listed in following test method part and measured when washing, the suitable the test procedure of the carpet loss in weight.Usually, in the test of this washability, carpet product herein demonstrates less than about 4.5% the loss in weight after 20 washings.More preferably herein carpet product demonstrates less than about 3.6% the loss in weight after 20 washings.

Also can be before the carpet washing operation and afterwards, by carrying out the tufting fixation measuring, quantize the washability of carpet.Carpet tufting is fixedly the parameter of measuring routinely in carpet industry.Also listed the operation of measuring the tufting fixation degree in test method part hereinafter.Usually, in this tufting fixation test, after 20 washings, carpet product herein demonstrates less than about 40% tufting dead loss.More preferably, after 20 washings, carpet product herein demonstrates less than about 25% tufting dead loss.

Certainly, also can measure in a single day washing by the impact of simple perusal one or many washing operation on the carpet outturn sample, carpet product resists deteriorated ability.Hereinafter also listed in test method part before washing and afterwards, based on grade 1-4, the suitable operation of vision evaluation its outward appearance of carpet product and integrality.The washability grade of preferred carpet product herein after 20 washing operations is for being less than or equal to 3.

The carpet product herein that has with the lining cloth surface of vae copolymer thing-based coating composition coating also can provide required especially non-skid property, and wherein the vae copolymer thing has relatively low glass transition temperature.Non-skid property refers to movably, the carpet product of load capacity along or the surface that covers across it, the ability of the anti-motion in floor for example is when carpet is subject to the parallel plane side force in its place.By the frictional resistance that the coating lining cloth of weighing produces on the surface that carpet product covers, anti-this flank movement is provided, namely slide.Can pull the carpet sample of weighing by measurement objectively and cross the required maximum, force of testing surface, measure anti-skidding tendency.Hereinafter also list the measurement of carrying out these kinds in the test method part, measured the operation of carpet non-skid property.Anti-skidding embodiment herein demonstrates the maximum drag force at least about 6.0 newton usually in this test, even after washing.More preferably, herein anti-skidding embodiment demonstrates the maximum drag force at least about 7.0 newton in this test.

Extra carpet feature

Carpet product herein has the vinyl acetate/ethene of the particular type of using-base co-polymer dispersion in forming coating layer, it also has required especially eco-friendly feature.Owing to not containing the crosslinking group (for example, there is no NMA or NMA-LF) that generates formaldehyde, with because their low TVOC content and TVOC discharge, therefore, the copolymer dispersion that uses does not cause in the potential problem material carpet product from here of this class and discharges.In addition, carpet product herein is substantially free of the halogenation comonomer, polyvinyl chloride and pitch, and these are material types of typically using in the commercial carpets product.At last, because herein carpet product does not utilize SBL coating or binding agent, so this carpet product also is substantially free of potential poisonous component, 4-benzyl ring hexene (4-PCH) for example, 4 vinyl cyclohexene (4-VCH), styrene and ethylbenzene.

Contain by contain herein copolymer dispersion and the carpet product of the coating layer that forms of the Aquo-composition of filler can have approximately 100g/m ²-3000g/m Yue ², 200g/m more preferably from about ²-2000g/m Yue ², 400g/m most preferably from about ²-1500g/m Yue ²Weight per unit area (dry basis).

Carpet product herein can be rug or mat form, and they can be used as the covering of used area.Perhaps, herein carpet product can be carpet square form or wall-to-wall carpet form.

Embodiment

With reference to following indefiniteness embodiment, more particularly described carpet product herein and made the coating composition that contains copolymer dispersion that this carpet product uses.Below described and be combined several test methods of using with these embodiment.

Test method

The granulometry of copolymer dispersion

Can pass through laser aerosol spectrum method (LAS), measure the solid particle size in copolymer dispersion as used herein.At publication Kunstharz Nachrichten28; " Characterization and Quality Assurance of Polymer Dispersions "; Oktober1992 has described this LAS method in Dr.J.Paul Fischer.The method is the Nd:YV04Laser (Millenia II) that uses by Spectra Physics supply, and its laser power is that 2W and wavelength length are 532nm.Detector is the Bialkali Photocathode Typ4517 by Burle (RCA in the past) supply.40 ⁰The scattered light of the spray-dired single particle of lower detection.Adopt the multichannel analyzer with 1024 passages of TMCA, carry out data evaluation.

In order to carry out granulometry, dilution 0.2ml dispersion samples in the water (conductivity is 18.2 μ S/m) of 100ml deionization and filtration.Spray drying sample on the Beckmann-nozzle, and use nitrogen drying.With in β radiation (Kr-85) and single particle, then by the research of single particle laser light scattering.After estimating, obtain number average and matter average and particle mean size value d in the 80nm-550nm scope _n, d _w, d _zAnd d _w/ d _n

Glass transition temperature (the T of copolymer _g) measure

Can by using business differential scanning calorimeter Mettler DSC820, under 10K/min, obtain glass transition temperature T _gIn order to estimate, to use the second heating curves, and calculate the DIN mid point.

