EP0520151B1 - Latex-, PVC- and plasticiser-free, foamed floor and wall coverings - Google Patents

Latex-, PVC- and plasticiser-free, foamed floor and wall coverings Download PDF

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Publication number
EP0520151B1
EP0520151B1 EP92106129A EP92106129A EP0520151B1 EP 0520151 B1 EP0520151 B1 EP 0520151B1 EP 92106129 A EP92106129 A EP 92106129A EP 92106129 A EP92106129 A EP 92106129A EP 0520151 B1 EP0520151 B1 EP 0520151B1
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Prior art keywords
foamed
process according
layer
polymer
parts
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German (de)
French (fr)
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EP0520151A1 (en
EP0520151B2 (en
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Horst Oppermann
Reinhold Blass
Joachim Dr. Dürkop
Klaus Schmidt-Ott
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Tarkett Pegulan AG
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Tarkett Pegulan AG
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Priority claimed from DE19914121401 external-priority patent/DE4121401A1/en
Priority claimed from DE4135937A external-priority patent/DE4135937C2/en
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/005—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by blowing or swelling agent
    • 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
    • D06N2205/00—Condition, form or state of the materials
    • D06N2205/04—Foam

Definitions

  • the present invention relates to the production of latex, PVC and plasticizer-free floor and wall coverings with chemically foamed and optionally structured foam layers.
  • Textile floor and wall coverings with a back-foamed layer made of a natural or synthetic latex and PVC plastic coverings are found today widely used due to its diverse decorative possibilities through simple installation and value for money.
  • the possibility of equipping the coverings with soft, foamed backs, which contributes significantly to the insulation of the impact sound and improves walking comfort, has ensured the further spread of such materials.
  • the foaming enables the generation of surface structures either by foaming in appropriate forms or embossing rollers or by partial chemical activation or inhibition of foam formation.
  • technically only mechanical foaming is carried out by injecting air into the latex mass, since chemical foaming requires high temperatures, which damage the textile pile.
  • floor coverings in particular are usually produced today in continuous webs with a width of up to 4 or 5 m, which extremely limits the possibilities both in terms of material and processing techniques.
  • Textile floor coverings are either manufactured using the tufting process or from needle punched nonwovens, which are fixed on the back with a styrene-butadiene or other latex material and then coated with a mechanically foamed synthetic or natural latex layer and fixed by drying.
  • the textile layer consists mainly of polyamide, polypropylene or polyester fibers, which can no longer be separated from the latex layers, so that such composite layers are not recyclable. From GB-A 2191209 and GB-A 1420624 it is also known to produce the back coating by sprinkling a powder of a polymer, fillers and possibly blowing agents, which are melted and possibly foamed and thus glue and stabilize the textile fibers.
  • Polyethylene, polyester, polyamide, EVA and their copolymers are mentioned as polymers.
  • plastic floor coverings have usually been produced from latex dispersions or PVC plastisols in a coating process on a tissue or release paper base and then hardened.
  • the plastisols consist of PVC particles, plasticizers, and usual auxiliary substances as well as fillers, which sinter together to form a matrix when dried in the warmth.
  • the layer can also be thermally foamed, and additional structuring can be achieved by applying blowing agent activators or deactivators to certain areas.
  • blowing agent activators or deactivators it is also possible to vary the properties to a very large extent by applying several layers of different composition (see e.g. "Solvic @ für Plastisole", company lettering of Deutsche Solvay-Werke GmbH, Solingen).
  • latex and PVC are ideal materials in terms of their cost-effectiveness and properties, the ecological aspects that need to be taken into account increasingly - recyclability of the products, avoidance of solvents and halogen-containing constituents - to search for processes for the production of coverings which latex, PVC and plasticizer-free. For economic and technical reasons, however, it is necessary to maintain the previous manufacturing widths and, if possible, the existing manufacturing devices.
  • the floor covering should also consist of different layers, one or more of which are chemically foamed and, if necessary, partially structured by activating or deactivating the foaming process.
  • plasticizer-free polyurethane foams by mechanically foaming the components while injecting air, but the foaming cannot be chemically prevented and no structure can be created as a result.
  • the mixtures according to the invention can be distributed uniformly over widths of 4-5 m using commercially available powder scattering machines, so that a homogeneous, uniformly thick foam layer is formed when they are subsequently passed through the drying oven.
  • Multiple layers can also be easily produced by sprinkling a second powder layer on a first solidified and, if necessary, leveled layer, drying or gelling again.
  • the layer can be colored by temporarily printing the color pattern, structuring by printing an activator or deactivator.
  • the polymers which can be processed according to the invention comprise a large number of thermoplastic products.
  • the most important parameter is the melt index (MFI 190 ° C / 2.16). It was found that with melt indices below 2.5 and above 40, the too high or too low melt viscosity no longer permits a good cellular structure of the foam. A melt index of around 10 - 20 seems to give optimal results.
  • the crystallite melting point of the polymers should be below the decomposition range of the blowing agent mixture, but not so low that the foam begins to flow, for example, under strong sunlight or weight. Crystallite melting points in a range from 70 to 110 seem to be well suited in this respect.
  • Suitable polymers are copolymers of ethylene and vinyl acetate, polyethylene, polypropylene, copolymers with polyvinyl acetate, polymethyl methacrylate, polyethylene acrylic acid ester copolymers, polyethylene acrylic acid esters, maleic anhydride copolymers and others.
  • the polymers are ground from the commercially available granules to a maximum particle size of 400-600 ⁇ m, preferably 10-400 ⁇ m, and mixed in this form with the other components.
  • additives that are also used in the usual foam mixtures are possible as additives.
  • examples include inorganic fillers such as chalk, silicates, magnesium or aluminum hydroxides, heavy spar, silica, glass powder, carbon black, titanium dioxide or other color pigments that simultaneously change the translucency of the foam.
  • wood or cork flour or also temperature-resistant plastics such as polyurethanes come into consideration as organic additives. These are mixed into the mixture as fine powders with grain sizes from 10 to about 500 ⁇ m, the fillers being added to the mixture in amounts of 5-50%, depending on the product.
