CN103119215B

CN103119215B - There is the carpet product washed of the coating layer formed by vinyl acetate/ethylene copolymer dispersion

Info

Publication number: CN103119215B
Application number: CN201180039275.0A
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: 2015-09-23
Anticipated expiration: 2031-08-12
Also published as: EP2603633A2; WO2012020321A3; US20130177733A1; BR112013003394A2; WO2012020321A2; CN103119215A

Abstract

Disclose carpet product, at least one deck coating layer that it comprises at least one flex substrate and is combined with at least one flex substrate.This coating layer is formed by the Aquo-composition comprising following substances: vinyl acetate/ethene (VAE) the emulsion copolymers dispersion that A) emulsifying agent is stable, wherein vae copolymer thing within it comprises comonomer, and described comonomer at least comprises the vinyl acetate with the comonomer of ethene and optionally also extra with other sense and/or non-functional; And B) be selected from least one particulate filler material in particulate inorganic compound and Particulate plastic materials.The granularity d of the vinyl acetate/ethylene copolymer in this copolymer dispersion _wscope be about 500nm for about 50-, this is by laser aerosol spectrographic determination.This carpet product maintains their integrality and outward appearance after the operation of repeatedly machine-washing.Some in these carpet products have the lining cloth be coated with coating composition more used herein, and they also demonstrate required non-skid property.

Description

There is the carpet product washed of the coating layer formed by vinyl acetate/ethylene copolymer dispersion

The cross reference of related application

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

Invention field

The research and development of the application relate to the carpet product with coating layer within it, and described coating layer comprises containing filler, and the vinyl acetate/ethylene-based copolymers dispersion of emulsifying agent-and/or colloid-stable is as the emulsion binding agent of small grain size.This carpet product demonstrates the required characteristic sum washed and preferably also can especially effectively be used as anti-slip carpet or apply wherein, such as, for bath mats or gymnasium pad.

Background technology

The carpet of most conventional comprises the main lining cloth of the yarn tufting having cutting or do not cut looped pile form, and described looped pile upwards extends to form 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 (i.e. adhesive) thereon.

Many houses and commercial carpets also adopt the woven woven scrim (typically being manufactured by polypropylene) be connected with carpet back to manufacture, to provide size of carpet stability.These are double-layer products, and wherein wet method adds two-layer coating layer (precoated shet fixed for tufting and the adhesive fixed for woven scrim), and adds woven scrim afterwards.After fixing woven scrim, at 130-200 DEG C, solidify carpet certain hour.

Important the physical property of adhesive coating successfully uses for it in carpet product.About this point, there is the many important requirement that must be met by these coatings.The technology and equipment being used for using routinely in the carpet industry of latex such as emulsion coating must be used, apply a coating on carpet also dry.Adhesive composition must provide the cohesiveness excellent to pile fiber, they is firmly fixed in lining cloth.This coating also typically has high filler load, the carpet lining cloth of such as calcium carbonate, clay, aluminum trihydrate, barite, feldspar, cullet, flyash and/or circulation.In addition, the coating on underlayment layer of cloth preferably must can also play the effect of anti-skidding substrate, thus makes to be prepared in the anti-slip material used in such as bathroom and rug or the application of gymnasium pad.

Adhesive in carpet material coating composition is usually emulsion polymer, i.e. latex dispersion, such as styrene-base emulsion copolymer, such as, and styrene-butadiene latex (SBL) material or such as acrylic polymer latex dispersion.Also the copolymer of vinyl acetate (such as vinyl acetate) and ethene can be used, and with rubber coating or containing compared with cinnamic coating such as SBL-based composition and use thereof in packaging, they usually can have cost and manufacture advantage.Such as, vinyl ester copolymers can be used, there is provided desirably VOC (volatile organic compounds) content low and not containing potential toxic material, such as 4-benzyl ring hexene (4-PCH) and the carpet product of related compound that may find in styrene based emulsion polymers.

Such as at WO2010/089142 with at 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, the emulsion binding agent of such as vinyl acetate/ethene (VAE) copolymer and carpet coating compositions.Some in these patent documents are noticed, this VAE adhesive and coating composition and in this carpet product, be commonly used for polyvinyl chloride (PVC) plastisol of lining cloth layer compatible.

By being polymerized suitable comonomer in aqueous emulsion, be prepared in the vinyl acetate/ethylene copolymer used in the adhesive and coating composition described in aforementioned patent literature.By adding conventional surfactant (anion, nonionic, CATION) as emulsifying agent, stablize these emulsions or dispersion.Also by comprising protective colloid, these emulsions or dispersion is stablized.

Although the various carpet coating compositions based on stable vinyl acetate and vinyl acetate/ethene (such as VAE) latex emulsion/dispersion adhesive can be obtained, advantageously identify and select the relatively soft (by the glass transition temperature (T of copolymer of particular type _g) quantize) VAE-base, eco-friendly adhesive agent emulsion/dispersion containing filler, described adhesive agent emulsion/dispersion demonstrates the required performance balance making them be particularly useful for preparing textile constructions such as carpet and carpet material.Research and development of the present invention provide once cyclic washing has washed feature required especially, i.e. the carpet product of minimum weight loss and integrality, and the carpet product of preferably required non-skid property and carpet element.These carpet products also can desirably have low VOC content.The carpet product of the VAE-of having based adhesive coating described herein has combination (such as, specific comonomer, crosslinking agent, stabilizing agent, relatively little polymer particle size, the T selecting feature _gand filler), it can provide this required performance balance, time particularly compared with the carpet product of the SBL-Carpets coating of use prior art.

