CN104105826A - Carpet products and processes for making same using latex coating compositions - Google Patents

Abstract

Disclosed are carpet products comprising at least one substrate and at least one adhesive layer associated with the at least one substrate, the adhesive layer being formed from a latex coating composition comprising (a) a first copolymer of at least a vinyl ester of an alkanoic acid having from 1 to 13 carbon atoms and ethylene; and (b) a second copolymer of at least styrene and butadiene, wherein the first and second copolymers are colloidally dispersed in an aqueous medium comprising a surfactant. The carpet products are particularly durable exhibiting high tuft bind values.

Description

Carpet product and method of making same using latex coating composition

priority claim

This application claims priority to US Provisional Application No. 61/599,127, filed February 15, 2012, the entire contents of which are hereby incorporated by reference.

field of invention

The present invention relates to latex coating compositions comprising vinyl ester/ethylene copolymer dispersions and styrene/butadiene copolymer dispersions useful in forming carpet products and methods of forming such carpet products.

Background of the invention

Most conventional carpets comprise a first backing having tufts of yarn extending upwardly from the backing in the form of cut or uncut loops to form the pile. For tufted carpet, the yarns are inserted through the tufting needles into a primary backing (usually woven or nonwoven material) and a precoat (ie, adhesive) is applied to it.

Most residential and commercial carpets are also manufactured with a scrim (usually made of polypropylene) called a secondary backing that is taped to the back of the carpet to provide dimensional stability. The scrim is adhered to the back of the pre-coated carpet with another adhesive formulation commonly referred to as a skipcoat or adhesive coat. The run-off coating was applied to a scrim which was subsequently applied to the carpet's pre-coated backing prior to sending the assembled carpet components into a curing oven. The purpose of the run-off paint or adhesive coat is to provide a layer of material that glues the scrim to the back of the carpet.

For precoats and runaway coatings, the physical properties of the binders are important to their successful use as carpet coatings. In this regard, there are a number of important requirements that such coatings must fulfill. The coating must be capable of being applied to carpet and dried using methods and equipment conventionally used in the carpet industry for latex coatings. The adhesive composition must be able to provide excellent bonding to the pile fibers in order to hold them securely in the backing. The coating will also typically have a high filler loading, such as calcium carbonate, clay, aluminum trihydrate, barite, feldspar, cullet, fly ash, and/or recycled carpet backing.

Binders in coating compositions for carpet products are often emulsion polymers, ie latex dispersions, which may contain copolymers of vinyl esters such as vinyl acetate and ethylene. Adhesive and carpet coating compositions based on vinyl ester/ethylene copolymers are disclosed, for example, in US Patent Nos. 4,735,986; 5,026,765; 5,849,389 and 6,359,076 and US Publication No. 2005/0287336, the entire contents of which are incorporated herein by reference. These copolymers are prepared by polymerizing appropriate comonomers in aqueous emulsions. Such emulsions or resulting dispersions can be stabilized by adding customary surfactants (anionic, nonionic or cationic) as emulsifiers. Such emulsions or dispersions can also be stabilized by including protective colloids, for example based on polyvinyl alcohol (PVOH), ionically modified starches, water-soluble starches, starch ethers, polyacrylic acid, carboxymethylcellulose , natural gums, gelatin, synthetic polymers or water-soluble cellulose ethers such as those of hydroxyethylcellulose (HEC).

While a wide variety of carpet coating and adhesive compositions based on stabilized vinyl acetate/ethylene (VAE) latex binders exist, it would be advantageous to identify and select properties that, inter alia, make them useful for preparing textile structures such as carpet products. A desirable balance of properties for a particular type of such adhesive.

There is therefore a need for improved VAE-based coating compositions and methods of making such coating compositions having the desired bond strength characteristics for carpet manufacturing applications.

Summary of the invention

It has now been found that by blending specific vinyl ester/ethylene copolymer dispersions, preferably vinyl acetate/ethylene (VAE) copolymer dispersions, with styrene/butadiene (SB) copolymer dispersions, it is possible to prepare Latex coating compositions having particularly desirable physical properties making them well suited for use in adhesive compositions such as precoats and/or runaway coating adhesives in carpet manufacturing. In particular, the process of the present invention can be used with latex coating compositions to form carpet products having exceptionally high tuft binding values.

In one embodiment, the present invention relates to a carpet product, such as a tufted or woven carpet product, comprising at least one substrate and at least one adhesive layer attached to said at least one substrate, such as directly or indirectly bonded to the substrate , the adhesive layer is formed from an adhesive composition comprising a latex coating composition comprising: (a) at least one vinyl ester of an alkanoic acid having 1 to 13 carbon atoms and ethylene; a copolymer; and (b) a second copolymer of at least styrene and butadiene, wherein the first and second copolymers are colloidally dispersed in an aqueous medium comprising a surfactant. The latex coating composition can be mixed into an adhesive composition that acts as a binder for the precoat and/or run-off coating. Thus, the substrate may comprise a first liner or a second liner. The carpet products of the present invention are preferably particularly durable, exhibiting a pile bind value of greater than 20N, such as greater than 27N.

In one embodiment, the latex coating composition serves as a precoat for bonding carpet fibers, such as pile, to the first backing. For example, in one embodiment, the invention is a method for forming a carpet product comprising the steps of: (a) providing an adhesive composition comprising a latex coating composition comprising: ( i) a first copolymer of at least one vinyl ester of an alkanoic acid having 1 to 13 carbon atoms and ethylene; and (ii) a second copolymer of at least styrene and butadiene, wherein the first and The second copolymer is colloidally dispersed in an aqueous medium comprising a surfactant; (b) contacting carpet fibers, such as tufted yarns, with a first backing material, such as a first tufted substrate or woven material; (c ) applying the adhesive composition to the carpet fibers and a first backing material; and (d) drying the adhesive composition under conditions effective to glue the carpet fibers to the first backing material.

