Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08J2327/06—Homopolymers or copolymers of vinyl chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
  • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
  • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

• the present invention relates to a process for the production of a PVC-based surface covering comprising a PVC-based wear layer and a polyvinyl alcohol- based layer.
• PVC-based surface coverings are widely used to decorate buildings, houses or vehicles.
• PVC-based surface coverings have the drawback of releasing volatile organic compounds (VOCs), which for some of them are toxics.
• a polyvinyl alcohol (PVA) layer was not commonly used as PVA has a poor adherence to PVC-based layers.
• PCT/EP2009/057107 discloses the use of a barrier layer composition comprising PVA and a silane compound comprising at least one amine function .
• this solution is not suitable to obtain sufficient adherence of PVA on a PVC-based wear layer comprising no inorganic fillers or very low concentration of inorganic fillers.
• an adhesion primer should be applied on the PVC-based wear layer comprising no fillers, which implies additional process steps and leads to an increase of production costs and technical difficulties .
• the present invention aims to provide a process for the production of a surface covering which does not have the drawbacks of the prior art.
• the invention aims to provide a process for the production a surface covering comprising a wear layer top coating having an improved adherence to a PVC-based wear layer comprising substantially no fillers.
• the invention aims to provide a process for the production of a surface covering combining physical resistance properties and chemical and gas barrier properties .
• the present invention relates to a process for the production of a surface covering comprising the steps of providing a PVC-based wear layer substantially free of inorganic fillers, applying on said PVC-based layer a top coating composition comprising polyvinyl alcohol (PVA) and a silane compound comprising at least one amine function, and heating said PVC-based layer and said top coating composition at a temperature equal or superior to 150°C to form a wear layer top coating.
• the process may comprise one, or a combination, of any of the following characteristics:
• silane compound has the following structure:
• R lr R 2 , R 3 are, independently of one another, an hydroxyl group, a methoxy group, or an ethoxy group, and wherein R 4 is (CH 2 ) n/ n being equal to 1, 2 or 3, and wherein R5 is, independently of Ri, R 2 , R 3 , an Hydrogen, a linear or cyclic alkyl, a phenyl, an amide group, or an amino-ethyl group having the formula -C 2 H 4 -NH-R7, wherein R 7 is hydrogen, an alkyl, a phenyl, a benzyl group or a vinyl- benzyl group.
• the silane compound is selected from the group consisting of 3-aminopropyl-triethoxysilane, 3-aminopropyl- trimethoxysilane, aminoethyl-aminopropyl-silane triol, aminoethyl-aminopropyl-trimethoxysilane, N- ( 2-Aminoethyl ) - 3-aminopropyl-trimethoxysilane, N- (2-Aminoethyl) -3- aminopropyl-methyldimethoxysilane, N-2- (Benzylamino ) -ethyl- 3-aminopropyl- trimethoxysilane, N-2- (Vinylbenzylamino ) - ethyl-3-aminopropyl- trimethoxysilane, N-Cyclohexyl- aminomethyl-methyldiethoxysilane, N-Cyclohexyl-aminomethyl-
• the silane compound represents in weight 6 to 40 % of the PVA weight
• the silane compound represents in weight around 35% of the PVA weight
• the PVC-based layer comprising substantially no inorganic fillers is provided on a liquid form and is pre-gelified at a temperature comprises between 80°C and 170°C prior the top coating composition is applied
• the step of applying the top coating composition is performed with a PVA-based composition in a liquid form
• the top coating composition is applied in a liquid form at between 5 and 100g/m 2 .
• the process further comprises the steps of providing a PVC-based support layer, applying on said PVC-based support the PVC-based wear layer before applying the top coating composition,
• the process further comprises the step of applying a decorative layer on the PVC-based support layer,
• the PVC-based support layer comprises a glass mat
• the PVC-based support layer is a foamable layer.
• the present invention relates also to a surface covering obtained by the process according to the invention .
• the surface covering according to the invention is a floor covering.
• Figure 1 represents schematically a surface covering according to a first embodiment of the invention.
