EP0511469A1 - Flat textile product reinforced with polyamide - Google Patents

Flat textile product reinforced with polyamide Download PDF

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Publication number
EP0511469A1
EP0511469A1 EP92103430A EP92103430A EP0511469A1 EP 0511469 A1 EP0511469 A1 EP 0511469A1 EP 92103430 A EP92103430 A EP 92103430A EP 92103430 A EP92103430 A EP 92103430A EP 0511469 A1 EP0511469 A1 EP 0511469A1
Authority
EP
European Patent Office
Prior art keywords
textile fabrics
fabrics according
polyamide
weight
paste
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP92103430A
Other languages
German (de)
French (fr)
Inventor
Armin Stei
Ulrich Simon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huels AG
Original Assignee
Huels AG
Chemische Werke Huels AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huels AG, Chemische Werke Huels AG filed Critical Huels AG
Publication of EP0511469A1 publication Critical patent/EP0511469A1/en
Withdrawn legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
    • D06N3/0093—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin by applying resin powders; by sintering
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/125—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
    • D06N7/0063—Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf
    • D06N7/0071—Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf characterised by their backing, e.g. pre-coat, back coating, secondary backing, cushion backing
    • D06N7/0076—Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf characterised by their backing, e.g. pre-coat, back coating, secondary backing, cushion backing the back coating or pre-coat being a thermoplastic material applied by, e.g. extrusion coating, powder coating or laminating a thermoplastic film
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/065—Polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2205/00—Condition, form or state of the materials
    • D06N2205/04—Foam
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2205/00—Condition, form or state of the materials
    • D06N2205/10—Particulate form, e.g. powder, granule
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/06—Building materials
    • D06N2211/063—Wall coverings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/26—Vehicles, transportation
    • D06N2211/263—Cars