In another embodiment, optionally in combination with the methods described above, the adhesive composition acts as a run-off paint binder in the manufacture of carpet products. For example, in one embodiment, the present invention is directed to a method for forming a carpet product comprising the steps of: (a) providing an adhesive composition comprising a latex coating composition comprising: ( i) a first copolymer of at least one vinyl ester of an alkanoic acid having 1 to 13 carbon atoms and ethylene; and (ii) a second copolymer of at least styrene and butadiene, wherein the first and The second copolymer is colloidally dispersed in an aqueous medium comprising a surfactant; (b) providing a first carpet layer comprising yarns tufted into a first backing; (c) applying the adhesive composition to the On at least one of the first carpet layer or the second backing; (d) contacting the first carpet layer with the second backing; and (e) effective to bond the first carpet layer to the second backing Dry the adhesive composition under certain conditions. The first carpet layer is optionally formed by a method using a pre-coat coating composition optionally comprising an adhesive composition used to secure the first carpet layer to the second backing. The same or similar latex paint composition used.

Detailed description of the invention

The present invention, in one embodiment, relates to latex coating compositions useful as coating and adhesive compositions for incorporation into textile structures, such as carpet products. The latex coating composition comprises a blend of a first copolymer (preferably in the form of a first copolymer dispersion) and a second copolymer (preferably in the form of a second copolymer dispersion). The first copolymer is a copolymer of at least one vinyl ester of an alkanoic acid having 1 to 13 carbon atoms, preferably vinyl acetate, and ethylene, and the second copolymer is a copolymer of at least styrene and butadiene copolymer. When used to form fabrics, the latex coating composition surprisingly and unexpectedly provides particularly desirable adhesive properties, particularly tuft tie values. The latex coating composition is particularly useful as a pre-coat or run-off coating in the formation of carpet products. The present invention thus also relates to carpet products formed using the latex coating compositions of the present invention, and to methods of forming such carpet products.

The relative amounts of the first copolymer and the second copolymer in the blended latex coating composition can depend, for example, on the desired properties of the carpet product and whether the latex coating composition is intended for a precoat, a runaway coating, or both. to change. In one embodiment, the blended latex coating composition comprises the first copolymer in an amount of 30 to 99 wt %, such as 40 to 75 wt %, based on the total weight of all copolymers in the blended latex coating composition, in an amount of 1 to An amount of 70% by weight, eg 25 to 60% by weight, comprises the second copolymer. The latex coating composition for the pre-coat preferably comprises a greater concentration of the first copolymer, optionally comprising the first copolymer in an amount of 50 to 99% by weight, for example 70 to 90% by weight, and 1 to 50% by weight %, for example in an amount of 10 to 30% by weight comprising the second copolymer. Latex coating compositions for leaky coatings preferably comprise a greater concentration of the second copolymer and may, for example, be present in an amount of 25 to 75% by weight, such as 25 to 50% by weight, based on the total weight of all copolymers in the latex coating composition The first copolymer is included and the second copolymer is included in an amount of 25 to 75% by weight, such as 50 to 75% by weight.

In some embodiments, the latex coating compositions of the present invention may include one or more external crosslinkers. Suitable external crosslinkers include carbonates such as ammonium zirconium carbonate (AZC) and potassium zirconium carbonate (KZC). The external crosslinker may optionally be added to the first dispersion and/or the second dispersion either before or after blending the first and second dispersions to form the blended latex coating composition. If present, the external crosslinker may be present in the latex coating composition in an amount of 1 to 10% by weight, such as 3 to 10% by weight, based on the total weight of the blended latex coating composition.

Since they are preferably formed as separate dispersions and subsequently blended together, the second copolymer is preferably not intimately mixed with the first copolymer, although it is conceivable that the external crosslinking agent, if present, can effectively crosslink the first copolymer. The carboxyl group on the copolymer and the carboxyl group on the second copolymer. To the extent that internal crosslinkers are used, it is preferred that such crosslinkers are used to crosslink the first copolymer with itself and/or the second copolymer with itself, but not to internally crosslink the first copolymer with the second copolymer. In one embodiment, the first and second copolymers each include an internal crosslinker, which may be the same or a different type of crosslinker, but such crosslinkers do not internally crosslink the first copolymer with the second copolymer. In another embodiment, the first and second copolymer dispersions, and the resulting blended latex coating composition of the present invention, are substantially free of internal and/or external crosslinkers.

As noted, the first and second copolymers used to form the latex coating compositions described herein are preferably made separately in a first dispersion and a second dispersion, respectively, which are blended together to form the latex coating compositions of the present invention. Latex coating composition. The first and second dispersions are preferably present in the blended latex coating composition in amounts sufficient to provide particularly good carpet strength.

The degree or tenacity to which the yarns are anchored to the carpet backing material is known as the "pile bond" strength. Carpets with sufficient pile bond strength exhibit good abrasion resistance and have a longer service life. In order to have good performance characteristics, the tacky gusset material should substantially penetrate the yarns (fiber bundles) exposed on the backside of the first gusset material and should substantially consolidate the individual fibers in the yarns. Good penetration of the yarn and consolidation of the fibers results in good abrasion resistance. Furthermore, in addition to good tuft bond strength and abrasion resistance, the adhesive material preferably provides or allows good flexibility to the carpet for installation of the carpet. In a preferred embodiment, the blended latex coating composition can be used in an adhesive composition, such as a carpet precoat or a run-off coating adhesive, to form an adhesive having a N of greater than 15 N, such as greater than 20 N or greater than N, as determined by ASTM D-1335. A carpet composition with a Pile Binding Value of 27N. For cut pile carpets, the pile tie value preferably exceeds 2.3 lbs f(10.2N). For loop pile carpets, the pile tie value preferably exceeds 3.5 lbs f (15.6 N), more preferably exceeds 6.25 lbs f (27.8 N) and most preferably exceeds 10 lbs f (44.5 N).

Since tuft binding values can vary depending on the type of carpet, the tuft binding strength can be characterized as "pile binding" relative to a similar carpet formed using a coating composition containing the first dispersion (not blended with the second dispersion). percentage". In this regard, the blended latex coating compositions of the present invention can provide carpets having a pile binding percentage of greater than 125%, greater than 150%, greater than 175%, or greater than 200%.

First and second dispersions containing the first and second copolymers, respectively, can be prepared using conventional emulsion polymerization procedures. Such methods are generally described, for example, in U.S. Patent No. 5,849,389, which is incorporated herein by reference in its entirety, and in Chorng-Shyan Chern, Principles and Applications of Emulsion Polymerization, John Wiley and Sons Inc. (2008), which is incorporated by reference in its entirety. This reference is incorporated herein.

