WO2006005752A1 - Rubber-polyolefin surface covering - Google Patents

Rubber-polyolefin surface covering Download PDF

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Publication number
WO2006005752A1
WO2006005752A1 PCT/EP2005/053326 EP2005053326W WO2006005752A1 WO 2006005752 A1 WO2006005752 A1 WO 2006005752A1 EP 2005053326 W EP2005053326 W EP 2005053326W WO 2006005752 A1 WO2006005752 A1 WO 2006005752A1
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WO
WIPO (PCT)
Prior art keywords
surface covering
rubber
acrylate
ethylene
granules
Prior art date
Application number
PCT/EP2005/053326
Other languages
French (fr)
Inventor
Peter Gustafsson
Roland Karlsson
Helena Martensson
Original Assignee
Tarkett Sas
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 Tarkett Sas filed Critical Tarkett Sas
Priority to CA002570505A priority Critical patent/CA2570505A1/en
Priority to EP05766819A priority patent/EP1765943A1/en
Priority to US11/632,261 priority patent/US7811371B2/en
Priority to UAA200701398A priority patent/UA84483C2/en
Publication of WO2006005752A1 publication Critical patent/WO2006005752A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D121/00—Coating compositions based on unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C08L23/0876—Neutralised polymers, i.e. ionomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the invention relates to a rubber - polyolefin surface covering.
  • Standard rubber floor coverings are well known in public.
  • the major advantages of such floor coverings are their dimensional stability, the absence of creeping and their relatively high resistance to abrasion.
  • the rubber floor coverings are suffering from low tear and stain resistance and are also sensitive for scratches. Smell is another disadvantage.
  • a standard rubber formulation is as follows:
  • the object of the present invention is to provide an improved surface covering as far as tear and stain resistance are concerned.
  • a surface covering comprising between 5 and 50% w/w of elastomer material, belween 5 and 50% w/w of thermoplastic material, between 25 and 70% w/w of filler and between 1% and 10% w/w of vulcanisation system.
  • vulcanisation system is TBBS, ZBEC, CBS 1 sulphur, stearic acid and zinc oxide.
  • Such surface coverings have a higher tear and stain resistance than the traditional rubber surface coverings.
  • An additional advantage of the rubber-PO surface coverings of the invention is that the sheets and tiles can be sealed, by welding them at their seams, as usual in PVC flooring which is not possible in standard rubber flooring.
  • thermoplastic material has to be between 5 and 50%
  • elastomer content of the material has to be between 5 and 50%
  • filler level between 25 and 70%.
  • the vulcanisation system is of traditional type.
  • the use of the following thermoplastic polymers or mixtures thereof in the formulations is especially preferred and enhances specific properties of the finished product:
  • UHMWPE Ultra High Molecular Weight Polyethylene
  • Acid copolymer such as E/MMA, E/AA
  • terpolymer improves the tear and scratch resistance and gives low friction.
  • Ionomer improves the scratch and tear resistance and gives low friction.
  • EBA Ethylene Butyl Acrylate
  • EMA Ethylene Methyl Acrylate
  • EVA Ethylene Vinyl Acetate
  • Ethylene Octane Copolymer improves the tear resistance.
  • PVC Poly Vinyl Chloride
  • PE Polyethylene
  • PP Polypropylene
  • thermoplastic polymers Polypropylene, Polybutylene or mixtures thereof can also be incorporated in the product.
  • ionomers are especially preferred since they give better results as far as the floor properties are concerned. They improve the tear resistance, the friction and the scratch resistance of the flooring even further.
  • the surface covering may further comprises a top coating comprising a
  • PU-dispersion a PU-solution, a 2-components PU, a PU acrylate, an epoxy acrylate, a polyester acrylate, a polyether acrylate, a silicone acrylate or a mixture thereof to further reinforce the scratch resistance and other properties.
  • the top coating comprises a water based UV-curable PU-acrylate dispersion with a dry content of between 5% and 80% w/w, preferably between 20 and 60% w/w.
  • the top coating has usually a thickness of between 0,5 ⁇ m to 100 ⁇ m.
  • Fig. 1 shows a schematic flow-sheet of the production process.
  • Typical formulations for the product according to the invention are as follows:
  • the vulcanisation package is of traditional type.
  • a rubber compounder delivers a single coloured compound in sheet form. Three sheets of different colours are granulated and calendered in a roller mill to form a marbled sheet. In this process stage the material is not supposed to vulcanise, therefore the temperature of the roller mill should be below 130 0 C.
  • the process parameters of the roller mill are set as follows: Speed: 5-10m/min, Temperature: ⁇ 13O 0 C.
  • the thus obtained sheet is then granulated to obtain granules of suitable sizes (e.g. 0,1 to 40 mm).
  • the granules are scattered on the steel belt in a double belt press and pressed to a multicoloured, marbled sheet.
  • the material is vulcanised.
  • the temperature of the heating zone in the belt press exceeds 130 0 C which is the temperature at which the vulcanisation package works.
  • the process parameters of the double belt press are set as follows: Pressure: 3-20 bar, Temperature: 130-200 0 C, Speed: >2m/min.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Floor Finish (AREA)

Abstract

A surface covering comprising between 5 and 50% w/w of thermoplastic material, between 5 and 50% w/w of elastomer material, between 5 and 20% w/w of a high styrene resin, between 25 and 70% w/w of filler and between 1% and 10% w/w of vulcanisation system.