Definitions

  • the invention relates to textile fabrics that are bound and optionally laminated.
  • the invention further relates to processes for their preparation and their use.
  • a characteristic of textile fabrics is their construction from materials of different chemical origins. They also have in common that they require a coating or finish to bind, solidify, reinforce and optimize their properties.
  • a tufted carpet mainly consists of a z. B. polyamide pole material, a primary carrier mostly made of polyolefin fibers (rare polyester), a coating for base coat and lamination based on styrene / butadiene copolymers containing carboxyl groups, which are mixed with fillers (chalk, etc.) and additives (dispersants, anti-aging agents, etc.).
  • a foam coating based on styrene-butadiene copolymers can be used in conjunction with vulcanization aids, fillers, and additives.
  • binders e.g. B. based on isocyanate / polydiol, bitumen, polyolefins are known.
  • the predominantly used binders based on copolymer dispersions made of styrene and butadiene contain small residual amounts of volatile components in the form of hydrocarbons.
  • vulcanization aids are required that form fission products during vulcanization.
  • the volatile components and fission products may be perceptible in terms of smell and lead to unpleasant smells at the end user.
  • the object of the present invention was to produce textile fabrics which, on the one hand, are free from odor impairments and, on the other hand, are recyclable.
  • the goal is achieved in that the fibers are strengthened by thermoplastic polyamides.
  • solidify not only includes all measures that serve for the basic mechanical stabilization of textile fabrics, such as. B. tying tufted carpets, needle fleece or the like, but also all measures that contribute to further improving the property profile, such as. B. the lamination of carpets.
  • Polyamides used as binders are (co) condensation products of diamines, dicarboxylic acids and alpha, omega-aminocarboxylic acids or the lactams derived therefrom or mixtures thereof. Copolyamides are particularly preferred.
  • Suitable are all diamines of the general formula NH2-R-NH2, where R is an unbranched or branched (cyclo) aliphatic radical which optionally interrupted by one or more identical or different heteroatoms (e.g. N, O, S).
  • R is an unbranched or branched (cyclo) aliphatic radical which optionally interrupted by one or more identical or different heteroatoms (e.g. N, O, S).
  • heteroatoms e.g. N, O, S
  • Examples of such compounds are diethylenetriamine, triethylenetetramine, diaminoethyl ether or the like.
  • Cycloaliphatic diamines such as, for. B. piperazine or isophoronediamine can be used. Ethylene diamine, hexamethylene diamine, 2-methylpentamethylene diamine and piperazine are the most commonly used.
  • Suitable dicarboxylic acids are compounds of the general formula HOOC-R'-COOH, where R 'is an unbranched or branched aliphatic radical. Examples include adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and dimer fatty acids. Adipic acid, dodecanedioic acid and dimer fatty acids are particularly preferred.
  • lactams used to produce (co) polyamides are e.g. B. caprolactam, laurolactam and the derived alpha, omega-aminocarboxylic acids such. B. aminoundecanoic acid.
  • the (co) polyamides used according to the invention and their preparation are known (DE-PSS 12 53 449, 15 94 233, 19 39 758, 23 24 160; DE-OSS 25 09 791, 34 41 708; US-PSS 3 515 702, 4,661,585).
  • the melting points of the (co) polyamides used have a maximum value of 170 ° C., preference is given to those (co) polyamides with melting points of not greater than 140 ° C.
  • the molecular mass of the (co) polyamides used is generally in a range from 1.3 to 1.8, preferably between 1.4 and 1.6.
  • the (co) polyamides can, for example, be applied to the textile fabrics in the form of pastes, powders, foils, nets or molten masses.
  • the pastes can optionally be in foamed form. It is also possible that the coating consists of a combination of the application forms mentioned. However, the invention is not limited to the aforementioned forms of use.
  • the agents according to the invention are preferably used as paste - compact or in foamed form.
  • a paste essentially consists of (co) polyamide powder, water, thickeners and dispersants, optionally plasticizers based on toluene or benzenesulfonic acid amides together (DE-PSS 22 29 308, 37 40 155, DE patent application file number P 40 06 766.1, U.S. Patent 3,956,213).
  • the (co) polyamide is present in the paste at 10 to 60% by weight, coating pastes with 20 to 40% by weight (co) polyamide are particularly preferred.
  • the grain diameter of the (co) polyamides used in the pastes is in the range from 10 to 500 ⁇ m, preferably between 10 and 80 ⁇ m. If the (co) polyamides are used as dry powders, the grain diameter is in the range from 200 to 500 ⁇ m, preferably 200 to 300 ⁇ m.
  • the coating pastes according to the invention can contain 8 to 15% by weight, preferably 10 to 12% by weight, of dispersant, 0.5 to 1.0% by weight, preferably 0.5 to 0.8% by weight, of thickeners and 5 to 12 wt .-%, preferably 5 to 8 wt .-%, contain plasticizers.
  • the paste may also contain other common auxiliaries.
  • the rest, 100% by weight, is water. The proportion of water is to be dimensioned such that the coating paste has a viscosity in the range from 1,000 to 2,000 mPas.s, preferably 1,000 to 1,500 mPas.s.
  • the coating paste can be applied compactly or foamed to consolidate the pole material, for capillary consolidation or to laminate the secondary back on the machines available in industry.
  • the application weight (calculated as solid) for the base coat is in the range from 75 to 300 g / m2, preferably from 100 to 250 g / m2.
  • an application weight of 50 to 250 g / m2, preferably 75 to 150 g / m2, of solid is required.
  • the solid portion is the portion of the paste that does not evaporate during the drying process.
  • the coating paste is applied using a doctor blade on the back of the z.
  • the drying and sintering temperature should be approx. 20 ° C above the melting temperature of the polyamide used.
  • the textile lamination material is calendered on the coated, preheated carpet.
  • additional binder is preferably applied to one of the two materials. This can be used in the form of a paste, powder, foil or melted. It is not necessary to apply these adhesives flat. A punctiform application is sufficient.
  • the additional lamination adhesive is first applied to one of the two substances and activated by heat immediately before lamination.
  • the primary purpose for solidifying the textile fabrics is primarily to use the aqueous paste.
  • the application of a second backing (lamination) can be carried out using both a paste and dry powder.
  • fibers for the construction of the textile fabrics come those based on polyamides, polyesters, polyolefins, polyacrylonitrile, regenerated cellulose and the like. ⁇ . in question. In principle, however, natural fibers such as wool, cotton, jute or the like can also be used.
  • synthetic fibers are preferred.
  • Textile fabrics in which fibers and binding or coating material consist of (co) polyamides are particularly advantageous.
  • the binder is for the manufacture of textile fabrics such.
  • B Suitable for floor and wall coverings.
  • textile fabrics for the automotive industry e.g. floor groups, wheel arch trim, trunk linings
  • this method since permanent deformation is guaranteed at the same time.
  • the textile fabrics according to the invention provide the necessary nub and capillary strength and, in the case of lamination, have an unexpectedly high laminate strength.
  • the measures according to the invention lead to textile fabrics which do not give rise to any odor complaints.
  • a particular advantage is that if the textile fabrics, including the back coating, are made of polyamide, they can be recycled without any problems. In this way it is possible to rework and reuse used textile floor coverings using known methods (crushing, granulating).
  • the coating paste described under A. is conveyed by means of a foam mixer (mixer) onto the pre-table of a technically customary coating system.
  • the textile tufting goods (loop goods; pile weight: 400 g / m2; pole material: polyamide; primary carrier material: polypropylene) passing through this table under a circular squeegee absorbs 520 g / m2 (corresponding to 175 g / m2 solids) coating paste with a given squeegee setting.
  • Downstream rubbing rollers massage the coating paste into the back of the carpet.
  • the water is then evaporated from the paste in the drying chambers of the coating system and sintered above the melting temperature of the copolyamide, the textile raw materials being joined together.
  • the pole material and the primary carrier are glued together in such a way that the required cutting edge strength is achieved.
  • a textile floor covering coated in this way already has the required properties for wear resistance and can be glued over the entire surface or stretched on so-called underlays.
  • the tufted carpet solidified according to B. is fed in a second process step to a calender with an upstream infrared heating field.
  • the material to be laminated (polyamide sewing fleece; basis weight: 200 g / m2) is coated with copolyamide powder (40% by weight laurolactam, 30% by weight caprolactam, 30% by weight AH salt; ⁇ rel : 1.5 ; Grain size 200 - 500 ⁇ m -) sprinkled (150 g / m2), sintered and then fed to a calender. Both materials are pressed together between the calender rolls.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Dispersion Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Carpets (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Manufacturing Of Multi-Layer Textile Fabrics (AREA)

Abstract

Textile materials in which the binding of the fibres is effected by thermoplastic polyamides. The advantage of the textile materials according to the invention is that these are suitable, after use, for reutilisation. Moreover, the disadvantages hitherto taken into account in the production of the textile materials, excessively objectionable odours and undesired decomposition products, are excluded.