In forming the first and second dispersions, the respective monomers can be polymerized in an aqueous medium in the presence of a catalyst and at least one emulsifier at a pressure not exceeding 100 atmospheres. For either dispersion, the aqueous system can be maintained at a pH of 2 to 6 or 4 to 6 by suitable buffers and the catalyst can be added incrementally or continuously. For the first dispersion, a vinyl ester, such as vinyl acetate, and 50% to 75% of another comonomer (if present) can be suspended in water and stirred thoroughly in the presence of ethylene at working pressure to obtain The solution of ethylene in this mixture is up to the substantial limit of its solubility under the conditions prevailing in the reaction zone. The vinyl acetate and other optional comonomers can then be gradually heated to polymerization temperature. In some embodiments, the first dispersion and/or the second dispersion or the resulting blended latex coating composition of the present invention is free or substantially free of colloidal stabilizers, such as polyvinyl alcohol, optionally containing less than 1.5 pphm of Polyvinyl alcohol, less than 1.0 pphm polyvinyl alcohol, or less than 0.5 pphm polyvinyl alcohol, which has now been found to be generally incompatible with SB dispersions. In other aspects, the first dispersion and/or the second dispersion or the resulting blended latex coating composition of the present invention comprises less than 1.0 wt. % polyvinyl alcohol, or less than 0.5 wt. % polyvinyl alcohol, based on the total weight of monomers . However, it is expected that certain protective colloids, such as hydroxyethyl cellulose, will be compatible with SB dispersions.

The homogenization period is usually followed by a polymerization period during which the catalyst comprising the procatalyst or initiator and possibly the activator is added incrementally or continuously together with the remaining comonomer, if present. The monomers used can be added as pure monomers or as premixed emulsions.

After polymerization, the solids content of the resulting first and/or second dispersion can be adjusted to the desired level by adding water or removing water by distillation. Typically, the desired level of polymer solids content for the first and second dispersions is 40 to 70%, 40 to 60%, or 45 to 55% by weight of the total weight of each dispersion.

The particle size of the first or second dispersion, or the resulting blend of first and second dispersions, can be adjusted by the amount of nonionic or anionic surfactant used. To obtain smaller particle sizes, greater amounts of surfactant are used. As a general rule, the greater the amount of surfactant used, the smaller the average particle size.

The dispersions and coating compositions described herein are optionally substantially free of alkylphenol ethoxylates (APE). For the purposes of this invention, such dispersions and coating compositions are considered to be substantially free of APE if they contain less than 500 wppm of APE. In other embodiments, the dispersion, eg, the first dispersion, the second dispersion, or the resulting blended latex dispersion of the present invention may contain small amounts of APE.

first dispersion

The first dispersion is preferably formed by emulsion polymerization of at least one vinyl ester of an alkanoic acid having 1 to 13 carbon atoms with ethylene and optionally one or more additional comonomers. A non-limiting list of examples of such alkanoic acids include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl 2-ethylhexanoate , vinyl isooctanoate, vinyl nonanoate, vinyl caprate, vinylpivalate, vinyl versatate and mixtures thereof. Of these, vinyl acetate is the preferred monomer due to its availability and low cost. Preferred monomer combinations for the first copolymer include vinyl acetate/ethylene, vinyl acetate/vinyl propionate/ethylene, vinyl acetate/vinyl neodecanoate/ethylene, vinyl acetate/ethylene/vinyl chloride.

Most preferably, the vinyl ester (such as vinyl acetate) content of the first copolymer used in this embodiment will be about 70 to 90 pphm, such as 72 pphm to 88 pphm, 75 pphm to 95 pphm, 75 pphm to 85 pphm, or about 78 pphm to 82 pphm (parts per hundred based on all monomers in the copolymer).

In general, the ethylene content of the first copolymer should be selected to provide a latex coating composition that is particularly effective in formulating an adhesive composition that provides a desirably high bond strength. In some embodiments, the ethylene will comprise from 10 pphm to 30 pphm of the first copolymer, such as from 10 to 25 pphm, from 12 pphm to 20 pphm, or from 18 to 22 pphm. More preferably, ethylene will typically comprise from 5 to 25 pphm of the first copolymer, such as from 5 to 20 pphm or from 8 to 18 pphm. More preferably, ethylene will be present in the first copolymer in an amount from 8 pphm to 16 pphm.

If the first copolymer further comprises a third comonomer, the first copolymer may for example comprise the third monomer in an amount of 0.1 to 10 pphm, eg 0.1 to 5 pphm. Such optional comonomers may for example be selected from vinyl halides such as vinyl chloride, ethylenically unsaturated acids or their salts, having at least one amide, epoxy, hydroxyl, N-methylol, trialkoxysilane or carbonyl ethylenically unsaturated monomers, and a combination of two or more monomers selected from any of the third monomer types. Optional comonomers may also be selected from vinyl esters other than vinyl acetate, alpha-olefins other than ethylene, vinyl aromatics, esters of ethylenically unsaturated monocarboxylic acids, and esters of ethylenically unsaturated dicarboxylic acids. diester.

Preferably, the first copolymer is formed during a surfactant stabilized emulsion polymerization rather than a protective colloid stabilized polymerization. As a result, the average particle size of the first copolymer tends to be smaller than that of the copolymer formed in the presence of the protective colloid. In an exemplary embodiment, the first copolymer has a 50 to 500 nm, e.g., 100 to 400 nm, 150 to 350 nm, or 200 nm measured by a 90 Plus Particle Size Analyzer (Brookhaven Instruments) using a 35 mW solid-state laser at a wavelength of 658 nm at room temperature. to an average particle size of 320nm.

Optionally, the first copolymer further comprises a comonomer that acts as an internal crosslinker. For example, the first copolymer optionally further comprises a polyethylenically unsaturated comonomer selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, diallyl maleate, fumaric acid Diallyl ester, divinylbenzene, diallyl phthalate, silane and glycidyl methacrylate (GMA). Incorporation of one or more of these comonomers can beneficially increase branching or crosslinking, increase molecular weight and improve performance.

In some embodiments, the first copolymer comprises α,β-ethylenically unsaturated C ₃ -C ₁₀ monocarboxylic acids, α,β-ethylenically unsaturated C ₄ -C ₁₀ dicarboxylic acids, and anhydrides thereof , and a crosslinking comonomer of the C ₁ -C ₁₈ alkyl half-ester of an α,β-ethylenically unsaturated C ₄ -C ₁₀ dicarboxylic acid. Exemplary comonomers of this type include acrylic and methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and _C4 - _C8 alkyl half-esters of maleic acid.