Summary of the invention

Research and development of the present invention relate to carpet product, at least one deck coating layer that described carpet product comprises at least one flex substrate and is combined with at least one flex substrate.This coating layer is formed: vinyl acetate/ethylene copolymer (VAE) dispersion that A) emulsifying agent is stable, and B by the Aquo-composition comprising following substances) be selected from least one particulate filler material in particulate inorganic compound and Particulate plastic materials.Vinyl acetate/ethylene copolymer in copolymer dispersion comprises the main monomers comprising vinyl acetate, described main monomers and ethene and optionally also extra with one or more different non-functional main monomers copolymerization, described non-functional main monomers can be C ₁-C ₁₈the vinyl acetate of monocarboxylic acid or the C of 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 about 500nm for about 50-, and this is by laser aerosol spectrographic determination.In addition, the vinyl acetate/ethylene copolymer in copolymer dispersion typically comprises the ethene that about 8wt%-is about 40wt%, based on whole main monomers within it, and glass transition temperature T _gfor about-25 DEG C to about+15 DEG C.

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

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

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

Describe in detail

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

Copolymer dispersion

The component being applied to formation film in the Aquo-composition in carpet flex substrate herein or coating is the vinyl acetate-base co-polymer comprising ethene and optionally one or more extra non-functional main monomers.In copolymer dispersion prepared by the emulsion polymerisation of the comonomer that this vinyl acetate/ethylene copolymer is present in by selecting suitably.

The main monomers used in the preparation of copolymer dispersion is vinyl acetate.This main vinyl acetate comonomer is about 80wt% with about 40%-usually, and more preferably from about the consumption of 60%-70wt% is present in dispersion copolymers, based on the whole main monomers in copolymer.The comonomer being incorporated into the second in dispersion copolymers main is ethene.Ethene usually accounts for about 8%-and is about 40wt%, and preferred 10%-is about 32wt%, and most preferably from about 12%-is about 30wt%, based on the whole main monomers in copolymer.

Vinyl acetate/ethylene copolymer in copolymer dispersion, except comprising vinyl acetate and ethene, also optionally comprises the non-functional main monomers that one or more are extra.This main non-functional comonomer optionally of one class comprises vinyl acetate comonomer.The example is the vinyl acetate (except vinyl acetate) of the monocarboxylic acid with 1-18 carbon atom, such as vinyl formate, propionate, vinyl butyrate, vinyl isobutyrate ester, vinyl benzoate, 2-ethyl-hexanoic vinyl acetate, there is the vinyl acetate of [the α]-branched carboxylic acids of 5-11 carbon atom, such as Versatic in acid moieties ^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 main non-functional optionally in the vinyl acetate/ethylene copolymer of dispersion comprises the ester of ethylenic unsaturated monocarboxylic or the diester of ethylenic unsaturated dicarboxylic.Especially favourable this kind of comonomer is the ester of the alcohol with 1-18 carbon atom.The example of the main monomers of this non-functional 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 monomers type of two or more aforementioned optional non-functional can be copolymerized in vinyl acetate/ethylene copolymer.If exist, then the main monomers of this non-functional can account for about 40wt% at most, based on the whole main monomers in copolymer.More preferably, the main monomers of this non-functional can account for about 5wt%-and be about 20wt%, based on the whole main monomers in vinyl acetate/ethylene copolymer.

Herein for vinyl acetate/vac emulsion copolymer of using in the coating of carpet product except containing vinyl acetate, beyond ethene or other main monomers types, the comonomer also optionally containing other types relatively in a small amount.Other optional comonomers this are usually containing one or more functional group and or once dry or solidify the film that formed by this composition and coating and can play those that be cross-linked between copolymer chain in the Aquo-composition that provides or promote containing copolymer dispersion.

This functional comonomer optionally existed can comprise ethylenic unsaturated acids, such as 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 this kind of optional functional comonomer 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 ₁₈unitary aliphatic series saturated alcohols), and alkali metal salt and ammonium salt, or (methyl) acrylate of sulfo group alkanol, one of them example is 2-sulfoethylmethylacrylic sodium.

The suitable optional functional comonomer of other types comprises and has at least one amide groups, epoxy radicals, hydroxyl, the ethylenic unsaturated comonomer of trialkoxy silane base or carbonyl.Especially it is suitable that ethylenic unsaturated epoxide compound, such as glycidyl methacrylate or glycidyl acrylate.Equally it is suitable that hydroxy compounds, comprising methacrylic acid and acrylic acid C ₁-C ₉hydroxyalkyl, the positive hydroxy methacrylate of such as acrylic acid and methacrylic acid, positive hydroxy propyl ester or positive hydroxybutyl.Other suitable functional comonomer comprise such as diacetone acrylamide, and the compound of the acetoacetoxyethyl methacrylate of acrylic acid and methacrylic acid; With the acid amides of ethylenic unsaturated carboxylic acid, such as acrylamide or Methacrylamide.

As noted, the comonomer of emulsion copolymers as used herein optionally containing trialkoxy silane official energy.Or emulsion copolymers as used herein can be substantially free of silylation comonomer.

The one class functional comonomer that should not be incorporated in vinyl acetate/ethylene copolymer as used herein comprises any comonomer containing crosslinkable moiety, form coating once by the composition containing these copolymers, described crosslinkable moiety will generate formaldehyde.Therefore, vinyl acetate/ethylene copolymer in copolymer dispersion should be substantially free of this comonomer, described comonomer comprises such as common crosslinking agent, the even low formaldehyde variant of such as N hydroxymethyl acrylamide (NMA) or N hydroxymethyl acrylamide, such as NMA-LF.Vinyl acetate/ethylene copolymer also in preferred copolymer dispersion should not contain halogenation comonomer, such as vinyl chloride comonomers.

Can by based on the whole main monomers in copolymer, the optional functional comonomer of consumption at most about 5wt% is incorporated in vinyl acetate as used herein/vac emulsion copolymer.More preferably, optional functional comonomer can account for about 0.5wt%-and be about 2wt%, based on the whole main monomers in copolymer.

The emulsion polymerization technology hereafter described more fully can be used, in copolymer dispersion, form emulsion copolymers.In this copolymer dispersion, copolymer is with average particle size d _wscope is the relatively little particle form existence that about 50nm-is about 500nm, and this is by laser aerosol spectroscopy measurements.More preferably, this copolymer dispersion is with average particle size d _wscope is the particle form existence that about 120nm-is about 350nm.Granularity is measured by laser aerosol spectroscopy technique.