  • the blowing agents used for the foam layers are the usual products for plastisols such as azodicarbonamide, oxibis-benzenesulfohydrazite, azoisobutyronitrile, toluenesulfohydrazite and others.
  • Azodicarbonamide is preferred, the decomposition temperature of which can be reduced to about 120 ° C. by adding activators such as zinc oxide, zinc octoate and other known activators. In this way, the foaming temperature can be easily adapted to the plastic to be foamed and its viscosity.
  • the blowing agents are added to the mixture in the form of fine powders (2 to 12/1. Grain size) or as a batch (rubbed with paraffin or antistatic agent) in amounts of 0.5-10%.
  • the substances known for such foam mixtures can be used as deactivators for those places where foaming is not desired. Trimelitic anhydride, benzotriazole or thiourea are preferably used. In contrast to the solvent-containing pastes, which enable the deactivators to diffuse into the foamable layer, in the agents according to the invention the deactivator must be printed on together with a means of transport. As a transport, liquid paraffins or liquid antistatic agents or crosslinkable derivatives of methacrylic acid are suitable. The deactivators should be used in an amount of approx. 0.5 - 2% based on the mass of the foam layer to be structured.
  • peroxides can be added to the mixture to crosslink the foam and to improve the temperature resistance of the polymers both during processing and during later use.
  • Bactericides, antistatic agents, antioxidants, etc., as are customary in latex and plastic processing, are also suitable as auxiliary substances.
  • the preliminary product is a common tufting covering without backing, needle felt covering, only with fiber impregnation or a heterogeneous, foam-structured elastic floor covering, which are pre-produced on the appropriate production machines.
  • a powder scattering machine available on the market is used as additional equipment; the overall system is shown schematically in Fig. 1.
  • the carrier material, textile covering or prefabricated heterogeneous elastic covering is fed continuously to the system by means of a roll (1) and storage metering.
  • a so-called fixing or base coat for closing the substrate surface is applied by means of a coating device (not shown) and, if necessary, heated by heating (air circulation duct or radiator) and smoothed using a smoothing device (3).
  • Example 1 In the second application unit (4), the EVA dry blend described in Example 1 is applied using a powder spreader and then melted in an infrared emitter station (5), but not yet chemically foamed or crosslinked.
  • the melted foam surface can also be smoothed and solidified using a smoothing drum (6).
  • the fabric thus obtained is heated in a drying / gelling oven (7) to approx. 120-200 ° C, causing the EVA powder to foam and crosslinked by reaction of the peroxides.
  • a smoothing unit (3), a cooling section (8) and a storage unit and reel (9) are in turn connected downstream. If necessary, the necessary finished goods inspection of the floor covering web can take place continuously in the system. Then it is cut to length and rolled on individual rolls before the material goes to the finished goods warehouse.
  • the heterogeneous elastic floor covering containing EVA foam layers can be produced on a conventional coating system suitable for PVC floor coverings. Powder spreaders available on the market are used as additional equipment.
  • the device used is shown schematically in FIG. 2.
  • the carrier material textile, glass and similar fabrics
  • the carrier material is fed to the system endlessly by means of unwinding (1) and storage metering.
  • the corresponding coating material for closing and smoothing the carrier substrate is applied by means of a coating device (not shown) as a so-called fixing or base coat, heated by means of radiators (5) and smoothed using a smoothing device (3).
  • the EVA dry blend described in Example 2 or 3 is applied using a powder scattering machine and then melted in an infrared emitter station (5), but not yet chemically foamed or crosslinked.
  • the melted foam surface can also be smoothed and solidified using a smoothing drum (6).
  • a multicolor print design is applied to the smooth foam surface obtained using a printing machine (7) using polymer binder printing ink.
  • the printing layer is covered by a transparent coating compound.
  • the fabric obtained in this way is heated in a drying / gelling oven to 160-200 ° C, which causes the EVA dry blend layer to foam - only partially when structured - and is crosslinked by the peroxides.
  • the transparent cover layer dries and reacts simultaneously.
  • a foamable EVA dry blend can be applied again in a further powder spreading machine (4), as described above, which then melted in accordance with (5), (3), (9) , solidified, smoothed and foamed.
  • a final surface treatment using a smoothing unit (3) serves to homogenize the foam surface.
  • a structured roller in the manner of an embossing mill can also be used here.
  • the material web is cooled in the cooling section (10) and then removed from a storage device and reel (11) of the system. If necessary, a Intermediate control with ready-made single rolls are carried out, which are then fed directly to the finished goods warehouse.
  • the above-described covering can also be produced in a batch process, in that lengths of approximately 500 m are rolled up after each of one or more of the above steps, stored temporarily and fed to the next processing station at a later point in time.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Floor Finish (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

A process for producing latex-, PVC- and plasticiser-free textile or plastic floor or wall coverings which contain, inter alia, a foamed layer, a powder mixture consisting of 100 parts of a thermoplastic polymer 0-100 parts of fillers 0.5-7 parts of blowing agent 0-30 parts of auxiliaries being scattered in an amount corresponding to the required thickness onto the base layer below the subsequent foamed layer and melted at temperatures of 70-110 DEG C, polished between polishing rolls and foamed at temperatures of 120-200 DEG C. The invention further relates to the novel means and to the coverings produced therewith. <IMAGE>

Description

Die vorliegende Erfindung betrifft die Herstellung von Latex-, PVC- und Weichmacher-freien Boden- und Wandbelägen mit chemisch geschäumten und ggf. strukturierten Schaumschichten Textile Boden- und Wandbeläge mit einer rückseitigen geschäumten Schicht aus einem natürlichen oder synthetischen Latex und PVC-Kunststoffbeläge finden heute in großem Umfang Verwendung aufgrund ihrer vielfältigen dekorativen Möglichkeiten durch einfache Verlegung und Preiswürdigkeit.The present invention relates to the production of latex, PVC and plasticizer-free floor and wall coverings with chemically foamed and optionally structured foam layers. Textile floor and wall coverings with a back-foamed layer made of a natural or synthetic latex and PVC plastic coverings are found today widely used due to its diverse decorative possibilities through simple installation and value for money.