In another embodiment, the first copolymer includes a crosslinking comonomer selected from ethylenically unsaturated silane compounds. Exemplary ethylenically unsaturated silane comonomers are disclosed, for example, in PCT Publication WO 2011/139267, which is hereby incorporated by reference in its entirety. Such comonomers generally correspond to substituted silanes of formula I:

wherein R represents an ethylenically unsaturated organic group at the ω-position, and R ¹ , R ² and R ³ , which may be the same or different, represent halogen, preferably chlorine, or the group -OZ, Z representing hydrogen or Primary or secondary alkyl or acyl optionally substituted with alkoxy.

Suitable unsaturated silane compounds of the formula I are preferably selected from the group wherein the radical R in the formula represents an ω-unsaturated alkenyl group of 2 to 10 carbon atoms, in particular of 2 to 4 carbon atoms, or consists of up to 4 Those of omega-unsaturated carboxylic acid esters of unsaturated carboxylic acids with carbon atoms and alcohols with Si groups having up to 6 carbon atoms. Suitable radicals R ¹ , R ² , R ³ are preferably the radical -OZ, Z representing a primary and/or secondary alkyl group of up to 10 carbon atoms, preferably up to 4 carbon atoms, or preferably up to 3 carbon atoms Alkyl substituted by alkoxy, or acyl of up to 6 carbon atoms, preferably up to 3 carbon atoms, or hydrogen. The most preferred unsaturated silane comonomer is vinyltrialkoxysilane.

Examples of preferred silane compounds of formula I include vinyltrichlorosilane, vinylmethyldichlorosilane, gamma-methacryloxypropyltris(2-methoxyethoxy)silane, vinylmethoxy Vinylsilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyldiethoxysilanol, Vinylethoxysilanediol, Allyltriethoxysilane, Vinyltripropoxy Vinyl silane, vinyl triisopropoxy silane, vinyl tributoxy silane, vinyl triacetoxy silane, trimethyl glycol vinyl silane, γ-methacryloxypropyl trimethyl Glycol silane, γ-acryloxypropyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane.

Another group of crosslinking comonomers consists of ethylenically unsaturated monomers containing epoxy groups, for example, allyl glycidyl ether, methacryl glycidyl ether, butadiene monoepoxide, 1, 2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, 8-hydroxy-6,7-epoxy-1-octene, 8-Acetoxy-6,7-epoxy-1-octene, N-(2,3-epoxypropyl)acrylamide, N-(2,3-epoxypropyl)methacrylamide, 4-acrylamidophenyl glycidyl ether, 3-acrylamidophenyl glycidyl ether, 4-methacrylamidophenyl glycidyl ether, 3-methacrylamidophenyl glycidyl ether, N- Glycidyloxymethacrylamide, N-glycidyloxypropylmethacrylamide, N-glycidyloxyethylacrylamide, N-glycidyloxyethylmethacrylamide, N-glycidyl Oxypropyl acrylamide, N-glycidyloxypropyl methacrylamide, N-glycidyloxybutyl acrylamide, N-glycidyloxybutyl methacrylamide, 4-acrylamidomethyl- 2,5-Dimethylphenyl glycidyl ether, 4-methacrylamidomethyl-2,5-dimethylphenyl glycidyl ether, acrylamidopropyl dimethyl (2,3-cyclo oxypropyl) ammonium chloride, methacrylamidopropyl dimethyl (2,3-epoxypropyl) ammonium chloride and glycidyl methacrylate.

The aforementioned crosslinking comonomer, if any, will typically be present in the first copolymer in an amount from 0.05 pphm to 5 pphm, for example 0.05 to 1 pphm or 0.05 pphm to 0.5 pphm. More preferably, such polyethylenically unsaturated comonomers/crosslinkers (if any) will be used in the first copolymer in an amount of 0.2 pphm to 0.8 pphm.

The first copolymer prepared herein and used in the latex coating composition can have both amorphous and crystalline ethylene segments. The content of amorphous ethylene segments in the copolymer is determined by the glass transition temperature (Tg) of the copolymer.

According to one embodiment, the first copolymer of the dispersions made herein may be prepared for use in carpet manufacture to have a Tg of from about -10°C to about 20°C, for example from about -10°C to about 15°C. In certain aspects, the Tg can be from -5°C to 5°C. In other aspects, the first dispersion can be prepared to have a Tg of about +5°C to about +15°C, preferably about +8°C to +10°C. The Tg of the first copolymer can be controlled by adjusting the ethylene content, ie generally, the more ethylene present in the polymer relative to other comonomers, the lower the Tg.

Dispersions comprising the first copolymer described above can be prepared using conventional emulsion polymerization methods, which are capable of preparing dispersions in the form of aqueous latexes. Such methods are described, for example, in US Patent No. 5,849,389, the disclosure of which is hereby incorporated by reference in its entirety.

In a typical polymerization process, the vinyl ester, preferably vinyl acetate, and ethylene and optionally one or more additional third comonomers can be reacted under a pressure not exceeding 100 atmospheres over a catalyst and at least one polymerized in aqueous medium in the presence of an emulsifier. The aqueous volume can be maintained at a pH of 2 to 6 by suitable buffers and the catalyst can be added incrementally or continuously. More specifically, vinyl acetate and 50% to 75% of another comonomer (if present) can be suspended in water and stirred thoroughly in the presence of ethylene under working pressure to obtain a solution of ethylene in the mixture Up to the substantial limit of its solubility under the conditions present in the reaction zone. The vinyl ester, such as vinyl acetate, and other comonomers, if present, can then be gradually heated to polymerization temperature.

As noted above, the homogenization period is usually followed by a polymerization period during which the catalyst comprising the procatalyst or initiator and which may include an activator is incrementally or continuously mixed with the remaining comonomer (if present), e.g. One or more third comonomers are added together. If used, one or more third comonomers may be added as neat monomers or as a pre-mixed emulsion.