Depend on the type of used comonomer, solubility, and monomer feed technology, vinyl acetate-ethylenic copolymer, in monomer structure and composition, can be homogeneous phase or heterogeneous.Homogeneous copolymers has single discrete glass transition temperature T _g, this is measured by differential canning calorimetry.Non-homogeneous copolymer demonstrates two or more discrete glass transition temperatures and can cause 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 about-25 DEG C to+15 DEG C, more preferably from about-20 DEG C to+5 DEG C.As known, can such as by regulating the T of ethylene contents control polymer _g, be namely present in copolymer relative to the usual more ethene of other comonomers, then T _glower.

For the stabilizing agent of polymeric dispersions

In the course of the polymerization process and afterwards, stablize with moisture copolymer dispersion or latex form the copolymer dispersion that Aquo-composition that preparation forms carpet adhesive layer or coating layer uses.Therefore under stabilising system exists, prepare copolymer dispersion, described stabilising system generally includes emulsifying agent, especially nonionic emulsifier and/or anion emulsifier.Also the mixture of nonionic and anion emulsifier can be used.

The consumption of the emulsifying agent used normally at least 0.5wt%, based on the total amount of the main monomers existed in copolymer dispersion.Usually the emulsifying agent of the maximum about 8wt% of consumption can be used, based on the total amount of main monomers in copolymer dispersion.In emulsifying agent, the weight ratio of nonionic and anion can fluctuate in wide scope, such as 1:1-50:1.Vinyl acetate/ethylene copolymer dispersion can comprise polymer stabilizer (protective colloid) in a small amount further.

The emulsifying agent herein preferably used be have epoxy alkyl nonionic emulsifier and there is sulfate, sulfonic group, the anion emulsifier of phosphate and phosphonate group.Optionally, these emulsifying agents can with the water-soluble polymer of molecule or dispersion, preferably use together with polyvinyl alcohol.Also preferably described emulsifying agent is not containing alkyl phenol ethoxylate (APEO).

The example of suitable nonionic emulsifier comprises acyl group, alkyl, oil base and alkaryl b-oxide.These products are such as with title , or be purchased.These comprise such as 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), particularly C 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, there is the polyoxyethylene sorbitol monoleate of 20 Oxyranyles, 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 it is suitable that poly(ethylene oxide) (4-40) ether of fatty alcohol, more specifically oleyl alcohol, stearyl alcohol, or C ₁₁alkylol.

Typically be about 1%-at the consumption preparing the nonionic emulsifier used in copolymer dispersion herein and be about 8wt%, preferably about 1%-is about 5wt%, and more preferably from about 1%-is about 4wt%, based on the consumption of whole principal monomer.Also the mixture of nonionic emulsifier can be used.

It is C that the example of suitable anion emulsifier comprises chain length ₁₂-C ₂₀the sodium of linear aliphatic carboxylic acids, potassium and ammonium salt, hydroxyoctadecanoic sodium sulfonate, chain length is C ₁₂-C ₂₀the sodium of hydroxy fatty acid, potassium and ammonium salt, 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 (C ₈-C ₁₈) ammonium chloride, and sulfonated products, lignin sulfonic acid and calcium, magnesium, sodium and ammonium salt, resin acid, hydrogenation and dehydrogenation resin acid, and alkali metal salt, myristalated diphenyl ether disulfonates, NaLS, EO degree is the sulphation alkyl or aryl b-oxide of 1-10, the such as salt of ethoxyquin sodium laureth sulfate (EO degree 3) or diester, preferably two-C ₄-C ₁₈the salt of alkane ester, has the salt of the sulfonated dicarboxylic acids of 4-8 carbon atom, or the mixture of these salt, the sulfonated salts of preferred succinate, more preferably two-C of sulfosuccinate ₄-C ₁₈the salt of alkane ester, such as alkali metal salt, or the phosphate of poly-ethoxyquin alkanol.

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

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

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

Separately or protective colloid can be combined.When combining, two or more colloids can be different in its molecular weight, or they can at its molecular weight and different on its chemical composition such as degree of hydrolysis.

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

The preparation of copolymer dispersion

Can use emulsion polymerisation operation, preparation is containing 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 kind of 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 are such as disclosed in U.S. Patent No. 5, and 849,389 and Encyclopedia of Polymer Scienceand Engineering, Vol.8, p.659ff in (1987).The disclosure of these publications is introduced by reference to full text at this.

According to known mode itself, at one, in two or more sections, different combination of monomers can be adopted, is polymerized, thus obtain that there is homogeneous phase or non-homogeneous particle, the such as polymeric dispersions of nucleocapsid or hemispherical pattern.Any reactor system can be used, such as interval, endless tube, continuously, cascade etc.

Polymerization temperatures range is generally about 20 DEG C of-Yue 150 DEG C, more preferably from about 50 DEG C of-Yue 120 DEG C.Usually be polymerized under pressure, preferably about 2-is about 150bar, and more preferably from about 5-is about 100bar.

In the typical polymerization operation involving such as vinyl acetate/ethylene copolymer dispersion; can in water-bearing media; under the pressure of maximum about 120bar; at one or more initators and at least one emulsifying agent; under optionally together with protective colloid, such as PVOH exists; polymerization vinyl acetate, ethene and other comonomers.By suitable buffer, the aqueous reaction mixture in maintenance aggregation container is under the pH of about 2-about 7.

In conjunction with several polymeric composition, i.e. emulsifying agent, comonomer, the mode of catalyst system component etc. can vary widely.Usually, in aggregation container, the water-bearing media containing at least some emulsifying agent can be formed at first, and afterwards other polymeric composition various are being joined in this container.

Can be continuous by comonomer, incrementally, or introduce the form of adding whole amount comonomer to be used with single comonomer is joined in aggregation container.Comonomer can be used with pure monomer form, or can use with premix emulsion form.Ethene as comonomer can be pumped in aggregation container, and within it maintains under suitable pressure.