The whole volatile organic compounds (TVOC) that discharge from the copolymer dispersion film (ISO16000-9)

Can use the general procedure of ISO-16000-9, measure the releasing degree of whole volatile organic compounds (TVOC) content in the copolymer dispersion sample, this test method is introduced by reference at this.In this operation, taking the 2g copolymer dispersion is in the aluminum pan of 4.2cm to diameter.Lower dry this dispersion of room temperature (23 ℃/50% humidity) is spent the night, and forms film, then tests in diameter is the miniature chamber of 4.5cm and volume 40ml.Continuous air flow (clean dry air that 100ml/min humidity is not regulated again) this chamber of flowing through, and allow the film sample balance time period of 20 minutes within it to arrive chamber conditions (25 ℃).

After 20 minutes, direct air flows in absorption plant, and described absorption plant is the Tenax pipe of filling with 111ngToluene D8, and described Toluene D8 is as absorbing reference material.(VOCs) was adsorbed on the Tenax pipeline through the time period of 60 minutes from the volatile organic compounds in the air stream of film sample.Then, for the VOCs amount of absorption thereon, by GC-MS, analyze the Tenax pipeline.

The result of utilizing GC-MS to measure obtains the VOCs amount that absorbs with respect to Toluene D8 reference material.If be considered as 1 in the systemic toluene reference material of Tenax pipeline amount, 1 the multiple that is reported as in the systemic VOCs of Tenax pipeline amount that the VOCs that discharges represents from the copolymer dispersion film.

The washability of carpet sample

After can washing carpet sample in the commercial laundering machine, by measuring the loss in weight of sample, " washability " of blanket sample definitely.For the copolymer dispersion of each test, wash together two carpet sample (22x26.5cm/ sews up with cotton WEB processed, approximately 20 ± 3g/ sample).Pack independently sample in washing bag (40x50cm has slide fastener), to avoid the contact between lining cloth in the wash cycle process.Washing all samples 20 times, and after each circulation, measure the weight of sample.

The washing machine that uses is Siemens Vario Perfect E14-32.For each circulation, use 15g washing powder.The washing powder that uses is Professional Clean andCleaver (15-30% phosphate, 5-15% oxygen bleaching agent,＜5% non-ionic surface active agent,＜5% soap class, spices, enzyme and brightening agent).For each wash cycle, adopt following condition: washing procedure: " Pflegeleicht ", 40 ℃ of rotating speed 600rpm and temperature.After each wash cycle, drying sample spends the night under 23 ℃ and 50% humidity.

After each wash cycle, the sample of weighing.For washed two samples of each copolymer dispersion that applies of testing, result is the mean value of the total weight loss after every the 5th wash cycle, unit gram [g].After every 5 wash cycle, the loss in weight percentage form of each sample of testing report result.In addition, also with this washability test combination, measure the non-skid property of carpet sample.The test method of the non-skid property of measuring washed carpet sample has hereinafter been described.

The non-skid property of carpet sample (TAPPI816om-92)

Can measure the non-skid property of carpet sample by using the modification variant of TAPPI816om-92 test method, described test method is introduced by reference at this.This determination of test method drags the required maximum, force of carpet sample that takes, the newton of unit [N] on glass plate.In the test of above-described washability, initial and after every the 5th wash cycle, measure non-skid property.

For each carpet type to be tested, use two samples (22x26.5cm/ sews up with cotton WEB processed, approximately 20 ± 3g/ sample).The sheet glass that is pasting on plate (60x30cm) at the back side of carpet sample is placed.Blanket sample positioningly in the vertical.Then, apply weight (1.18kg/8x5x4cm) in the centre of carpet sample.Carpet sample is placed towards testing arrangement with its longest side at the far-end of plate, and contact area is 40cm ²The testing arrangement that uses is the LF Plus universal testing machine available from Lloyd Instruments.Under the speed of 150mm/min, drag the distance of sample 10cm on glass plate.During dragging operation, measure the required power of mobile carpet, the newton of unit [N].Measure maximum, force between 10-90mm.The result that provides is 2 mean values of measuring.

The tufting of carpet sample is fixed (ISO4919)

For each class adhesive coating to be tested, the carpet sample that to prepare 8 sizes be 11x26.5cm (4 washed and 4 do not wash), and before measuring, storage is minimum 24 hours under 23 ℃ and 50% humidity.Then according to ISO4919, measure the tufting constant intensity in these samples, described test method is introduced by reference at this.