• Figure 2 represents schematically a surface covering according to a second embodiment of the invention.
• Figure 3 represents schematically a surface covering according to a third embodiment of the invention.
• Figure 4 represents schematically a surface covering according to a forth embodiment of the invention. Detailed description of the invention
• a barrier composition, or wear layer top coating composition comprising polyvinyl alcohol (PVA) and a silane compound comprising at least one amine function, is applied on a PVC-based wear layer 1, or film, comprising substantially no fillers, to form a PVA-based top coating 2.
• PVA polyvinyl alcohol
• silane compound comprising at least one amine function
• the wear layer of a surface covering is translucent or transparent and therefore comprises no fillers or only a very low concentration of fillers. Therefore, the term "substantially free of inorganic fillers” means that the amount of the inorganic filler (s) contained is below 0.5% by weight of the total weight of the PVC-based wear layer composition.
• the wear layer 1 is non-expandable or non- foamable .
• the wear layer 1 comprises 100 phr of PVC, being Lacovyl ® PB 1704 H from Arkema, and 40 phr of a di-isononylphthalate plasticizer, being Vestinol ® 9 from Evonik.
• the wear layer top coating composition is an aqueous composition comprising polyvinyl alcohol and a silane compound.
• the silane compound is selected from the group consisting of silanes, functionalised silanols, and silanes or silanols compounds comprising at least one amine function .
• the silane compound have the following formula:
• Ri, R 2 , R 3 are, independently of one another, an hydroxyl group, a methoxy group, or an ethoxy group, and wherein R4 is (CH 2 ) n/ n being equal to 1, 2 or 3, and wherein R5 is, independently of Ri, R 2 , R 3 , an Hydrogen, a linear or cyclic alkyl, a phenyl, an amide group, or an amino-ethyl group having the formula -C 2 H 4 -NH-R7, wherein R 7 is hydrogen, an alkyl, a phenyl, a benzyl group or a vinyl- benzyl group.
• the silane compound is selected from the group consisting of 3-aminopropyl-triethoxysilane, 3-aminopropyl-trimethoxysilane, aminoethyl-aminopropyl- silane triol, aminoethyl-aminopropyl-trimethoxysilane, N- ( 2-Aminoethyl ) -3-aminopropyl-trimethoxysilane, N- (2-
• Cyclohexyl-aminomethyl-triethoxysilane N-Cyclohexyl-3- aminopropyl-trimethoxysilane, N-Phenyl-aminomethy1- trimethoxysilane, 3-Ureidopropyl-trimethoxysilane and
• the silane compound represents preferably between 6 and 40% in weight of the weight of the PVA, more preferably 35%.
• the wear layer top coating composition may further comprises a wetting agent, for example a polyether- siloxane type wetting agent.
• the wear layer top coating composition is a blend of between 80 and 95% in weight of water, between 5 and 20% in weight of PVA and optionally between 0.4 and 1.5% in weight of a wetting agent.
• the blend is heated between 90 and 95°C, preferably at 85°C.
• the composition is then allowed to stand at 85°C for 60 minutes.
• the silane compound which represent between 6 and 40% by weight of PVA is added. Any additive or wetting agent is added at this stage.
• compositions comprising a functionalised silane compound are given in tables 1.
• the proportion of each component is given in phr, in percentage by weight of PVA.
• the PVA is Elvanol ® 90-
• the silane compound sil-1 is the 3- aminopropyl-triethoxy-silane, for example the Z-6011 from Dow Corning ® .
• the silane compound sil-2 is the glycidoxy- propyl-trimethoxysilane, for example Z6040 from Dow Corning ® , or Geniosil ® GF 82 from Wacker
• Sil-3 is the methacryloxy-propyl-trimethoxysilane, for example Geniosil ® GF 31 from Wacker
• Sil-4 is the vinyl-triethoxysilane, for example Geniosil ® GF 56 from Wacker.
• the wetting agent is a poly-dimethylsiloxane polyether, for example BYK ® -307 from BYK, or Tego ® Wet 270 from Evonik.