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

As polymerization initiator, also so-called redox initiator can be used.The example is that such as (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, with acetone-bisulfite adduct), or and ascorbic acid, sodium isoascorbate, or the t-butyl hydroperoxide be combined with reducing sugar and/or hydrogen peroxide.

Change in the scope that consumption aqueous polymerization in heterogeneous system that initator used in the method or initator combine is common.Usually, the consumption of the initator used is no more than 5wt%, based on the total amount of comonomer to be polymerized.Based on the total amount of comonomer to be polymerized, the preferred 0.05%-2.0wt% of consumption of the initator used.

In the context of the present invention, the initator of whole consumption can be included in the initial charge of arrival reactor when being polymerized and starting.Preferably, or when a part of initator is included in beginning in initial charge, and all the other add in one or more steps or continuously after polymerization causes.Can add independently or together with other components such as emulsifying agent or monomer emulsions.Also can use seed latex, the about 0.5-of such as dispersion is about the seed latex of 15wt%, starts emulsion polymerisation.

Except the vinyl acetate/ethylene copolymer of emulsion polymerisation, copolymer dispersion as used herein can contain by (methyl) acrylic acid C in addition 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 is formed.This extra copolymer can comprise such as about 0.5-about 20 weight portion, 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 be combined to form of di-2-ethylhexyl maleate or these esters.

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

The range of viscosities of the copolymer dispersion herein prepared under the solid of 45-55% normally about 100mPas-is about 5000mPas, and more preferably from about 200mPas-is about 4000mPas, most preferably 400-3000mPas, this adopts Brookfield viscosimeter, at 25 DEG C, under 20rpm, suitable spindle is adopted to measure.By adding thickener and/or water in copolymer dispersion, adjusting viscosity.Suitable thickener can comprise polyacrylate or polyurethane, such as Borchigel and Tafigel PUR .Or this copolymer dispersion can be substantially free of thickener.

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

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

Moisture copolymer dispersion as used herein usually containing being less than 0.5wt%TVOC, based on the gross weight of moisture copolymer dispersion.Preferred moisture copolymer dispersion contains and is less than 0.3wt%TVOC, based on the gross weight of moisture copolymer dispersion.According to the ISO11890-2 hereafter described in test method part, these numerical value can be measured.

When being exposed under air, moisture copolymer dispersion as used herein also discharges TVOC content relatively in a small amount usually.Especially, copolymer dispersion herein discharges TVOC material to the degree of about 15 times being not more than Toluene D8 reference material, when the film formed by these dispersions is tested according to the operation of the ISO16000-9 hereafter described in test method part.More preferably copolymer dispersion release TVOC material is herein to the degree of about 10 times being not more than TolueneD8 reference material.

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

Optional additives for the typical routine of copolymer dispersion herein can comprise such as film adjuvants, such as white spirit, butanediol, butyldiglycol, butyl dipropylene glycol, and butyl tripropylene glycol; Humectant, such as defoamer, such as mineral oil antifoam agent or silicone defoamer; UV protective agent, such as regulate the reagent of pH; Preservative agent; Plasticizer, such as repefral, diisobutyl phthalate, diisobutyl adipate, with the stabilization of polymer added subsequently, such as polyvinyl alcohol or cellulose ether; With preparation binding agent and adhesive typically other additives and auxiliary agent kind.The consumption of these additives used in vae copolymer thing dispersion herein can change in wide region, and can be selected in view of required Application Areas by expert.

Aqueous coating composition

In conjunction with foregoing copolymer dispersion and filler material and extra water, formed herein for the aqueous coating composition of carpet product.Then this coating composition is applied in the textile substrate of the carpet product formed herein.Once dry, then then the aqueous coating composition applied provides coating layer in carpet product.Carpet product can comprise only a kind of or be greater than a kind of coating layer.

Usually, carpet product herein always contains adhesive-coated layer, with fixing carpet fiber in main lining cloth substrate.Therefore carpet product herein also optionally comprises second or extra layer, described second or extra layer can be adhesive phase, auxiliary lining cloth substrate is fixed on the main lining cloth of coating.

In one embodiment, both the coating layer that the Aquo-composition that carpet product can comprise from here described identical type is formed and adhesive phase.Or, carpet product herein can comprise coating layer described herein and dissimilar adhesive phase, and described adhesive phase also can be formed by the composition of type identical with coating composition herein or can be formed by diverse traditional binders coating composition.

Aqueous coating composition is herein also containing the particulate filler material be selected from particulate inorganic compound and Particulate plastic materials.Therefore, the filler used can be any filler being substantially suitable for using in carpet manufactures.This filler is commercially available widely.

The example of filler comprises inorganic, such as mineral, filler or pigment, such as flyash and cullet, with known in the art those, such as calcium carbonate, 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 Particulate plastic materials, such as synthetic polymer pigment, the carpet lining cloth of hollow polymeric 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 about 200nm-1000 μm usually, more preferably 1 μm-500 μm, most preferably 10 μm-300 μm.The preferred coating composition load that carpet product produced according to the present invention uses has filler to be about 70wt% with the gross weight obtained based on solid in Aquo-composition containing about 10-, more preferably from about 20-is about 60wt%, more preferably from about 20-is about the dry copolymer of 50wt% and about 30-is about 90wt%, preferably about 40-is about 80wt%, the most preferably from about aqueous coating composition of 50-80wt% filler, this part depends on type and the form of carpet to be constructed.

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

Carpet product

Form coating layer, i.e. adhesive layer in previously described coating composition carpet product herein herein, described carpet product also comprises at least one flex substrate.This flex substrate such as can 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.The equipment easily obtained in most of carpet weaving mill can be used in, by applying the Aquo-composition containing emulsion copolymers, and dry, prepare this carpet product.

Pile carpet product comprises the main lining cloth with pile yarns, and described pile yarns extend from main lining cloth substrate, forms pile tufting.By a) tufting or hosiery yarns to weave or in non-woven lining cloth substrate; B) moisture carpet coating compositions described herein is applied to lining cloth back, so that yarn is embedded in carpet coating compositions; And c) dry gained carpet backing and installation system, prepare pile or tufted carpet.In this tufted carpet of production, also passable, but not necessary, and before or after dry carpet coating, apply auxiliary lining cloth on main lining cloth, this depends on used lining cloth type.For tufted carpet, main lining cloth substrate can the woven polypropylene of right and wrong, polyethylene or polyester or woven jute fiber, polypropylene or polyamide (synthesis and natural).