Make the test machine of using and be called LF Plus universal testing machine by Lloyd Instruments.Under the test speed of the preload of 0.5N power setting value and 100mm/min, Operational Test Plan.Blanket sample is to fixture clampingly, and described fixture is the 10x10cm/ hole of level Stainless steel pallet 5cm).Hook is fixed on a tufting, and uses this hook, the tractive tufting is until it separates from carpet sample.

Measure the maximum disruptive force of tufting.Should reach breakpoint in second at 2-10.For each carpet sample, test 20 tuftings, obtain the mean value of maximum disruptive force.Measure disruptive force with newton (N).

Naked eyes evaluation and the feel of carpet sample outward appearance

Also but naked eyes are estimated lining cloth outward appearance and the feel of carpet sample.More unwashed carpet sample and the identical sample that washed 20 times.Important evaluation criterion comprises the integrality of lining cloth, with the visible loss in weight of the carpet sample that the embedding fiber is combined and the pliability that has the carpet sample of lining cloth after 20 washings of initial sum.

Express based on grade 1-4 the result that these naked eyes are estimated.The integrality of judgement lining cloth as described below: the lining cloth of 1=closure; Some losses in weight of 2=and uncoated fiber are visible; The more loss in weight of 3=and the uncoated fiber of Geng Duo are visible; Except the visible loss in weight and uncoated fiber, in the lining cloth surface, be full of cracks also appears with 4=.Also judgement feel as described below: 1=is soft; 2=is slightly harder; 3=is hard; Stone with 4=.For each class carpet sample to be evaluated, by these standard judgement two samples (two unwashed samples and two washed samples).

Embodiment 1

The preparation of polymeric dispersions

Be to add the group water solution of following component in the pressure reactor of 6.4 liters be furnished with fixedly agitator (turning round), heating jacket, measuring pump and volume under 150rpm:

24490g water (deionization)

1375g alkyl poly-dihydric alcohol ether (28mol oxirane)-nonionic emulsifier

2164g alkyl sulfate (15% anion emulsifier in deionized water)

82g sodium acetate (anhydrous)

549g sodium vinyl sulfonate (30%)

13.0g sodium hydrogensulfite

0.07g Mohr's salt

With the nitrogen blowing reactor to remove oxygen.In reactor, add 5.0% (vinyl acetate+glycidyl methacrylate) to aqueous phase from the total amount of (25316g vinyl acetate+325g glycidyl methacrylate).Open the ethene valve, and at ambient temperature, pressurized reactor is to 15bar (approximately 1000g ethene), and then closes (ethene total amount: 7140g).Temperature of reactor surges to 65 ℃.Under 35 ℃, (approximately in 8 minutes) add the first initator (it is sodium persulfate (145g in the 575g deionized water)) rapidly in reactor.

[00100] under 65 ℃, the charging of beginning (vinyl acetate+glycidyl methacrylate), and all the other 95% vinyl acetates+glycidyl methacrylate was incorporated into reactor in 300 minutes in.Meanwhile, again open the ethene valve, until residual ethylene is fed in reactor.After the feed time of the vinyl acetate+glycidyl methacrylate of 270 minutes, through approximately starting initiator feed (the 35g sodium persulfate is in the 575g deionized water) for the second time in 30 minutes.After the charging of completing vinyl acetate+glycidyl methacrylate, temperature of reactor surged to 85 ℃ in 30 minutes.Kept this temperature other 40 minutes.Then cooling reactor is to approximately 40 ℃.At this point place, can be by introducing Br ü ggolit FF6 (sodium salt of the sulfinate derivant) (33g available from L.Br ü ggemann KG, in the 312g deionized water), and Trigonox AW70 (70g) afterwards, carry out final redox and process.

[00101] the vae copolymer thing dispersion of embodiment 1 has following characteristics:

Solids content: 54.0%

pH:4.2

Brookfield viscosity (25 ° of C, spindle 3,20rpm): 600mPas

Residual vinyl acetate:＜0.1%

Glass transition temperature, T _g, (10K/min, mid point) :-9 ° of C

Size distribution (LAS): d _w=149nm, d _w/ d _n=1.2

TVOC(ISO11890-2)980ppm

Embodiment 2

The preparation of polymeric dispersions

[00102] be to add the group water solution of following component in the pressure reactor of 68.6 liters be furnished with fixedly agitator (turning round), heating jacket, measuring pump and volume under 150rpm:

19738g water (deionization)

The poly-vinyl alcohol solution (29%) of 1786g in deionized water, i.e. partial hydrolysis [88 hydrolysis (mol%)], it forms 4% solution viscosity of 4.50cP ± 0.50 under 20 ℃.

The poly-vinyl alcohol solution (15%) of 3149g in deionized water), i.e. partial hydrolysis [88 hydrolysis (mol%)], it forms 4% solution viscosity of 8.50cP ± 0.50 under 20 ℃.