Insbesondere die Möglichkeit, die Beläge mit weichen, geschäumten Rückseiten auszurüsten, was erheblich zur Dämmung des Trittschalls beiträgt und den Gehkomfort verbessert, haben für die weitere Verbreitung solcher Materialien gesorgt. Darüber hinaus ermöglicht die Schäumung eine Erzeugung von Oberflächenstrukturierungen entweder durch Aufschäumen in entsprechenden Formen bzw. Prägewalzen oder durch partielle chemische Aktivierung oder Inhibierung der Schaumbildung. Bei textilen Belägen wird technisch nur die mechanische Schäumung durch Einpressen von Luft in die Latexmasse durchgeführt, da die chemische Verschäumung hohe Temperaturen erfordert, welche den Textilflor schädigt.In particular, the possibility of equipping the coverings with soft, foamed backs, which contributes significantly to the insulation of the impact sound and improves walking comfort, has ensured the further spread of such materials. In addition, the foaming enables the generation of surface structures either by foaming in appropriate forms or embossing rollers or by partial chemical activation or inhibition of foam formation. In the case of textile coverings, technically only mechanical foaming is carried out by injecting air into the latex mass, since chemical foaming requires high temperatures, which damage the textile pile.

Um beim Verlegen Stöße zu vermeiden, werden insbesondere Fußbodenbeläge heute üblicherweise in Endlosbahnen in einer Breite von bis zu 4 oder 5 m hergestellt, was sowohl vom Material als auch von den Verarbeitungstechniken her die Möglichkeiten außerordentlich einschränkt.In order to avoid bumps when laying, floor coverings in particular are usually produced today in continuous webs with a width of up to 4 or 5 m, which extremely limits the possibilities both in terms of material and processing techniques.

Textile Bodenbeläge werden entweder nach dem Tuftingverfahren oder aus Nadelvliesen hergestellt, die rückseits mit einer Styrolbutadien- oder anderen Latexmasse verfestigt und danach mit einer mechanisch verschäumten Synthese- oder Naturlatexschicht beschichtet und durch Trocknen fixiert werden. Die Textilschicht besteht dabei vorwiegend aus Polyamid, Polypropylen oder Polyesterfasern, welche nicht mehr von den Latexschichten getrennt werden können, so daß solche Verbundschichten nicht recyclisierbar sind. Aus der GB-A 2191209 und GB-A 1420624 ist ferner bekannt, die rückseitige Beschichtung auch durch Aufstreuen eines Pulvers aus einem Polymeren, Füllstoffen und ggf. Treibmitteln herzustellen, welche aufgeschmolzen und ggf. aufgeschäumt werden und damit die Textilfasern verkleben und stabilisieren. Als Polymere werden Polyethylen, Polyester, Polyamide, EVA und ihre Copolymerisate genannt.Textile floor coverings are either manufactured using the tufting process or from needle punched nonwovens, which are fixed on the back with a styrene-butadiene or other latex material and then coated with a mechanically foamed synthetic or natural latex layer and fixed by drying. The textile layer consists mainly of polyamide, polypropylene or polyester fibers, which can no longer be separated from the latex layers, so that such composite layers are not recyclable. From GB-A 2191209 and GB-A 1420624 it is also known to produce the back coating by sprinkling a powder of a polymer, fillers and possibly blowing agents, which are melted and possibly foamed and thus glue and stabilize the textile fibers. Polyethylene, polyester, polyamide, EVA and their copolymers are mentioned as polymers.

Bisher werden Kunststoffbodenbeläge üblicherweise aus Latexdispersionen oder PVC-Plastisolen im Streichverfahren auf einer Gewebe- oder Releasepapierunterlage und anschließendes Aushärten hergestellt. Die Plastisole bestehen dabei aus PVC-Partikeln, Weichmachern, und üblichen Hilfsstoffen sowie Füllstoffen, die beim Trocknen in der Wärme zu einer Matrix zusammensintern. Durch Zufügung von chemischen Schaummitteln kann die Schicht zusätzlich noch thermisch verschäumt werden, wobei durch Aufbringen von Treibmittelaktivatoren oder -desaktivatoren auf bestimmte Bereiche noch eine zusätzliche Strukturierung erreicht werden kann. Selbstverständlich ist es auch möglich, durch Aufbringen mehrerer Schichten unterschiedlicher Zusammensetzung die Eigenschaften in sehr weitem Maße zu variieren (vgl. z.B. "Solvic@ für Plastisole", Firmenschrift der Deutschen Solvay-Werke GmbH, Solingen).So far, plastic floor coverings have usually been produced from latex dispersions or PVC plastisols in a coating process on a tissue or release paper base and then hardened. The plastisols consist of PVC particles, plasticizers, and usual auxiliary substances as well as fillers, which sinter together to form a matrix when dried in the warmth. By adding chemical foaming agents, the layer can also be thermally foamed, and additional structuring can be achieved by applying blowing agent activators or deactivators to certain areas. Of course, it is also possible to vary the properties to a very large extent by applying several layers of different composition (see e.g. "Solvic @ für Plastisole", company lettering of Deutsche Solvay-Werke GmbH, Solingen).

