MXPA97000865A - Pi coverage - Google Patents

Abstract

The present invention relates to sheet materials suitable for use in, or as, a floor covering. The sheet materials comprise a polyalkene resin in intimate mix with at least one additive comprising a filler, wherein the polyalkene resin has a relatively narrow molecular weight distribution (MWD), and a small amount of long chain branching, and which is produced by a single site catalyzed polymerization of at least one linear, branched, or cyclic alkene of 2 to 20 carbon atoms. The present invention also extends to processes for the production of these sheet materials and pee coatings

Description

FLOOR COVERING The present invention relates to floor coverings, and more particularly, to floor coverings in the form of mosaic or durable sheets, made of one or more layers of suitable polymers, for example, for pedestrian traffic in domestic situations and / or other situations, over an extended period of time. Most floor coverings of this type are based on polyvinyl chloride (PVC) polymer. In greater detail, the PVC polymer resin is generally mixed with a plasticizer (solid or liquid) (usually with other different additives, such as fillers, polymeric stabilizers, and processing aids), to form an extensible paste, which is it can be formed into sheets by extension coating using knife or roller coating equipment, and then cured thermally, for example, by heating in the oven. The use of PVC, however, presents significant environmental problems, due to the use of chlorine, and in accordance with the above, there is a need for floor coverings based on alternative polymers. Polyalkylene polymers are generally preferred from an environmental point of view, but the use of conventional peraalkylenes presents significant processing problems, and they are not suitable for use in coating technology manufacturing facilities based on coating technology. extended and passed by calandria. In addition, a particular problem in the use of conventional polyalkylene polymers in floor coverings is that they do not provide the necessary physical characteristics required in the final product. In greater detail, it has been known that floor coverings produced using conventional Lilene polya, give insufficient tensile and tear strength, resistance to abrasion and stains, and elastic recovery. It is an object of the present invention to eliminate or minimize one or more of the above drawbacks. It has now been discovered that a particular class of polyalkylenes, which are produced by single-site catalyzed polymerization, can be successfully used in the manufacture of floor coverings based on the more or less conventional extended coating or calender coating technology. More particularly, suitable polyalkylenes according to the present invention are those which have a relatively narrow molecular weight distribution (MWD), and a small amount of long chain branching, and which are produced by polymerization catalyzed in a only site, and that have the following characteristics: a) melting index (MI) from 0.1 to 100 b) density from 0.86 to 0.97; and c) a DRI of 0.1 to 6.0, preferably 0.4 to 5.5.

As used herein, the following terms have the indicated meanings: Fusion index (MI) or I2, is the amount (in grams) of polymeric resin that is extruded in a predetermined period of time (10 minutes), measured in accordance with ASTM (American Standard Test Method) D-12..8 (190 / 2.16). The Molecular Weight Distribution (MWD) is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (ie, Mw / Mn). The density is the mass (in grams) of 1 cubic centimeter of resin, measured in accordance with the ASTM D-792 standard. The Dow Rheology Index (DRI) is a long-chain branching index measured by comparing the movement to the right (due to a longer relaxation time), in relation to a polymer resin with zero long-chain branching. (LCB), in a graph of zero shear viscosity versus relaxation time (both from a cross-viscosity equation). Other abbreviations used herein, which are common in the art, include: PHR - parts per 100 parts by weight of polymer resin (or main polymeric resin component). Suitable polyalkylenes according to the present invention, may also comprise a relatively narrow molecular weight (Mw) distribution, and a small amount of long chain branching, and are produced by a single site catalyzed polymerization of at least one linear, branched or cyclic alkene having 2 to 20 carbon atoms. Conveniently, the polyalkene comprises a copolymer produced by the copolymerization of two or more alkenes comprising a linear or branched first alkene having from 2 to 8 carbon atoms, and a second linear, branched, or cyclic alkene having from 2 to 20 carbon atoms. carbon atoms. This allows for greater design flexibility in relation to obtaining sheet materials with particular combinations of desired physical characteristics. In general, up to 15 mole percent of the second monomer can be used. Of course, it will be understood that, where cyclic alkenes are used, they may have more than one carbon ring, and therefore, may include bicyclic and tetracyclic alkenes, such as norbornene and tetracyclododecene. In another aspect, the present invention provides a sheet material suitable for use in, or as, a floor covering, and comprising a polyalkylene resin in intimate admixture with one or more additives selected from a filler and an auxiliary. extended coating processing, wherein the polyalkylene resin has a relatively narrow molecular weight distribution (MWD), preferably less than 3.0, and a small amount of long chain branching, and which is produced by catalyzed polymerization in a single site , and that has the following characteristics: a) Fusion index (MI) from 0.1 to 100, b) Density from 0.86 to 0.97; and c) a DRI of 0.1 to 6, preferably 0.4 to 5.5.