• the wear layer top coating composition is applied on a PVC-based wear layer 1. More generally, this composition may be applied on any suitable wear layer of any suitable surface covering to form a top coating.
• the surface covering may be a multiple layer and comprise a support layer 3 (Fig.2), which may be compact or foamable.
• the top coating composition is then applied over the surface of the wear layer 1 which is opposite to the surface which is intended to contact, and which contacts in the final product, the support layer 3.
• the support layer 3 may be reinforced by a glass mat 5 (Fig. 4) .
• a compact, or non- foamable, support layer 1 comprises 100 phr PVC, for example PVC (Lacovyl PB 1702 H) , 156 phr of inorganic filler (Omya BL20), 45 phr of DIHP (Jayflex 77), 28 phr of DIBP (Palatinol IC) and 5 phr of a viscosity lowering agent (Exxsol D100), « phr » meaning parts per hundred parts of PVC.
• PVC-based support layer 1 comprise 100 phr PVC, for example Pevikon ® P682 and Pevikon ® DP 2170, 117 phr of calcium carbonate (Omya BL 20), 2.9 phr of a foaming agent (Porofor ADCL-C2), 1.38 phr of zinc oxide (ZnO), 0.7 phr of Titane RC 82, 30.3 phr of DIHP (Jayflex 77), 26.2 phr of DIBP (Palatinol ® IC) , and 14.5 phr of a viscosity lowering agent (Exxsol D100), « phr » meaning parts per hundred parts of PVC.
• the surface covering may further comprise a decorative layer 4 (Fig. 3 and Fig.4) .
• the process according to the invention may further comprise a step of providing a PVC- based support layer 3 onto which the PVC-based wear layer 1 is applied.
• the process may further comprises a step of providing a decorative layer 4 which may be applied between the support layer 3 and the wear layer 1.
• the top coating composition may be applied on the wear layer 1 either simultaneously, before or after, the wear layer 1 is applied on the support layer 3.
• the top coating composition may be applied once to form a monolayer or in successive layers.
• the top coating composition is applied by any suitable method, for example by printing, heliogravure or cylinder coating, wire bar or Meyer bar coating.
• the top coating composition is applied in a liquid form at between 5 and 100g/m 2 , preferably around 40g/m 2 , or around 50g/m 2 .
• the top coating composition is applied at a temperature comprised between 80 and 170°C, during 1 to 3 minutes, more preferably at 150°C during 2 minutes. If the top coating composition is applied at a temperature lower than 150°C, then the top coating composition should be submitted to another heating step at a temperature equal or superior to 150 °C to get an improved adhesion between the top coating composition and the PVC-based wear layer 1.
• the final thickness in the final surface covering of the wear layer top coating or coatings is comprised between 0.5 ⁇ and 10 ⁇ , preferably between 4 ⁇ and 8 ⁇ , more preferably around 4 ⁇ .
• the PVC-based wear layer 1 is in a liquid form and is pre-gelified by action of heat, using any suitable device, prior the application of the top coating composition.
• the gelling of the wear layer 1 is performed at a temperature comprises between 80°C and 170°C, more preferably at around 150°C. The gelling is performed during 1 to 3 minutes, preferably during 2.5 minutes.
• the PVC-based wear layer 1 and the wear layer top coating 2 are then submitted, during between 2 and 3 minutes, to heat at a temperature equal or superior to 150 °C, a temperature which allow to get an improved adhesion between the top coating composition and the PVC-based wear layer 1.
• the heating of the PVC-based wear layer 1 and the top coating composition is performed by any suitable device or apparatus, incorporated, or not, to a system for producing a surface covering.
• the PVC-based layer 1 and the top coating composition are submitted to heat at a temperature of around 185°C during 2.5 minutes.
• the heating at a temperature equal or superior to 150 °C present the advantage of further allowing the expansion of the support layer 3, the process needing thus no further steps to obtain a foamed support layer .
• the top coating composition is applied by wire bar in the form of a continuous monolayer of around 4 ⁇ of thickness.
