Heavy-duty laminated mat

Abstract

A composition for a heavy-duty layer suitable for forming a heavy-duty laminated mat and comprising: 5 wt% - 30 wt% of a propylene-based elastomer; 5 wt% - 30 wt% of low-density polyethylene; 0 wt% - 15 wt% of linear low-density polyethylene; 50 wt% - 90 wt% of a filler; and 0.1 wt% - 5 wt% of a processing aid. Optionally, the composition may further comprise 0.1 wt% - 20 wt% of a stabilizer and / or antioxidant. Optionally, the composition may further comprise 0.1 wt% - 10 wt% of an EVA copolymer, or the composition may be free of an EVA copolymer.

Description

[0001] Cross - reference to related applications

[0002] This application claims the priority of U.S.S.N. 62 / 809,219 filed on February 22, 2019 and EP application 19173686.7 filed on May 10, 2019, which are incorporated herein by reference. Background of the Invention

[0003] The present disclosure relates to a heavy layered mat, which is used, for example, as a sound insulator in a vehicle.

[0004] In automotive technology, heavy layered molded articles or heavy layered mats are particularly used as sound insulating materials in passenger compartments to withstand engine and driving noises. Moreover, heavy layered mats are used for sound attenuation of vibrating vehicle bodies (body noise damping).

[0005] The heavy layered mat includes a sound insulating heavy layer and a foam layer and / or a pile fabric layer. The heavy layer is made of ethylene - vinyl acetate (EVA) copolymer and / or ethylene - propylene - diene monomer (EPDM) rubber and contains fillers such as calcium carbonate or barium sulfate. The heavy layer has a relatively high weight. Generally, it has a unit area weight of 2 kg / m 2 - 4 kg / m 2 and sometimes even 4 kg / m 2 - 8 kg / m 2 of unit area weight.

[0006] Generally, before applying the foam and / or pile fabric layer, the heavy layer is molded into a desired shape. However, the heavy layer made of EPDM rubber can change in thickness, resulting in non - uniform thickness during the pre - heating step and cracking or breaking related to the application of additional layer(s) during the thermoforming step. It is believed that this thickness change is caused by insufficient melt strength of EPDM. Incorporating EVA copolymer improves the melt strength, but the EVA copolymer gives the heavy layer a residual vinegar smell. Newer heavy layer formulations have included linear low - density polyethylene (LLDPE) to improve the melt strength. However, when preparing a heavy layered mat with this composition, cracking and breaking of the heavy layer are still observed. Summary of the Invention

[0007] The present disclosure relates to a heavy layered mat, which is used, for example, as a sound insulator in a vehicle.

[0008] Embodiments of the present invention are compositions comprising the following components: 5 wt% - 30 wt% propylene-based elastomer; 5 wt% - 30 wt% low density polyethylene; 0 wt% - 15 wt% linear low density polyethylene; 50 wt% - 90 wt% filler; and 0.1 wt% - 5 wt% processing aid. Optionally, the composition may further include 0.1 wt% - 20 wt% stabilizer and / or antioxidant. Optionally, the composition may further comprise 0.1 wt% - 10 wt% EVA copolymer, or the composition is substantially free of EVA copolymer.

[0009] Another embodiment is a heavy-duty laminated mat, comprising: a heavy-duty layer composed of the above composition; and a polyurethane layer on the surface of the heavy-duty layer.

[0010] Yet another embodiment is a heavy-duty laminated mat, comprising: a heavy-duty layer composed of the aforementioned composition; a polyurethane foam layer on the surface of the heavy-duty layer; and a plurality of fibers on the polyurethane foam layer such that the polyurethane foam layer is between the heavy-duty layer and the plurality of fibers.

[0011] Another embodiment is a heavy-duty laminated mat, comprising: a heavy-duty layer composed of the aforementioned composition; a polyurethane foam layer on the surface of the heavy-duty layer; and a multi-layer adhesive film on the polyurethane foam layer such that the polyurethane foam layer is between the heavy-duty layer and the multi-layer adhesive film, wherein the multi-layer adhesive film comprises a polar layer and a non-polar layer.