One of the very versatile characteristics of metallocene catalysts is the range of comonomer that can be incorporated into polymer chains, -through the use of these catalysts in the polymerization of a single site of alkenes. Metallocene catalysts, for example, are capable of incorporating, in the polymer chains, cyclic monomers, conveniently polycyclic monomers, including cyclic monomers such as norbornene (C7H10). Accordingly, it is possible to incorporate materials such as norbornene in copolymer with ethylene, which has the benefit of raising the hardness and melting point over conventional polyethylene resins. The new sheet materials provided by the present invention have the additional property advantage to incorporate different design features. It is possible to incorporate graphic images on the floors in a way that gives an image with depth perception. Systems that use ion projection technology are well known in the art. These systems use an electrostatic charge that corresponds to the desired image. This image is deposited on the material with a drum or band. The material carrying the electrostatic image moves through a revealing station, where a matting material of opposite charge adheres to the charged areas of the dielectric surface, to form a visible image. Another layer of polymer can be deposited on top of this, and another image can be produced in this layer. By adding successive layers, each with its own image, it is possible to build a structure with a perception of image depth. This technique, which uses conventional resins, is explained in U.S. Patent Number US 5347296. An advantage of using metallocene-derived catalysts, ee presents during the image forming process. In a more particular way, the use of catalysts * metallocene allows incorporation of end groups containing boron, and / or very high levels of unsaturation. These end groups can be functionalized to provide additional means to facilitate image formation. Imaging can be created either by electrostatic projection systems, or by functionalizing these end groups, so that the polymer chains are better combined with the matizer or the pigments. In another aspect, the present invention provides a sheet material suitable for use in, or as, a floor covering, and comprising a polyalkene resin in intimate admixture with at least one additive comprising a filler, wherein the resin of polyalkene has a relatively narrow molecular weight distribution (MWD), and a small amount of long chain branching, and is produced by single-site catalyzed polymerization of a linear or branched first alkene having from 2 to 8 carbon atoms, and preferably, a second linear, branched, or cyclic alkene having from 2 to 20 carbon atoms. Although processing aids can be used in the novel materials of the present invention, to adjust or accentuate particular processing characteristics, such as reduced energy requirements, and / or higher processing speed, it is a characteristic of the polyalkene resins used in the present invention, which do not require the use of a plasticizer, thereby significantly reducing the environmental problems caused by the migration of the liquid plasticizers out of the material, and / or the loss of performance associated with the use of the plasticizers . However, in cases where it is desired to increase processability, then a processing aid or a plcistificante can be used, and it is an advantage of the present invention that a significantly smaller amount of plasticizer can be used., comparing with the polymeric resins conveniently used in floor coverings. In a particularly preferred form of the invention, moreover, a plasticizer or processing aid is used which comprises a selectively polymerizable liquid monomer system, which is substantially non-polymerizable under the conditions of sheet formation, eg, extrusion, coating Extended, or calendered, used in the manufacturing process of the floor covering sheet material, while substantially subsequently polymerizable to produce a material material free of liquid plasticizer. In general, the polymerizable monomer can be used in an amount, relative to the polyalkylene resin, from 20 to 80: 80 to 20. Further details of suitable plasticizers are discussed hereinafter. In connection with this, it will be understood that an initiator substance is normally used for the purpose of inducing the polymerization of the monomer, and that it is included together with the monomer in the monomeric system. Accordingly, in those cases, it is important that the initiator be one that can be selectively activated, ie, that is substantially inactive under the conditions of polyolefin product formation, but that subsequently can be activated under polymerization conditions. or curing of the appropriate plasticizer monomer. Various polyalkene resins suitable for use in the materials of the present invention are known in the art. In general, they are produced by the polymerization of alkene monomers in the presence of particular catalysts that restrict the progress of the polymerization, and are known as metallocenes (the resulting polymers being commonly referred to as metallocene polyolefins, conveniently abbreviated as MPOs). These polyolefins and processes for their production are described, inter alia, in U.S. Patent Number 5,272,236.

Preferred polyalkylenes which may be mentioned comprise copolymers of ethylene and an alpha-alkene having from 4 to 20 carbon atoms, conveniently from 4 to 10 carbon atoms, for example propylene, butene-1, or hexene-1, or a cyclic olefin such as norbornene; copolymers of propylene and an alpha-alkene having from 2 to 10 carbon atoms, for example butene-1, hexene-1, of a cyclic olefin such as norbornene; and copolymers of 4-methyl-1-pentene and an alpha-alkene which has from 2 to 10 carbon atoms, for example, butene-1, hexene-1, or a cyclic olefin such as norbornene. Preferably, a copolymer containing up to 15 mole percent comonomer is used. Furthermore, it will be appreciated that more than one comonomer may be used, ie, a terpolymer may be used, for example, where different 2-alpha-alkenes are employed, each having 2 to 20 carbon atoms. Suitable polyalkene resins that are commercially available from Exxon Chemical Company of USA, and The Dow Chemical Company of Midland, Michigan, USA, are mentioned in Tables 1 and 2 below.

Table 1 Exxon EX (CT) Resins (MR) Product Properties Key EXACT 3017 Density 0.901 Fusion index 27 EXACT 3025 Density 0.910 Fusion Index 1.2 EXACT 4038 Density 0.885 Fusion index 125 EXACT 4041 Density 0.878 Fusion Index 3.0 EXACT 5008 Density 0.865 Fusion index 10 EXACT 4006 Density 0.880 Fuel Ratio 10.0 EXACT 4003 Density 0.895 Fusion Index 9.0 EXACT 4023 Density 0.882 Fusion Index 35.0 EXACT 4033 Density • 0.880 Fusion Index 0.80 Table 2 - INSITE (MR) TECHNOLOGY POLYMER (ITP) from Dow Product Properties Key Engage CL8200 Density 0.870 Fusion index 5.0 Dow rheology index 0.5 Engage CL8150 Density 0.868 Fusion index 0.5 Rheology index Dow 2.0 Affinity SM1300 Density 0.902 Fusion index 30.0 Dow rheology index 0.4 Affinity SM1250 Density 0.885 Fusion Index 30.0 Dow Rheology Index - Engage LG 8005 Density 0.870 Fusion index 1.0 Rheology index Dow 2.0 In a further aspect, the present invention provides a floor covering based on polymeric resin comprising at least one layer of a sheet material of the invention. It will be appreciated that, in general, this covering of piezoe comprises doe or more different layers having particular functions, linked together. Typically, layers such as a foamed layer can be included to provide cushioning; a structural layer comprising a reinforcing carrier or substrate impregnated and / or coated with a saturating formula; a solid backing layer, and a transparent top or protective layer. For some types of applications, little or no expansion will be required in some or all of the layers of the floor covering structure. The present invention includes a range of floor coverings, from those in which all the layers, except the upper layer, are foamed with those in which none of the constituent layers are foamed. The sheet materials of the invention can be produced by a process comprising the steps of: providing a suitable polyalkylene resin in accordance with the present invention, and at least one additive comprising a filler and optionally a forming processing aid. sheet, typically an extended coating or calender step; placing the polyalkylene resin in intimate admixture with the at least one additive in a high shear mixer, for a period of at least 10 minutes, at an elevated temperature of at least 75 ° C, preferably from 100 ° C to 250 ° C ° C, more preferably from 130 ° C to 200 ° C, to melt the polyalkenes and sufficiently bring the mixture into a substantially fluid state without substantial degradation of the mixture; forming the fluid mixture in a sheet form; and allow the sheet to cool and solidify.