Description

Die Erfindung bezieht sich auf textile Flächengebilde, die gebunden und ggf. kaschiert sind. Weiterer Gegenstand der Erfindung sind Verfahren zu ihrer Herstellung sowie ihre Verwendung.The invention relates to textile fabrics that are bound and optionally laminated. The invention further relates to processes for their preparation and their use.

Es ist bekannt, textile Flächengebilde z. B. für Fußbodenbeläge, Wandteppiche o. ä. nach verschiedenen Verfahren herzustellen. Als Herstellungsverfahren kommen z. B. die Technik des Webens, des Wirkens, des Nähwirkens, des Tuftens, des Nadelns oder des Ondulierens in Frage.It is known to use textile fabrics e.g. B. for floor coverings, tapestries or the like by various methods. As a manufacturing process such. B. the technique of weaving, knitting, sewing, tufting, needling or undulating in question.

Charakteristisch für textile Flächengebilde ist ihr Aufbau aus Material unterschiedlicher chemischer Herkunft. Weiterhin ist ihnen gemeinsam, daß sie zur Bindung, Verfestigung, Verstärkung sowie zur Optimierung von Gebrauchseigenschaften eine Beschichtung bzw. Appretur benötigen.A characteristic of textile fabrics is their construction from materials of different chemical origins. They also have in common that they require a coating or finish to bind, solidify, reinforce and optimize their properties.

Am Beispiel eines getufteten Teppichs sollen Konstruktion und Materialaufbau diskutiert werden.The construction and material structure will be discussed using the example of a tufted carpet.

Ein getufteter Teppich besteht vorwiegend aus einem z. B. Polyamid-Polmaterial, einem Primärträger meist aus Polyolefinfasern (seltener Polyester), einer Beschichtung für Grundstrich und Kaschierung auf Basis carboxylgruppenhaltiger Styrol/Butadien-Copolymeren, die mit Füllstoffen (Kreide u.a.) und Additiven (Dispergatoren, Alterungsschutzmittel u.a.) versetzt sind. Alternativ zur Kaschierung kann eine Schaum-Beschichtung auf Basis von Styrol Butadien-Copolymeren in Verbindung mit Vulkanisationshilfsmitteln, Füllstoffen, Additiven verwendet werden.A tufted carpet mainly consists of a z. B. polyamide pole material, a primary carrier mostly made of polyolefin fibers (rare polyester), a coating for base coat and lamination based on styrene / butadiene copolymers containing carboxyl groups, which are mixed with fillers (chalk, etc.) and additives (dispersants, anti-aging agents, etc.). As an alternative to lamination, a foam coating based on styrene-butadiene copolymers can be used in conjunction with vulcanization aids, fillers, and additives.

Andere Bindemittel, z. B. auf Basis von Isocyanat/Polydiol, Bitumen, Polyolefinen, sind bekannt.Other binders, e.g. B. based on isocyanate / polydiol, bitumen, polyolefins are known.

Die überwiegend eingesetzten Bindemittel auf Basis von Copolymerdispersionen aus u. a. Styrol und Butadien enthalten geringe Restmengen flüchtiger Anteile in Form von Kohlenwasserstoffen.The predominantly used binders based on copolymer dispersions made of styrene and butadiene contain small residual amounts of volatile components in the form of hydrocarbons.

Für eine Schaumrückenbeschichtung werden Vulkanisationshilfsmittel benötigt, die beim Vulkanisieren Spaltprodukte bilden. Die flüchtigen Anteile und Spaltprodukte können geruchlich wahrnehmbar sein und beim Endverbraucher zu Geruchsbelästigungen führen.For a foam back coating, vulcanization aids are required that form fission products during vulcanization. The volatile components and fission products may be perceptible in terms of smell and lead to unpleasant smells at the end user.

Bedingt durch den geschilderten Aufbau aus Material auf unterschiedlicher chemischer Basis sind darüber hinaus solche textilen Flächengebilde einem Recycling-Verfahren nicht zuführbar. Sie müssen verbrannt oder auf geordneten Deponien gelagert werden.Due to the described structure of material based on different chemical bases, such textile fabrics cannot be fed to a recycling process. They have to be incinerated or stored in orderly landfills.

Aufgabe der vorliegenden Erfindung war die Herstellung von textilen Flächengebilden, die zum einen frei von geruchlichen Beeinträchtigungen und zum anderen wiederzuverwerten sind.The object of the present invention was to produce textile fabrics which, on the one hand, are free from odor impairments and, on the other hand, are recyclable.

Das Ziel wird dadurch erreicht, daß die Fasern durch thermoplastische Polyamide verfestigt sind.The goal is achieved in that the fibers are strengthened by thermoplastic polyamides.