80g sodium acetate (anhydrous)

543g sodium vinyl sulfonate (30%)

931g alkyl poly-dihydric alcohol ether (28mol oxirane)-nonionic emulsifier

0.33g Mohr's salt

[00103] in through 2 hours, polyvinyl alcohol being dissolved in deionized water with 15%/29% under 90 ℃.With the nitrogen blowing reactor to remove oxygen.In reactor, add 5% vinyl acetate to aqueous phase from the total amount of (28753g vinyl acetate).Open the ethene valve, and at ambient temperature, pressurized reactor is to 15bar (approximately 1000g ethene), and then closes (ethene total amount: 3828g).Temperature of reactor surges to 65 ℃.Under 35 ℃, (approximately in 1-2 minute) adds the first initator (reductant) of 9% rapidly in reactor, and it is sodium metabisulfite (sodium metabisulfite) (44g is in the 1043g deionized water).Under 50 ℃, (approximately in 1-2 minute) adds the second initator (oxidant) of 5% rapidly in reactor, and it is Trigonox AW-70 (the 29g t-butyl hydroperoxide is in the 2196g deionized water).

Under 65 ℃, the charging of beginning vinyl acetate and is incorporated in reactor according to following proposal: in 120 minutes 55% and in extra 150 minutes all the other 40%.Meanwhile, again open the ethene valve, until residual ethylene is fed in reactor.Meanwhile, introduce all initator raw materials according to following proposal: the 51% the first initators and the 55% the second initators in 120 minutes, and in extra 150 minutes all the other each initators of 40%.Located, and surged to 85 ℃ at 50 minutes internal reaction actuator temperatures in 50 minutes before the vinyl acetate charging finishes.After introducing all vinyl acetates and first and second initator, through approximately starting the charging (the 33g sodium persulfate is in the 763g deionized water) of the 3rd initator in 10 minutes.Keep the temperature of reactor 1 hour of 85 ℃.Then cooling reactor is to approximately 40 ℃.At this point place, can be by introducing Br ü ggolit FF6 (sodium salt of the sulfinate derivant) (33g available from L.Br ü ggemann KG, in the 489g deionized water), and Trigonox AW70 (95g) afterwards, carry out final redox and process.

The vae copolymer thing dispersion of embodiment 1 has following characteristics:

Solids content: 52.7%

pH:5.2

Brookfield viscosity (25 ° of C, spindle 4,20rpm): 5400mPas

Residual vinyl acetate:＜0.1%

Glass transition temperature, T _g, (10K/min, mid point): 13 ° of C

Size distribution (LAS): d _w=297nm

d _w/d _n=1.8

TVOC(ISO11890-2)960ppm

Embodiment 3

The SBL latex (Litex T5260) of contrast

Litex

T5260 is a kind of commercial product of polymer emulsion and is styrene-butadiene latex.

Below provided the feature of this contrast copolymer dispersion Litex T5260:

Solids content: 52.0%

pH:8.7

Brookfield viscosity (25 ° of C, spindle 3,20rpm): 398mPas

Glass transition temperature (10K/min, mid point) :-20.1 ° of C

Size distribution (LAS): d _w=146nm

d _w/d _n=1,1

TVOC(11890-2)339ppm

Embodiment 4

TVOC – release-copolymer dispersion film

Embodiment 1,2 and 3 copolymer dispersion

Two analog copolymer dispersions described in embodiment 1,2 and 3 are formed film, and according to the ISO16000-9 operation of describing in above test method part, test the tendency that they discharge volatile organic compounds.Multiple with the Toluene D8 reference material of TVOC (all volatile organic compounds) expression that discharges provides result.Result has been shown in table 1.

Table 1

TVOC from the copolymer dispersion film discharges

Discharge about the TVOC of copolymer dispersion film table 1 result of measuring and show, the VAE dispersion film of embodiment 1 obtains the TVOC slightly lower than the SBL dispersion film of Comparative Examples 3 and discharges.The TVOC release ratio Comparative Examples 3 of embodiment 2 is much lower.

Embodiment 5

The preparation of carpet sample

(based on the copolymer dispersion of embodiment 1,2 and 3)

In the laboratory, be coated on by using foam box (foam box) base substrate of inserting fiber cluster suede in it, the coating that then applies by curing comes the embedding tufting in base substrate, thus the preparation carpet sample.Base substrate is woven polypropylene tufting pedestal.Tufting is made by the polypropylene yarn of inserting in the tufting pedestal, accounts for 500g/m so that tufting adds the consumption of basic material ²

Copolymer dispersion by embodiment 1,2 and 3 prepares the coating composition that uses.Beyond copolymer dispersion except embodiment 1,2 or 3, these coating compositions also contain filler material, and it is calcium carbonate.Based on the consumption of dry copolymer, these aqueous coating compositions all have following formula: 40% copolymer dispersion (drying) of preparing together with 60% calcium carbonate (producer Omnia, tradenameOmniacarp5GU).

