• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A method is provided for the manufacture of a vinyl flooring product, having at least a backing board, an impregnation layer, a printing layer and a top layer. At least one of a PVC, a filler material, a plasticizer, a viscosity suppressor, and a thermal stabilizer is used to make each of the individual layers. The plasticizer used for each of the individual layers comprises, for the most part, a plasticizer having a molecular weight above c22. Preferably, the viscosity suppressor used for each of the individual layers comprises, for the most part, a fatty acid ester having a molecular weight of C18 to C24.
    公开号:BE1019307A3
    申请号:E2011/0378
    申请日:2011-06-22
    公开日:2012-05-08
    发明作者:Stijn Michel Vermeulen
    申请人:Ivc N V；
    IPC主号:
    专利说明:

    Method for the manufacture of a vinyl floor product and the vinyl floor product obtained thereby
    The invention relates in the first place to a method for the manufacture of a vinyl floor product, with at least one backing layer, an impregnation layer, a printing layer and an upper layer, wherein for the manufacture of each of the individual layers at least one of a PVC , a filler material, a plasticizer, a viscosity suppressor and a thermal stabilizer are used.
    The composition of each of these layers is determined, among other things, by the production process, the final purpose or function of the layer in the finished product and the quality requirements for the finished products. These factors are important for the selection of a specific base material and the added amount of each of the specific base materials in a respective layer.
    Moreover, other factors have also become increasingly important with regard to the choice of these basic materials. One of these factors is the emission of harmful substances, in particular volatile organic components (VOCs), which must comply with a number of national and international standards.
    For PVC floor products, the most suitable standard is the German Agbb standard, which is widely accepted today as an international standard for assessing the VOC emissions of PVC floor products. In accordance with this Agbb standard, the VOCs are divided into two categories: TVOCs with a molecular mass from C6 to C16 and sVOCs with a molecular mass from C16 to C22. For each of these categories, the emission quantities are maximized at specific times after the production of the product: for TVOCs, first 3 days after manufacture, with a maximum of 10 g / m3 and, secondly, 28 days after manufacture, with a maximum of 1 g / m3, and for sVOCs only 28 days after manufacture with a maximum of 0.1 g / m3. In addition, the Agbb standard uses an R value to take into account the individual emissions of certain components. When a specific lowest concentration of interest (LCI) and a measured concentration (C) are defined for each of these components, the R value for a number of components i can be obtained as follows:
    In accordance with the Agbb standard, it is required that R ^ 1.
    It is an object of the present invention to provide a method for the manufacture of a vinyl floor product that allows compliance with the Agbb standard with regard to the emissions of the finished product.
    It should be noted that such a vinyl floor product will also contain components that are not relevant to such emissions and therefore play no role within the scope of the present invention. Examples of such components are PVC (e.g., extender PVC or paste-like PVC), and filler materials (e.g., calcium carbonate, calcium magnesium carbonate, kaolin, limestone, or barite) that are present in virtually every layer of the product (excluding a transparent PVC top layer).
    Thus, in accordance with the present invention, the method is characterized in that the plasticizer used for each of the individual layers comprises for the most part a plasticizer with a molecular mass above C22.
    A plasticizer is a liquid product that is present in any plastisol composition. Because there is only a physical bond between the PVC matrix and the plasticizer, it will play an important role in the VOC emissions of the finished product. This will lead to a migration of a certain amount of plasticizer from the product over time. Furthermore, the volatility of the plasticizer is important: the lower the molecular mass, the higher the volatility and therefore the emission. Therefore, by using a plasticizer with a molecular mass above C22, the VOC emission could be significantly reduced in order to meet the Aggb standard.
    In a preferred embodiment of the method of the present invention, the plasticizer further comprises a plasticizer with a molecular mass of C16 to C22 in an amount of 3-20% by weight of the total amount of plasticizer used in the vinyl floor product.
    Such an addition of a plasticizer with relatively low molecular mass does not have a negative influence on the ability of the finished vinyl floor product to comply with the Agbb standard.
    Preferably, the plasticizer contains said plasticizer with a molecular mass of C16 to C22 in an amount of 3-8% by weight of the total amount of plasticizer used in the vinyl floor product.
    As an example of such a plasticizer with a molecular mass of C16 to C22, the invention proposes the use of a monobenzoate.
    Another important component in the manufacture of such a vinyl product is a viscosity suppressor that is a liquid that also contributes to VOC emissions. According to current practice, (dearomatized) hydroalkanes with a molecular mass between C10 and C14 are used, which leads to unacceptably high emission quantities after 3 days.
    Thus, in accordance with another embodiment of the method of the present invention, the viscosity suppressor used for each of the individual layers comprises for the most part a fatty acid ester with a molecular mass of C18 to C24.