In dem Begriff "verfestigen" sind nicht nur alle Maßnahmen einbezogen, die zur mechanischen Grundstabilisierung von textilen Flächengebilden dienen, wie z. B. das Binden bei Tuftingteppichen, Nadelvliesen o. ä., sondern auch alle Maßnahmen, die zur weiteren Verbesserung des Eigenschaftsbildes beitragen, wie z. B. das Kaschieren von Teppichen.The term "solidify" not only includes all measures that serve for the basic mechanical stabilization of textile fabrics, such as. B. tying tufted carpets, needle fleece or the like, but also all measures that contribute to further improving the property profile, such as. B. the lamination of carpets.

Als Bindemittel zum Einsatz kommende Polyamide sind (Co)Kondensationsprodukte aus Diaminen, Dicarbonsäuren und alpha,omega-Aminocarbonsäuren bzw. die daraus abgeleiteten Lactame oder Mischungen derselben. Besonders bevorzugt sind hierbei Copolyamide.Polyamides used as binders are (co) condensation products of diamines, dicarboxylic acids and alpha, omega-aminocarboxylic acids or the lactams derived therefrom or mixtures thereof. Copolyamides are particularly preferred.

In Betracht kommen Diamine und Dicarbonsäuren mit einem Kohlenstoffgerüst von C₂ bis C₃₆, vorzugsweise C₅ bis C₁₆, besonders bevorzugt C₆ bis C₁₂; des weiteren alpha,omega-Aminocarbonsäuren und daraus abgeleitete Lactame mit 6 bis 12 Kohlenstoffatomen.Diamines and dicarboxylic acids with a carbon skeleton of C₂ to C₃₆, preferably C₅ to C₁₆, particularly preferably C₆ to C₁₂; furthermore alpha, omega-aminocarboxylic acids and lactams derived therefrom with 6 to 12 carbon atoms.

Geeignet sind alle Diamine der allgemeinen Formel NH₂-R-NH₂, wobei R ein unverzweigter oder verzweigter (cyclo)aliphatischer Rest ist, der gegebenenfalls durch ein oder mehrere gleiche oder verschiedene Heteroatome (z. B. N, O, S) unterbrochen sein kann. Beispiele derartiger Verbindungen sind Diethylentriamin, Triethylentetramin, Diaminoethylether, o. ä. Weiterhin können cycloaliphatische Diamine wie z. B. Piperazin- oder Isophorondiamin verwendet werden. Ethylendiamin, Hexamethylendiamin, 2-Methylpentamethylendiamin sowie Piperazin werden am häufigsten verwendet.Suitable are all diamines of the general formula NH₂-R-NH₂, where R is an unbranched or branched (cyclo) aliphatic radical which optionally interrupted by one or more identical or different heteroatoms (e.g. N, O, S). Examples of such compounds are diethylenetriamine, triethylenetetramine, diaminoethyl ether or the like. Cycloaliphatic diamines such as, for. B. piperazine or isophoronediamine can be used. Ethylene diamine, hexamethylene diamine, 2-methylpentamethylene diamine and piperazine are the most commonly used.

Als Dicarbonsäuren kommen Verbindungen der allgemeinen Formel HOOC-R'-COOH, wobei R' einen unverzweigten oder verzweigten aliphatischen Rest bedeutet, in Betracht. Z. B. seien Adipinsäure, Azelainsäure, Sebazinsäure, Dodekandisäure, Dimerfettsäuren genannt. Besonders bevorzugt sind dabei Adipinsäure, Dodekandisäure und Dimerfettsäuren.Suitable dicarboxylic acids are compounds of the general formula HOOC-R'-COOH, where R 'is an unbranched or branched aliphatic radical. Examples include adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and dimer fatty acids. Adipic acid, dodecanedioic acid and dimer fatty acids are particularly preferred.

Die zur Herstellung von (Co)Polyamiden verwendeten Lactame sind z. B. Caprolactam, Laurinlactam und die daraus abgeleiteten alpha,omega-Aminocarbonsäuren wie z. B. Aminoundekansäure.The lactams used to produce (co) polyamides are e.g. B. caprolactam, laurolactam and the derived alpha, omega-aminocarboxylic acids such. B. aminoundecanoic acid.

Die erfindungsgemäß eingesetzten (Co)Polyamide sowie ihre Herstellung sind bekannt (DE-PSS 12 53 449, 15 94 233, 19 39 758, 23 24 160; DE-OSS 25 09 791, 34 41 708; US-PSS 3 515 702, 4 661 585).The (co) polyamides used according to the invention and their preparation are known (DE-PSS 12 53 449, 15 94 233, 19 39 758, 23 24 160; DE-OSS 25 09 791, 34 41 708; US-PSS 3 515 702, 4,661,585).

Die Schmelzpunkte der verwendeten (Co)Polyamide weisen einen Wert von maximal 170 °C auf, bevorzugt werden solche (Co)Polyamide mit Schmelzpunkten von nicht größer als 140 °C.The melting points of the (co) polyamides used have a maximum value of 170 ° C., preference is given to those (co) polyamides with melting points of not greater than 140 ° C.

Die Molekularmasse der verwendeten (Co)Polyamide, ausgedrückt als relative Viskosität (ηrel), liegt im allgemeinen in einem Bereich von 1,3 bis 1,8, bevorzugt zwischen 1,4 und 1,6.The molecular mass of the (co) polyamides used, expressed as relative viscosity (η rel ), is generally in a range from 1.3 to 1.8, preferably between 1.4 and 1.6.