In a preferred aspect of the invention, a fluid mixture is used that is substantially free of any plasticizer. However, as discussed elsewhere herein, one or more plasticizers or processing aids may be included in the blend. Where a polymerizable plasticizer is used, then the process includes another treatment of the solidified sheet in order to also solidify the plasticizer. Where a fugitive plasticizer is used, the process conveniently includes the step of volatilizing the plasticizer. The production processes of the sheet material of the present invention have significant advantages over those made using conventional polyalkylene or polyolefin resins. Apart from the superior processability that allows the use of the existing conventional production plant previously used for PVC resin based sheet materials with minimal modifications, they also have lower energy consumption costs due to the normally reduced curing temperatures required, comparing with the production based on PVC resin, which involves an increasing temperature to effect a thermal cure, as opposed to a cooling to effect the "crystallization cure" by means of "solidification". Other benefits that can be obtained in connection with the particular floor covering layers in the products of the invention, include better hardness of the transparent outer layer with better impact resistance resulting from the lower crietalinity associated with the lower density; better cell recovery in the foamed cushion layers; and better acceptance of filler due to the more homogeneous nature of the polymer (narrow molecular weight distribution); and a good flowability of the saturated layer resulting from the high melt index with little or no blocking of the comonomer. Regarding the different aspects of the present invention, it will be appreciated that other polymeric resins other than those specified may be used, mixed with those specified, for example, for the purpose of "spreading" the specified polyalkene resin, for reasons of economy , by using a cheaper polyalkene resin, or modify the finish or other characteristics. The amount of that other polymeric resin that can be used will depend primarily on the manner in which it affects the flowability and the extended coating characteristics of the materials of the invention. Accordingly, for example, up to about 50 to 60 weight percent / weight of the other polymeric resin (relative to the total polymeric resin) may be used, depending on the use and the required properties of the sheet layer. Therefore, for example, in relation to the transparent layer, the amount of that other polymeric resin would normally be re-stripped to a minor amount of not more than about 15 to 20 weight percent / weight. The additives that may be used in the materials of the present invention, and the amounts thereof, will depend on the function and the desired properties of the sheet material, and also, to some extent, may depend on the particular polymeric resins used. . The main additives and additional processing steps generally well known in the art, which may be mentioned, include the following: 1. Inorganic fillers and reinforcements can improve the different polyolefin-based layers in the floor covering material, which is the object of this invention. This improvement can be through improvements in appearance, physical properties, or chemical characteristics. The particular attributes of the inorganic filler / reinforcement that are important are the nature of the inorganic material, the shape of the material, and any surface treatment or coating. Expose many important aspects of inorganic material. Density is important in the application and in the long-term utility of a floor covering. Highly-filled backing layers (for example, up to 85 percent by weight of filler) can be very useful in this regard. Another attribute of the basic material is hardness. A higher hardness in the final product is desirable, but a too hard filler (such as silica) can have negative effects on the wear of the processing equipment, such as the flame mixers and the extruders. Table A mentions some inorganic fillers / reinforcements.