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

Preparing in carpet product herein, apply Aquo-composition, its mode makes the fiber of its infiltration carpet yarn, obtains good cohesiveness, fibre bundle integrality, anti-fiber-loss property and suitable tufting-cementing value.By apply amount ranges be about 100g/m ²-Yue 3000g/m ², more preferably from about 200g/m ²-Yue 2000g/m ², and most preferably from about 400g/m ²-Yue 1500g/m ²aqueous coating/the adhesive composition of (dry basis), realizes suitable carpet performance.

Some carpet product embodiments substituted

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

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

The vae copolymer thing of this selection also can comprise the further comonomer of about 10pphm at most, described further comonomer can with vinyl acetate and ethylene comonomer copolymerization.This further comonomer can comprise ethylenic unsaturated acids, or its salt, there is the ethylenically unsaturated monomers of at least one amide groups, epoxy radicals, hydroxyl, N-methylol, trialkoxy silane or carbonyl, and two kinds of these further monomer types any or the combination of several monomeric.Or 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.

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

The washability of carpet and non-slip feature

Carpet product herein has washability required especially, and in some cases, non-slip feature required equally especially.Washability refers to once in machine-washing operation and washs, moveable carpet product, such as rug, twisted filament carpet, runner, carpet square, tapestry or wall hanging, doormat, the moveable carpet product of motor vehicle foot pad or gymnasium mat form maintains the ability of its integrality.The maintenance of carpet integrality comprises once carry out one or many machine-washing, and carpet product tends to not bodies lost weight.Carpet integrality after one or many washing involves carpet further and tends to maintain its initial outward appearance, its feel, and its lining cloth integrality and its fixed tuft hair yarn and fiber (pile) are in carpet lining cloth.

By following the test procedure, measure the washability of carpet, described the test procedure takes carpet product sample before and after involving similar wash operation.List in following test method part and measure once washing, the suitable the test procedure of the carpet loss in weight.Usually, in the test of this washability, carpet product herein, after 20 washings, demonstrates the loss in weight being less than about 4.5%.More preferably carpet product herein demonstrates the loss in weight being less than about 3.6% after 20 washings.

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

Certainly, also by simple perusal one or many washing operation on the impact of carpet outturn sample, measure once washing, the ability of carpet product resist degradation.Hereafter also list in test method part before and after washing, based on grade 1-4, the suitable operation of its outward appearance of visual assessment 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.

Have and also can provide non-skid property required especially with the carpet product herein on the lining cloth surface of vae copolymer thing-based coating composition coating, wherein 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 such as floor, when carpet is subject to the parallel plane side force with 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 slides.Can the carpet sample of weighing be pulled cross maximum, force needed for testing surface by measuring objectively, measure anti-skidding tendency.In test method part, hereafter also list the measurement carrying out these kinds, measure the operation of carpet skid performance.Anti-skidding embodiment herein demonstrates the maximum drag force at least about 6.0 newton usually in this test, even after wash.More preferably, anti-skidding embodiment herein demonstrates the maximum drag force at least about 7.0 newton in this test.

Extra carpet feature

Carpet product herein has in the vinyl acetate/ethylene-based copolymers dispersion forming the particular type used in coating layer, and it also has eco-friendly feature required especially.Owing to not containing the crosslinking group of generation formaldehyde (such as, there is no NMA or NMA-LF), with due to their low TVOC content and TVOC release, therefore, the copolymer dispersion used does not cause in this kind of potential problem material carpet product from here and discharges.In addition, carpet product is herein substantially free of halogenation comonomer, polyvinyl chloride and pitch, and these are the material types typically used in commercial carpets product.Finally, because carpet product herein does not utilize SBL coating or binding agent, therefore this carpet product is also substantially free of potential poisonous component, such as 4-benzyl ring hexene (4-PCH), 4 vinyl cyclohexene (4-VCH), styrene and ethylbenzene.

Carpet product containing the coating layer formed by the Aquo-composition containing copolymer dispersion herein and filler can have about 100g/m ²-Yue 3000g/m ², more preferably from about 200g/m ²-Yue 2000g/m ², most preferably from about 400g/m ²-Yue 1500g/m 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.Or carpet product herein can be carpet square form or wall-to-wall carpet form.

Embodiment

With reference to following nonlimiting examples, more particularly describe the coating composition containing copolymer dispersion that carpet product herein uses with this carpet product of manufacture.The following describe and be combined used several test methods with these embodiments.

Test method

The granulometry of copolymer dispersion

By laser aerosol spectroscopic methodology (LAS), measure the solid particle size in copolymer dispersion as used herein.At publication Kunstharz Nachrichten28; " Characterization and Quality Assurance of Polymer Dispersions "; This LAS method is described in Oktober1992, Dr.J.Paul Fischer.The method is that its laser power is 2W and wavelength length is 532nm with the Nd:YV04Laser supplied by Spectra Physics (Millenia II).Detector is the Bialkali Photocathode Typ4517 supplied by Burle (in the past RCA).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 at 100ml deionization and in the water (conductivity is 18.2 μ S/m) filtered.Sample Spray dry on Beckmann-nozzle, and use nitrogen drying.With in β radiation (Kr-85) and single particle, then studied by single particle laser light scattering.After evaluation, obtain number within the scope of 80nm-550nm all with matter average and average particle angle value d _n, d _w, d _zand d _w/ d _n.

Glass transition temperature (the T of copolymer _g) measure

By using business differential scanning calorimeter Mettler DSC820, under 10K/min, obtain glass transition temperature T _g.In order to evaluate, use the second heating curves, and calculate DIN mid point.