Adopt IKA RE166 agitator, premix copolymer dispersion and pearl filler form level and smooth and uniform mixture.Use Moulinex Supermix170 device, make the foam volume of 350 ± 50ml of this mixture.Adopt specific gravity bottle (Erichson PycnometerTyp290), measure the density (500 ± 100g/1) of foams.Foam box (stainless steel/adjustable clearance 0-15mm/25x5.4x5cm) is placed in the substrate of weighing of carpet, then fills with this mixture.Slowly also drag continuously foam box on the back side of carpet sample, form uniform film.After coating, blanket sample 30 minutes (GallencampOven300Plus) dryly under 110 ℃.In climatic chamber, under 23 ℃ and 50% humidity, minimum 24 hours of storage place blanket sample.The sample of weighing is to measure the coating weightening finish as 550 ± 100g/m ²

After regulating, the cutting carpet sample is to the size (edge is sewed up to prevent to decompose with cotton WEB processed) of 22x26.5cm, and the washability of description hereinafter, anti-skidding, tufting is fixed and the naked eyes evaluation in use.

Embodiment 6

The test of carpet sample washability

(based on the copolymer dispersion of embodiment 1,2 and 3)

According to the test step that in above test method part, test is described for the carpet sample washability, test the loss in weight of several carpet sample after washing of preparation described in above embodiment 4.For each class carpet sample to be tested, be determined at every 5 wash cycle loss in weight afterwards, the unit gram, and calculate and be reported in every 5 wash cycle loss in weight percentage afterwards.Listed result in table 2.

Table 2

The washability test-5,10, the loss in weight after 15 and 20 washings

The data of table 2 show, have carpet sample based on the coating of the vae copolymer thing of embodiment 1 and demonstrate and have based on the suitable loss in weight of the carpet sample of the coating of the SBL copolymer of embodiment 3.Having carpet sample based on the coating of the vae copolymer thing of embodiment 2 demonstrates than the slightly good washability of carpet sample that has based on the coating of the SBL copolymer of embodiment 3.

Embodiment 7

The non-skid property of carpet sample

(based on the copolymer dispersion of embodiment 1,2 and 3)

According to the test step (TAPPI816om-92) of describing for the non-skid property of carpet sample in above test method part, test at first and the non-skid property of the several carpet sample that prepare described in above embodiment 5 after washing.Measure non-skid property, the newton of unit [N] with the maximum, force form that drags sample on glass plate.Result is the result of two samples, and lists in table 3.

Table 3

Initial and 5,10, the non-skid property of carpet after 15 and 20 washings

The result of table 3 shows, compares with the carpet that has based on the coating of the SBL of embodiment 3, and the carpet of VAE-base coating with copolymer dispersion of embodiment 1 and 2 demonstrates suitable initial non-skid property.

5,10, after 15 and 20 washings, to compare with the carpet of the SBL-base coating with embodiment 3, the carpet with VAE-base coating of embodiment 1 demonstrates better non-skid property.5,10, after 15 and 20 washings, the carpet with VAE-base coating of embodiment 2 demonstrates the non-skid property suitable with the carpet of the SBL-base coating with embodiment 3.

Embodiment 8

The tufting of carpet sample is fixed

(based on the copolymer dispersion of embodiment 1,2 and 3)

According in above test method part for the fixing test step (ISO4919) of describing of the tufting of carpet sample, after 20 wash cycle, test is fixed as the tufting of several carpet sample of preparation as described in above embodiment 5 in initial sum.The tufting fixing test is measured maximum, force, and described maximum, force is measured take newton (N) as unit.Tufting fixation test result has been shown in table 4.

Table 4

The tufting of carpet sample is fixed after 20 washings of initial sum

The tufting fixation test result of table 4 shows, compares with the carpet that has based on the coating of the SBL of embodiment 3, and the carpet sample with VAE-base coating of embodiment 1 demonstrates lower initial tufting and fixes.Compare with the carpet of the SBL-base coating with embodiment 3, the carpet sample with VAE-base coating of embodiment 2 demonstrates better initial tufting and fixes.

, demonstrate constant tufting and fix after 20 washings based on the carpet of the coating of the vae copolymer thing of embodiment 1.Have carpet based on the coating of the vae copolymer thing of embodiment 2 after 20 washings, demonstrate the tufting that only slightly reduces and fix.Have carpet (Comparative Examples) based on the SBL of embodiment 3 after 20 wash cycle, demonstrate the approximately tufting dead loss of 2.5 times.

Embodiment 9

Naked eyes are estimated carpet sample

(based on the copolymer dispersion of embodiment 1,2 and 3)

Also according to the outward appearance of the above carpet sample of listing in test method part and the naked eyes evaluation method of feel standard, several carpet sample of preparation as described in example 5 above more than naked eyes are estimated.For lining cloth integrality and feel (pliability), based on grade 1-4, after 20 wash cycle of initial sum, estimate carpet sample.The result of the naked eyes evaluation of carpet sample has been shown in table 5.In table 5, grade 1 is to be well poor with 4.