Suitable polymerization catalysts for forming the first dispersion include the water-soluble free radical formers described above and commonly used in emulsion polymerization, such as hydrogen peroxide, sodium, potassium and ammonium persulfate, and tertiary Butyl hydroperoxide, optionally in an amount of 0.01% to 3% by weight, preferably 0.01% to 1% by weight, of the total amount of the emulsion. The catalyst can be used together with a reducing agent such as sodium formaldehyde sulfoxylate, ferrous salt, sodium dithionite, sodium bisulfite, sodium sulfite, sodium thiosulfate, ascorbic acid, erythorbic acid or its salt in the amount of 0.01% by weight to 3% by weight of the total amount of the emulsion. % by weight, preferably in amounts of 0.01% to 1% by weight, are used as redox catalysts. The radical former can be loaded in an aqueous emulsifier solution or dosed during polymerization. In a preferred embodiment, the reducing agent Bruggolite FF6 ^™ is used in the polymerization process. FF6 contains three sulfur-based reducing agents: (i) 2-hydroxy-S-sulfinyl acetate disodium salt (50-60%); (ii) sodium sulfite (30-35%); and (iii) 2- Hydroxy-2-sulfoacetic acid disodium salt (10-15%).

The way of combining the polymerization components can be carried out by various known monomer feeding methods, such as continuous monomer addition, incremental monomer addition or adding the whole amount of monomer at once. The entire amount of aqueous medium containing polymerization additives may be present in the polymerization vessel prior to introduction of the monomers, or the aqueous medium, or a portion thereof, may be added continuously or incrementally during the course of the polymerization reaction.

The emulsion polymerization process for the preparation of the first copolymer in the form of an aqueous latex is preferably carried out in the presence of a stabilizing system comprising one or more anionic and/or nonionic surfactants as emulsifiers .

Suitable nonionic surfactants that may be used as emulsifiers in the emulsion stabilization system of the coating compositions herein include polyoxyethylene condensates. Such ethoxylated nonionic surfactants for stabilizing the adhesive dispersions of the present invention preferably exclude alkylphenol-based ethoxylated nonionic surfactants. Exemplary polyoxyethylene condensates that can be used include polyoxyethylene aliphatic ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; polyoxyethylene alkaryl ethers such as polyoxyethylene nonylphenol ether and polyoxyethylene Vinyl octylphenol ether; polyoxyethylene esters of higher fatty acids, such as polyoxyethylene laurate and polyoxyethylene oleate, and condensates of ethylene oxide with resin acids and tall oleic acid; polyoxyethylene amides And amine condensates, such as N-polyoxyethylene laurylamide, and N-lauryl-N-polyoxyethyleneamine, etc.; and polyoxyethylene sulfides, such as polyoxyethylene n-dodecyl sulfide.

Nonionic surfactants that may be used also include a series of surfactants available from BASF under the tradenames Pluronic ^™ and Tetronic ^™ . Pluronic surfactants are ethylene oxide (EO)/propylene oxide (PO)/ethylene oxide block copolymers prepared by the controlled addition of PO to the two hydroxyl groups of propylene glycol. EO is then added to sandwich the hydrophobic segment between two hydrophilic groups, controlled by length to constitute 10% to 80% (w/w) of the final molecule. Pluronic surfactants are PO/EO/PO block copolymers prepared by adding EO to ethylene glycol to provide a hydrophilic segment of designed molecular weight. PO is then added to obtain a hydrophobic block on the outside of the molecule. Tetronic surfactants are tetrafunctional block copolymers derived from the sequential addition of EO and PO to ethylenediamine. Tetronic surfactants are manufactured by the sequential addition of EO and PO to ethylenediamine. Furthermore, a series of ethylene oxide adducts of acetylenic diols sold under the tradename Surfynol ^™ by Air Products are also suitable as nonionic surfactants.

Suitable anionic surfactants useful as emulsifiers in the binder latex component of the carpet coating compositions described herein include alkylaryl sulfonates, alkali metal alkyl sulfates, sulfonated alkyl esters and fatty acid soaps. Specific examples include sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate, sodium lauryl sulfate, disodium dodecyldiphenyl ether disulfonate, N-octadecylsulfosuccinate and Sodium Dioctyl Sulfosuccinate. The surfactant is used in an amount effective to achieve proper emulsification of the polymer in the aqueous phase and to provide the desired particle size and particle size distribution. Other ingredients known in the art to be useful for various specific purposes in emulsion polymerization, such as acids, salts, chain transfer agents and chelating agents, may also be used in the preparation of the polymers. For example, if the polymerizable constituents comprise monoethylenically unsaturated carboxylic acid monomers, polymerization under acidic conditions (pH 2 to 7, preferably 2 to 5) is preferred. In such cases, the aqueous medium can include those known weak acids and salts thereof that are commonly used to provide a buffer system at the desired pH range.

Conventionally, instead of or in addition to surfactant emulsifiers, various protective colloids have been used to stabilize vinyl acetate/ethylene emulsions of the type described above. For dispersions to be used in fabric construction, up to about 2% by weight of protective colloids such as cellulose ethers or other conventional protective colloid forming materials may be used. The use of hydroxyethyl cellulose, for example, may be acceptable or desirable in combination with one or more surfactants. The dispersions used for this purpose can also be substantially free of protective colloids. In some embodiments, the first dispersion, the second dispersion, and/or the blended latex coating composition of the present invention are free or substantially free of polyvinyl alcohol, optionally containing less than 1.5 pphm of polyvinyl alcohol, less than 1 pphm polyvinyl alcohol or less than 0.5pphm polyvinyl alcohol. In other embodiments, small amounts of polyvinyl alcohol may be used as long as it does not render the first dispersion incompatible with the second dispersion. For example, in some embodiments, in latex coating compositions used to form textile structures such as tufted carpets, the first dispersion may comprise about 1 to 2% by weight polyvinyl alcohol.

As noted above, the first copolymer in the dispersions prepared herein may generally have a value of 50 to 500 nm, for example 100 to Average particle size dw of 400 nm, 150 to 350 nm, 150 to 200 nm or 200 to 320 nm. The copolymers prepared in the dispersion for tufted carpets may have an average particle size dw of 200 to 600 nm. The viscosity of the dispersion can vary widely, in some respects from 50 to 400 mPas, or can be greater, perhaps from 400 to 1,600 mPas, as measured with a Brookfield viscometer at 25°C.

second dispersion

The second dispersion is preferably formed by emulsion polymerization of at least styrene with butadiene (SB) and optionally one or more additional comonomers such as acrylonitrile (SBA) or acrylic comonomers.