Whole volatile organic compounds (TVOC) (ISO16000-9) that discharge from copolymer dispersion film

The general procedure of ISO-16000-9 can be used, measure the releasing degree of all volatile organic compounds (TVOC) content in copolymer dispersion sample, this test method at this by reference to introducing.In this operation, taking 2g copolymer dispersion is in the aluminum pan of 4.2cm to diameter.Under room temperature (23 DEG C/50% humidity), this dispersion dry is spent the night, and forming film, is then test in the miniature chamber of 4.5cm and volume 40ml at diameter.Continuous air flow (clean dry air that 100ml/min humidity does not regulate again) flows through this chamber, and allows film sample within it to balance the time period of 20 minutes to chamber conditions (25 DEG C).

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 used as to absorb reference material.Be adsorbed on Tenax pipeline through the time period of 60 minutes from the volatile organic compounds (VOCs) in the air stream of film sample.Then, for the VOCs amount of adsorbing, by GC-MS, Tenax pipeline is analyzed thereon.

Utilize the result that GC-MS measures, obtain the VOCs amount absorbed relative to Toluene D8 reference material.If be considered as 1 in Tenax pipeline systemic toluene reference material amount, be then reported as the multiple of the VOCs that discharges from copolymer dispersion film represents 1 in Tenax pipeline systemic VOCs amount.

The washability of carpet sample

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

The washing machine used is Siemens Vario Perfect E14-32.For each circulation, use 15g washing powder.The washing powder used 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 ", rotating speed 600rpm and temperature 40 DEG C.After each wash cycle, under 23 DEG C and 50% humidity, drying sample spends the night.

After each wash cycle, weighed samples.For washed two samples of each tested copolymer dispersion applied, result is the mean value of the total weight loss after every 5th wash cycle, unit of gram [g].After every 5 wash cycle, the percent weight loss form report result of each sample tested.In addition, also test with this washability and combine, measure the non-skid property of carpet sample.Described below is the test method of the non-skid property measuring washed carpet sample.

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

By using the modified variant thereof of TAPPI816om-92 test method, measure the non-skid property of carpet sample, described test method at this by reference to introducing.This determination of test method drags the maximum, force needed for carpet sample taken on a glass, units Newtons [N].In the test of above-described washability, initial and after every 5th wash cycle, measure non-skid property.

For each carpet type to be tested, use two samples (the cotton WEB processed of 22x26.5cm/ is sewed up, about 20 ± 3g/ sample).The sheet glass that against at the back side of carpet sample on plate (60x30cm) is placed.Positioningly blanket sample in the vertical.Then, in the middle of carpet sample, weight (1.18kg/8x5x4cm) is applied.The far-end of carpet sample at plate is placed towards testing arrangement with its longest side, and contact area is 40cm ².The testing arrangement used is the LF Plus universal testing machine available from Lloyd Instruments.Under the speed of 150mm/min, drag the distance of sample 10cm on a glass.During dragging operation, measure the power needed for mobile carpet, units Newtons [N].Maximum, force is measured between 10-90mm.The result provided is 2 mean values measured.

The tufting of carpet sample is fixed (ISO4919)

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

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

Measure the maximum disruptive force of tufting.Breakpoint should be reached within 2-10 second.For each carpet sample, test 20 tuftings, obtain the mean value of maximum disruptive force.Disruptive force is measured with newton (N).

The gross evaluations of carpet sample outward appearance and feel

Also can the lining cloth outward appearance of gross evaluations carpet sample and feel.More unwashed carpet sample and the identical sample of washed 20 times.Important evaluation criterion comprises the integrality of lining cloth, the visible loss in weight of carpet sample be combined with embedding fiber and the pliability after initial sum is washed for 20 times with the carpet sample of lining cloth.

The result of these gross evaluations is expressed based on grade 1-4.The lining cloth that the integrality of judgement lining cloth as described below: 1=is closed; 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; With 4=except the visible loss in weight and uncoated fiber, in lining cloth surface, also there is be full of cracks.Also judgement feel as described below: 1=is soft; 2=is slight harder; 3=is hard; Stone with 4=.For each class carpet sample to be evaluated, judge two samples (two unwashed samples and two washed samples) by these standards.

Embodiment 1

The preparation of polymeric dispersions

Be furnished with fixing agitator (operating under 150rpm), heating jacket, measuring pump and volume is the group water solution adding following component in the pressure reactor of 6.4 liters:

24490g water (deionization)

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

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

82g sodium acetate (anhydrous)

549g sodium vinyl sulfonate (30%)

13.0g sodium hydrogensulfite

0.07g Mohr's salt

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

[00100] at 65 DEG C, start the charging of (vinyl acetate+glycidyl methacrylate), and all the other 95% vinyl acetates+glycidyl methacrylate was incorporated in reactor in 300 minutes.Meanwhile, again ethene valve is opened, until residual ethylene is fed in reactor.After the feed time of the vinyl acetate+glycidyl methacrylate of 270 minutes, started second time initiator feed (35g sodium persulfate, in 575g deionized water) through about 30 minutes.After the charging completing vinyl acetate+glycidyl methacrylate, temperature of reactor surged to 85 DEG C in 30 minutes.Maintain this temperature other 40 minutes.Then cooling reactor is to about 40 DEG C.At this point place, by introducing Br ü ggolit FF6 (sodium salt of the sulfinate derivant) (33g available from L.Br ü ggemann KG, in 312g deionized water), and Trigonox AW70 (70g) afterwards, carry out final redox 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] fixing agitator (operating under 150rpm), heating jacket, measuring pump and volume is the group water solution adding following component in the pressure reactor of 68.6 liters is being furnished with:

19738g water (deionization)

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

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

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

At 65 DEG C, start the charging of vinyl acetate, and be incorporated in reactor according to following proposal: in 120 minutes 55% and in extra 150 minutes all the other 40%.Meanwhile, again ethene valve is opened, 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%.50 minutes places before vinyl acetate charging terminates, in 50 minutes, temperature of reactor surges to 85 DEG C.After all vinyl acetates of introducing and first and second initator, started the charging (33g sodium persulfate, in 763g deionized water) of the 3rd initator through about 10 minutes.Maintain the temperature of reactor 1 hour of 85 DEG C.Then cooling reactor is to about 40 DEG C.At this point place, by introducing Br ü ggolit FF6 (sodium salt of the sulfinate derivant) (33g available from L.Br ü ggemann KG, in 489g deionized water), and Trigonox AW70 (95g) afterwards, carry out final redox 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.