TABLE A The bleaching filler is used to increase the opacity. In general, less than 500 PHR, preferably 20 to 120 PHR, are used in the saturant formula and foamable cushioning materials, and up to 200 PHR in the solid backing layers. The optical properties of titanium dioxide make it a particularly good pigment in obtaining a white color with good opacity. This color is desirable in the layer on which the printed design is placed. This is located below the transparent wear layer. Lower levels of titanium dioxide (2 to 6 PHR) may be employed if a white filler such as calcium carbonate is used at moderate levels in this layer. Calcium carbonate is of particular utility in polyolefin-based compositions. Hardness, rigidity, heat deformation temperature, resistance to skidding, resistance to stress cracking, possibility of welding, possibility of printing, and characteristics against blocking; all are also improved. They reduce thermal shrinkage and elongation, as well as the permeability to water vapor and oxygen. Talc is another suitable filler to improve the polyolefin formulations for covering floors. This has a lamellar structure in contraete with the structure of low aspect particles of calcium carbonate. This lamellar shape allows talc to be more effective than calcium carbonate with respect to increasing stiffness, heat deformation temperature, and dimensional stability. The advantage of talc in relation to calcium carbonate is focused on reduced impact resistance, matte surface, and lower stability to thermooxidation. Mica also has a lamellar structure, and has similar advantages and disadvantages. High aspect ratio fillers / reinforcers, such as wollastonite and glass fibers, have an even stronger effect than talc and mica, on the increase of modulus of elasticity, tensile strength, and distortion temperature by heat of the bath systems polyolefin. The improvements provided by the high aspect ratio inorganic additives would be of particular assistance in these floor covering systems made using a plasticizer or permanent processing aid, such as liquid paraffin. In these cases, the hardening action of these additives would compensate the loss of rigidity produced by the liquid paraffin. Silica, in its vaporized or precipitated forms, can be useful at low levels (from 0.1 to 1.5 percent) in polyolefin formulations where antiblocking and the possibility of printing is important. In the floor covering system, this would be in the wear layer, and in the layer on which the printed design is applied. Alumina trihydrate and magnesium hydroxide, in the correct particle sizes, which for most systems are less than 40 microns in diameter, can provide the same type of property improvement provided by calcium carbonate. In addition, they can provide useful characteristics of fire resistance and smoke control. This will be discussed in more detail in the Fire Resistance section. 2. The polyolefin materials for the floor covering systems are improved by the use of thermal and light stabilizers. For thermal stabilizers, the amount and type to be used will vary with the actual process used to manufacture the final structure. The melt extender approach will provide a product that has less heat history than any of the calender through melt or extrusion pathways. In all caoe involving foamed systems, however, polyolefin resins will be exposed to temperatures higher than 180 ° C for some time during the process. Suitable stabilizers include hindered phenol in 0.05 to 0.30 PHR, optionally with co-stabilizers, for example, organosulfur compounds such as DSTDP in 0.2 to 1.0 PHR. More particularly, good thermal stability can be obtained in these polyolefin systems, using a high molecular weight hindered phenol, such as Irganox 1010 from Ciba-Geigy, with one or more secondary antioxidants, such as thioesters and compounds of match. Distearyl thiodipropionate (DSTDP) and Ultranox 626 from GE are examples of these types of materials. An effective thermal stabilizer package of these systems is 0.1 percent Irganox 1010, 0.1 percent DSTDP, and 0.05 percent Ultranox 626. The light hindered stabilizer (HALS) stabilizers are particularly effective in protecting the polyolefins of photooxidation. A polymeric HALS such as Luchem HA-B18 from Atochem is particularly effective in its own right, and has the additional advantage of not showing antagonism to other additives such as DSTDF. The inclusion of 0.3 percent Luchem HA-B18 in the outer wear layer, and 0.15 percent in the layer just below the transparent wear layer, will greatly improve the light resistance of the polyolefin floor covering system object. 3. Lubricants and pre-processing aids can be helpful in making the polyolefin-based floor system. This will depend a lot on the specific process. For extrusion or calendering by melting operations, an external lubricant may be of assistance. Calcium and zinc stearates are suitable as external lubricants. They can also provide some additional stabilization support. They can be added in the scale from 0.1 to 1.0 percent, preferably from 0.2 to 1.0 percent. 4. Depending on the process and conditions of extended coating or calendering, the improvement of the melting strength of the polyolefin system may be useful. Polyolefin and acrylic grafts are useful in the 0.1 to 1.0 percent scale, proving to be a more elastic and stronger fusion. 5. In the polyolefin-based floor covering that is the subject of this invention, for most applications, it is desirable to have one or more of the layers in the structure (but not the wear layer) expanded in the form of a foam of closed cells. An effective route for this expanded layer is through the use of a chemical blowing agent. In polyolefin systems, azo compounds are especially effective. An example of this class of compounds is azodicarbonamide (Celogen AZ from Uniroyal). A particularly useful feature of this compound is that its point of decomposition can be reduced from 220 ° C to less than 270 ° C, through the use of activators, such as zinc oxide. This activated system can be deactivated through the use of inhibitors, such as benzotriazole. If inks containing benzotriazole are used to print on the surface of a polyolefin containing Celogen AZ and zinc oxide, and the resulting structure, with an added wear layer on the foamable layer, is heated to a temperature between the decomposition temperatures activated and inactivated, then an enhanced pattern (chemical enhancement) is created in the sample. A complementary blowing agent, such as aluminum trihydrate, may be employed in these structures. Although its primary role is that of a fire retardant additive and an inorganic filler, it has a useful auxiliary role as a blowing agent, in which water vaporizes when heated above 200 ° C. A fugitive processing aid or volatile plasticizer may also have a useful role as a complementary blowing agent. In the case of azodicarbonamide, it is generally used for foamable cushioning layers in 2.0 to 4.5 PHR, together with a suitable foaming activator such as zinc oxide. Some or all chemical blowing agents can be replaced with mechanical foaming, given the right conditions. These conditions involve mixing in the polyolefin-based mixture, which will become one of the layers in the floor, air or other gas covering material, under conditions that produce the desired number and size of cells in the resulting foam. In the extended coating system, the applied mixture needs to have a foam structure close to that of the desired product. In the process of extrusion or calendering, the gas needs to be in solution in the polymer, or as small microbubbles at the fusion pressure in the extruder system. The expansion takes place as the melt exits the extruder and goes from the high pressure (from 7 to 49 kg / cm2) to the atmoeferic pressure. In both cases, it is important that the structure of the cells is frozen to the desired size by a rapid fall in the temperature of the sheet to below that necessary for the contraction or deformation of the cells. 6. The properties of the polyolefin structures in the covering of the piezoe object, can be improved through the use of crosslinking, conveniently by means of an organic peroxide, for example, in 0.1 to 5.0 PHR, to increase the hardness and / or the stiffness of the sheet layer. Dicumyl peroxide is a reagent widely used for these reactions. This material becomes an effective crosslinking agent at 190 ° C. In the case of the polyolefin systems and cross-linked foams, it is known that a better structure of the foam cells is developed if the crosslinking is done before the foam is formed. In systems involving Celogen AZ for foaming, and dicumyl peroxide for crosslinking, both processes would take place at the same time and at the same temperature. If a peroxide with a lower activation temperature, such as 2,2-bis (tertiary butyl-peroxy) butane, is used, then the cross-linking would be carried out at about 170 ° C, followed by a foaming process at 190 ° C. The development of the strong filled and cross-linked foam polyolefin systems can be further improved by treating the inorganic filler to be used with vinyl silane. The vinyl groups that come to join the filler particles, become active in the formation of the reticulated network initiated by the free radicals produced by the peroxide. In the non-expanded layers, dicumyl peroxide would be a good cross-linking agent. In the layers to be expanded, the use of 2, 2-bie (tertiary butyl-peroxy) butane in conjunction with a blowing system of activated Celogen AZ would be desirable. In all the filled layers to be foamed, the filling must be treated with an agent such as vinylsilane, which provides sites of unsaturation on the filler particles. 7. The flammability and smoke generation of the polyolefin-based floor covering system is important. Fire characteristics can be improved through a wide range of additives. Different inorganic compounds, such as aluminum trihydrate and magnesium hydroxide, which give off water at elevated temperatures, are useful as double fire retardants / fillers. Phosphorus compounds, borates, and zinc oxide can all have useful roles to improve the fire characteristics of polyolefin-based systems. 8. Other polymeric resins other than the specified MPOs, as noted above, can be used as extenders or modifiers in amounts of 10 to 30 PHR. Examples that may be mentioned include LLDPE (Low Density Linear Polyethylene), EVA (Ethylene Vinyl Acetate), ionomers, for example SURLYN (MR) available from the DuPont Company, and VLDPE (Very Low Density Polyethylene). In addition, mixtures of two or more polyolefins prepared with metallocene can be used to obtain particular combinations of desired properties. To improve the impact properties, ee can use different types of additives with elastomeric components in a generally known manner. These generally comprise small particles with a number of an elastomer, for example, butadiene or acrylic polymer coated with an outer coating that provides good adhesion to the polymeric matrix of MPO. An example of this cover modifier additive / elastomeric component number is Paraloid EXL-330 from the Rohm and Haas Company. This resin has an acrylate rubber number and a polymethyl methacrylate shell. Other types of modifiers can be used to improve impact properties, including EPDM rubbers, such as Polysar manufactured by Bayer; block copolymer A / B / A, such as Kraton manufactured by Shell; and multi-domain elastomeric systems, such as those described in European Patent Number 583,926. 9. Other additives that may be mentioned include colorants, inks, antioxidants, etc., which are generally used in relatively small amounts in less than 50 PHR. Anti-static features can also be important for some applications. In this case, the use of different internal antistatic agents in the wear layer would be appropriate. Many antistatic additives are compounds with hydrophilic and hydrophobic sections. A common material of this type is a monoester of a polyol, such as glycerol, with a long chain fatty acid, such as stearic acid. The polyol portion is very polar, and would enter the surface of a polyolefin, while the fatty acid is "in the form of polyolefin", and would stay inside the plastic. The hydrophilic part can also be cationic, anionic, or non-ionic. Levels of 0.1 to 0.5 PHR are appropriate in the outer layer of the structure. 10. The carriers or substrates used with saturating formulations can have different shapes, for example, mesh or spun or non-spun fabric, or fabric, of more or less thermally stable materials, such as glass fiber. The polyalkene or polyolefin resins used in accordance with the present invention can be of different types, including random copolymers and terpolymers, and block copolymers, based on a variety of onomeric units, including lower alkene, preferably 1-alkene, which has from 2 to 8 carbon atoms, for example, propylene, but more preferably ethylene; dienes; cycloalkenes; and vinyl aromatics. Additional preferred features of the invention will appear from the following detailed examples, given by way of illustration, and from the accompanying schematic drawings, in which: Figure 1 is a schematic side view showing a first part of a line of production of floor covering. Figure 2 is a similar view of the second part of the production line of Figure 1. Figure 1 shows a production line of the first stage 1, to produce a three-layer sheet material 2 of the first stage, by the application of saturant, foam gel, and backing layer formulations 3, 4, 5, on a glass fiber fabric (approximately 0.45 millimeters thick) 6, supplied from a supply drum 7 by means of a first accumulator 8. The fabric is passed by means of a first weight measurement system / unit area 9, up to a first extended coating unit 10, where the hot melting saturated formulation 3 (at about 90 ° C) is applied on a side 11 of a first roller 12, up to a previously determined thickness of approximately 0.55 millimeters, controlled by a first blade 13, from a first barrel type mixer of high continuous shearing stress 14. In the other side 15 of the first roller 12, the saturating formulation is transferred to the fabric 6 in a tightening 16 between the first roller 12 and an opposite tissue support roller 17. The impregnated fabric 18 is then passed around a large diameter cooled drum 19 established for a surface temperature of about 25 ° C to 40 ° C, and other cooling drums of smaller diameter 20 for "curing by crystallization" or solidification. The hot melt foam and backing layer formulations 4, 5 are then applied successively to the coated fabric 18 in a thickness of approximately 0.2 and 0.6 millimeters, respectively, generally in a manner similar to the second and third extended coating units. 