[0012] Another embodiment is a method, comprising: thermoforming a polymer sheet having a front surface and a back surface with a mold to prepare a molded polymer sheet, the polymer sheet comprising: the above composition; and injecting a polyurethane foam into the mold such that the polyurethane foam is on the back surface of the molded polymer sheet. Description of the Drawings

[0013] The following drawings are included to illustrate certain aspects of the embodiments and should not be regarded as exclusive embodiments. As will be appreciated by those skilled in the art upon reading this disclosure, the disclosed subject matter is capable of numerous modifications, variations, combinations, and equivalents in form and function.

[0014] Figure 1 is an overview of the steps of Example Method 100 for forming a heavy-duty layer and a heavy-duty laminated mat.

[0015] Figure 2 is at 0.01 s -1 The measured values of the extensional viscosity of various samples at a strain rate.

[0016] Figure 3are the tensile viscosity measurement values of various samples at a strain rate of 0.1 s -1

[0017] Figure 4 are the tensile viscosity measurement values of various samples at a strain rate of 1 s -1

[0018] Figure 5 are the tensile viscosity measurement values of various samples at a strain rate of 10 s -1

[0019] Figure 6 are the maximum elongation viscosities of various samples at various strain rates.

[0020] Figure 7 are the tensile strengths of various injection-molded samples.

[0021] Figure 8 are the flexural moduli of various injection-molded samples.

[0022] Figure 9 are the Izod test measurements of various samples at room temperature and low temperature.

[0023] Figure 10 are the tensile viscosity measurement values of various samples at a strain rate of 0.01 s -1

[0024] Figure 11 are the tensile viscosity measurement values of various samples at a strain rate of 0.1 s -1

[0025] Figure 12 are the tensile viscosity measurement values of various samples at a strain rate of 1 s -1

[0026] Figure 13 are the tensile viscosity measurement values of various samples at a strain rate of 10 s -1

[0027] Figure 14 are the maximum elongation viscosities of various samples at various strain rates.

[0028] Figure 15 are pictures of cracks in the molded comparison heavy layer.

[0029] Figure 16 are photos of the molded heavy layer of the present invention without cracks.

[0030] Detailed Description

[0031] ​​​​​​​The present disclosure relates to heavy-duty laminated pads, which are used, for example, as sound insulation in vehicles. More specifically, the present invention includes a heavy-duty layer composition having a sufficiently increased melt strength to be processed by conventional methods to prepare a heavy-duty laminated pad. Additionally, the heavy-duty layer composition described herein preferably is substantially free of EVA copolymer and thus does not have the associated vinegar odor.

[0032] The heavy-duty layer composition of the present invention may comprise 5 wt% - 30 wt% propylene-based elastomer; 5 wt% - 30 wt% low density polyethylene (LDPE) having a melt index (ASTM D1238-13, 2.16 kg, 190 °C) of 0.5 g / 10 min - 1.5 g / 10 min; 0 wt% - 15 wt% LLDPE; 50 wt% - 90 wt% filler; and 0.1 wt% - 5 wt% processing aid. Optionally, the composition may further comprise 0.1 wt% - 20 wt% stabilizer and / or antioxidant. Optionally, the composition may further comprise 0.1 wt% - 10 wt% EVA copolymer, or the composition is substantially free of EVA copolymer. Without wishing to be bound by theory, it is believed that replacing some or all of the LLDPE with LDPE increases the melt strength of the formulation and prepares a heavy-duty layer that is more effective for preparing high-quality heavy-duty laminated pads.

[0033] Definitions

[0034] As used herein, "wt%" means weight percent, "mol%" means mole percent, "vol%" means volume percent, and all molecular weights, such as Mw, Mn, Mz, are in g / mol units unless otherwise specified. Additionally, all molecular weights are Mw unless otherwise specified.

[0035] The term "polymer" refers to any carbon-containing compound having repeating units derived from one or more different monomers and includes homopolymers, copolymers, terpolymers, etc. "Copolymer" is a polymer having two or more monomer units that are different from each other. "Terpolymer" is a polymer having three monomer units that are different from each other. Thus, the definition of copolymer used herein includes terpolymers and analogs.

[0036] As used herein, when a polymer is said to contain a monomer, the monomer is present in the polymer in the polymerized form of the monomer or in the form of a derivative of the monomer. As used herein, a "derived unit" means the polymerized form of the monomer from which the polymer is derived. For example, when a copolymer is said to have an "ethylene" content of 35 wt% - 55 wt%, it should be understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction and the derived units are present at 35 wt% - 55 wt%, based on the weight of the copolymer. Additionally, polyethylene contains ethylene-derived units. Additionally, a terpolymer of propylene / ethylene / butene contains propylene-derived units, ethylene-derived units, and butene-derived units.