Description

RUBBER - POLYOLEFIN SURFACE COVERING
Field of the Invention
The invention relates to a rubber - polyolefin surface covering.
Description of the-Related Art
Standard rubber floor coverings are well known in public. The major advantages of such floor coverings are their dimensional stability, the absence of creeping and their relatively high resistance to abrasion. However, the rubber floor coverings are suffering from low tear and stain resistance and are also sensitive for scratches. Smell is another disadvantage.
A standard rubber formulation is as follows:
- rubber 20 - 32% - Filler (clay + silicates) 63%
- Vulcanisation agent + processing aids 5 - 7% ,
Object of the invention
The object of the present invention is to provide an improved surface covering as far as tear and stain resistance are concerned.
SUMMARY OF THE INVENTION
In accordance with the present invention, a surface covering comprising between 5 and 50% w/w of elastomer material, belween 5 and 50% w/w of thermoplastic material, between 25 and 70% w/w of filler and between 1% and 10% w/w of vulcanisation system.
An example of vulcanisation system is TBBS, ZBEC, CBS1 sulphur, stearic acid and zinc oxide. Such surface coverings have a higher tear and stain resistance than the traditional rubber surface coverings.
An additional advantage of the rubber-PO surface coverings of the invention is that the sheets and tiles can be sealed, by welding them at their seams, as usual in PVC flooring which is not possible in standard rubber flooring.
Formulation evaluations have shown that the content of thermoplastic material has to be between 5 and 50%, the elastomer content of the material has to be between 5 and 50% and the filler level between 25 and 70%. The vulcanisation system is of traditional type. The use of the following thermoplastic polymers or mixtures thereof in the formulations is especially preferred and enhances specific properties of the finished product:
UHMWPE (Ultra High Molecular Weight Polyethylene): improves the surface of the flooring. Acid copolymer (such as E/MMA, E/AA) or terpolymer: improves the tear and scratch resistance and gives low friction.
Ionomer: improves the scratch and tear resistance and gives low friction.
Polystyrene: improves the scratch and scuffmark resistance. Acrylate: EBA (Ethylene Butyl Acrylate) improves the tear resistance and gives low friction.
EMA (Ethylene Methyl Acrylate) improves the tear resistance. EVA (Ethylene Vinyl Acetate) improves the tear resistance. Ethylene Octane Copolymer improves the tear resistance. Furthermore, PVC (Poly Vinyl Chloride), PE (Polyethylene), PP
(Polypropylene), Polybutylene or mixtures thereof can also be incorporated in the product. Of the tested thermoplastic polymers, ionomers are especially preferred since they give better results as far as the floor properties are concerned. They improve the tear resistance, the friction and the scratch resistance of the flooring even further. An addition of 5 to 50% w/w ionomers, preferably between 15 to 20% gives the best results.
The following elastomer materials (rubbers) are suitable to use in the context of the invention:
SBR (Styrene Butadiene Rubber) NBR (Nitrile Butadiene Rubber) NR (Natural Rubber)
IR (Isoprene rubber) EPDM (Ethylene Propylene Rubber)
All rubber types improve the dimensional stability and the creeping properties since the polymer chains are crosslinked in the vulcanisation process. First triafe have shown that, by simply mixing the different components, it was hardly possible to process the formulation due to the very high viscosity at high temperature. Significant improvements in the processability were obtained by adding an EBA polymer and/or by adding high styrene resin (SBR with a high amount of bound styrene, such as from 50 to 85%, preferably 55 to 75% of bound styrene), preferably in quantities between 5 and 20% w/w, especially between 7 and 15% w/w.
It was also helpful to add silicones, e.g. polymethylsiloxan, between 0.5 and 5% w/w, preferably between 1.5 and 2.5% w/w to lower friction during the production process. The surface covering may further comprises a top coating comprising a
PU-dispersion, a PU-solution, a 2-components PU, a PU acrylate, an epoxy acrylate, a polyester acrylate, a polyether acrylate, a silicone acrylate or a mixture thereof to further reinforce the scratch resistance and other properties.
In a preferred embodiment, the top coating comprises a water based UV-curable PU-acrylate dispersion with a dry content of between 5% and 80% w/w, preferably between 20 and 60% w/w. The top coating has usually a thickness of between 0,5 μm to 100 μm.
Detailed description with respect to the figures
The present invention will be more apparent from the following description of a not limiting embodiment with reference to the attached drawings, wherein
Fig. 1 shows a schematic flow-sheet of the production process.
Typical formulations for the product according to the invention are as follows:
Figure imgf000005_0001
The vulcanisation package is of traditional type.
The production process for a homogenous rubber-PO floor is described below with regard to Figure 1.
A rubber compounder delivers a single coloured compound in sheet form. Three sheets of different colours are granulated and calendered in a roller mill to form a marbled sheet. In this process stage the material is not supposed to vulcanise, therefore the temperature of the roller mill should be below 130 0C. The process parameters of the roller mill are set as follows: Speed: 5-10m/min, Temperature: < 13O0C.
The thus obtained sheet is then granulated to obtain granules of suitable sizes (e.g. 0,1 to 40 mm). The granules are scattered on the steel belt in a double belt press and pressed to a multicoloured, marbled sheet. In this process stage, the material is vulcanised. The temperature of the heating zone in the belt press exceeds 130 0C which is the temperature at which the vulcanisation package works. The process parameters of the double belt press are set as follows: Pressure: 3-20 bar, Temperature: 130-2000C, Speed: >2m/min.
The properties of a standard rubber floor compared to the rubber-PO floor according to the invention.
Figure imgf000006_0001