    Such a fatty acid ester has a sufficiently high molecular mass to reduce the emission (irrespective of the specific weight of the vinyl product), but also sufficiently low not to compromise the compatibility (with associated unfavorable outgrowth of the viscosity suppressor).
    This fatty acid ester can be used in the top layer in a dosage of 2-7 phr, and preferably 3-4 phr, in the pressure layer in a dosage of 4-8 phr, and preferably 4-5 phr, in the impregnation layer in a dosage of 3-8 phr, and preferably 4-6 phr and in the backing layer in a dosage of 3-8 phr, and preferably 4-6 phr.
    Alternatively, the fatty acid ester can be replaced with an aromatized hydroalkane with an average molecular weight of C22 that comes from an isodewaxing process. This also leads to permissible VOC emissions within the Agbb standard.
    In an embodiment using a fatty acid ester, it is also possible for the viscosity suppressor to further contain mineral oils with a molecular mass of C15 to C18 in an amount of 10-50% by weight of the total amount of viscosity suppressor.
    Preferably, the viscosity suppressor may contain said mineral oils with a molecular mass of C15 to C18 in an amount of 35% by weight of the total amount of viscosity suppressor.
    In yet another embodiment of the process, the fatty acid esters contain at most 12% fatty acid esters with at most two double bonds, and preferably at most 6% fatty acid esters with at most two double bonds.
    Such double bonds form an important restriction in the selection of the fatty acid esters. The fatty acid esters, when used as a viscosity suppressor, will also be present in a transparent PVC top layer and double bonds would damage the UV stability of such a transparent PVC top layer.
    During the manufacture of a vinyl floor product using a coating process (as opposed to a laminating process), an impregnation layer is used to fill the glass fiber support, after which this layer is pre-gelled at a temperature in the range of 140-150 ° C. To allow the impregnation layer to pass through a gel roller more easily, a thermal stabilizer is added. Known thermal stabilizers are metal soap stabilizers (Ca / Zn or Ba / Zn) which contain, inter alia, ethylhexanoic acid (EHA) and phenol impurities.
    However, these components have a low LCI value that is unfavorable for the above-mentioned R value according to the Agbb standard. The same applies to the printing layer that contains a comparable thermal stabilizer.
    Therefore, in accordance with another embodiment of the method of the present invention, the impregnation layer and the printing layer each contain a thermal stabilizer free of phenol and free of ethylhexanoic acid but containing dodecanoic acid.
    Due to the substitution of phenol and ethylhexanoic acid with dodecanoic acid, the thermal stabilizer in the impregnation layer and in the printing layer appears to play no role anymore in the emission of VOCs in the finished vinyl floor product.
    The top layer contains, in particular if it is transparent, a liquid stabilizer which must provide thermal and UV stability, and which includes, inter alia, a metal complex responsible for thermal stability and phosphites responsible for UV stability . Although ideally not only should EHA be eliminated from this top layer, but also the phosphites (which are based on phenol or nonyl-phenol), the elimination of the phosphites is not an option because this would unacceptably influence UV stability.
    In view of this problem, therefore, in another embodiment of the method of the present invention, the top layer contains a ethylhexanoic acid-free thermal stabilizer with an amount of up to 0.5% by weight of phenol in a dosage of 1 -4 phr. The said dosage of the thermal stabilizer is then preferably 2-3 phr. It has been found that, as a result, the R-value according to the Agbb standard no longer poses a problem for a large variety of thicknesses of the top layer (e.g. from 0.1 to 1 mm).
    As an alternative solution to this problem, in another embodiment of the method according to the present invention, the upper layer contains a liquid thermal stabilizer that is free of phenol but contains alkyl phosphites, in a dosage of 1-4 phr, preferably 2-3 phr.
    These alkyl phosphites are used in place of traditional aryl phosphites based on phenol or nonylphenol.
    As yet another embodiment of the process that does not use phenol, the top layer contains a solid thermal stabilizer that is free of phenol. This thermal stabilizer can be based on Ca / Zn.
    This can be achieved in various ways. For example, the solid thermal stabilizer is concentrated as a powder in a dosage of 0.2-2 phr, preferably a dosage of 0.5-1 phr. Alternatively, the solid thermal stabilizer may be a dispersion in a plasticizer.
    The invention relates in the second place to a vinyl floor product obtained with a method according to the present invention, which forms, for example, a tile or plank-shaped floor product.
    By using the method according to the present invention, it is possible to manufacture a vinyl floor product whose VOC emissions meet the Agbb standard without the need to provide an additional protective "blocking" layer on top of the finished product, as is used with many prior art vinyl floor products.
    The invention is not limited to the embodiments described above and can be varied in many ways within the scope of the invention as defined by the claims. In that regard, although the invention has been described with reference to a vinyl floor product, the invention also relates to vinyl products intended for another use, such as for walls and ceilings.