Table 5

The naked eyes evaluation of carpet lining cloth and the feel of sample

The result of table 5 shows, the carpet sample that has based on the coating of the copolymer of embodiment 1,2 and 3 all has at first closed lining cloth and do not chap and have uniform outward appearance.After 20 washings, compare with the carpet sample that has based on the coating of the SBL of embodiment 3, the sample lining cloth of coating with VAE-base co-polymer of embodiment 1 and 2 demonstrates the less visible loss in weight, less uncoated fiber and less be full of cracks.

Compare with the carpet sample (it touches quite hard) of the coating of the SBL with embodiment 3, have carpet sample based on the coating of the vae copolymer thing of embodiment 1 and demonstrate much soft initial feel.Have sample based on the coating of the VAE of embodiment 2 and touch in unwashed situation and get up firmly, but this flintiness is suitable with the sample that has based on the coating of the SBL of embodiment 3.

After 20 washings, embodiment 1-base coating still has the level and smooth feel same with their start-up phases.Embodiment 3-base coating is lost its initial flintiness after 20 washings, then have the sense of touch of the softness identical with embodiment 1-base coating.The feel of embodiment 2 basic coatings is identical after 20 washings.

Claims

1. a carpet product, comprise at least one flex substrate and the coating layer of one deck at least or the adhesive phase of being combined with described at least one flex substrate, forms described coating layer or adhesive phase by the Aquo-composition that comprises following substances:

A) the stable vinyl acetate/ethylene copolymer dispersion of emulsifying agent, wherein within it vinyl acetate/ethylene copolymer comprises comonomer, described comonomer comprises the vinyl acetate copolymerization monomer with ethylene copolymer, and the granularity d of vinyl acetate/ethylene copolymer dispersion wherein _wScope is 50-500nm, and this measures by laser aerosol spectrum method; With

B) be selected from least a particulate filler material of particulate inorganic compound and granular plastic material.

2. a carpet product, comprise at least one flex substrate and the coating layer of one deck at least or the adhesive phase of being combined with described at least one flex substrate, forms described coating layer or adhesive phase by the Aquo-composition that comprises following substances:

A) the stable vinyl acetate/ethylene copolymer dispersion of emulsifying agent, wherein within it vinyl acetate/ethylene copolymer comprises comonomer, described comonomer comprises the vinyl acetate copolymerization monomer with ethylene copolymer; With

B) be selected from least a particulate filler material of particulate inorganic compound and granular plastic material;

Wherein in washability test described herein, after 20 wash cycle, carpet product demonstrates and is not more than 4.5% the loss in weight.

3. the carpet product of claim 2, wherein the granularity d of vinyl acetate/ethylene copolymer dispersion _wScope is 50-500nm, and this measures by laser aerosol spectrum method.

4. any one carpet product of claim 1-3, wherein said vinyl acetate/ethylene copolymer comprises based on C ₁-C ₁₈The C of the vinyl acetate of monocarboxylic acid or ethylenic unsaturated monocarboxylic ₁-C ₁₈The C of ester or ethylenic unsaturated dicarboxylic ₁-C ₁₈The main comonomer of the different non-sense that one or more of diester are extra.

5. any one carpet product of claim 1-4 is in case wherein the described vinyl acetate/ethylene copolymer in copolymer dispersion is substantially free of the crosslinkable comonomer part that generates formaldehyde when forming described coating layer or adhesive phase.

6. any one carpet product of claim 1-5, wherein the described vinyl acetate/ethylene copolymer in copolymer dispersion is substantially free of the crosslinkable comonomer part of N hydroxymethyl acrylamide or its low formaldehyde generates variant.

7. any one carpet product of claim 1-6, wherein the described vinyl acetate/ethylene copolymer in copolymer dispersion comprises the ethene of 8wt%-40wt%, based on whole main comonomers within it.

8. any one carpet product of claim 1-7, wherein vinyl acetate/ethylene copolymer comprises the ethene of 10wt%-32wt%, based on whole main comonomers within it.

9. any one carpet product of claim 1-8, wherein the glass transition temperature T of the described vinyl acetate/ethylene copolymer in copolymer dispersion _gBe-25 ℃ to+15 ℃.

10. any one carpet product of claim 1-9, wherein the glass transition temperature T of the described vinyl acetate/ethylene copolymer in copolymer dispersion _gBe-20 ℃ to approximately+5 ℃.

11. any one carpet product of claim 1-10, wherein vinyl acetate/the ethylene copolymer in copolymer dispersion comprise maximum 40wt% can from the main comonomer of the extra different non-sense of described vinyl acetate and ethylene comonomer copolymerization, based on whole principal monomers within it.