Claims

Claims
1. A surface covering comprising between 5 and 50% w/w of thermoplastic material chosen among the group constituted of UHMWPE (Ultra High Molecular Weight Polyethylene), ionomer, acid copolymer or terpolymer, Polystyrene, EBA (Ethylene Butyl Acrylate), EMA (Ethylene Methyl Acrylate),
EVA (Ethylene Vinyl Acetate), Ethylene Octane Copolymers, PVC (Poly Vinyl Chloride), PE (Polyethylene), PP (Polypropylene), Polybutylene or mixtures thereof, between 5 and 50% w/w of elastomer material chosen among the group constituted of SBR (Styrene Butadiene Rubber), NBR (Nitrile Butadiene Rubber), NR (Natural Rubber), IR (Isoprene rubber), EPDM (Ethylene
Propylene Rubber) or mixtures thereof, between 5 and 20% w/w of a high styrene resin, between 25 and 70% w/w of filler and between 1% and 10% w/w of vulcanisation system.
2. The surface covering according to claim 1 , wherein the surface covering further comprises . between 0.5 and 5% w/w silicones, preferably between J\ .5 and
2.5% w/w silicones.
3. The surface covering according to any of the preceding claims, wherein the surface covering comprises between 5 to 50% w/w ionomers, preferably between 15 to 20% w/w ionomers.
4. The surface covering according to any of the preceding claims, wherein the surface covering comprises a top coating comprising a PU-dispersion, a PU- solution, a 2-components PU1 a PU acrylate, an epoxy acrylate, a polyester acrylate, a polyether acrylate, a silicone acrylate or a mixture thereof.
5. The surface covering according to claim 4, wherein the top coating comprises a water based UV-curable PU-acrylate dispersion with a dry content of between 5 and 80% w/w, preferably between 20 and 60% w/w.
6. The surface covering according to any of claims 4 or 5, wherein the top coating 5 has a thickness of between 0,5 μm to 100 μm.
7. A process for producing a surface covering comprising the following steps:
a. mixing between 5 and 50% w/w of thermoplastic material chosen among the group constituted of UHMWPE (Ultra High Molecular Weight Polyethylene), ionomer, acid copolymer or terpolymer, Polystyrene, EBA
10 (Ethylene Butyl Acrylate), EMA (Ethylene Methyl Acrylate), EVA (Ethylene
Vinyl Acetate), Ethylene Octane Copolymers, PVC (Poly Vinyl Chloride), PE
(Polyethylene), PP (Polypropylene), Polybutylene or mixtures thereof, between 5 and 50% w/w of elastomer material chosen among the group n# constituted of SBR (Styrene Butadiene Rubber), NBR (Nitrile Butadiene
15 Rubber), NR (Natural Rubber), IR (Isoprene rubber), EPDM (Ethylene
Propylene Rubber) or mixtures thereof, between 5 and 20% w/w of a high styrene resin, between 25 and 70% w/w of filler and between 1% and 10% w/w of vulcanisation system,
b. calendering said mixture at temperature and pressure conditions that do 20 not vulcanise the elastomer material to form at least two calendered sheets,
c. granulating the sheets so as to obtain granules,
d. mixing said granules and forming a marbled surface covering with the granules and vulcanising the elastomer material.
8. The process according to claim 7, wherein the process further comprises the following steps :
c1) forming a marbled sheet of the granules,
c2) granulating said marbled sheet so as to form granules.
9. The process according to claim 8, wherein the forming of a marbled surface covering of step d. comprises depositing the granules on a double belt type press and pressing and vulcanising the granules so as to form a surface covering.
PCT/EP2005/053326 2004-07-13 2005-07-12 Rubber-polyolefin surface covering WO2006005752A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA002570505A CA2570505A1 (en) 2004-07-13 2005-07-12 Rubber-polyolefin surface covering
EP05766819A EP1765943A1 (en) 2004-07-13 2005-07-12 Rubber-polyolefin surface covering
US11/632,261 US7811371B2 (en) 2004-07-13 2005-07-12 Rubber-polyolefin surface covering
UAA200701398A UA84483C2 (en) 2004-07-13 2005-12-07 Covering for the surface of composition rubber resin-polyolefin and the process for its preparation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP04291801A EP1616923A1 (en) 2004-07-13 2004-07-13 Rubber-polyolefin surface covering
EP04291801.1 2004-07-13