Die (Co)Polyamide können zum Beispiel in Form von Pasten, Pulvern, Folien, Netzen oder geschmolzenen Massen auf die textilen Flächengebilde aufgebracht werden. Die Pasten können gegebenenfalls in geschäumter Form vorliegen. Es ist auch möglich, daß die Beschichtung aus einer Kombination der genannten Anwendungsformen besteht. Die Erfindung ist jedoch nicht auf die vorgenannten Anwendungsformen beschränkt.The (co) polyamides can, for example, be applied to the textile fabrics in the form of pastes, powders, foils, nets or molten masses. The pastes can optionally be in foamed form. It is also possible that the coating consists of a combination of the application forms mentioned. However, the invention is not limited to the aforementioned forms of use.

Für die Verfestigung werden die erfindungsgemäßen Mittel bevorzugt als Paste - kompakt oder in geschäumter Form eingesetzt.For solidification, the agents according to the invention are preferably used as paste - compact or in foamed form.

Eine Paste besteht im wesentlichen aus (Co)Polyamid-Pulver, Wasser, Verdickungsmittel und Dispergatoren, gegebenenfalls Weichmachern auf Basis von Toluol- oder Benzolsulfonsäureamiden zusammen (DE-PSS 22 29 308, 37 40 155, DE-Patentanmeldung Aktenzeichen P 40 06 766.1, US-PS 3 956 213).A paste essentially consists of (co) polyamide powder, water, thickeners and dispersants, optionally plasticizers based on toluene or benzenesulfonic acid amides together (DE-PSS 22 29 308, 37 40 155, DE patent application file number P 40 06 766.1, U.S. Patent 3,956,213).

Das (Co)Polyamid ist in der Paste zu 10 bis 60 Gew.-% vorhanden, besonders bevorzugt sind Beschichtungspasten mit 20 bis 40 Gew.-% (Co)Polyamid.The (co) polyamide is present in the paste at 10 to 60% by weight, coating pastes with 20 to 40% by weight (co) polyamide are particularly preferred.

Der Korndurchmesser der in den Pasten eingesetzten (Co)Polyamide liegt im Bereich von 10 bis 500 µm, bevorzugt zwischen 10 und 80 µm. Sofern die (Co)Polyamide als trockene Pulver eingesetzt werden, liegt der Korndurchmesser im Bereich von 200 bis 500 µm, vorzugsweise 200 bis 300 µm.The grain diameter of the (co) polyamides used in the pastes is in the range from 10 to 500 μm, preferably between 10 and 80 μm. If the (co) polyamides are used as dry powders, the grain diameter is in the range from 200 to 500 μm, preferably 200 to 300 μm.

Die Zugabe der anderen Komponenten richtet sich nach der Menge des verwendeten (Co)Polyamids. So können die erfindungsgemäßen Beschichtungspasten 8 bis 15 Gew.-%, vorzugsweise 10 bis 12 Gew.-% Dispergator, 0,5 bis 1,0 Gew.-%, vorzugsweise 0,5 bis 0,8 Gew.-%, Verdickungsmittel und 5 bis 12 Gew.-%, vorzugsweise 5 bis 8 Gew.-%, Weichmacher enthalten. Darüber hinaus können noch andere, übliche Hilfsmittel in der Paste enthalten sein. Der Rest zu 100 Gew.-% ist Wasser. Der Anteil an Wasser ist so zu bemessen, daß die Beschichtungspaste eine Viskosität im Bereich von 1 000 bis 2 000 mPas.s, vorzugsweise 1 000 bis 1 500 mPas.s, aufweist.The addition of the other components depends on the amount of (co) polyamide used. Thus, the coating pastes according to the invention can contain 8 to 15% by weight, preferably 10 to 12% by weight, of dispersant, 0.5 to 1.0% by weight, preferably 0.5 to 0.8% by weight, of thickeners and 5 to 12 wt .-%, preferably 5 to 8 wt .-%, contain plasticizers. The paste may also contain other common auxiliaries. The rest, 100% by weight, is water. The proportion of water is to be dimensioned such that the coating paste has a viscosity in the range from 1,000 to 2,000 mPas.s, preferably 1,000 to 1,500 mPas.s.

Die Beschichtungspaste kann kompakt bzw. geschäumt zur Verfestigung des Polmaterials, zur Kapillarverfestigung oder zur Kaschierung des Zweitrückens auf den in der Industrie vorhandenen Maschinen appliziert werden.The coating paste can be applied compactly or foamed to consolidate the pole material, for capillary consolidation or to laminate the secondary back on the machines available in industry.

Das Auftragsgewicht (gerechnet als Feststoff) liegt für den Grundstrich im Bereich von 75 bis 300 g/m², vorzugsweise von 100 bis 250 g/m². Beim Kaschieren ist ein Auftragsgewicht von 50 bis 250 g/m², vorzugsweise 75 bis 150 g/m², Feststoff erforderlich. Als Feststoff wird derjenige Anteil der Paste bezeichnet, der beim Trocknungsvorgang sich nicht verflüchtigt.The application weight (calculated as solid) for the base coat is in the range from 75 to 300 g / m², preferably from 100 to 250 g / m². When laminating, an application weight of 50 to 250 g / m², preferably 75 to 150 g / m², of solid is required. The solid portion is the portion of the paste that does not evaporate during the drying process.