12. any one carpet product of claim 1-11, wherein the vinyl ester copolymers in copolymer dispersion comprise maximum 5wt% can with the extra sense comonomer of described main comonomer copolymerization, based on whole principal monomers within it, described extra sense comonomer is selected from the ethylenic unsaturated acids, or its salt, has at least one amide groups, epoxy radicals, hydroxyl, the ethylenically unsaturated monomers of trialkoxy silane base or carbonyl, and the combination of two or more comonomers of any described extra sense comonomer type.

13. any one carpet product of claim 1-12, wherein vinyl acetate/the ethylene copolymer in copolymer dispersion comprises the unsaturated bridging property comonomer of the extra ethylenic with epoxy radicals.

14. the carpet product of claim 13, wherein the bridging property comonomer in the vinyl acetate-ethylene copolymer in copolymer dispersion is selected from glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether, and the combination of described bridging property comonomer.

15. any one carpet product of claim 1-14, wherein except vinyl acetate/ethylene copolymer, this copolymer dispersion further contains by (methyl) acrylic acid C ₁-C ₁₈The alkane ester, the C of other ethylenic unsaturated monocarboxylics ₁-C ₁₈Ester, or the C of ethylenic unsaturated dicarboxylic ₁-C ₁₈One or more copolymers that diester forms.

16. the carpet product of claim 15, wherein except vinyl acetate/ethylene copolymer, this copolymer dispersion further contains by ethyl acrylate, butyl acrylate, 2-EHA, dibutyl maleate, one or more copolymers that are combined to form of di-2-ethylhexyl maleate or these esters.

17. any one carpet product of claim 1-16, wherein the vinyl acetate/ethylene copolymer in copolymer dispersion is substantially free of silane-Ji comonomer.

18. any one carpet product of claim 1-17, wherein the vinyl acetate/ethylene copolymer in copolymer dispersion does not contain the halogenation comonomer.

19. any one carpet product of claim 1-18, wherein copolymer dispersion does not contain the crosslinking agent of rear interpolation.

20. any one carpet product of claim 1-19, wherein the Brookfield viscosity of copolymer dispersion is 100-5000mPa.s.

21. any one carpet product of claim 1-20; wherein use based on one or more emulsifying agents of 0.5wt% at least of the whole main comonomers in described copolymer, and based on the protective colloid-stabilised described copolymer dispersion of 0.2wt%-2wt% for example of the whole mainly comonomer 0wt%-3wt% in described copolymer.

22. the carpet product of claim 21, wherein the protective colloid that uses of stable copolymer dispersion is polyvinyl alcohol.

23. any one carpet product of claim 1-20, wherein the stabilising system in copolymer dispersion is substantially free of protective colloid.

24. any one carpet product of claim 1-23 is wherein used stabilising system emulsifying agent-stable copolymer dispersion, described stabilising system is selected from anion and non-ionic surface active agent, but is substantially free of the alkylphenol b-oxide.

25. any one carpet product of claim 1-24, wherein whole volatile organic compounds (TVOC) content of copolymer dispersion is less than 0.5%, and based on the gross weight of moisture copolymer dispersion, this measures by ISO11890-2.

26. any one carpet product of claim 1-25, wherein when according to the operation test of ISO16000-9, with respect to the toluene reference material, the film that is formed by copolymer dispersion discharges its TVOC content to the degree that is not more than 15 times.

27. any one carpet product of claim 1-26, wherein the particulate filler in Aquo-composition accounts for the 10wt%-70wt% of dispersion and is selected from granular calcium carbonate and granular plastic material.

28. any one carpet product of claim 1-27, it is substantially free of polyvinyl chloride and pitch.

29. any one carpet product of claim 1-28, it is substantially free of 4-benzyl ring hexene (4-PCH), 4 vinyl cyclohexene (4-VCH), styrene and ethylbenzene.

30. any one carpet product of claim 1-29, it comprises at least one layer binder coating and one deck adhesive phase at least, and they differ from one another on forming.

31. any one carpet product of claim 1-30, wherein within it flex substrate is selected from supatex fabric, Woven fabric, unidirectional braided fabric, knit goods and fleece.

32. any one carpet product of claim 1-31, wherein flex substrate is selected from non-woven polypropylene, polyethylene or polyester, and weave jute, polypropylene or polyamide substrate.

33. any one carpet product of claim 1-32, wherein within it flex substrate is based on polypropylene or polyamide fiber.

34. any one carpet product of claim 1-33, take dry weight as the basis, the weight of its unit are is 100g/m ²-3000g/m ²

35. any one carpet product of claim 1-34, in tufting fixation test described herein, after 20 wash cycle, it demonstrates and is not more than 40% tufting dead loss.

36. any one carpet product of claim 1-35, in the naked eyes of carpet sample outward appearance described herein and hand test were estimated, after 20 wash cycle, it demonstrated not lining cloth integrity levels and feel grade higher than 3.