Publications (1)

Publication Number Publication Date
WO2006005752A1 true WO2006005752A1 (en) 2006-01-19

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Country Status (6)

Country Link
US (1) US7811371B2 (en)
EP (2) EP1616923A1 (en)
CA (1) CA2570505A1 (en)
RU (1) RU2381248C2 (en)
UA (1) UA84483C2 (en)
WO (1) WO2006005752A1 (en)

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WO2008083973A1 (en) * 2007-01-12 2008-07-17 Tarkett Sas Composition and manufacturing process of a decorative surface covering
US20100201025A1 (en) * 2007-09-27 2010-08-12 Tarkett Sas Method for making ground coatings
CN102731897A (en) * 2012-07-16 2012-10-17 江苏达胜高聚物有限公司 High wear-resistant low-smoke halogen-free irradiation crosslinking sheathing material and preparation method thereof
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DE102015118618A1 (en) * 2015-10-30 2017-05-04 Nora Systems Gmbh Method of making a patterned floor covering and patterned floor covering
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WO2019086977A1 (en) * 2017-11-03 2019-05-09 American Biltrite (Canada) Ltd. Resilient surface coverings and methods of making and using thereof
CN109081979B (en) * 2018-06-22 2021-07-23 上海化工研究院有限公司 Preparation method of ultrahigh molecular weight polyethylene nano composite material
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RU2697807C1 (en) * 2019-06-03 2019-08-20 Федеральное государственное бюджетное образовательное учреждение высшего образования "Волгоградский государственный технический университет" (ВолгГТУ) Thermoplastic elastomeric coating composition
CN111393963A (en) * 2020-03-23 2020-07-10 浙江优涂新材料科技有限公司 Environment-friendly energy-saving L ED photocuring woodenware spraying primer easy to polish
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008083973A1 (en) * 2007-01-12 2008-07-17 Tarkett Sas Composition and manufacturing process of a decorative surface covering
EP1953202A1 (en) * 2007-01-12 2008-08-06 Tarkett SAS Composition and manufacturing process of a decorative surface covering
US8192846B2 (en) 2007-01-12 2012-06-05 Tarkett Sas Composition and manufacturing process of a decorative surface covering
US20100201025A1 (en) * 2007-09-27 2010-08-12 Tarkett Sas Method for making ground coatings
US9266264B2 (en) * 2007-09-27 2016-02-23 Tarkett Sas Method for making ground coatings
CN102731897A (en) * 2012-07-16 2012-10-17 江苏达胜高聚物有限公司 High wear-resistant low-smoke halogen-free irradiation crosslinking sheathing material and preparation method thereof
WO2016184845A1 (en) 2015-05-18 2016-11-24 Tarkett Gdl Halogen-free decorative homogeneous surface coverings
EP3741820A1 (en) 2015-05-18 2020-11-25 Tarkett GDL Process for the preparation of a halogen-free decorative homogeneous surface covering
US11254835B2 (en) 2015-05-18 2022-02-22 Tarkett Gdl Halogen-free decorative homogeneous surface coverings
CN106832731A (en) * 2017-01-05 2017-06-13 上海力茵地面弹性材料有限公司 Elastic ground, its rubber grain mixture, its construction method and circular thermoplasticity polyolefin particles preparation method
CN106832731B (en) * 2017-01-05 2019-12-10 上海力茵地面弹性材料有限公司 elastic floor, rubber particle mixture thereof, construction method thereof and method for manufacturing round thermoplastic polyolefin particles

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EP1765943A1 (en) 2007-03-28
EP1616923A1 (en) 2006-01-18
RU2381248C2 (en) 2010-02-10
US7811371B2 (en) 2010-10-12
CA2570505A1 (en) 2006-01-19
UA84483C2 (en) 2008-10-27
US20080053335A1 (en) 2008-03-06
RU2007105140A (en) 2008-08-20

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