[0037] As used herein, the term "elastomer" or "elastomeric composition" means any polymer or composition of polymers (e.g., blends of polymers) as defined in ASTM D1566-11. Elastomers include blended blends of polymers, such as melt blends and / or reactor blends of polymers. The term may be used interchangeably with the term "rubber(s)".

[0038] As used herein, the terms "low density polyethylene" and "LDPE" refer to polyethylene homopolymers or copolymers having a density of 0.915 g / cm 3 - 0.935 g / cm 3 , a melt flow index of 0.2 g / 10 min - 10 g / 10 min (ASTM D1238-13, 2.16 kg, 190 °C), and a melt flow ratio greater than 40 (ASTM D1238-13, 21.6 kg, 190 °C divided by ASTM D1238-13, 2.16 kg, 190 °C).

[0039] As used herein, the terms "linear low density polyethylene" and "LLDPE" refer to polyethylene homopolymers or copolymers having a density of 0.900 g / cm 3 - 0.955 g / cm 3 , a melt flow index of 0.1 g / 10 min - 30 g / 10 min (ASTM D1238-13, 2.16 kg, 190 °C), and a melt flow ratio of 15 - 40 (ASTM D1238-13, 21.6 kg, 190 °C divided by ASTM D1238-13, 2.16 kg, 190 °C).

[0040] As used herein, a composition "substantially free of" a substance means that the composition does not contain any amount of the substance or the amount of the substance is so small that the substance does not substantially affect the essential and novel feature(s) of the composition. In particular, for EVA, a composition substantially free of EVA may contain no EVA (0 wt%), or it may contain a small amount of EVA that does not result in a vinegar odor or does not affect the melt strength of the composition.

[0041] Propylene-based elastomer

[0042] The propylene-based elastomer may be a copolymer of propylene-derived units and units derived from at least one of ethylene or C4-C 10 α-olefins. The propylene-based elastomer may contain at least 60 wt% propylene-derived units, based on the weight of the propylene-based elastomer. The propylene-based elastomer may have a crystallinity limited by adjacent isotactic propylene units and a melting point as described herein. The crystallinity and melting point of the propylene-based elastomer are reduced due to misinsertion during the insertion of propylene compared to highly isotactic polypropylene. The propylene-based elastomer generally does not contain any significant intermolecular non-uniformity in terms of stereoregularity and comonomer composition, and furthermore generally does not contain any significant non-uniformity in terms of intramolecular composition distribution.

[0043] The amount of propylene-derived units present in the propylene-based elastomer may be present in an amount of at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt%, at least 84 wt%, at least 85 wt%, at least 88 wt%, at least 90 wt%, at least 92 wt%, at least 94 wt%, at least 96 wt% or at least 98 wt% based on the weight of the propylene-based elastomer. Additionally or alternatively, the amount of propylene-derived units present in the propylene-based elastomer may be present in an amount of at most 98 wt%, at most 96 wt%, at most 94 wt%, at most 92 wt%, at most 90 wt%, at most 88 wt%, at most 85 wt%, at most 84 wt% or at most 80 wt% based on the weight of the propylene-based elastomer. The specifically disclosed ranges include any combination of the values listed above, such as 60 wt% - 98 wt%, 70 wt% - 98 wt%, 80 wt% - 98 wt%, 85 wt% - 98 wt%, 90 wt% - 98 wt%, 70 wt% - 96 wt%, 75 wt% - 96 wt%, 80 wt% - 96 wt%, 85 wt% - 96 wt%, 90 wt% - 96 wt%.

[0044] Derived from ethylene or C4-C 10Units of at least one of the α-olefins, or comonomers, may be present in an amount of 1 wt% - 35 wt%, or 2 wt% - 35 wt%, or 5 wt% - 35 wt%, or 7 wt% - 32 wt%, or 8 wt% - 25 wt%, or 10 wt% - 25 wt%, or 12 wt% - 20 wt%, or 8 wt% - 20 wt%, or 8 wt% - 18 wt%, or 5 wt% - 20 wt%, or 5 wt% - 15 wt%, or 2 wt% - 10 wt%, or 2 wt% - 6.0 wt%, based on the weight of the propylene-based elastomer.