As described above for the first copolymer, the second copolymer optionally further comprises a comonomer that acts as an internal crosslinker. For example, the second copolymer optionally further comprises a polyethylenically unsaturated comonomer selected from triallyl cyanurate, triallyl isocyanurate, diallyl maleate, fumaric acid Diallyl esters, divinylbenzene, and diallyl phthalate. Preferred comonomers of this type include diallyl maleate, diallyl fumarate and diallyl phthalate. Polyethylenically unsaturated comonomers of this type, if present, are typically present in the second copolymer in an amount of 0.05 pphm to 0.5 pphm. More preferably, such polyethylenically unsaturated comonomers/crosslinkers (if any) will be used in the second copolymer in an amount of 0.1 pphm to 0.3 pphm.

The method of making the second dispersion prior to blending can vary depending on whether the second polymer is SB or SBA. In general, such second dispersions can be formed by well-known emulsion polymerization techniques, exemplary methods for which are disclosed, for example, in US Patent Nos. 5,288,787; 5,326,853; 5,362,798; and 6,365,647, the entire contents of which are incorporated herein by reference. The catalyst used to form the second dispersion may be selected from those described above in connection with forming the first dispersion.

Raw materials used to form the second dispersion typically include, for example, monomers (styrene and butadiene for SB, or styrene, butadiene and acrylonitrile for SBA), water, emulsifiers, initiator systems, modified Antioxidants, free radical scavengers (such as dimethyl dithiocarbamate or diethylhydroxylamine) and stabilizer systems. The polymerization process can be carried out batchwise or continuously. In a continuous process, the monomers are metered into the reactor chain and emulsified together with emulsifiers and catalysts. The initiator system may be, for example, a redox reaction between chelated iron and an organic peroxide using a reducing agent such as sodium formaldehyde sulfoxide (SFS). Alternatively, potassium peroxodisulfate can be used as the initiator. The process can be carried out as a cold polymerization process or as a hot polymerization process. Mercaptan chain transfer agents can be used to provide free radicals and control molecular weight distribution. During polymerization, reaction conditions such as temperature, flow and agitation can be controlled to provide the desired level of conversion.

The relative amounts of monomers of the second dispersion can also vary widely. In embodiments where the second polymer is SB, styrene may be present in an amount of 20 to 80 pphm, and butadiene may be present in an amount of 20 to 80 pphm. In other embodiments, styrene may be present in an amount of 5 to 50 pphm, 10 to 40 pphm, or 20 to 30 pphm, and butadiene may be present in an amount of 50 to 95 pphm, 60 to 90 pphm, or 70 to 80 pphm, based on the second dispersion All monomers in the body. Larger ratios of styrene to butadiene are also possible. The styrene may, for example, be present in an amount of 40 to 75 pphm, 55 to 70 pphm, or 60 to 65 pphm of the total monomers in the second dispersion, and the butadiene may be present in an amount of 25 to 60 pphm, 30 to 45 pphm, or 35 to 40 pphm .

When the second polymer is SBA, styrene may be present, for example, in amounts of 30 to 70 pphm, 40 to 60 pphm, or 45 to 55 pphm, butadiene may be present in amounts of 1 to 40 pphm, 5 to 30 pphm, or 10 to 25 pphm, propylene The nitrile may be present in an amount of 5 to 45 pphm, 15 to 35 pphm, or 20 to 30 pphm, all based on total monomer in the second dispersion. For a further description of SBAs and methods of making SBAs see Harper C.A., Handbook of Plastic and Elastomers, McGraw-Hill, New York (1975), which is hereby incorporated by reference in its entirety.

Adhesive composition

The fabric structures herein typically have the latex coating composition of the present invention mixed therein as part of the adhesive composition. Such adhesive compositions may contain various conventional additives in addition to the latex coating compositions described hereinabove to modify their properties. Among them, these additives may include fillers, thickeners, catalysts, foaming agents, dispersants, colorants, bactericides, defoamers and the like. Fabric structures containing adhesive compositions prepared from the latex coating compositions described herein may have a weight per unit area of about 1000 to 4000 grams per square meter, such as 1000 to 3000 grams per square meter.

The viscosity of the adhesive composition can vary widely, depending primarily on the desired use of the composition. In a general aspect, the adhesive composition may have a viscosity of 2,000 to 60,000 cP. Lower viscosities, such as 4000 to 15000 cP, may be preferred for adhesive compositions for precoat applications. For run-off coating applications, viscosities of 10,000 to 18,000 cP may be required for coaters using the roll or pan method, and viscosities of 25,000 to 45,000 cP may be required for Tilitson type coaters. The latex coating composition or adhesive composition described herein may also contain sufficient base to maintain a pH of 6 to 10, more preferably 7 to 9.

Thus, in another embodiment, the present invention is directed to an adhesive composition, preferably a carpet precoat or run-off paint adhesive, comprising an aqueous surfactant stabilized copolymer latex coating composition, and sufficient to achieve 6 a base having a pH of 10 to 10, the latex coating composition has dispersed therein a first copolymer of alkanoic acid and ethylene having 1 to 13 carbon atoms and a second copolymer of at least styrene and butadiene, Wherein the latex coating composition is stabilized with anionic and/or nonionic emulsifiers. Preferably, the latex coating composition is formed as a blend of a first dispersion comprising a VAE copolymer as described above and a second dispersion comprising at least styrene and butadiene. The composition is preferably substantially free of APEs.

The latex coating compositions of the present invention, and the performance of such latex coating compositions in carpet compositions, are described by the following non-limiting examples.

Example 1-4

Several blended latex coating compositions were prepared by blending various VAE dispersions as shown in Table 1 with SB dispersions in different ratios to test their compatibility with each other. The SB dispersion used in Examples 1-4 was Rovene 4487 (Mallard Creek Polymers), which had a solids content of 54.5 to 55.5% by weight, a weight ratio of styrene to butadiene of about 62:38, 200 to Brookfield viscosity of 1500 cps and Tg of about +11°C.

Formulations and ratios are provided in Table 1 for Examples 1-4. As shown in Table 1, each example was run with a different VAE and/or SB and at several different VAE:SB ratios and different filler loadings. Examples 1-4 also included an unblended VAE-based adhesive with an unblended SB-based adhesive for comparison. All amounts shown in the tables are dry parts by weight.