Die Beschichtungspaste wird mittels eines Rakels auf der Rückseite des z. B. Tuftingteppichs verteilt. Dabei penetriert das Compound in die Noppenfüsse des Polmaterials. Nach Verdampfen des Wassers verschmelzen Polyamid und Zuschlagstoffe.The coating paste is applied using a doctor blade on the back of the z. B. Tufted carpet distributed. The compound penetrates into the dimpled feet of the pole material. After the water has evaporated, the polyamide and aggregates fuse.

Die Trocknungs- und Sintertemperatur soll ca. 20 °C über der Schmelztemperatur des eingesetzten Polyamids liegen.The drying and sintering temperature should be approx. 20 ° C above the melting temperature of the polyamide used.

Um unterschiedliche Auftragsgewichte je m² Teppichboden zu erhalten, ist das Einarbeiten von Luft in das Compound von Vorteil. Hierbei können die nach dem Stand der Technik bekannten Geräte (Schaummischgeräte) verwendet werden. Die Auftragsverfahren sind bekannt (s. Verarbeitungsbeispiel).In order to obtain different application weights per m² of carpeting, it is advantageous to incorporate air into the compound. The devices known from the prior art (foam mixing devices) can be used here. The application methods are known (see processing example).

Für das Kaschieren eines Zweitrückens wird das textile Kaschiermaterial auf den beschichteten, vorgeheizten Teppich kalandriert. Für besonders hohe Haftwerte zwischen dem verfestigten Fasermaterial des Teppichbodens und dem Zweitrücken wird bevorzugt zusätzliches Bindemittel auf eines der beiden Materialien aufgebracht. Dieses kann sowohl in Form einer Paste, von Pulver, Folie oder geschmolzen eingesetzt werden. Es ist nicht notwendig, diese Kleber flächenförmig aufzubringen. Es genügt ein punktförmiger Auftrag. Der zusätzliche Kaschierkleber wird zunächst auf eines der beiden Substanzen aufgebracht und unmittelbar vor dem Kaschieren durch Wärme aktiviert.For the lamination of a second back, the textile lamination material is calendered on the coated, preheated carpet. For particularly high adhesion values between the solidified fiber material of the carpet and the second backing, additional binder is preferably applied to one of the two materials. This can be used in the form of a paste, powder, foil or melted. It is not necessary to apply these adhesives flat. A punctiform application is sufficient. The additional lamination adhesive is first applied to one of the two substances and activated by heat immediately before lamination.

Es ist festzustellen, daß für die primäre Grundverfestigung der textilen Flächengebilde in erster Linie die Verwendung der wässrigen Paste in Frage kommt. Demgegenüber kann das Aufbringen eines Zweitrückens (Kaschieren) sowohl unter Verwendung einer Paste als auch von trockenem Pulver erfolgen.It should be noted that the primary purpose for solidifying the textile fabrics is primarily to use the aqueous paste. In contrast, the application of a second backing (lamination) can be carried out using both a paste and dry powder.

Als Fasern für den Aufbau der textilen Flächengebilde kommen solche auf Basis von Polyamiden, Polyestern, Polyolefinen, Polyacrylnitril, Zelluloseregenerat u. ä. in Frage. Grundsätzlich können aber auch Naturfasern wie Wolle, Baumwolle, Jute o. ä. eingesetzt werden.As fibers for the construction of the textile fabrics come those based on polyamides, polyesters, polyolefins, polyacrylonitrile, regenerated cellulose and the like. Ä. in question. In principle, however, natural fibers such as wool, cotton, jute or the like can also be used.

Erfindungsgemäß werden synthetische Fasern bevorzugt. Besonders vorteilhaft sind textile Flächengebilde, bei denen Fasern und Binde- bzw. Beschichtungsmaterial aus (Co)Polyamiden bestehen.According to the invention, synthetic fibers are preferred. Textile fabrics in which fibers and binding or coating material consist of (co) polyamides are particularly advantageous.

Das Bindemittel ist für die Herstellung textiler Flächengebilde wie z. B. Boden- und Wandbeläge geeignet. Außerdem können textile Flächengebilde für den Bereich des Automobilbaues (z. B. Bodengruppen, Radhausverkleidung, Kofferraumauskleidungen) nach diesem Verfahren vorteilhaft hergestellt werden, da gleichzeitig eine bleibende Verformung gewährleistet ist.The binder is for the manufacture of textile fabrics such. B. Suitable for floor and wall coverings. In addition, textile fabrics for the automotive industry (e.g. floor groups, wheel arch trim, trunk linings) can advantageously be produced using this method, since permanent deformation is guaranteed at the same time.

Die erfindungsgemäßen textilen Flächengebilde erbringen die notwendige Noppen- und Kapillarfestigkeit und haben im Falle des Kaschierens eine in unerwarteter Weise hohe Laminatfestigkeit.The textile fabrics according to the invention provide the necessary nub and capillary strength and, in the case of lamination, have an unexpectedly high laminate strength.

