Classifications

• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0016—Plasticisers

Definitions

• the present invention relates to a composition of a surface covering layer, the composition comprising a citrate- based plasticizer and also relates to a method to produce a surface covering comprising such a layer.
• VOCs emissions are also due to other plasticizers such as dibenzoate plasticizers, thermal stabilizers, viscosity reducers and other additives, which are commonly used in surface covering layer compositions.
• a barrier layer within the surface covering or a varnish layer generally a polyurethane (PU) layer, applied on the top surface of the surface covering.
• PU polyurethane
• the present invention aims to provide a composition for a surface covering layer, a surface covering comprising such a layer, and a method to produce such a surface covering that do not have the drawbacks of the prior art.
• the invention aims to provide a surface covering layer and a surface covering with suitable level of stiffness and very low VOCs emission.
• the present invention relates to a PVC-based composition of a surface covering layer, said composition comprising at least one PVC resin, at least one non phthalate- based plasticizer generating VOCs and/or at least one additive generating VOCs, said composition further comprises at least one citrate-based plasticizer.
• the PVC-based composition may comprise one, or a combination, of any of the following characteristics:
• the citrate-based plasticizer is selected from the group consisting in triethyl citrate (TEC) , tributyl citrate (TBC) , acetyl tributyl citrate (ATBC) , acetyl triethyl citrate (ATEC) and acetyl tri 2-ethyl-hexyl citrate (ATEHC) .
• TEC triethyl citrate
• TBC tributyl citrate
• ATBC acetyl tributyl citrate
• ATEC acetyl triethyl citrate
• ATEHC acetyl tri 2-ethyl-hexyl citrate
• citrate-based plasticizer represents between 8 and 72 phr
• the non phthalate-based plasticizer represents between 0 and 36 phr
• the additives represent between 0 and 15 phr
• the non phthalate-based plasticizer is selected from the group consisting in adipates, benzoates, monobenzoates and dibenzoates, trimellitates, FAME (fatty acid methyl ester) terephthalates and cyclohexanoates ,
• the additive is selected in the group consisting in liquid stabilizers, viscosity reducers, blowing agents, liquid kickers, antistatic agents and fire retardants,
• the citrate-based plasticizer is acetyl tributyl citrate (ATBC)
• the non phthalate-based plasticizer is diisononyl adipate (DINA) and isononyl benzoate (INB) .
• the present invention relates to the use of the
• PVC-based composition according to the invention to obtain a surface covering layer having a reduced VOCs emission.
• the surface covering layer is a support layer, a wear layer, a saturation layer, a back foam or a top foam layer of a multiple layer surface covering .
• the present invention relates to the use of the
• PVC-based composition according to the invention to obtain a surface covering having a reduced VOCs emission.
• the present invention relates to a method to produce a surface covering comprising the steps of providing a composition according to the invention, gelling the composition at a temperature comprised between 130°C and 200°C to form a film or a layer, assembling the layer to at least another layer to form a surface covering.
• At least another layer has a composition according to the invention .
• the present invention relates to a surface covering comprising at least one layer comprising the composition according to the invention.
• the surface covering is a floor covering.
• Figure 1 represents the surface covering according to the invention.
• the surface covering according to the invention is a multilayer PVC-based surface covering comprising at least one layer having a PVC-based composition which comprises at least one PVC resin and at least one citrate-based plasticizer.
• This composition presents the advantage of getting a layer, and thus a resilient surface covering, with sustainable reduced VOCs emission (according to ISO 19000-9) even if volatile plasticizers or volatile additives generating VOCs, such as liquid stabilizers or viscosity reducers, are used to get a layer with suitable properties, such as for example stiffness .
• the composition of the layer according to the invention comprises at least one non phthalate-based plasticizer, preferably a plurality of non phthalate-based plasticizers.
• These non phthalate-based plasticizers may, or not, be volatile, and may, or not, generate VOCs.
• Non phthalate-based plasticizers should be understood as being plasticizers which are not ortho-phthalate esters .
• the non phthalate-based plasticizers is selected from the group consisting in adipates, benzoates, monobenzoates and dibenzoates, cyclohexanoates , pyrrolidones , trimellitates , FAME (fatty acid methyl esters) terephthalates and cyclohexanoates and mixtures thereof.
• the non phthalate-based plasticizers represent between 0 and 36 phr .