• the adherence is assessed by scratching the wear layer top coating 2 applied onto the PVC-based wear layer 1 and the peel resistance of the wear layer top coating is evaluate with an adhesive tape TESA ® 4124.
• the adherence is considered as satisfying when no parts of the wear layer top coating 2 are removed from the wear layer 1.
• a mark of "1" is given when the adherence is satisfying and a mark of "3" means that no adherence was obtained.
• the results are given in table 2.
• Table 2 Adherence of barrier compositions of table 1 for a PVC-based wear layer without fillers.
• the PVC-based wear layer 1 used in the adherence test comprises 70% in weight of PVC and 22% in weight of plasticizer Vestinol ® 9 from Evonik.
• composition 1 and 2 present a better adhesion to the PVC-based wear layer 1 comprising substantially no fillers. Furthermore, it appears that the top coating compositions comprising a silane compound with at least one amine and submitted to a temperature equal or superior to 150°C present a better adherence in comparison to the same compositions being submitted to a temperature of 100 to 140°C.
• the barrier properties of the wear layer top coating 2 was also assessed by measuring, according ISO 16000-10, the release of the Total Volatile Organic Compounds (TVOC) and the Semi-Volatile Organic Compound (SVOC) of a PVC-based surface covering comprising a top coating over a PVC-based wear layer in comparison to a PVC-based surface covering without top coating (T) , with a polyurethane (PU) top coating (samples 1 to 4) and with the top coating 2 according to the invention (samples 5 to 9) .
• the results are given in table 4.
• the thicknesses of the top coatings are given in weight/m 2 for the humid form.
• the top coating according to the invention allows to reduce the release of TVOC, SVOC and phenol in comparison to a PVC-base wear layer without a top coating.
• the top coating according to the invention allows to reduce significantly the SVOC and TVOC emission, or, for TVOC, to maintain this emission to a level equivalent to the one obtained with a thick layer of polyurethane.
• composition n°2 of table 1 The physical or mechanical resistance properties of the top coating (composition n°2 of table 1), applied on PVC-based layer comprising 100 phr of PVC (Lacovyl ® PB 1704 H from Arkema) and 40 phr of a plasticizer (Vestinol ® 9 from Evonik) , and dried at 185°C for 2 minutes and 30 seconds, is assessed in a "Lisson" test and in soiling conditions.
• the "Lisson” test reflects the resistance to traffic.
• a treadwheel is positioned above the top coating and rolled to-and-fro across the sample 2000 times stepwise by 10 cycles of 200 to-and-fro.
• a soiling composition according to ISO 11378 and comprising soiling agents and sand is scattered all over the test surface.
• the gloss measured at an incidence angle of 60°
• the mechanical resistance of the top coating according to the invention is also assessed under soling conditions.
• the test consists in tumbled a surface covering sample (20.5 cm x 30 cm) placed on the wall of a revolving metal drum with a bitumen composition and a tetrapod which "walks" along the surface covering samples, mimicking thus a real walking situation.
• the test is performed during 1000 cycles, each cycle comprising one rotation of the drum.
• the surface covering sample is then clean with a cloth and dried using a Dry Buffing device.
• 10 ml of a detergent (0.003 % Teepol) is deposited onto the top coating and a rotating weight (around 5kg) wipes 6 times the top surface of the sample.
• the surface covering sample is then rise with clear water before being dry with a cloth.
• the L* value (according to CIE L*a*b*), the YI (Yellowness Index) and the gloss are then measured. The results are given in table 6.
• the surface covering obtained by the process according to the invention comprises a PVA-based top coating, or top layer, over the wear layer 1.
• the surface covering present the advantage of having a top coating 2 having a good adhesion to the wear layer 1 and having thus barrier properties.
• the surface covering of the invention present also mechanical or stain resistance properties.
• the surface covering obtained by the process according to the invention may be a floor or wall covering or a vehicle covering.
• PVC-based wear layer comprising substantially no inorganic fillers

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)

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• 2011
  • 2011-09-23 EP EP11775922.5A patent/EP2627696A2/de not_active Withdrawn

Non-Patent Citations (2)

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