[0045] In a preferred embodiment, the comonomer is ethylene, 1-hexene or 1-octene. In some embodiments, the propylene-based elastomer comprises ethylene-derived units or consists essentially of units derived from propylene and ethylene, i.e., the propylene-based elastomer does not contain any other comonomer in an amount other than that typically present as an impurity in the ethylene and / or propylene feed streams used during polymerization, or does not contain any other comonomer in an amount that would significantly affect the 1% secant flexural modulus and / or melt mass flow rate of the propylene-based elastomer, or does not contain any other comonomer deliberately added to the polymerization process. In such embodiments, the propylene-based elastomer may comprise 2 wt% - 25 wt%, or 5 wt% - 25 wt%, or 10 wt% - 25 wt%, or 6 wt% - 22 wt%, or 12 wt% - 20 wt%, or 7 wt% - 20 wt%, or 5 wt% - 20 wt%, or 5 wt% - 15 wt%, or 8 wt% - 17 wt%, or 9 wt% - 16 wt%, or 2 wt% - 10 wt% or 2 wt% - 6.0 wt% ethylene-derived units, based on the weight of the propylene-based elastomer.

[0046] The propylene-based elastomer may comprise more than one comonomer. Preferred embodiments of propylene-based elastomers having more than one comonomer include propylene-ethylene-octene, propylene-ethylene-hexene and propylene-ethylene-butene polymers. In embodiments where there are more than one comonomer derived from ethylene or C4-C 10 In embodiments where there is at least one comonomer of an α-olefin, the amount of one comonomer may be less than 5 wt% of the propylene-based elastomer, but the total amount of comonomers in the propylene-based elastomer is 5 wt% or greater of the total propylene-based elastomer.

[0047] In some embodiments, the propylene-based elastomer may further comprise a diene. The optional diene can be any hydrocarbon structure having at least two unsaturated bonds, wherein at least one unsaturated bond is readily incorporated into the polymer. For example, the optional diene can be selected from straight-chain acyclic olefins such as 1,4-hexadiene and 1,6-octadiene; branched-chain acyclic olefins such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, and 3,7-dimethyl-1,7-octadiene; monocyclic alicyclic olefins such as 1,4-cyclohexadiene, 1,5-cyclooctadiene, and 1,7-cyclododecadiene; polycyclic alicyclic fused and bridged cycloolefins such as tetrahydroindene, norbornadiene, methyl-tetrahydroindene, dicyclopentadiene, bicyclo(2.2.1)-hepta-2,5-diene, norbornadiene, vinylnorbornene, alkylidene norbornene such as ethylidene norbornene (“ENB”), cycloalkenyl norbornene, and cycloalkylidene norbornene (e.g., 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene); and cycloalkenyl-substituted olefins such as vinylcyclohexene, allylcyclohexene, vinylcyclooctene, 4-vinylcyclohexene, allylcyclodecene, vinylcyclododecene, and tetracyclo(A-11,12)-5,8-dodecadiene. The amount of diene-derived units present in the propylene-based elastomer can range from an upper limit of 15 wt%, 10 wt%, 7 wt%, 5 wt%, 4.5 wt%, 3 wt%, 2.5 wt%, or 1.5 wt% to a lower limit of 0%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, or 1 wt%, based on the total weight of the propylene-based elastomer. In some embodiments, the propylene-based elastomer does not contain any diene-derived units.

[0048] The propylene-based elastomer can have a triad tacticity of at least 75%, at least 80%, at least 82%, at least 85%, or at least 90% of the three propylene units as measured by 13 13C NMR. Preferably, the propylene-based elastomer has a triad tacticity of 50% - 99%, 60% - 99%, 75% - 99%, or 80% - 99%. In some embodiments, the propylene-based elastomer can have a triad tacticity of 60% - 97%.

[0049] The propylene-based elastomer can have a heat of fusion (“ΔH f”). The propylene-based elastomer can have a lower limit ΔH of 0.5 J / g, 1 J / g, or 5 J / g f . For example, ΔH f values can range from any value between 1.0 J / g, 1.5 J / g, 3.0 J / g, 4.0 J / g, 6.0 J / g, or 7.0 J / g to 30 J / g, 35 J / g, 40 J / g, 50 J / g, 60 J / g, 70 J / g or 75 J / g.