    权利要求:
    Claims (23)
    [1]
    Method for the manufacture of a vinyl floor product with at least one backing layer, an impregnation layer, a printing layer and an upper layer, wherein for the manufacture of each of the individual layers at least one of a PVC, a filler material, a plasticizer , a viscosity suppressor and a thermal stabilizer are used, characterized in that the plasticizer used for each of the individual layers comprises for the most part a plasticizer with a molecular mass above C22.
    [2]
    The method of claim 1, wherein the plasticizer further comprises a plasticizer with a molecular mass of C16 to C22 in an amount of 3-20% by weight of the total amount of plasticizer used in the vinyl floor product.
    [3]
    The method of claim 2, wherein the plasticizer contains said plasticizer with a molecular mass of C 16 to C 22 in an amount of 3-8% by weight of the total amount of plasticizer used in the vinyl floor product.
    [4]
    Method according to claim 2 or 3, wherein the plasticizer with a molecular mass of C16 to C22 comprises a monobenzoate.
    [5]
    The method of any one of claims 1-4, wherein the viscosity suppressor used for each of the individual layers comprises for the most part a fatty acid ester with a molecular mass of C18 to C24.
    [6]
    The method of claim 5, wherein the fatty acid ester in the upper layer is used in a dosage of 2-7 phr, and preferably 3-4 phr.
    [7]
    A method according to claim 5 or 6, wherein the fatty acid ester in the pressure layer is used in a dosage of 4-8 phr, and preferably 4-5. phr.
    [8]
    A method according to any one of claims 5-7, wherein the fatty acid ester in the impregnation layer is used in a dosage of 3-8 phr, and preferably 4-6 phr.
    [9]
    The method of any one of claims 5-8, wherein the fatty acid ester in the backing layer is used in a dosage of 3-8 phr, and preferably 4-6 phr.
    [10]
    The method of any one of claims 5-9, wherein the fatty acid ester is replaced by a dearomatized hydroalkane with an average molecular weight of C22 from an isodewaxing process.
    [11]
    The method of any one of claims 5-9, wherein the viscosity suppressor further comprises mineral oils with a molecular mass of C15 to C18 in an amount of 10-50% by weight of the total amount of viscosity suppressor.
    [12]
    The method of claim 11, wherein the viscosity suppressor contains said mineral oils with a molecular mass of C15 to C18 in an amount of 35% by weight of the total amount of viscosity suppressor.
    [13]
    A method according to any of claims 5-9, 11 and 12, wherein the fatty acid esters contain at most 12% fatty acid esters with at most two double bonds.
    [14]
    The method of claim 13, wherein the fatty acid esters contain at most 6% fatty acid esters with at most two double bonds.
    [15]
    The method of any one of claims 1-14, wherein the impregnation layer and the printing layer each contain a thermal stabilizer that is free of phenol and free of ethylhexanoic acid but contains dodecanoic acid.
    [16]
    A method according to any one of claims 1-15, wherein the top layer contains a thermal stabilizer free of ethyl hexanoic acid and with an amount of at most 0.5% by weight of phenol in a dosage of 1-4 phr.
    [17]
    The method of claim 16, wherein said dosage of the thermal stabilizer is 2-3 phr.
    [18]
    A method according to any of claims 1-15, wherein the top layer contains a liquid thermal stabilizer that is free of phenol but contains alkyl phosphites, in a dosage of 1-4 phr, preferably 2-3 phr.
    [19]
    The method of any one of claims 1 to 15, wherein the top layer contains a solid thermal stabilizer that is free of phenol, preferably based on Ca / Zn.
    [20]
    The method of claim 19, wherein the solid thermal stabilizer is concentrated as a powder in a dose of 0.2-2 phr, preferably a dose of 0.5-1 phr.
    [21]
    The method of claim 19, wherein the solid thermal stabilizer is a dispersion in a plasticizer.
    [22]
    A vinyl floor product obtained by a method according to any one of the preceding claims.
    [23]
    A vinyl floor product according to claim 22 that forms a tile or plank-shaped floor product.
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    同族专利:
    公开号 | 公开日
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO1993023466A1|1992-05-19|1993-11-25|Witco Corporation|Electrical grade polyvinyl chloride resin composition stabilized with a non-lead stabilizer|
    EP0718351A1|1994-12-22|1996-06-26|Basf Aktiengesellschaft|Additives for plastics, especially for PVC|
    EP1050562A1|1999-05-04|2000-11-08|Fina Research S.A.|Low aromatics composition|
    EP1342774A1|2002-03-06|2003-09-10|ExxonMobil Chemical Patents Inc.|A process for the production of hydrocarbon fluids|
    WO2009025725A1|2007-08-21|2009-02-26|Eastman Chemical Company|Low volatile organic content viscosity reducer|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    EP11169289|2011-06-09|
    EP11169289|2011-06-09|
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