Following present 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

The copolymer dispersion of embodiment 1,2 and 3

Two analog copolymer dispersions described in embodiment 1,2 and 3 are formed as film, and according to the ISO16000-9 operation described in above test method part, test the tendency of their release volatile organic compounds.The multiple of the Toluene D8 reference material represented with the TVOC (whole volatile organic compounds) of release, provides result.Result has been shown in table 1.

Table 1

TVOC from copolymer dispersion film discharges

Table 1 result measured about the TVOC release of copolymer dispersion film shows, the VAE dispersion film of embodiment 1 obtains the TVOC release slightly lower than the SBL dispersion film of comparative example 3.The TVOC release ratio comparative example 3 of embodiment 2 is much lower.

Embodiment 5

The preparation of carpet sample

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

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

Used coating composition is prepared by the copolymer dispersion of embodiment 1,2 and 3.Beyond copolymer dispersion except embodiment 1,2 or 3, these coating compositions are also containing 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) prepared 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, this mixture is foamed to the volume of 350 ± 50ml.Adopt specific gravity bottle (Erichson PycnometerTyp290), measure the density (500 ± 100g/1) of foams.What foam box (stainless steel/adjustable clearance 0-15mm/25x5.4x5cm) is placed on carpet weighs in substrate, then fills with this mixture.The back side of carpet sample slowly also drags foam box continuously, forms uniform film.After coating, blanket sample 30 minutes (GallencampOven300Plus) dryly at 110 DEG C.In climatic chamber, under 23 DEG C and 50% humidity, minimum 24 hours of storage place blanket sample.Weighed samples, to measure coating weightening finish for 550 ± 100g/m ².

After adjustment, cutting carpet sample to the size (the cotton WEB stitching processed in edge is to prevent decomposition) of 22x26.5cm, and is fixed at washability described below, anti-skidding, tufting and uses in gross evaluations.

Embodiment 6

Carpet sample washability is tested

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

According to testing the test step described in above test method part for carpet sample washability, test several carpet sample loss in weight after wash of preparation described in above embodiment 4.For the carpet sample that each class is to be tested, be determined at the loss in weight after every 5 wash cycle, unit of gram, and the percent weight loss calculating and be reported in after every 5 wash cycle.Result is listed in table 2.

Table 2

Washability test-5,10,15 and 20 times washing after the loss in weight

The data of table 2 show, the carpet sample with the coating of the vae copolymer thing based on embodiment 1 demonstrates the loss in weight suitable with the carpet sample of the coating of the SBL copolymer had based on embodiment 3.The carpet sample with the coating of the vae copolymer thing based on embodiment 2 demonstrates the washability slightly better than the carpet sample of the coating of the SBL copolymer had based on embodiment 3.

Embodiment 7

The non-skid property of carpet sample

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

According to the test step (TAPPI816om-92) that the non-skid property for carpet sample in above test method part describes, the non-skid property of the several carpet sample prepared as described in above embodiment 5 after testing initial and washing.Non-skid property is measured, units Newtons [N] with the maximum, force form dragging sample on a glass.Result is the result of two samples, and lists in table 3.

Table 3

Non-skid property that is initial and carpet after 5,10,15 and 20 washings

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

5,10,15 and 20 times washing after, with have embodiment 3 SBL-base coating carpet compared with, the carpet with the VAE-base coating of embodiment 1 demonstrates better non-skid property.After 5,10,15 and 20 washings, the carpet with the 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

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

Fix the test step (ISO4919) of description according to the tufting for carpet sample in above test method part, in initial sum after 20 wash cycle, the tufting testing several carpet sample of preparation as described in above embodiment 5 is fixed.Tufting fixing test measure maximum, force, described maximum, force with newton (N) for unit measure.Tufting fixation test result has been shown in table 4.

Table 4

After initial sum 20 washings, the tufting of carpet sample is fixed

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

Based on the coating of the vae copolymer thing of embodiment 1 carpet 20 times washing after, demonstrate constant tufting and fix.The carpet with the coating of the vae copolymer thing based on embodiment 2, after 20 washings, demonstrates the tufting only slightly reduced and fixes.The carpet (comparative example) with the SBL based on embodiment 3, after 20 wash cycle, demonstrates the tufting dead loss of about 2.5 times.

Embodiment 9

Gross evaluations carpet sample

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

Also according to the outward appearance of carpet sample listed in test method part above and the Visual evaluation method of feel standard, the several carpet sample more than gross evaluations prepared as described in example 5 above.For lining cloth integrality and feel (pliability), based on grade 1-4, after initial sum 20 wash cycle, evaluate carpet sample.The result of the gross evaluations of carpet sample has been shown in table 5.In table 5, grade 1 is good is poor with 4.

Table 5

The gross evaluations of carpet lining cloth and the feel of sample

The result of table 5 shows, the carpet sample with the coating of the copolymer based on embodiment 1,2 and 3 all has closed lining cloth at first and do not chap and have uniform outward appearance.After 20 washings, compared with the carpet sample of the coating of the SBL had based on embodiment 3, the sample lining cloth with the coating of the 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.

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

After 20 washings, embodiment 1-base coating still has identical level and smooth feel initial with them.Embodiment 3-base coating, after 20 washings, is lost its initial flintiness, is then had the sense of touch of the softness identical with embodiment 1-base coating.The feel of embodiment 2 base coating is identical after 20 washings.

Claims

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

A) the vinyl acetate/ethylene copolymer dispersion that emulsifying agent is stable, wherein vinyl acetate/ethylene copolymer within it comprises comonomer, described comonomer comprises the vinyl acetate comonomer with ethylene copolymer, and the granularity d of wherein vinyl acetate/ethylene copolymer dispersion _wscope is 50-500nm, and this is by laser aerosol spectrographic determination; With

B) at least one particulate filler material of particulate inorganic compound and Particulate plastic materials is selected from.