[0050] The propylene-based elastomer can have a percent crystallinity of 2%-65%, or 0.5%-40%, or 1%-30%, or 5%-35% of the crystallinity of isotactic polypropylene as determined by the DSC procedure described herein. The highest order heat energy of propylene (i.e., 100% crystallinity) is estimated to be 189 J / g. In some embodiments, the copolymer has a crystallinity of less than 40%, or 0.25%-25%, or 0.5%-22% of isotactic polypropylene. Embodiments of the propylene-based elastomer can have a tacticity index m / r with a lower limit of 4 or 6 and an upper limit of 8 or 10 or 12. In some embodiments, the propylene-based elastomer has a tacticity index greater than 0%, or in the range having an upper limit of 50% or 25% and a lower limit of 3% or 10%.

[0051] The propylene-based elastomer can have a 1% secant flexural modulus of at least 5.0 MPa, at least 10 MPa, at least 20 MPa, at least 30 MPa, at least 40 MPa, at least 50 MPa, at least 60 MPa, at least 70 MPa, at least 80 MPa, at least 90 MPa, at least 100 MPa, at least 125 MPa, at least 150 MPa, at least 175 MPa, at least 200 MPa, at least 225 MPa, at least 250 MPa, at least 275 MPa, at least 300 MPa, at least 325 MPa, at least 350 MPa, at least 375 MPa, at least 400 MPa, at least 425 MPa, at least 450 MPa, at least 475 MPa or 500 MPa as measured according to ASTM D790-17. Additionally or alternatively, the propylene-based elastomer can have a 1% secant flexural modulus of at most 500 MPa, at most 475 MPa, at most 450 MPa, at most 425 MPa, at most 400 MPa, at most 375 MPa, at most 350 MPa, at most 325 MPa, at most 300 MPa, at most 275 MPa, at most 250 MPa, at most 225 MPa, at most 200 MPa, at most 175 MPa, at most 150 MPa, at most 125 MPa, at most 100 MPa, at most 90 MPa, at most 80 MPa, at most 70 MPa, at most 60 MPa, at most 50 MPa, at most 40 MPa, at most 30 MPa, at most 20 MPa, at most 10 MPa or 5.0 MPa as measured according to ASTM D790-17. The specifically disclosed ranges include any combination of the values listed above such as 5.0 MPa - 500 MPa, 5.0 - 250 MPa, 5.0 MPa - 100 MPa, 5.0 MPa - 50 MPa, 5 MPa - 20 MPa, 20 MPa - 500 MPa, 20 MPa - 250 MPa, 20 MPa - 100 MPa, 20 MPa - 50 MPa, 40 MPa - 500 MPa, 40 MPa - 250 MPa, 40 - 100 MPa, 40 MPa - 70 MPa, 40 MPa - 60 MPa, 50 MPa - 500 MPa, 50 MPa - 250 MPa, 50 MPa - 100 MPa, 100 MPa - 500 MPa, 100 MPa - 250 MPa, 200 MPa - 500 MPa, 200 MPa - 450 MPa, 200 MPa - 400 MPa, 200 MPa - 350 MPa, 200 MPa - 300 MPa, 300 MPa - 500 MPa, 300 MPa - 450 MPa, 300 MPa - 400 MPa, 300 MPa - 350 MPa, 350 MPa - 500 MPa, 350 MPa - 450 MPa, 350 MPa - 400 MPa.