Obwohl Latex und PVC von der Wirtschaftlichkeit und den Eigenschaften her an sich ideale Werkstoffe sind, verlangen jedoch die immer stärker zu berücksichtigenden ökologischen Aspekte - Recyclisierbarkeit der Produkte, Vermeidung von Lösungsmitteln und halogenhaltigen Bestandteilen - Verfahren zur Herstellung von Belägen zu suchen, welche Latex-, PVC- und Weichmacher-frei sind. Aus ökonomischen und technischen Gründen ist es jedoch notwendig, die bisherigen Herstellungsbreiten und nach Möglichkeit auch die vorhandenen Herstellungsvorrichtungen beizubehalten. Weiterhin sollte auch der Bodenbelag aus unterschiedlichen Schichten bestehen, von denen eine oder mehrere chemisch geschäumt und ggf. partiell durch Aktivierung oder Desaktivierung des Schäumvorgangs strukturiert sind.Although latex and PVC are ideal materials in terms of their cost-effectiveness and properties, the ecological aspects that need to be taken into account increasingly - recyclability of the products, avoidance of solvents and halogen-containing constituents - to search for processes for the production of coverings which latex, PVC and plasticizer-free. For economic and technical reasons, however, it is necessary to maintain the previous manufacturing widths and, if possible, the existing manufacturing devices. Furthermore, the floor covering should also consist of different layers, one or more of which are chemically foamed and, if necessary, partially structured by activating or deactivating the foaming process.

Aufgabe der vorliegenden Erfindung war es daher ein Verfahren zu finden, mit dem sich Latex-, PVC-und Weichmacher-freie Kunststoffboden- und Wandbeläge hergestellt werden können, welche mindestens aus einer chemisch geschäumten Schicht und einer Trägerschicht bestehen, ggf. eine Strukturierung durch Aktivierung oder Desaktivierung der Treibmittel zu erlauben und übliche Herstellungsbreiten von 4-5 m auf vorhandenen Vorrichtungen zu fertigen gestattet. Für die Herstellung von Bodenbelägen ist zusätzlich noch mindestens eine nicht geschäumte Deckschicht vorhanden.It was therefore an object of the present invention to find a process by means of which latex, PVC and plasticizer-free plastic floor and wall coverings can be produced, which consist of at least one chemically foamed layer and a carrier layer, possibly structuring by activation allow or deactivation of the propellant and allowed to manufacture usual manufacturing widths of 4-5 m on existing devices. For the production of floor coverings there is also at least one non-foamed cover layer.

Diese Aufgabe wird durch die im Hauptanspruch wiedergegebenen Merkmale gelöst und durch die in den Unteransprüchen gekennzeichneten Merkmale gefördert.This object is achieved by the features set out in the main claim and promoted by the features characterized in the subclaims.

Aus dem sogenannten Furukawa-Verfahren ist es bekannt, vernetzte Polyethylenschäume herzustellen, indem man Polyethylen, Azodicarbonamid als Treibmittel und Dicumolperoxid als Vernetzungsmittel mit Hilfe eines Extruders mit nachgeschalteter Breitschlitzdüse zu einer Matrix in Form eines Films oder einer ungeschäumten Platte extrudiert, wobei diese Extrusion bei einer Temperatur erfolgen muß, bei der das Polyethylen flüssig ist, das Vernetzungsmittel jedoch noch nicht zersetzt wird. Entweder nach einer Zwischenlagerung oder durch direktes Einführen der Matrix in einen Schäumofen wird der radikalische Zerfall des Peroxids initiiert und das Polyethylen vernetzt unter gleichzeitiger chemischer Zersetzung des Treibmittels und Aufschäumung der Matrix. Dies Verfahren erlaubt zur Zeit Schäume mit Raumgewichten zwischen 30 und 175 kg/m3 und Dicken zwischen 5 und 15 mm herzustellen. Die Breite dieser Schäume ist jedoch mit etwa 2 m begrenzt, da sich Breitschlitzdüsen größeren Ausmaßes nicht herstellen lassen. Eine wirtschaftliche Herstellung von herkömmlichen Bodenbelägen ist nach diesem Verfahren nicht möglich.From the so-called Furukawa process, it is known to produce crosslinked polyethylene foams by extruding polyethylene, azodicarbonamide as a blowing agent and dicumol peroxide as a crosslinking agent with the aid of an extruder with a downstream slot die to form a matrix in the form of a film or a non-foamed sheet, this extrusion being carried out in one Temperature must be at which the polyethylene is liquid, but the crosslinking agent is not yet decomposed. The radical decomposition of the peroxide is initiated either after an intermediate storage or by direct introduction of the matrix into a foaming furnace and the polyethylene crosslinks with simultaneous chemical decomposition of the Blowing agent and foaming of the matrix. This process currently allows foams with densities between 30 and 175 kg / m3 and thicknesses between 5 and 15 mm to be produced. However, the width of these foams is limited to about 2 m, since it is not possible to produce wide-slit nozzles of a larger size. It is not possible to produce conventional floor coverings economically using this method.

Es ist weiterhin bekannt, daß man auch aus Ethylenvinylacetatcopolymeren (EVA) oder Mischungen von EVA mit Polyethylen (PE) formbare Schäume herstellen kann, indem man Polymere, Füllstoffe, Aktivatoren, Schäumungsmittel sowie ggf. Vernetzungsmittel bei Temperaturen von 90 - 100 °C, d.h. einer Temperatur, bei der das Polymer bereits weich bzw. flüssig ist, die Zusatzstoffe jedoch noch chemisch stabil bleiben, vermischt und die Mischung granuliert. Das Granulat wird anschließend in Formen gefüllt, durch Erhitzen aufgeschäumt und nach dem Wiederabkühlen aus der Form entnommen. Kleinere, auch komplizierte Formteile, lassen sich auf diese Art und Weise gut herstellen. Beispiele dafür sind Schuhsohlen, Bälle, Dichtungen, Matten, Masken etc. Die Produktion von 4 - 5 m breiten Endlosbahnen, wie sie bei Fußbodenbelägen notwendig sind, ist nach diesem Verfahren jedoch nicht möglich.It is also known that it is also possible to produce moldable foams from ethylene-vinyl acetate copolymers (EVA) or mixtures of EVA with polyethylene (PE) by using polymers, fillers, activators, foaming agents and, if appropriate, crosslinking agents at temperatures of 90-100 ° C, i.e. a temperature at which the polymer is already soft or liquid, but the additives still remain chemically stable, is mixed and the mixture is granulated. The granules are then filled into molds, foamed by heating and removed from the mold after cooling again. Smaller, even complicated, molded parts can be easily produced in this way. Examples of this are shoe soles, balls, seals, mats, masks etc. However, the production of 4 - 5 m wide continuous webs, as are necessary for floor coverings, is not possible with this process.