2. the carpet product of claim 1, wherein said vinyl acetate/ethylene copolymer comprises based on C ₁-C ₁₈the vinyl acetate of monocarboxylic acid or the C of ethylenic unsaturated monocarboxylic ₁-C ₁₈the C of ester or ethylenic unsaturated dicarboxylic ₁-C ₁₈the main monomers of one or more extra different non-functional of diester.

3. the carpet product of claim 1, the described vinyl acetate/ethylene copolymer wherein in copolymer dispersion is substantially free of the crosslinkable comonomer part once form described coating layer or adhesive phase generation formaldehyde.

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

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

6. the carpet product of claim 1, wherein vinyl acetate/ethylene copolymer comprises the ethene of 10wt%-32wt%, based on whole main monomers within it.

7. the carpet product of claim 1, the glass transition temperature T of the described vinyl acetate/ethylene copolymer wherein in copolymer dispersion _gfor-25 DEG C to+15 DEG C.

8. the carpet product of claim 1, the glass transition temperature T of the described vinyl acetate/ethylene copolymer wherein in copolymer dispersion _gfor-20 DEG C to+5 DEG C.

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

10. the carpet product of claim 1, vinyl ester copolymers wherein in copolymer dispersion comprise maximum 5wt% can with the extra functional comonomer of main monomers copolymerization, based on whole principal monomers within it, described extra functional comonomer is selected from ethylenic unsaturated acids, or its salt, there is 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 functional comonomer's type.

The carpet product of 11. claims 1, the vinyl acetate/ethylene copolymer wherein in copolymer dispersion comprises the unsaturated bridging property comonomer of the extra ethylenic with epoxy radicals.

The carpet product of 12. claims 11, bridging property comonomer in vinyl copolymer wherein in copolymer dispersion is selected from glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether, and the combination of described bridging property comonomer.

The carpet product of 13. claims 1, wherein except vinyl acetate/ethylene copolymer, this copolymer dispersion contains further by (methyl) acrylic acid C ₁-C ₁₈ester, 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 is formed.

The carpet product of 14. claims 13, wherein except vinyl acetate/ethylene copolymer, this copolymer dispersion contains further by ethyl acrylate, butyl acrylate, 2-EHA, dibutyl maleate, one or more copolymers be combined to form of di-2-ethylhexyl maleate or these esters.

The carpet product of 15. claims 1, the vinyl acetate/ethylene copolymer wherein in copolymer dispersion is substantially free of silylation comonomer.

The carpet product of 16. claims 1, the vinyl acetate/ethylene copolymer wherein in copolymer dispersion is not containing halogenation comonomer.

The carpet product of 17. claims 1, wherein copolymer dispersion is not containing the crosslinking agent of rear interpolation.

The carpet product of 18. claims 1, wherein the Brookfield viscosity of copolymer dispersion is 100-5000mPa.s, and it adopts Brookfield viscosimeter, at 25 DEG C, under 20rpm, adopts suitable spindle to measure.

The carpet product of 19. claims 1; wherein with one or more emulsifying agents based at least 0.5wt% of the whole main monomers in described copolymer, with based on the protective colloid-stabilised described copolymer dispersion of the whole main monomers 0wt%-3wt% in described copolymer.

The carpet product of 20. claims 1; wherein with one or more emulsifying agents based at least 0.5wt% of the whole main monomers in described copolymer, with based on the protective colloid-stabilised described copolymer dispersion of the whole main monomers 0.2wt%-2wt% in described copolymer.

The carpet product of 21. claims 19 or 20, the protective colloid that wherein stable copolymer dispersion uses is polyvinyl alcohol.

The carpet product of 22. claims 1, the stabilising system wherein in copolymer dispersion is substantially free of protective colloid.

The carpet product of 23. claims 1, wherein use 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 alkyl phenol ethoxylate.

The carpet product of 24. claims 1, 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 is measured by ISO 11890-2.

The carpet product of 25. claims 1, wherein when testing according to the operation of ISO 16000-9, relative to toluene reference material, the film formed by copolymer dispersion discharges its TVOC content to the degree being not more than 15 times.

The carpet product of 26. claims 1, the particulate filler wherein in Aquo-composition accounts for the 10wt%-70wt% of dispersion and is selected from granular calcium carbonate and Particulate plastic materials.

The carpet product of 27. claims 1, it is substantially free of polyvinyl chloride and pitch.

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

The carpet product of 29. claims 1, it comprises at least one layer binder coating and at least one deck adhesive phase, and they are different from each other on composition.

The carpet product of 30. claims 1, wherein flex substrate is within it selected from supatex fabric, Woven fabric, unidirectional braided fabric, knit goods and fleece.

The carpet product of 31. claims 1, wherein flex substrate is selected from non-woven polypropylene, polyethylene or polyester, and woven jute, polypropylene or polyamide substrate.

The carpet product of 32. claims 1, wherein flex substrate is within it based on polypropylene or polyamide fiber.

The carpet product of 33. claims 1, based on dry weight, the weight of its unit are is 100g/m ²-3000g/m ².

The carpet product of 34. claims 1, in tufting fixation test, after 20 wash cycle, it demonstrates the tufting dead loss being not more than 40%.

The carpet product of 35. claims 1, in the gross evaluations of carpet sample outward appearance and hand test, after 20 wash cycle, it demonstrate not higher than 3 lining cloth integrity levels and feel grade.

The carpet product of 36. claims 1, it is the anti-slip carpet form of woven anti-slip carpet or tufting, and the distally that described carpet type is trampling side is coated with by the dispersion containing vinyl acetate/ethylene copolymer.

The carpet product of 37. claims 36, when testing T 816om-92 test according to TAPPI, it demonstrates non-skid property, and result needs the maximum drag being more than or equal to 6.0 newton, the sample of mobile described carpet product.