21, 22, except that the cooled drum of large diameter 19 is omitted in the stage of the backing layer. The resulting three-ply sheet material 2 is then collected on a embossing drum 23 downstream of a second accumulator 24. If desired, this sheet material is then passed to a rotogravure station or other printing station to apply a graphic design material, etc., in a generally known manner, for example, using ink designed for chemical enhancement. Figure 2 shows a production line of the second stage 101, where similar parts corresponding to those of Figure 1 are indicated by similar reference numerals to which 100 have been added. The three layer sheet material 2 produced in the production line 1 of the first stage, is supplied from a supply drum 107 by means of an accumulator 108 to a fourth extended coating unit 110, wherein a transparent layer formulation 125 is applied to the sheet material 2 in a thickness of about 0.2 millimeters, and cured as before, except that, in this case, a heat shield 126 is provided between the cooled drum 119 and the hot mixer 114, to help improve temperature control, etc. . If desired, an additional foamed backing layer can be applied using yet another extended covering applicator (not shown). It will be incidentally appreciated that, in accordance with common practice in the industry, the order of application of the different layers can be varied to a greater or lesser degree. Finally, where a polish or lacquer finish is required, it can be applied using a fluted roller applicator 127. The resultant multilayer sheet material 140 is then passed through a multi-hot air oven. steps 141 on a band support 142 established at a maximum temperature of about 200 ° C, with a residence time of about 1.5 minutes, to allow foaming expansion of the foam layer (from about 0.2 to about 0.5 millimeters) ), with a selective control of the same by chemical enhancement where it is used, on which the final cooling of the finished sheet material takes place in the additional cooling drums 120, before being collected on the embobinator drum. It can also be used step by calender of the fusion, to produce the floor coverings that are the object of this invention. Although both sheet lamination and calender coating of the viscous material can be employed, sheet lamination is preferred, with the preferred substrate being a glass fiber fabric. A multilayer laminate is prepared by applying a series of fusions based on polyalkene or polyolefin resins as described in this invention. These calendering step operations of the melt can all be done in a continuous manner, using a series of calender rollers, or they can be done in a segmented manner, applying a single layer, followed by a winding operation, adding additional layers in separate operations. In addition, a combination of continuous and discontinuous calender operations can be employed. Accordingly, for example, a saturating formulation can be applied to a glass fiber fabric, followed by a foam layer on top, and a base layer below. These three operations are performed in a consecutive manner, as the material is passed through three different sets of calender rolls before winding. Additional processing steps can be made between the calender operations. For example, the material produced by applying three polymeric layers to a glass fiber fabric could be passed through a printing process to provide a decorative image and to facilitate chemical enhancement. This different printing step could be followed by another step by calender of the fusion, to apply a wear layer to the floor covering. Could follow a step of heat treatment to the application of the wear layer, either in a continuous or discontinuous way. The heat treatment could expand the different layers through the formulation of a chemical foam, in the layers containing a chemical blowing agent. In addition, the physical and chemical properties of the polyolefin resins could be improved through a crosslinking formation in these layers by the use of a crosslinking ether. In the process of calender passage of the melt, a polymeric melt is applied to a series of two or more heated rollers, in such a way that a polymer layer of a uniform thickness is produced. The source is prepared by mixing the polymers and the non-polymeric components of the material under conditions of high temperature and shear stress. For this process, devices such as extruders or mixers can be used. More detailed descriptions of the calender passage process of The Fusion can be found in Chapter 83 of the "Handbook of Plastic Materials and Technology" by Irvin I. Rubin, and published by John Wiley and Sons, Inc. (ISBN 0-471 -09634-2). The floor covering structure, which is the subject of this invention, can also be prepared by melt extrusion. In this process, one or more polymeric layers can be applied to a continuous glass fiber fabric in a single extrusion operation. When coextrusion is used to provide multiple layers in a single pass, a separate extruder is used to feed each melt to the block of the sheet die. The extrusion operations can be intermixed with other processing steps in the preparation of the final structure. For example, a glass fabric can be saturated and encapsulated between a base layer and a foamable layer in a single pass of coextrusion involving a die sheet of three fusions. This structure can then be subjected to a printing process, followed by the addition of a single layer by extrusion. A heat treatment can follow the application of the wear layer either in a continuous or discontinuous manner. This treatment could improve the final product by expanding the layers containing chemical blowing agents and / or the crosslinking of the layers containing sietemae reticulantee. The procedure initially decribed to develop the desired floor covering structure through the use of a fusion extension approach, as shown in Figures 1 and 2, can be extended in its scope through the use of processing aids or fugitive and / or permanent plasticizers. This involves the addition of a liquid or liquids to the different polyolefin formulations used to make the layers separate from the final structure. This addition can be used to lower the temperature necessary to obtain the necessary viscosity for good processing. For example, white alcohol, petroleum ether, or mineral spirits can be mixed with a polyolefin layer system, using heat and mixing with shear to produce a homogeneous low viscosity material, which can be processed to a lower temperature than would otherwise be possible. This is a fugitive system, since white alcohol or other plasticizer evaporates from the surface of the structure after the system has been applied. Preferably, the vaporized white alcohol or other plasticizer is captured, condensed, and recycled. Alternatively, a non-volatile liquid plasticizer, such as liquid paraffin (mineral oil) can be used. In this case, the resulting floor covering structure will retain this material as a permanent component. Mixed systems of fugitive and permanent liquids can also be used. The scale for these additives may range from 200 percent to less than 5 percent, on a weight basis of polyolefin. More desirably, a polymerizable plasticizer is used. The polymerizable plastifying monomers that can be used in accordance with the present invention are those which are solvents for the main polymer components of the polyolefin product. They do not need to be, and normally would not be, solvents for inorganic components or for other components, which may themselves be polymers, such as impact modifiers, texturing aids, pigments, and some compatibilizers. The monomers will generally have a long segment that is "in the form of a polyolefin", with an end group that is capable of free radical polymerization. Typical "polyolefin-shaped" structures are hydrocarbons with 10 or more carbon atoms, and examples of such groups would be lauryl (C12H25) and stearyl (C18H35). These structures can be linear, branched, or cyclical; depending in part on the structure of the polyolefin. The terminal polymerizable group can be a single unsubstituted double bond, such as is in 1-dodecene, or a more complex unit, such as a methacrylate, such as in stearyl methacrylate. Along with the monomer or plasticizing monomers, compounds which generate free radicals at elevated temperatures, and optionally crosslinking monomers, can be used to cure the resulting products and to provide better properties. Many kinds of free radical generators can be used, but materials from the families of peroxide, ketone peroxide, peroxycarbonate, peroxydiester, hydroperoxide, and peroxycetal are of particular use. Various kinds of azo compounds and a variety of photoinitiators are also useful. The necessary characteristics in these compounds is that they are substantially non-polymerizable, that is, they remain essentially dormant during the initial mixing, composition, and manufacturing process of the product, but that they can be induced to produce free radicals at a rate that initiates a polymerization of the monomer, for example, when the temperature is increased, or when exposed to the appropriate radiation. For example, a material such as tertiary butyl perbenzoate, has a half-life of more than 1,000 hours at 100 ° C, while having a half-life of less than 2 minutes at 160 ° C. In a polymer / monomer system containing this initiator, it would be possible to process the system to obtain the finished product form (ie shape or configuration) at 100 ° C, and then the system is cured by brief exposure to the system. 160 ° C. When polyfunctional monomers are included in the system, then a continuous cross-linked polymer system can be formed from the monomer. Optionally additional optional radical generators that provide crosslinking of the previously existing polyolefin system may be included. A semi-IPN (interpenetrating network) is obtained when one of the co-continuous systems is cross-linked (i.e., the previously existing polyolefin and the polymerized plasticizer monomer). When both systems are crosslinked, an interpenetrating network is formed. To prevent premature polymerization of the plasticizer monomer, it may be useful to add additional inhibitors to the system. Most commercial monomers are provided with inhibitors to prevent polymerization during handling and processing. The level of these inhibitors must be increased to compensate for the time spent under the conditions of polyolefin polymer product formation, ie the conditions used to form the polyolefin base polymer in a sheet, or in some other form or configuration. In this regard, temperature is usually the most significant factor, but other conditions may also be relevant. Accordingly, for example, stearyl methacrylate is commercially provided with 275 parts per million (ppm) of the hydroquinone monomethyl ether (MEHQ) Depending on the times and temperature involved, 1,000 ppm of MEHQ or more may be required. Inhibitors of a wide range of chemical families can be used for this purpose.The polymeric system and the monomeric ether ee can be combined in a variety of ways to give a low viscosity plasticized material that can be used to make many types of products. using several different manufacturing techniques The combination of solid and liquid components can be done in any suitable manner, for example, by using a continuous or batch mixer, different types of continuous and batch mixing devices, and different types of extruders In all these types of equipment, the solid components are mixed together at sufficient temperature and with sufficient shear to achieve both a distributive and dispersive mixture. The liquid is introduced at the temperature and shear required to dissolve the main polymer components, and to obtain a good distributive mixture and a good dispersive mixture of the insoluble components with the resulting fluid. Then the fluid system is maintained at a temperature that retains the fluidity required for the manufacture of the final product form. In general, this will normally be from 80 ° C to 120 ° C. It will be appreciated that the polymerization of the polymerizable liquid plasticizer will result in the creation of polymer chains that extend through, and interpenetrate the previously formed network of MPO polymer chains. When both the MPO polymer chains and the polymerized plasticizer are crosslinked, then the two polymeric materials interbred captively with one another, forming the so-called interpenetrating polymer network (IPN), although if only one of these is crosslinked, then the poly chains Non-crosslinked metals could, in principle, be pulled outwards. The last type of material is conveniently referred to as an interpenetrating polymeric i-network. These interpenetrating polymeric network and interpenetrating polymeric network materials, while generally having physical properties similar to that of the other novel materials provided by the present invention, offer additional advantages in terms of improved stain resistance and / or greater resistance to solvents, both during installation and in the use of the covering of floors provided by the present invention.