Die erfindungsgemäßen Maßnahmen führen zu textilen Flächengebilden, die keinen Anlaß zu geruchlichen Beanstandungen bieten. Ein besonderer Vorteil liegt darin, daß, wenn die textilen Flächengebilde einschließlich der Rückenbeschichtung einheitlich aus Polyamid aufgebaut sind, unproblematisch einem Recycling zugeführt werden können. Auf diese Weise ist es möglich, gebrauchte textile Bodenbeläge nach bekannten Verfahren (Zerkleinern, Granulieren) umzuarbeiten und wiederzuverwenden.The measures according to the invention lead to textile fabrics which do not give rise to any odor complaints. A particular advantage is that if the textile fabrics, including the back coating, are made of polyamide, they can be recycled without any problems. In this way it is possible to rework and reuse used textile floor coverings using known methods (crushing, granulating).

Die nachstehenden Parameter wurden mit Hilfe der folgenden Verfahren ermittelt.The following parameters were determined using the following procedures.

Beispielexample A. Beschichtungspaste für die Herstellung eines getufteten textilen Bodenbelags.A. Coating paste for the manufacture of tufted textile flooring.

GewichtsteileParts by weight Wasserwater 440,00440.00 Verdickungsmittel1) Thickener 1) 6,006.00 Dispergator2) Dispersant 2) 120,00120.00 p-Toluolsulfonsäureamidp-toluenesulfonic acid amide 60,0060.00 Polyurethanacrylat3) Polyurethane acrylate 3) 1,661.66 Copolyamidpulver4) Copolyamide powder 4) 280,00280.00 Polyethylenoxid5) Polyethylene oxide 5) 40,0040.00 1) = TANAPRINTR ST 170 (Natriumpolyacrylat - Fa. Sybron, Ede, NL) 1) = TANAPRINT R ST 170 (sodium polyacrylate - Sybron, Ede, NL) 2) = ATESYNTHR HSE 69 (Ethylenoxid-Fettsäure - Fa. Dr. Th. Böhme, Geretsried, DE) 2) = ATESYNTH R HSE 69 (ethylene oxide fatty acid - Dr. Th. Böhme, Geretsried, DE) 3) = COLLACRALR SK (Polyurethanacrylat - Fa. BASF AG, Ludwigshafen, DE) 3) = COLLACRAL R SK (polyurethane acrylate - from BASF AG, Ludwigshafen, DE) 4) = VESTAMELTR 350 P1 (Copolyamid aus 40 Gew.-% Laurinlactam, 30 Gew.-% Caprolactam, 30 Gew.-% AH-Salz; ηrel 1,5; Korngröße: 10 - 80 µm - Fa. Hüls AG, Marl, DE) 4) = VESTAMELT R 350 P1 (copolyamide made of 40% by weight laurolactam, 30% by weight caprolactam, 30% by weight AH salt; η rel 1.5; grain size: 10 - 80 µm - Hüls AG , Marl, DE) 5) = MIRAPLASTR 5147 (Polyethylenoxid (1 Gew.-%ige wäßrige Lösung), Molekulargewicht: 2 000 000 - Fa. Dr. Th. Böhme, Geretsried, DE) 5) = MIRAPLAST R 5147 (polyethylene oxide (1% by weight aqueous solution), molecular weight: 2,000,000 - Dr. Th. Böhme, Geretsried, DE)

B. Beschichtung eines TuftingteppichsB. Coating a tufted carpet

Die unter A. beschriebene Beschichtungspaste wird mittels eines Schaummischgerätes (Mixer) auf den Vorstrichtisch einer technisch üblichen Beschichtungsanlage befördert.The coating paste described under A. is conveyed by means of a foam mixer (mixer) onto the pre-table of a technically customary coating system.

Die über diesen Tisch unter einer Rundrakel durchlaufende textile Tuftingware (Schlingenware; Polgewicht: 400 g/m²; Polmaterial: Polyamid; Primärträgermaterial: Polypropylen) nimmt bei gegebener Rakeleinstellung 520 g/m² (entsprechend 175 g/m² Feststoff) Beschichtungspaste auf.The textile tufting goods (loop goods; pile weight: 400 g / m²; pole material: polyamide; primary carrier material: polypropylene) passing through this table under a circular squeegee absorbs 520 g / m² (corresponding to 175 g / m² solids) coating paste with a given squeegee setting.

Nachgeschaltete Verreibewalzen massieren die Beschichtungspaste in den Teppichrücken ein.Downstream rubbing rollers massage the coating paste into the back of the carpet.

Anschließend wird in den Trockenkammern der Beschichtungsanlage das Wasser aus der Paste verdunstet und oberhalb der Schmelztemperatur des Copolyamids gesintert, wobei die textilen Rohstoffe miteinander verbunden werden.The water is then evaporated from the paste in the drying chambers of the coating system and sintered above the melting temperature of the copolyamide, the textile raw materials being joined together.

Gleichzeitig werden Polmaterial und Primärträger so miteinander verklebt, daß die erforderliche Schnittkantenfestigkeit erzielt wird.At the same time, the pole material and the primary carrier are glued together in such a way that the required cutting edge strength is achieved.

Ein so beschichteter textiler Bodenbelag besitzt bereits die benötigten Eigenschaften für Verschleißfestigkeit und kann vollflächig verklebt oder auf sog. Underlays verspannt, verlegt werden.A textile floor covering coated in this way already has the required properties for wear resistance and can be glued over the entire surface or stretched on so-called underlays.