Weiterhin ist bekannt, weichmacherfreie Polyurethanschäume durch mechanisches Verschäumen der Komponenten unter Einpressung von Luft zu erzeugen, jedoch kann das Aufschäumen dabei nicht chemisch gehindert und dadurch keine Struktur erzeugt werden.It is also known to produce plasticizer-free polyurethane foams by mechanically foaming the components while injecting air, but the foaming cannot be chemically prevented and no structure can be created as a result.

Es ist außerordentlich überraschend, daß über handelsübliche Pulverstreumaschinen die erfindungsgemäßen Mischungen sich gleichmäßig über Breiten von 4 - 5 m verteilen lassen, so daß beim anschließenden Durchleiten durch den Trockenofen eine homogene gleichmäßig dicke Schaumschicht entsteht. Mehrfachschichten können so auch einfach hergestellt werden, indem man auf eine erste verfestigte und ggf. egalisierte Schicht eine zweite Pulverschicht aufstreut, wiederum trocknet oder geliert. Eine Einfärbung der Schicht ist durch zwischenzeitliches Aufdrucken des Farbmusters, eine Strukturierung durch Aufdrucken eines Aktivators oder Desaktivators möglich.It is extremely surprising that the mixtures according to the invention can be distributed uniformly over widths of 4-5 m using commercially available powder scattering machines, so that a homogeneous, uniformly thick foam layer is formed when they are subsequently passed through the drying oven. Multiple layers can also be easily produced by sprinkling a second powder layer on a first solidified and, if necessary, leveled layer, drying or gelling again. The layer can be colored by temporarily printing the color pattern, structuring by printing an activator or deactivator.

Die erfindungsgemäß verarbeitbaren Polymeren umfassen eine Vielzahl von thermoplastischen Produkten. Der wichtigste Parameter ist der Schmelzindex (MFI 190°C/2.16). Es wurde festgestellt, daß bei Schmelzindizes unter 2,5 und über 40 die zu hohe bzw. zu niedere Schmelzviskosität keine gute Zellstruktur des Schaumes mehr zuläßt. Ein Schmelzindex von etwa 10 - 20 scheint insofern optimale Ergebnisse zu ergeben. Der Kristallitschmelzpunkt der Polymeren sollte unterhalb des Zersetzungsbereiches des Treibmittelgemisches liegen, jedoch nicht so niedrig, daß der Schaum z.B. unter starker Sonneneinstrahlung oder Gewichtsbelastung zu fließen beginnt. Kristallitschmelzpunkte in einem Bereich von 70 - 110 scheinen insofern gut geeignet zu sein. Sehr niedere Schmelzpunkte des Polymeren können jedoch durch eine nachträgliche Vernetzung, beispielsweise durch Zugaben von Peroxid oder durch Behandlung mit energiereicher Strahlung, angehoben werden. Infrage kommende Polymere sind Copolymere aus Ethylen und Vinylacetat, Polyethylen, Polypropylen, Copolymere mit Polyvinylacetat, Polymethylmethacrylat, Polyethylenacrylsäureestercopolymere, Polyethylenacrylsäureester, Maleinsäureanhydridcopolymere und andere.The polymers which can be processed according to the invention comprise a large number of thermoplastic products. The most important parameter is the melt index (MFI 190 ° C / 2.16). It was found that with melt indices below 2.5 and above 40, the too high or too low melt viscosity no longer permits a good cellular structure of the foam. A melt index of around 10 - 20 seems to give optimal results. The crystallite melting point of the polymers should be below the decomposition range of the blowing agent mixture, but not so low that the foam begins to flow, for example, under strong sunlight or weight. Crystallite melting points in a range from 70 to 110 seem to be well suited in this respect. However, very low melting points of the polymer can be increased by subsequent crosslinking, for example by adding peroxide or by treatment with high-energy radiation. Suitable polymers are copolymers of ethylene and vinyl acetate, polyethylene, polypropylene, copolymers with polyvinyl acetate, polymethyl methacrylate, polyethylene acrylic acid ester copolymers, polyethylene acrylic acid esters, maleic anhydride copolymers and others.

Die Polymeren werden aus den handelsüblichen Granulaten auf Korngrößen von maximal 400 - 600 um, vorzugsweise 10 - 400 um, vermahlen und in dieser Form mit den übrigen Komponenten gemischt.The polymers are ground from the commercially available granules to a maximum particle size of 400-600 μm, preferably 10-400 μm, and mixed in this form with the other components.

Als Zuschlagstoffe sind alle diejenigen möglich, die auch in sonst üblichen Schaummischungen verwendet werden. Beispielhaft seien anorganische Füllstoffe wie Kreide, Silikate, Magnesium- oder Aluminiumhydroxyde, Schwerspat, Kieselsäure, Glaspulver, Ruß, Titandioxid oder auch andere Farbpigmente, welche gleichzeitig die Lichtdurchlässigkeit des Schaumes verändern, genannt. Als organische Zuschlagsstoffe kommen insbesondere Holz oder Korkmehl oder auch temperaturbeständige Kunststoffe wie Polyurethane in Frage. Diese werden der Mischung als feine Pulver mit Korngrößen von 10 bis etwa 500 um zugemischt, wobei die Füllstoffe je nach Produkt in Mengen von 5 - 50 % der Mischung zugefügt werden.All additives that are also used in the usual foam mixtures are possible as additives. Examples include inorganic fillers such as chalk, silicates, magnesium or aluminum hydroxides, heavy spar, silica, glass powder, carbon black, titanium dioxide or other color pigments that simultaneously change the translucency of the foam. In particular, wood or cork flour or also temperature-resistant plastics such as polyurethanes come into consideration as organic additives. These are mixed into the mixture as fine powders with grain sizes from 10 to about 500 μm, the fillers being added to the mixture in amounts of 5-50%, depending on the product.