• the adipate plasticizer may be diisononyl adipate
• DINA dioctyl adipate
• DOA di- (2-ethylhexyl) adipate
• BOA benzyl octyl adipate
• the benzoate plasticizer may be isononyl benzoate
• the citrate-based plasticizer is a citrate ester of a primary alcohols comprising between two and eight carbon atoms .
• the citrate-based plasticizer is selected from the group consisting in triethyl citrate (TEC) , tributyl citrate (TBC) , acetyl tributyl citrate (ATBC) , acetyl triethyl citrate (ATEC) and acetyl tri 2-ethyl-hexyl citrate (ATEHC) .
• TEC triethyl citrate
• TBC tributyl citrate
• ATBC acetyl tributyl citrate
• ATEC acetyl triethyl citrate
• ATEHC acetyl tri 2-ethyl-hexyl citrate
• the citrate-based plasticizer represents preferably between 8 and 72 phr .
• the citrate-based plasticizer represents at least 20% wt of the total amount of plasticizers in the composition and the non phthalate-based plasticizer represents maximum 80% wt of the total amount of plasticizers in the composition.
• the layer composition comprises between 20 and 30 phr of diisononyl adipate (DINA) and 20 to 30 phr of acetyl tributyl citrate (ATBC) .
• DINA diisononyl adipate
• ATBC acetyl tributyl citrate
• the layer composition comprises between 13 and 17 phr of diisononyl adipate (DINA) , between 8 to 13 phr of acetyl tributyl citrate (ATBC) and between 13 and 17 phr of isononyl benzoate (INB) .
• DINA diisononyl adipate
• ATBC acetyl tributyl citrate
• IOB isononyl benzoate
• the composition may further comprise one or a plurality of additives, such as a liquid stabilizer, a viscosity reducer, a blowing agent, a liquid kicker, an antistatic agent, a fire retardant, or a mixture thereof.
• additives may, or not, be volatile and may, or not, generate VOCs .
• the additives may represent between 0 and 15 phr.
• the liquid stabilizer may be for example a Ca/Zn stabilizer or a Ba/Zn stabilizer.
• the viscosity reducer may be for example either a linear or branched paraffin or a fatty acid methyl ester.
• the blowing agent may be for example an azodicarbonamide-based agent or baking soda.
• the liquid kickers may be for example a mixed metal soaps, based for example on potassium or Zinc.
• the antistatic agent may be based on polyethyleneglycolether, for example Markstat from Artek Surfin Chemicals .
• the layer according to the invention is obtained from the composition according to the invention by gelling the composition at a temperature of between 130°C and 200°C using either gelling drums or an oven.
• the layer according to the invention may be a film or a foam.
• the viscosity increase thus obtained can be balanced by using an adipate-based plasticizer and a citrate-based plasticizer. By doing so, the blowing ratio and the cell structure are not affected in comparison to a layer comprising phthalate plasticizers .
• the layer may be used as a support layer, a wear layer, a saturation layer, a back foam or a top foam layer of a multiple layer surface covering.
• the VOCs emission is defined as the sum of VVOC (Very Volatile Organic Compound), TVOC (Total Volatile Organic Compound) and SVOC (Semi Volatile Organic Compound) . It is measured at 3 days according to a test method based on ISO 16000 using microchamber carried out in Eurofins or at 28 days according to ISO 16000-9 or ISO 16000-10.
• the VOCs emission of the layer and of a surface covering comprising such a layer represents less then 10 yg/m 3 .
• the use of the PVC-based composition comprising the citrate-based plasticizer allows getting a layer and a surface covering which complies with the main requirements of conventional PVC-based floor coverings comprising phthalate plasticizers, in terms of viscosity, PVC paste ageing, exudation, thermal stability, ageing ....
• the surface covering according to the invention is either a mono-layer surface covering or a multiple layer surface covering ( Figure 1).
• the surface covering may comprise one or a plurality of layers having a composition comprising citrate-based plasticizer with non phthalate-based plasticizers and/or additives which both may generate VOCs.
• the plurality of layers may be assembled by calendering or by spread coating layer by layer .
• Comparative examples are monolayer surface coverings having a composition comprising a phthalate plasticizer .
• the PVC is Lacovyl PB 1704H from Arkema or
• the filler is Omya BL 20 from Omya.