C. Kaschieren eines ZweitrückensC. Laminating a second back

Der gemäß B. verfestigte Tuftingteppich wird in einem 2. Verfahrensschritt einem Kalander mit vorgeschaltetem Infrarotheizfeld zugeführt.The tufted carpet solidified according to B. is fed in a second process step to a calender with an upstream infrared heating field.

Gleichzeitig wird das zu kaschierende Material (Polyamid-Nähvlies; Flächengewicht: 200 g/m²) mit Copolyamidpulver (40 Gew.-% Laurinlactam, 30 Gew.-% Caprolactam, 30 Gew.-% AH-Salz; ηrel: 1,5; Korngröße 200 - 500 µm -) bestreut (150 g/m²), gesintert und anschließend einem Kalander zugeführt. Beide Materialien werden zwischen den Kalanderwalzen durch Verpressen miteinander verbunden.At the same time, the material to be laminated (polyamide sewing fleece; basis weight: 200 g / m²) is coated with copolyamide powder (40% by weight laurolactam, 30% by weight caprolactam, 30% by weight AH salt; η rel : 1.5 ; Grain size 200 - 500 µm -) sprinkled (150 g / m²), sintered and then fed to a calender. Both materials are pressed together between the calender rolls.

Nach Abkühlen des Verbundes auf unterhalb der Schmelztemperatur des Copolyamids ist die erforderliche Laminatfestigkeit von > 40 N/5 cm Prüfstreifen (DIN 53 278) gewährleistet.After the composite has cooled to below the melting temperature of the copolyamide, the required laminate strength of> 40 N / 5 cm test strips (DIN 53 278) is guaranteed.

Claims (11)

Textile Flächengebilde,
dadurch gekennzeichnet,
daß die Fasern durch thermoplastische Polyamide verfestigt sind.Textile fabrics,
characterized,
that the fibers are strengthened by thermoplastic polyamides. Textile Flächengebilde nach Anspruch 1,
dadurch gekennzeichnet,
daß die thermoplastischen Polyamide aus Copolyamiden bestehen.Textile fabrics according to claim 1,
characterized,
that the thermoplastic polyamides consist of copolyamides. Textile Flächengebilde nach Anspruch 1 und 2,
dadurch gekennzeichnet,
daß die Copolyamide einen Schmelzpunkt von nicht größer als 170 °C besitzen.Textile fabrics according to claims 1 and 2,
characterized,
that the copolyamides have a melting point of not greater than 170 ° C. Textile Flächengebilde nach Anspruch 1 und 2,
dadurch gekennzeichnet,
daß die Copolyamide vorzugsweise einen Schmelzpunkt von nicht größer als 140 °C besitzen.Textile fabrics according to claims 1 and 2,
characterized,
that the copolyamides preferably have a melting point of not greater than 140 ° C. Textile Flächengebilde nach den Ansprüchen 1 bis 4,
dadurch gekennzeichnet,
daß die thermoplastischen Polyamide in Form von wäßrigen Pasten verwendet werden.Textile fabrics according to claims 1 to 4,
characterized,
that the thermoplastic polyamides are used in the form of aqueous pastes. Textile Flächengebilde nach den Ansprüchen 1 bis 5,
dadurch gekennzeichnet,
daß die wäßrigen Pasten in geschäumter Form zur Anwendung kommen.Textile fabrics according to claims 1 to 5,
characterized,
that the aqueous pastes are used in foamed form. Textile Flächengebilde nach den Ansprüchen 1 bis 4,
dadurch gekennzeichnet,
daß die thermoplastischen Polyamide in Pulverform verarbeitet werden.Textile fabrics according to claims 1 to 4,
characterized,
that the thermoplastic polyamides are processed in powder form. Verfahren zur Herstellung von textilen Flächengebilden gemäß den Ansprüchen 1 bis 7,
dadurch gekennzeichnet,
daß die Fasern mit thermoplastischem Polyamid gebunden werden.Process for the production of textile fabrics according to claims 1 to 7,
characterized,
that the fibers are bound with thermoplastic polyamide. Verfahren zur Herstellung von textilen Flächengebilden gemäß Anspruch 8,
dadurch gekennzeichnet,
daß das Bindemittel als Paste, kompakt und/oder in geschäumter Form, aufgetragen wird.Process for the production of textile fabrics according to claim 8,
characterized,
that the binder is applied as a paste, compact and / or in foamed form. Verfahren zur Herstellung von textilen Flächengebilden nach Anspruch 8,
dadurch gekennzeichnet,
daß das Bindemittel als Pulver aufgebracht wird.Process for the production of textile fabrics according to claim 8,
characterized,
that the binder is applied as a powder. Verwendung der textilen Flächengebilde gemäß den Ansprüchen 1 bis 10 als Bodenbeläge, Wandverkleidungen oder Automobilteppiche.Use of the textile fabrics according to claims 1 to 10 as floor coverings, wall coverings or automobile carpets.
EP92103430A 1991-04-30 1992-02-28 Flat textile product reinforced with polyamide Withdrawn EP0511469A1 (en)

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BE1006624A3 (en) * 1993-01-08 1994-11-03 Bercopa Sa Recyclable synthetic carpet and method for manufacturing it
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US6860953B1 (en) 1994-02-09 2005-03-01 Collins & Aikman Floorcoverings, Inc. Process for manufacturing a floor covering having a foamed backing formed from recycled polymeric material
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