Als Treibmittel für die Schaumschichten verwendet man die auch sonst bei Plastisolen üblichen Produkte wie Azodicarbonamid, Oxibis-benzolsulfohydrazit, Azoisobuttersäuredinitril, Toluolsulfohydrazit u.a. Bevorzugt ist Azodicarbonamid, dessen Zersetzungstemperatur von ca. 200 °C durch Zusatz von Aktivatoren wie Zinkoxid, Zinkoctoat und anderen bekannten Aktivatoren bis zu Temperaturen von 120 reduziert werden kann. Die Schäumungstemperatur läßt sich auf diese Art und Weise an den jeweils zu verschäumenden Kunststoff und seine Viskosität gut anpassen. Die Treibmittel werden als feine Pulver (2 bis 12 /1. Korngröße) oder als Batch (abgerieben mit Paraffin oder Antistatica) in Mengen von 0,5 - 10% der Mischung zugefügt.The blowing agents used for the foam layers are the usual products for plastisols such as azodicarbonamide, oxibis-benzenesulfohydrazite, azoisobutyronitrile, toluenesulfohydrazite and others. Azodicarbonamide is preferred, the decomposition temperature of which can be reduced to about 120 ° C. by adding activators such as zinc oxide, zinc octoate and other known activators. In this way, the foaming temperature can be easily adapted to the plastic to be foamed and its viscosity. The blowing agents are added to the mixture in the form of fine powders (2 to 12/1. Grain size) or as a batch (rubbed with paraffin or antistatic agent) in amounts of 0.5-10%.

Als Desaktivatoren für die Stellen, an denen ein Aufschäumen nicht erwünscht ist, können die für solche Schaummischungen bekannten Substanzen verwendet werden. Vorzugsweise werden Trimelittsäureanhydrid, Benzotriazol oder Thioharnstoff verwendet. Im Gegensatz zu den lösungsmittelhaltigen Pasten, die eine Diffusion der Desaktivatoren in die schaumfähige Schicht ermöglichen, muß bei den erfindungsgemäßen Mitteln der Desaktivator zusammen mit einem Transportmittel aufgedruckt werden. Als Transportmittel eignen sich z.B. flüssige Paraffine oder flüssige Antistatica oder vernetzbare Derivate der Methacrylsäure. Die Desaktivatoren sollten in einer Menge von ca. 0,5 - 2% bezogen auf die Masse der zu strukturierenden Schaumschicht angewendet werden.The substances known for such foam mixtures can be used as deactivators for those places where foaming is not desired. Trimelitic anhydride, benzotriazole or thiourea are preferably used. In contrast to the solvent-containing pastes, which enable the deactivators to diffuse into the foamable layer, in the agents according to the invention the deactivator must be printed on together with a means of transport. As a transport For example, liquid paraffins or liquid antistatic agents or crosslinkable derivatives of methacrylic acid are suitable. The deactivators should be used in an amount of approx. 0.5 - 2% based on the mass of the foam layer to be structured.

Ferner können der Mischung noch Peroxyde zur Vernetzung des Schaumes und zur Verbesserung der Temperaturbeständigkeit der Polymeren sowohl bei der Verarbeitung als auch beim späteren Gebrauch zugefügt werden. Als Hilfsstoffe kommen ferner Bakterizide, Antistatika, Antioxydanzien etc. infrage, wie sie in der Latex- und Kunststoffverarbeitung üblich sind.In addition, peroxides can be added to the mixture to crosslink the foam and to improve the temperature resistance of the polymers both during processing and during later use. Bactericides, antistatic agents, antioxidants, etc., as are customary in latex and plastic processing, are also suitable as auxiliary substances.

In den folgenden Beispielen ist die Erfindung näher erläutert.The invention is explained in more detail in the following examples.

Rezeptur-BeispieleRecipe examples Beispiel 1example 1

Figure imgb0001
Figure imgb0001

Beispiel 2Example 2

Figure imgb0002
Figure imgb0002

Beispiel 3Example 3

Figure imgb0003
Verfahrens-Beispiele
Figure imgb0003
 Process examples

Beispiel 4Example 4 Herstellung von schaumhaltigen, textilen oder elastischen Bodenbelägen mit gestreuten, chemisch geschäumten EVA-DryblendsManufacture of foam-containing, textile or elastic floor coverings with scattered, chemically foamed EVA dry blends

Das Vorprodukt ist ein üblicher Tuftingbelag ohne Rückseitenverfestigung, Nadelfilzbelag, nur mit Faserimprägnierung oder ein heterogener, schaumstrukturierter elastischer Bodenbelag, die auf den dafür geeigneten Produktionsmaschinen vorproduziert sind. In die üblichen Rückseitenausrüstungs- und Beschichtungsanlagen ist eine auf dem Markt erhältliche Pulverstreumaschine als Zusatzausrüstung eingesetzt; die Gesamtanlage ist schematisch in Fig. 1 dargestellt. Das Trägermaterial, Textilbelag oder vorgefertigter heterogener elastischer Belag, wird mittels einer Abrollung (1) und Speicherdosierung der Anlage endlos zugeführt. In dem ersten Auftragswerk (2) wird mittles einer nicht dargestellten Beschichtungsvorrichtung ein sog. Fixier- oder Grundstrich zum Schließen der Substratoberfläche aufgetragen und wenn nötig, durch Ausheizung (Umluftkanal oder Strahler) erwärmt und über eine Glättvorrichtung (3) geglättet.The preliminary product is a common tufting covering without backing, needle felt covering, only with fiber impregnation or a heterogeneous, foam-structured elastic floor covering, which are pre-produced on the appropriate production machines. In the usual rear side finishing and coating systems, a powder scattering machine available on the market is used as additional equipment; the overall system is shown schematically in Fig. 1. The carrier material, textile covering or prefabricated heterogeneous elastic covering, is fed continuously to the system by means of a roll (1) and storage metering. In the first application unit (2), a so-called fixing or base coat for closing the substrate surface is applied by means of a coating device (not shown) and, if necessary, heated by heating (air circulation duct or radiator) and smoothed using a smoothing device (3).