Example 1 - Preparation of Multi-Layer Floor Cover Using Calender A floor covering structure is prepared by first de-winding three layers in a continuous melting calender step operation, in a first stage production line (see Figure 1) ). In this operation, a continuous fiberglass mat is fed through a line through calender by stations. Each station is fed by a separate melting mixer. In the first station, the glass mat is saturated with composition A. In the next station, the backing layer, composition B is applied. In the third station, the foamable layer, composition C, is applied. It is collected on a rewinder roller. In a separate operation, this system is fed through a printing line, where a decorative design is applied to the foamable layer. In a third processing step, this printed material is fed to the single melting calender pass station, in a second step production line, and then to a two-zone furnace system (see Figure 2). At the calandria passage station, a transparent top layer, composition D, is applied. In the first zone of the oven, which is at 160 ° C, the cross-linking of each layer is presented. In the second zone at 190 ° C, the expandable layer is foamed. The final product is then collected on an embobinator roll. The compositions of the different layers are as follows: (Saturing Layer) Parts X 100 Resin MPO Exact 4038 100 Resin Magnesium hydroxide fire retardant inorganic filler. 60 Free radical source of dicumyl peroxide for crosslinking polymerization. 2 Thermal stabilizer of hindered phenol Irganox 1010, to reverse the degradation of the polymer, manufactured by Ciba-Geigy Corp. 0.1 DSTDP (distearyl thiodipropionate), secondary thioester antioxidant to prevent polymer degradation. 0.1 Ultranox 626 secondary antioxidant from Berg-Warner Chemical. 0.05 B. (Backing layer) Exact 4038 100 'Magnesium hydroxide' 150 Cross-linking polymerization of free radical source of 2,2-bis (tertiary butyl-peroxy) butane. 2 Irganox 1010 0.1 DSTDP 0.1 Ultranox 626 0.05 C. (Foamable Layer) Exact 5008 100 Calcium metasilicate reinforcement filling with a high aspect ratio of Wolastonite. 30 Fire retardant inorganic filler of aluminum trihydrate 30 Chemical foaming agent of azodicarbonamide (releasing nitrogen gas). • 2 Zinc oxide to lower the decomposition temperature of the azodicarbonamide, to reduce the polymer foaming temperature. 0.8 2, 2-bis (tertiary butyl peroxy) butane 2 Irganox 1010 0.1 DSTDP 0.1 Ultranox 626 0.05 Polymorphized amide light stabilizer Luchem HA-B18 from Atochem, to prevent photodegradation of the polymer. 0.15 D. (Top Wear Layer) Exact 5008 100 Vinyltriethoxysilane, which provides additional recovery hardness and solvent resistance. 4 2, 2-bis (tertiary butyl-peroxy) butane 2 Luchem HA-B18 0.3 Irganox 1010 0.1 DSTDP 0.1 Ultranox 626 0.05 Example 2 - Preparation of Multilayer Floor Coating Utilizing Extended Coating In Pio Axis 2, the same sequence of steps and stations as in Example 1 is employed, except that each application station involves an extension operation of the merger, rather than a calender step operation of the merger. The composition of the four layers is the same, except that 80 parts of Jayflex 215, and 20 parts of monomer X980 (a crosslinking monomer of Rohm and Haas) are added to each of the four formulations. It will be appreciated that various modifications may be made to the above-described embodiment without departing from the scope of the present invention. Accordingly, for example, electron beam initiated crosslinking may be an alternative or complementary process for chemically initiated crosslinking. This cross-linking can be carried out by subjecting a sample to high-energy electrons in a dose of approximately 6 to 8 mega-rads for a period of 30 seconds to 2 minutes. The addition of the reactive monomer such as trimethylolpropane trimethacrylate (TMPTMA) in approximately 2 to 5 parts, it is useful to obtain a good result of this process.