37. any one carpet product of claim 1-36, it is the anti-slip carpet form of woven anti-slip carpet or tufting, described carpet type in the distally of trampling side with the dispersion coating that contains vinyl acetate/ethylene copolymer.

38. the carpet product of claim 37, when according to TAPPI test T816om-92 test, it demonstrates non-skid property, and result need to be dragged power more than or equal to 6.0 newton's maximum, the sample of mobile described carpet product.

39. a carpet product, described carpet product comprise at least one flex substrate and the coating layer of one deck at least or the adhesive phase of being combined with described at least one flex substrate, form described coating layer or adhesive phase by the Aquo-composition that comprises following substances:

A) contain the stable copolymer dispersion of emulsifying agent of vinyl acetate/ethylene copolymer; With

B) be selected from least a particulate filler material in granular calcium carbonate and granular plastic material;

Wherein

I) ethylene contents of the described vinyl acetate/ethylene copolymer in copolymer dispersion is 8wt%-40wt%, based on whole main comonomer within it, and glass transition temperature T _gBe-20 ℃ to+5 ℃;

Ii) in case the described vinyl acetate/ethylene copolymer in copolymer dispersion does not comprise the crosslinkable part that generates formaldehyde when forming described coating layer or adhesive phase;

Iii) the granularity d of the described vinyl acetate/ethylene copolymer in copolymer dispersion _wScope be 120-350nm, this measures by laser aerosol spectrum method;

Iv) use based on the whole monomers in described copolymer one or more anion and/or the nonionic emulsifier of 0.5wt% at least, and based on the described copolymer dispersion of the combination emulsifying agent of the polyvinyl alcohol protective colloid of the maximum 3wt% of whole comonomers in described copolymer-stablize;

V) the Brookfield range of viscosities of described copolymer dispersion is 200mPa.s-4000mPa.s;

Vi) described carpet product is substantially free of polyvinyl chloride and pitch; With

Vii) in washability test described herein, after 20 wash cycle, described carpet product demonstrates and is not more than 4.5% the loss in weight.

40. carpet product, it comprises the textile fabric structure of processing with the vinyl acetate/ethylene copolymer dispersion, copolymer in described dispersion comprises vinyl acetate and the 20-30pphm of 70-80pphm, the ethene of preferred 20-24pphm, wherein the glass transition temperature of this copolymer is 0 ℃ to-10 ℃, preferably-3 ℃ to-6 ℃, average grain diameter d _wBe 150-200nm, and with 1wt% emulsifying agent and 0wt%-2wt% at least by polyvinyl alcohol or cellulose ether form protective colloid-stabilised.

41. the carpet product of claim 40, wherein the vinyl acetate/ethylene copolymer dispersion comprise maximum 10pphm can with the further monomer of vinyl acetate and ethylene copolymer.

42. the carpet product of claim 40 or 41, wherein the viscosity of vinyl acetate/ethylene copolymer dispersion is 400-1600mpa.s, and this adopts the Brookfield viscosimeter to measure under 25 ℃.

43. any one carpet product of claim 40-42 wherein by in the situation that there is not the protective colloid polymerization, obtains the vinyl acetate/ethylene copolymer in copolymer dispersion.

44. any one carpet product of claim 40-43, wherein the vinyl acetate/ethylene copolymer in copolymer dispersion comprise can with the further comonomer of vinyl acetate and ethylene copolymer, described further comonomer is selected from the ethylenic unsaturated acids, or its salt, ethylenically unsaturated monomers with at least one amide groups, epoxy radicals, hydroxyl, N-methylol, trialkoxy silane base or carbonyl, and two kinds or the combination of several monomers of any described further monomer type.

45. any one carpet product of claim 40-44, wherein the vinyl acetate/ethylene copolymer in copolymer dispersion comprise can with the further comonomer of vinyl acetate and ethylene copolymer, described further comonomer is selected from the vinyl acetate of non-vinyl acetate, nonvinylic alpha-olefin, vinyl-arene, the ester of ethylenic unsaturated monocarboxylic, and the diester of ethylenic unsaturated dicarboxylic.

46. any one carpet product of claim 40-45, wherein the emulsifying agent in copolymer dispersion is selected from anion and non-ionic surface active agent, but does not contain the alkyl phenyl b-oxide.

47. any one carpet product of claim 40-46, wherein copolymer dispersion has the solids content of 45-55wt%.

48. any one carpet product of claim 40-47, wherein the textile fabric structure comprises at least a fabric that is selected from supatex fabric, Woven fabric, unidirectional braided fabric, knit goods and fleece.

49. any one carpet product of claim 40-48, wherein the textile fabric structure comprises the fleece of using based on the coating composition coating of copolymer dispersion, and coating is being trampled on the distally of side.