Im zweiten Auftragswerk (4) wird mittels einer Pulverstreumaschine das in Beispiel 1 beschriebene EVA-Dryblend aufgetragen und anschließend in einer Infrarot-Strahlerstation (5) angeschmolzen, aber noch nicht chemisch verschäumt oder vernetzt.In the second application unit (4), the EVA dry blend described in Example 1 is applied using a powder spreader and then melted in an infrared emitter station (5), but not yet chemically foamed or crosslinked.

Die angeschmolzene Schaumoberfläche kann zusätzlich über eine Glätt-Trommel (6) geglättet und verfestigt werden. Das so erhaltene Flächengebilde wird in einem Trocken-/Gelierofen (7) auf ca. 120-200 °C erhitzt, wodurch das EVA-Pulver aufschäumt und durch Reaktion der Peroxide vernetzt. Nachgeschaltet sind wiederum ein Glättwerk (3), eine Kühlstrecke (8) sowie Speichereinheit und Aufrollung (9). Gegebenenfalls kann die notwendige Fertigwarenkontrolle der Bodenbelagsbahn direkt kontinuierlich in der Anlage erfolgen. Dann wird auf Länge geschnitten und auf Einzelrollen gerollt, bevor das Material ins Fertigwarenlager geht.The melted foam surface can also be smoothed and solidified using a smoothing drum (6). The fabric thus obtained is heated in a drying / gelling oven (7) to approx. 120-200 ° C, causing the EVA powder to foam and crosslinked by reaction of the peroxides. A smoothing unit (3), a cooling section (8) and a storage unit and reel (9) are in turn connected downstream. If necessary, the necessary finished goods inspection of the floor covering web can take place continuously in the system. Then it is cut to length and rolled on individual rolls before the material goes to the finished goods warehouse.

Beispiel 5Example 5 Herstellung von schaumhaltigen Bodenbelägen mit gestreuten, chemisch geschäumten und strukturierten EVA-DryblendsProduction of foam-containing floor coverings with scattered, chemically foamed and structured EVA dry blends

Der heterogene, EVA-Schaumschichten enthaltende elastische Bodenbelag kann auf einer üblichen, für PVC-Bodenbeläge geeigneten Beschichtungsanlage hergestellt werden. Als Zusatzausrüstung sind auf dem Markt erhältliche Pulver-Streumaschinen eingesetzt. Die verwendete Vorrichtung ist schematisch in Fig. 2 dargestellt. Das Trägermaterial (Textil-, Glas- u. ä. -Gewebe) wird mittels Abrollung (1) und Speicherdosierung der Anlage endlos zugeführt. In dem ersten Auftragswerk (2) wird mittels einer nicht dargestellten Beschichtungsvorrichtung als sog. Fixier- oder Grundstrich das entsprechende Beschichtungsmaterial zum Schließen und Glätten des Trägersubstrates aufgetragen, mittels Strahler (5) erwärmt und über eine Glättvorrichtung (3) geglättet.The heterogeneous elastic floor covering containing EVA foam layers can be produced on a conventional coating system suitable for PVC floor coverings. Powder spreaders available on the market are used as additional equipment. The device used is shown schematically in FIG. 2. The carrier material (textile, glass and similar fabrics) is fed to the system endlessly by means of unwinding (1) and storage metering. In the first application unit (2), the corresponding coating material for closing and smoothing the carrier substrate is applied by means of a coating device (not shown) as a so-called fixing or base coat, heated by means of radiators (5) and smoothed using a smoothing device (3).

Im zweiten Auftragswerk (4) wird mittels einer Pulver-Streumaschine das in Beispiel 2 oder 3 beschriebene EVA-Dryblend aufgetragen und anschließend in einer Infrarot-Strahlerstation (5) angeschmolzen, aber noch nicht chemisch verschäumt oder vernetzt.In the second application unit (4), the EVA dry blend described in Example 2 or 3 is applied using a powder scattering machine and then melted in an infrared emitter station (5), but not yet chemically foamed or crosslinked.

Die angeschmolzene Schaumoberfläche kann zusätzlich über eine Glätt-Trommel (6) geglättet und verfestigt werden. Alternativ wird auf die erhaltene glatte Schaumoberfläche mit einer Druckmaschine (7) ein mehrfarbiges Druckdessin mittels Polymer-Binderdruckfarbe aufgetragen. In einem dritten Auftragswerk (8) wird die Druckschicht mittels einer transparenten Beschichtungsmasse abgedeckt. Das so erhaltene Flächengebilde wird in einem Trocken-/Gelierofen auf 160-200 °C erhitzt, wodurch die EVA-Dryblendschicht aufschäumt - bei Strukturierung nur partiell - und durch die Peroxide vernetzt wird. Trocknung und Reaktion der transparenten Abdeckschicht findet gleichzeitig statt.The melted foam surface can also be smoothed and solidified using a smoothing drum (6). Alternatively, a multicolor print design is applied to the smooth foam surface obtained using a printing machine (7) using polymer binder printing ink. In a third application unit (8), the printing layer is covered by a transparent coating compound. The fabric obtained in this way is heated in a drying / gelling oven to 160-200 ° C, which causes the EVA dry blend layer to foam - only partially when structured - and is crosslinked by the peroxides. The transparent cover layer dries and reacts simultaneously.