Example 3 - Formulations of the Individual Layers The following polymeric resin formulations have been prepared: A. (Clear Coating Layer) Parts X 100 Resin MPO resin, Engage EP8500 (Dow Chemical Co.) (melt index 5.0, density 0.87, DRI 0.5). 100 Antioxidant Stabilizer Irganox 1010 0.05 Antioxidant stabilizer of BHT 0.05 2.5-TRI 0.1 crosslinking agent B. (Foamy Gel Layer) Parts X 100 Resin MPO Engage 8500 Resin (Dow Chemical Company) 100 Bleach Filler (generic) 15 Azo Blow Agent (Generic) 3 Zinc Oxide Foaming Catalyst 1. 5 Pigmentation component of titanium oxide 4 Stabilizer Irganox 1010 0.075 Stabilizer of DSTDP 0.05 Calcium Stearate Flow Agent 0.10 Fire retardant Firebrake (MR) 5 Antimony Oxide Fire Retardant 4 C. (Saturating Layer) Parts X 100 of Resin Resin of MPO Engage 8500 (Dow Chemical Company) 100 Bleaching filler (generic) 50 Stabilizer Irganox 1010 0. 1 Zinc stearate flow aid 0. 4 D. (Solid Backing Layer) Parts X 100 Resin MPO Engage 8500 Resin (Dow Chemical Company) 100 Bleaching filler (generic) 200 Titanium Oxide Pigmentation Component 4 Irganox 1010 0.075 Stabilizer Stabilizer of DSTDP 0.05 Calcium Stearate Flow Agent 0.10 Firebrake (MR) Fire Retardant 5 Antimony Oxide Fuels 4 Retardant Example 4 - Formulations of the Individual Layers An additional set of polymeric resin formulations is prepared as in Example 1, above, but with Affinity SM 1250 from Dow Chemical Co., as the resin component of MPO instead of EP 8500.