• the phthalate-based plasticizer is DINP, for example Vestinol 9 from Evonik.
• the benzoate-based plasticizer is Vestinol INB from Evonik or Benzoflex 9-88 from Eastman.
• the viscosity reducer is fatty acid methyl ester, for example Byk-LP R 21151 from Byk-Chemie.
• the stabilizer is Lankromark LZC 393 from Akcros .
• composition of monolayer surface coverings examples according to the invention (SI to S3) are given in table 2.
• the PVC is Lacovyl PB 1704H from Arkema or
• the filler is Omya BL 20 from Omya.
• the citrate-based plasticizer is ATBC, for example Pacizer 6412 from Patech.
• the adipate plasticizer is DOA, for example Plastomoll DOA from BASF, or DINA, for example Plastomoll DNA from BASF.
• the stabilizer is Lankromark LZC 393 from Akcros .
• VOCs emissions of the comparative samples and the samples according to the invention are given in table 3.
• the VOCs were measured at 3 days according to a test method based on ISO 16000 using microchamber carried out in Eurofins.
• the samples S3 and S4 were tested according to ISO 16000-10.
• the layers comprising phthalate plasticizer release a high amount of VOCs, particularly TVOCs and SVOCs.
• the layers having a composition comprising a citrate-based plasticizer show a reduced VOCs emission.
• Comparative example CE3 is a surface covering comprising a compact layer 1 above which is laid a back foam 2, above which is laid a saturation layer 3, above which is laid a top foam layer 4, above which is laid a wear layer 5.
• the composition of each layers are given in table 4 in phr .
• the characteristics of the CE3 are given in table 5.
• Table 4 Composition of the different layers of CE3.
• Table 5 Characteristics of a surface covering CE3.
• Comparative example CE4 is a surface covering having the same structure and layers composition as CE3, except that the plasticizer used is a non phthalate plasticizer, i.e. castor oil plasticizer, and that the wear layer further comprises 12 phr INB, in replacement of DIBP.
• the plasticizer used is a non phthalate plasticizer, i.e. castor oil plasticizer
• the wear layer further comprises 12 phr INB, in replacement of DIBP.
• the characteristics of the CE3 are given in table 6.
• the multilayer surface covering according to the invention has the same structure as CE3 ( Figure 1) but with layers having the composition of table 7 and having the characteristics of table 8.
• Table 7 Composition of the different layers of S5.
• the PVC is either Pevikon P682 from Ineos, Vinnolit EP 6953 from Vinnolit, Solvin 266 SF from Solvin, Solvin 372 NA from Solvin, EP 6602 C from Vinnolit, Vinnolit E 80 TT or Vestolit B 7021 Ultra from Vestolit, Solvin 372 NA from Solvin, Vinnolit E 68 FO from Vinnolit, LG PB 1202 or a mixture thereof .
• the phthalate-based plasticizer 1 is DOP, for example Eastman DOP from Eastman.
• the phthalate-based plasticizer 2 is DINP for example Vestinol 9 from Evonik.
• the phthalate-based plasticizer 3 is DIBP for example Palatinol IC from BASF.
• the benzoate-based plasticizer is INB (isononyl monobenzoate) for example Vestinol INB from Evonik.
• the citrate-based plasticizer is ATBC, for example Citrofol BII from Jungbunzlauer, or Pacizer 6412 from Patech.
• the castor oil is Grindsted Soft-N-Safe from Danisco .
• the filler is calcium carbonate Mikhart 40 from Provencale.
• the viscosity reducer is Vegalon PB 0505 from Vega-him or Atepas 5316 from Byk-Chemie.
• the blowing agent is an azodicarbonamide, for example Unifoam VI 40 from Hebron.
• the stabilizer is Lankromark LZC 393 from Akcros.
• ESBO is an Epoxidized SoyBean Oil, for example Drapex 39 from Chemtura.
• S5 should have a VOCs emission in-between CE4 and CE3, or substantially equal to CE3 as S5 comprises a benzoate non-phtalate plasticizer which is volatile and might participate to VOCs emission.
• S5 presents an important decrease of VOCs emission. This might be due to the structure of the layer obtained from the composition comprising the citrate-based plasticizer .

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• 2011
  • 2011-07-01 RU RU2014102917/05A patent/RU2578146C2/ru not_active IP Right Cessation
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