Zur Verbesserung der Trägermaterial-Rückseite und des Gesamtrückfederungsverhaltens der Bodenbelagskonstruktion kann in einer weiteren Pulver-Streumaschine (4) noch einmal ein schäumbares EVA-Dryblend aufgebracht werden, wie oben beschrieben, was dann gemäß (5), (3), (9) angeschmolzen, verfestigt, geglättet und ausgeschäumt wird. Eine abschließende Oberflächenbehandlung mittels Glättwerk (3) dient zur Homogenisierung der Schaumoberfläche. Gegebenenfalls kann hier auch eine strukturierte Walze nach Art eines Prägewerks eingesetzt werden. In der Kühlstrecke (10) wird die Materialbahn gekühlt und dann einer Speichervorrichtung und Aufrollung (11) der Anlage entnommen. Gegebenenfalls kann eine zwischengeschaltete Kontrolle mit Konfektion auf fertige Einzelrollen erfolgen, die dann dem Fertigwarenlager direkt zugeführt werden.In order to improve the backing of the backing material and the overall springback behavior of the floor covering construction, a foamable EVA dry blend can be applied again in a further powder spreading machine (4), as described above, which then melted in accordance with (5), (3), (9) , solidified, smoothed and foamed. A final surface treatment using a smoothing unit (3) serves to homogenize the foam surface. If necessary, a structured roller in the manner of an embossing mill can also be used here. The material web is cooled in the cooling section (10) and then removed from a storage device and reel (11) of the system. If necessary, a Intermediate control with ready-made single rolls are carried out, which are then fed directly to the finished goods warehouse.

Alternativ kann der vorstehend beschriebene Belag auch im Batch-Verfahren hergestellt werden, indem Längen von ca. 500 m jeweils nach einem oder mehreren der vorstehenden Schritte aufgerollt, zwischengelagert und zu einem späteren Zeitpunkt der nächsten Bearbeitungsstation zugeführt werden.Alternatively, the above-described covering can also be produced in a batch process, in that lengths of approximately 500 m are rolled up after each of one or more of the above steps, stored temporarily and fed to the next processing station at a later point in time.

Claims (11)

1. Process for the production of latex-, PVC- and plasticiser-free synthetic material floor and wall coverings in a width of up to 4 or 5 m which contain at least one foamed layer and a carrier layer,
characterised in that on the carrier layer, subsequently present under the foamed layer, there is scattered on a powder mixture consisting of
100 parts of a latex-, PVC- and plasticiser-free thermoplastic polymer with a melt index (MFI
190 C/2.16) of 2 to 40
0 - 100 parts filling materials
0.5 - 7 parts propellant
0 - 30 parts adjuvants
in an amount corresponding to the desired thickness of the foamed layer and melted at temperatures of
70 - 110 ° C, smoothed between smoothing rollers and foamed up at temperatures of 120 - 200 ° C.
2. Process according to claim 1, characterised in that the foam layer, after the gelling, smoothing and/or possible printing, is covered with one or more further not foamed covering layers and only thereafter foamed up.
3. Process according to claim 1, characterised in that the carrier layer and/or additional covering layers are produced in appropriate manner from a powder mixture according to claim 1 without propellant and without the foaming step.
4. Process according to claim 1 or 2, characterised in that the propellant contains an activator and the foam layer is, after the smoothing, partly printed with a deactivator.
5. Process according to one of claims 1 - 4, characterised in that the propellant is azodicarbonamide, the activator a zinc compound and the deactivator a triazole.
6. Process according to one of claims 1 - 5, characterised in that, as substrate, there is used a gel layer, fabric or release paper on which is possibly applied a priming layer of non-foamed polymers.
7. Process according to one of claims 1 to 6, characterised in that the mixture is composed of a grain fraction of the size 0 - 600 µm, preferably of 10 - 400 µm.
8. Process according to one of claims 1 - 7, characterised in that the polymer has a melt index (MFI 190°C/2.16)of 10 - 20.
9. Process according to claim 7 or 8, characterised in that the crystallite melting point of the polymer lies at 70 - 1100 C.
10. Process according to claim 8 or 9, characterised in that the polymer is a co-polymer of ethylene and vinyl acetate, polyethylene, polypropylene, co-polymer with polyvinyl acetate, polymethyl methacrylate, polyethylene acrylic acid ester co-polymer, polyethylene acrylic acid ester, maleic acid anhydride co- polymer.
11. Process according to one of claims 1 - 10, characterised in that the mixture contains a crosslinker, especially an organic peroxide, in an amount of up to 10 parts.
EP92106129A 1991-06-28 1992-04-09 Latex-, PVC- and plasticiser-free, foamed floor and wall coverings Expired - Lifetime EP0520151B2 (en)

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BE1006982A3 (en) * 1993-04-06 1995-02-07 Dsm Nv Method for manufacturing a thermally mouldable floor covering
CN105398233A (en) * 2015-12-10 2016-03-16 中山市恒辉印花有限公司 Three-dimensional foaming digital air brush printing production system
EP3568272B1 (en) 2017-01-11 2022-08-03 Flooring Industries Limited, SARL Method for manufacturing a substrate for a floor panel
WO2018130924A1 (en) * 2017-01-11 2018-07-19 Ivc, Bvba Method for manufacturing a substrate for a floor panel
BE1024909B1 (en) * 2017-01-11 2018-08-16 Ivc Bvba Method for manufacturing a substrate for a floor panel
CN109537421A (en) * 2018-11-22 2019-03-29 浙江晶通塑胶有限公司 A kind of forming method of plastic floor solid grain
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DE2621195C2 (en) * 1976-05-13 1982-10-14 Giulini Chemie Gmbh, 6700 Ludwigshafen Stiffening materials for shoes and parts of shoes
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