Example 5 - Preparation of Multi-Layer Floor Coating Using Multiple Extension A floor covering material is prepared as a four-layer structure by a multiple-extension application technique. In an initial station, a glass fiber fabric is saturated with polymer having a composition A at a temperature of about 100 ° C. In a separate station, a backing coating of composition B is applied to the underside of the glass fabric saturated with polymer at about 100 ° C. In another separate station, the foamable layer, composition C, is expanded to the upper side of the glass fabric saturated with polymer at about 100 ° C. A decorative pattern is then printed on the foam layer, using a continuous printing process that employs, in one of several inks, benzotriazole, to deactivate the accelerated foaming system, to thereby produce a chemical de-enhancement effect on foaming. In a further separate coating step of the process, a transparent wear layer of the composition D is applied to the foamable layer at approximately 100 ° C. The structure is then passed through an oven system to crosslink the layers at about 170 ° C, and then the foam layer is expanded to about 200 ° C. The cured, decorated and final enhanced product constitutes the floor covering material.

A. (Saturation Layer) Parts X 100 Resin MPO Exact 4038 100 resin Calcium carbonate 66.7 Stearyl methacrylate (plasticizer). 90 Trimethylolpropane trimethacrylate (plasticizable plasticizer). 10 Lupersol 230 (initiator of free radical polymerization of Atochem). 5 Irganox 1010 0.1 DSTDP 0.1 Ultranox 626 0.05 B. (Backing layer) Parts X 100 of Resin Exact 4038 100 Calcium carbonate 300 Stearyl methacrylate 90 Trimethylolpropane trimethacrylate 10 Lupersol 230 5 Irganox 1010 0.1 DSTDP 0.1 Ultranox 626 0.05 C. (Foamable Layer) Parts X 100 of Resin Exact 5008 100 Calcium carbonate 66.7 Stearyl methacrylate 90 Trimethylolpropane trimethacrylate 10 Lupersol 230 5 Celogen OT (Uniroyal chemical blowing agent) 4 Zinc oxide 2 Luchem HA -B18 0.15 Irganox 1010 0.1 DSTDP 0.1 Ultranox 626 0.05 D. (Wear Layer) Parts X 100 Resin Exact 3017 100 Stearyl methacrylate 70 Trimethylolpropane trimethacrylate 30 Lupersol 230 5 Vinyltrimethoxysilane 4 Luchem HA -B18 0.3 Irganox 1010 0.1 DSTDP 0.1 Ultranox 0.05

Claims (22)

1. A sheet material suitable for use in, or as, a floor covering, and comprising a polyalkene resin in intimate admixture with at least one additive comprising a filler, wherein the polyalkene resin has a molecular weight distribution ( MWD) relatively narrow, and a small amount of long chain branching, and is produced by a single site catalyzed polymerization of at least one linear, branched, or cyclic alkene having from 2 to 20 carbon atoms.

2. A sheet material according to claim 1, which is suitable for use as a floor covering component layer, selected from a backing layer, a structural layer, and a top coat layer.

3. A sheet material according to claim 1 or claim 2, wherein the molecular weight distribution of the polyalkene resin is less than 3.

4. A sheet material according to any use of the claims 1 to 3, where the polyalkene is one that has the following characteristics: a) Fusion index (MI) from 0.1 to 100, b) Density from 0.86 to 0.97; and c) a DRI (Dow Rheology Index) of 0.1 to 6.0, where the Dow rheology index is a long-chain branching index measured by comparing movement to the right (due to a longer relaxation time), in relationship with a polymer resin with zero long chain branching (LCB), on a graph of zero shear viscosity versus relaxation time (both from a cross viscosity equation).

5. A sheet material according to claim 4, wherein the polyalkene resin has a Dow rheology index of 0.4 to 5.5.

6. A sheet material according to any of claims 1 to 5, wherein the polyalkene comprises a copolymer produced by the copolymerization of at least two alkenes comprising a linear or branched first alkene having from 2 to 8 carbon atoms , and at least one additional linear, branched, or cyclic alkene having from 2 to 20 carbon atoms.

7. A sheet material according to claim 6, wherein the first monomer comprises ethylene, and the additional monomer is select from butene-1, hexene-1, and norbornene.

8. A sheet material according to claim 6 or claim 7, wherein . 1 i i 53 uses up to 15 mole percent of the additional monomer.

A sheet material according to any one of the preceding claims, wherein the sheet material comprises at least one interpenetrating semi-network of the polyalkene and a polymer of a selectively polymerizable liquid plasticizer monomer system, which is substantially non-polymerizable under the sheet forming conditions employed in the manufacture of the sheet material for covering the floors, while being substantially polymerizable subsequently to produce a material substantially free of liquid plasticizer.

10. A sheet material according to claim 9, wherein the plasticizer monomer comprises an alkene, linear, branched, or cyclic, having at least 10 carbon atoms, and a polymerizable terminal functional group.

11. A floor covering based on polymeric resin, which comprises at least one layer of a sheet material according to any of claims 1 to 10.

12. A floor covering according to claim 11, which has a plurality of layers comprising a structural layer comprising a reinforcing carrier or substrate impregnated and / or coated with a saturating formula; a layer of; solid backup; and a transparent topcoat or protective layer.

A process for the production of a sheet material suitable for use in, or as, a floor covering, which process comprises the steps of: providing a polyalkene resin according to any of the preceding claims, and at least one additive comprising a filling; placing the polyalkene resin in intimate admixture with the at least one additive in a high shear mixer, for a period of at least 10 minutes, at an elevated temperature of at least 75 ° C, to melt the polyalkenes, and sufficient to putting the mixture in a substantially fluid state without substantially degrading the mixture; forming the fluid mixture in a sheet form; and allow the sheet to cool and solidify.

14. A process according to claim 13, which includes the step of incorporating a sheet forming processing aid into the mixture.

15. A process according to claim 13 or claim 14, wherein the step of the sheet forming process comprises extended coating.

16. A process according to claim 15, wherein an extended coating aid of liquid plasticizer is used.

17. A process according to claim 16, wherein an extended liquid paraffin coating aid is used.

18. A process according to any of claims 14 to 16, wherein a selectively polymerizable liquid plasticizer monomer system is used, which is substantially 'non-polymerizable under the conditions of sheet formation employed in the manufacture of the material of floor covering sheet, while substantially substantially polymerizable subsequently, to produce a material substantially free of liquid plasticizer.

19. A process according to claim 18, which process includes the step of treating the sheet material to induce the polymerization of the liquid plasticizer monomer system to thereby produce a sheet material substantially free of liquid plasticizer .

20. A process according to claim 19, wherein the sheet forming step is performed from 70 ° C to 120 ° C, and the polymerization step is carried out from 150 ° C to 250 ° C.

21. A process for the production of a floor covering, which comprises a plurality of layers comprising a structural layer comprising a reinforcing carrier or substrate impregnated and / or coated with a saturating formula; a solid backing layer; and a transparent topcoat or protective layer, in which process, at least one of the layers is produced by a process according to any of claims 13 to 20.

22. A process according to claim 21, for the production of a floor covering, which includes at least one layer that is foamed, whose process includes the step of producing said foamed layer.