As shown in Table 2, various viscosity measurements were made for each example to determine VAE/SB compatibility. Initial viscosity reflects the viscosity of the blended adhesive prior to the addition of fillers. The final viscosities included fillers in the amounts shown in Table 1. After the filler was added, the blended adhesive was allowed to stand without agitation at ambient conditions for 24 hours and the 24-hour unstirred viscosity was measured, followed by stirring for approximately 5 minutes and the 24-hour stirred viscosity measured. Table 2 also shows the amount of thickener (sodium polyacrylate thickener, CT1015) added to the different adhesive formulations.

Because of its exceptionally high initial viscosity, 3.2 grams of water were added to Example 4B without any thickener. The high initial viscosity of Example 4B when compared to the other examples indicates that the surfactant stabilized VAE dispersion is surprisingly and unexpectedly more compatible with SB than the PVOH stabilized VAE dispersion. The results presented in Table 2 show that polyvinyl alcohol stabilized VAE cannot be the same as SB. Blends with higher viscosities (indicative of instability) were not tested further for precoat compound stability.

Blends with acceptable viscosities were then formulated with pre-coat adhesives according to the formulations shown in Table 3.

The precoat adhesive was formed to a solids level of 84% by weight and a target viscosity of 9000-10,000 cPs. Once formed, this precoat adhesive is applied as a precoat to Beaulieu carpet (made of 300 denier polypropylene fibers) at a target coat weight of approximately 22-24oz/sq yd (746-813 grams per square meter). , The fiber surface weight is 20oz/sq yd (678 grams/square meter)). The resulting precoat adhesive was then dried and the carpet samples were tested for tuft binding values and the results are reported in Table 4.

As shown in Table 4, several blended precoat adhesives, particularly those of Examples IB and 3B, exhibited particularly surprising and unexpected high tuft attachment values.

Example 5

In Example 5A, several VAE/SB dispersions were prepared from two different VAEs and two different SBs in different ratios. The VAE (VAE1) in Example 5A was stabilized with 2.5 parts by weight of surfactant and 2.5 parts by weight of polyvinyl alcohol, while the VAE (VAE2) in Example 5B was stabilized with 4.5 parts by weight of polyvinyl alcohol and 0.5 parts by weight of Surfactant stabilization. Viscosity measurements were then obtained over time to determine the relative stability of the dispersion blend. Relative composition and viscosity results are provided in Tables 5 and 6 for Examples 5A and 5B, respectively. Without wishing to be bound by theory, the high polyvinyl alcohol of the VAE in Example 5B appears to increase the viscosity of the resulting dispersion blend, reflecting the increased incompatibility with SB.

While exemplary embodiments of the present disclosure have been described in detail, it is to be understood that various other modifications will be apparent to those skilled in the art and can be readily made without departing from the spirit and scope of the present disclosure. Accordingly, the scope of the appended claims is not intended to be limited to the examples and description given herein, but the claims should be construed to cover all features of novelty which are present in this disclosure, including the All features are treated as equivalents by those skilled in the art.

Claims (53)

1. carpet product, comprises at least one substrate and at least one adhesive layer being connected with described at least one substrate, and described adhesive layer is formed by latex paint composition, and described latex paint composition comprises:

(a) at least one has the vinyl esters of alkanoic acid and first copolymer of ethene of 1 to 13 carbon atom; With

(b) the second copolymer of styrene and butadiene at least, wherein this first and second copolymers colloidal state is dispersed in the aqueous medium that comprises surfactant.

2. carpet product according to claim 1, at least one adhesive layer being wherein connected with at least one substrate is that carpet fiber is bonded to this suprabasil precoated shet.

3. carpet product according to claim 1, at least one adhesive layer being wherein connected with at least one substrate is that the first backing layer is bonded to the race holiday bed of material on the second backing layer.

4. according to the carpet product described in aforementioned claim any one, there is the tuft bind value that is greater than 20N.

5. according to the carpet product described in aforementioned claim any one, there is the tuft bind value that is greater than 27N.

6. according to the carpet product described in aforementioned claim any one, there is the tuft bind percentage as defined herein that is greater than 150%.

7. according to the carpet product described in aforementioned claim any one, wherein this first copolymer exists with the amount of 30 to 99 % by weight, and this second copolymer exists with the amount of 1 to 70 % by weight.

8. according to the carpet product described in aforementioned claim any one, wherein this first copolymer exists with the amount of 40 to 75 % by weight, and this second copolymer exists with the amount of 25 to 60 % by weight.

9. according to the carpet product described in aforementioned claim any one, wherein this first copolymer is to have vinyl esters, ethene and the acrylic monomers of alkanoic acid of 1 to 13 carbon atom or the copolymer of its ester.

10. according to the carpet product described in claim 1-8 any one, the copolymer that wherein this first copolymer comprises vinyl acetate, vinyl neodecanoate and ethene.

11. according to the carpet product described in claim 1-8 any one, and wherein this first copolymer comprises 75 to 95pphm vinyl acetate and 5 to 25pphm ethene.

12. according to the carpet product described in aforementioned claim any one, and wherein this first copolymer has 100 to 400nm the particle mean size that uses by 90 Plus Particle Size Analyzer that the 35mW solid-state laser of 658 nano wave lengths at room temperature measures.

13. according to the carpet product described in aforementioned claim any one, and wherein this second copolymer comprises 20 to 80pphm styrene and 20 to 80pphm butadiene.

14. according to the carpet product described in claim 1-12 any one, the copolymer that wherein this second copolymer is styrene, butadiene and acrylonitrile.

15. according to the carpet product described in aforementioned claim any one, wherein this first copolymer or this second copolymer further comprise polyenoid and belong to unsaturated comonomer, and this monomer is selected from triallyl cyanurate, triallyl isocyanurate, diallyl maleate, diallyl fumarate, divinylbenzene, diallyl phthalate, silane and GMA.

16. according to the carpet product described in aforementioned claim any one, wherein this adhesive layer further comprises filler, and described filler is selected from the combination of kaolin, calcium carbonate, aluminum trihydrate ATH, recirculation filler, cullet, silica, flying dust and described filler.

17. according to the carpet product described in aforementioned claim any one, and wherein this latex paint composition is stable with at least one anionic or nonionic surface active agent.

18. according to the carpet product described in aforementioned claim any one, and wherein this latex paint composition has the solid content of 40 to 70 % by weight.