[0052] The propylene-based elastomer can have a melt mass flow rate of at least 5 g / 10 min, at least 15 g / 10 min, at least 50 g / 10 min, at least 100 g / 10 min, at least 1,000 g / 10 min, at least 2,500 g / 10 min, at least 5,000 g / 10 min, at least 7,500 g / 10 min, at least 10,000 g / 10 min, at least 12,500 g / 10 min, at least 15,000 g / 10 min, at least 17,500 g / 10 min, at least 20,000 g / 10 min, at least 22,500 g / 10 min, at least 25,000 g / 10 min, at least 27,500 g / 10 min or 30,000 g / 10 min as measured according to ASTM D1238-13 (2.16 kg, 230 °C). Additionally or alternatively, the propylene-based elastomer can have a melt mass flow rate of at most 30,000 g / 10 min, at most 27,500 g / 10 min, at most 25,000 g / 10 min, at most 22,500 g / 10 min, at most 20,000 g / 10 min, at most 17,500 g / 10 min, at most 15,000 g / 10 min, at most 12,500 g / 10 min, at most 10,000 g / 10 min, at most 7,500 g / 10 min, at most 5,000 g / 10 min, at most 2,500 g / 10 min, at most 1,000 g / 10 min, at most 100 g / 10 min, at most 50 g / 10 min, at most 15 g / 10 min, or 5 g / 10 min as measured according to ASTM D1238-13 (2.16 kg, 230 °C).The specifically disclosed ranges include any combination of the values listed above, such as 5 g / 10 min - 30,000 g / 10 min, 5 g / 10 min - 20,000 g / 10 min, 5 g / 10 min - 10,000 g / 10 min, 5 g / 10 min - 1,000 g / 10 min, 5 g / 10 min - 100 g / 10 min, 5 g / 10 min - 50 g / 10 min, 5 g / 10 min - 15 g / 10 min, 1,000 g / 10 min - 30,000 g / 10 min, 1,000 g / 10 min - 20,000 g / 10 min, 1,000 g / 10 min - 10,000 g / 10 min, 1,000 g / 10 min - 5,000 g / 10 min, 10,000 g / 10 min - 30,000 g / 10 min, 10,000 g / 10 min - 20,000 g / 10 min, 10,000 g / 10 min - 15,000 g / 10 min, 20,000 g / 10 min - 30,000 g / 10 min, 20,000 g / 10 min - 27,500 g / 10 min, 22,500 g / 10 min - 30,000 g / 10 min, 22,500 g / 10 min - 27,500,000 g / 10 min, 22,500 g / 10 min - 25,000 g / 10 min.

[0053] The propylene-based elastomer can have a melting point temperature (Tm) of 105 °C or lower, 100 °C or lower, 90 °C or lower, 80 °C or lower, 70 °C or lower. In some embodiments, the propylene-based elastomer has a Tm of 25 °C - 105 °C, 60 °C - 105 °C, 70 °C - 105 °C, or 90 °C - 105 °C.

[0054] Determine the Tm and ΔH of the propylene-based elastomer fThe DSC procedure is as follows. Press the polymer in a hot press at a temperature of 200 °C - 230 °C, and suspend the resulting polymer sheet in air at ambient conditions (20 °C - 23.5 °C) to cool. Remove a 6 - 10 mg polymer sheet sample using a die. Anneal this 6 - 10 mg sample at room temperature (22 °C) for 80 - 100 hours. At the end of this stage, place the sample in a DSC (Perkin Elmer Pyris One Thermal Analysis System) and cool it at a rate of 10 °C / min to - 30 °C to - 50 °C and hold at - 50 °C for 10 minutes. Heat the sample at 10 °C / min to reach a final temperature of 200 °C. Hold the sample at 200 °C for 5 minutes. Then, perform a second cooling - heating cycle using the same conditions as above. Record the events "first melting" and "second melting" from these two cycles separately. The heat of fusion is recorded as the area under the sample melting peak, which typically exists between 0 °C and 200 °C. It is measured in joules and is the ΔH of the polymer. f The melting point temperature and ΔH f mentioned herein refer to the first melting.

[0055] The propylene - based elastomer can have a density of 0.850 - 0.920 g / cm 3 or 0.860 g / cm 3 - 0.890 g / cm 3 measured at room temperature according to ASTM D1505 - 18.

[0056] The propylene - based elastomer can have an elongation at break of at least 200%, at least 500%, at least 1000%, at least 1500%, at least 2000% or at least 3000% measured according to ASTM D638 - 14.

[0057] The propylene - based elastomer can have a weight - average molecular weight (Mw) of 5,000 g / mol - 5,000,000 g / mol, 10,000 g / mol - 1,000,000 g / mol, 20,000 g / mol - 750,000 g / mol, 30,000 g / mol - 400,000 g / mol.

[0058] The propylene - based elastomer can have a number - average molecular weight (Mn) of 2,500 g / mol - 250,000 g / mol, 10,000 g / mol - 250,000 g / mol, or 25,000 g / mol - 200,000 g / mol.