19. according to the carpet product described in aforementioned claim any one, the blend that wherein this latex paint composition comprises the first dispersion that contains the first copolymer and the second dispersion that contains the second copolymer.

20. according to the carpet product described in aforementioned claim any one, and wherein this first dispersion comprises the polyvinyl alcohol that is less than 1.0pphm.

21. according to the carpet product described in aforementioned claim any one, and wherein this first dispersion comprises the polyvinyl alcohol that is less than 0.5pphm.

22. according to the carpet product described in claim 1-19 any one, the polyvinyl alcohol that is less than 1.0 % by weight that wherein this first dispersion comprises all total monomer weights.

23. according to the carpet product described in aforementioned claim any one, and wherein this first and second copolymer does not mix closely.

24. according to the carpet product described in aforementioned claim any one, and wherein this adhesive compound has 2,000 to 60,000cP viscosity.

25. according to the carpet product described in aforementioned claim any one, and wherein this latex paint composition has after 48 hours and to improve the final viscosity as defined herein that is no more than 50%.

26. according to the carpet product described in aforementioned claim any one, and wherein this latex paint composition further comprises hydroxyethylcellulose.

27. form the method for carpet product, and the method comprises the following steps:

(a) provide the adhesive compound that comprises latex paint composition, described latex paint composition comprises:

(i) at least one has the vinyl esters of alkanoic acid and first copolymer of ethene of 1 to 13 carbon atom; With

(ii) the second copolymer of styrene and butadiene at least, wherein this first and second copolymers colloidal state is dispersed in the aqueous medium that comprises surfactant;

(b) make carpet fiber contact with the first wadding material;

(c) apply this adhesive compound to this carpet fiber and the first wadding material; With

(d) dry this adhesive compound under the condition that effectively carpet fiber is glued to the first wadding material.

28. methods according to claim 27, wherein this carpet product has the tuft bind value that is greater than 20N.

29. methods according to claim 27, wherein this carpet product has the tuft bind value that is greater than 27N.

30. according to the method described in claim 27-29 any one, and wherein this carpet product has the tuft bind percentage as defined herein that is greater than 150%.

31. according to the method described in claim 27-30 any one, and wherein this first copolymer exists with the amount of 30 to 99 % by weight, and this second copolymer exists with the amount of 1 to 70 % by weight.

32. according to the method described in claim 27-31 any one, and wherein this first copolymer exists with the amount of 40 to 75 % by weight, and this second copolymer exists with the amount of 25 to 60 % by weight.

33. according to the method described in claim 27-32 any one, the copolymer that wherein this first copolymer comprises vinyl acetate, vinyl neodecanoate and ethene.

34. according to the method described in claim 27-32 any one, and wherein this first copolymer is to have vinyl esters, ethene and the acrylic monomers of alkanoic acid of 1 to 13 carbon atom or the copolymer of its ester.

35. according to the method described in claim 27-32 any one, and wherein this first copolymer comprises 75 to 95pphm vinyl acetate and 5 to 25pphm ethene.

36. according to the method described in claim 27-35 any one, and wherein this first copolymer has 100 to 400nm the particle mean size that uses by 90 Plus Particle Size Analyzer that the 35mW solid-state laser of 658 nano wave lengths at room temperature measures.

37. according to the method described in claim 27-36 any one, the copolymer that wherein this second copolymer is styrene, butadiene and acrylonitrile.

38. according to the method described in claim 27-36 any one, and wherein this second copolymer comprises 20 to 80pphm styrene and 20 to 80pphm butadiene.

39. according to the method described in claim 27-38 any one, wherein this first copolymer or this second copolymer further comprise polyenoid and belong to unsaturated comonomer, and this monomer is selected from triallyl cyanurate, triallyl isocyanurate, diallyl maleate, diallyl fumarate, divinylbenzene, diallyl phthalate, silane and GMA.

40. according to the method described in claim 27-39 any one, wherein this adhesive compound further comprises filler, and described filler is selected from the combination of kaolin, calcium carbonate, aluminum trihydrate ATH, recirculation filler, cullet, silica, flying dust and described filler.

41. according to the method described in claim 27-40 any one, and wherein this latex paint composition is stable with at least one anionic or nonionic surface active agent.

42. according to the method described in claim 27-41 any one, and wherein this latex paint composition has the solid content of 40 to 70 % by weight.

43. according to the method described in claim 27-42 any one, the blend that wherein this latex paint composition comprises the first dispersion that contains the first copolymer and the second dispersion that contains the second copolymer.

44. according to the method described in claim 27-43 any one, and wherein this first dispersion comprises the polyvinyl alcohol that is less than 1.0pphm.

45. according to the method described in claim 27-43 any one, and wherein this first dispersion comprises the polyvinyl alcohol that is less than 0.5pphm.

46. according to the method described in claim 27-43 any one, the polyvinyl alcohol that is less than 1.0 % by weight that wherein this first dispersion comprises all total monomer weights.

47. according to the method described in claim 27-46 any one, and wherein this first and second copolymer does not mix closely.

48. according to the method described in claim 27-47 any one, and wherein this adhesive compound has 2,000 to 60,000cP viscosity.

49. according to the method described in claim 27-48 any one, and wherein this latex paint composition has after 48 hours and to improve the final viscosity as defined herein that is no more than 50%.

50. according to the method described in claim 27-49 any one, and wherein this latex paint composition further comprises hydroxyethylcellulose.

51. form the method for carpet product, and the method comprises the following steps:

(a) provide the adhesive compound that comprises latex paint composition, described latex paint composition comprises:

(i) at least one has the vinyl esters of alkanoic acid and first copolymer of ethene of 1 to 13 carbon atom; With

(ii) the second copolymer of styrene and butadiene at least, wherein this first and second copolymers colloidal state is dispersed in the aqueous medium that comprises surfactant;

(b) provide and comprise first carpet layer of tufting to the yarn in the first wadding material;

(c) this adhesive compound is applied at least one of this first carpet layer or the second wadding;

(d) this first carpet layer is contacted with the second wadding; With

(e) dry this adhesive compound under the condition that effectively the first carpet layer is glued to the second wadding.

52. according to the method for claim 51, and wherein precoated shet bonds to yarn on this first wadding material.

53. according to the method for claim 51, and wherein this precoated shet comprises identical latex paint composition as this adhesive compound.