[0059] The propylene-based elastomer may have a z-average molecular weight (Mz) of 10,000 g / mol - 7,000,000 g / mol, 80,000 g / mol - 700,000 g / mol, or 100,000 g / mol - 500,000 g / mol.

[0060] The propylene-based elastomer may have a molecular weight distribution ("MWD") of 1.5 - 20, or 1.5 - 15, preferably 1.5 - 5, more preferably 1.8 - 3, and most preferably 1.8 - 2.5.

[0061] The molecular weights (weight-average molecular weight Mw, number-average molecular weight Mn, and molecular weight distribution Mw / Mn or MWD) are determined using high-temperature size exclusion chromatography (SEC) equipped with a differential refractive index detector (DRI), an on-line light scattering detector (LS), and a viscometer (obtained from Wanters Corporantion or Polymer Lanborantories). Three Polymer Laboratories PLgel 10 mm Mixed-B columns are used. The nominal flow rate is 0.5 cm 3 / min, and the nominal injection volume is 300 μL. The oven maintained at 145 °C houses various transfer lines, columns, and a differential refractometer (DRI detector). A polystyrene calibration instrument is used. The solvent for the SEC experiment is prepared by dissolving 6 g of butylated hydroxytoluene as an antioxidant in 4 L of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). Then the TCB mixture is filtered through a 0.7 micron glass pre-filter and subsequently through a 0.1 micron Teflon filter. Then the TCB is degassed using an on-line degasser and then enters the SEC. The polymer solution is prepared as follows: The dry polymer is placed in a glass container, the required amount of TCB is added, and then the mixture is heated at 160 °C while continuously stirring for several hours. All amounts are measured gravimetrically. The TCB density for expressing the polymer concentration in mass / volume units is 1.463 g / ml at room temperature and 1.324 g / ml at 135 °C. The injection concentration range is 1.0 - 2.0 mg / mL, and lower concentrations are used for higher molecular weight samples. Before testing each sample, the DRI detector and syringe are purged. Then the flow rate in the apparatus is increased to 0.5 mL / min, and the DRI is allowed to stabilize for 8 - 9 hours before injecting the first sample. The LS laser is turned on 1 hour - 1.5 hours before testing the sample. The concentration (c) at each point in the chromatogram is calculated from the DRI signal (I DRI ) after subtracting the baseline using the following equation:

[0062] c = K DRI I DRI / (dn / dc)

[0063] where K DRI is a constant determined by calibrating the DRI, and (dn / dc) is the same as described below for LS analysis. The units of the parameters throughout the description of this SEC method satisfy: concentration is expressed in g / cm 3 , molecular weight is expressed in kg / mol, and intrinsic viscosity is expressed in dL / g.

[0064] The light scattering detector used is the Wyatt Technology High Temperature mini-DAWN. The polymer molecular weight M at each point on the chromatogram is determined by analyzing the LS output values using the Zimm model of static light scattering (M.B. Huglin, Light Scattering from Polymer Solutions, Academic Press, 1971):

[0065]

[0066] where ΔR(θ) is the excess Rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined from the DRI analysis, A2 is the second virial coefficient, P(θ) is the shape factor of a monodisperse random coil (described in the above reference), and Ko is the optical constant of the system:

[0067]

[0068] where N A is Avogadro's constant, and dn / dc is the refractive index increment of the system. For TCB at 135 °C and λ = 690 nm, the refractive index n = 1.500. Additionally, for ethylene polymers, A2 = 0.0015 and dn / dc = 0.104, while for propylene polymers, A2 = 0.0006 and dn / dc = 0.104.

[0069] The average molecular weight is typically defined as follows: Consider the discontinuity in the distribution where macromolecules are present in a discrete fraction i containing N i molecules of molecular weight M i . The weight-average molecular weight M w is defined as the sum of the products of the molecular weight M i of each fraction multiplied by its weight fraction w i :

[0070]

[0071] Since the weight fraction w i is defined as the weight of the molecules of molecular weight M i divided by the total weight of all the molecules present:

[0072]

[0073] Number-average molecular weight M n is defined as the sum of the products of the molecular weight M i of each fraction multiplied by its mole fraction x i :

[0074]

[0075] Since the mole fraction x i is defined as N i divided by the total number of molecules:

[0076]

[0077] In SEC, a high-temperature Viscotek Corporation viscometer is used, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure sensors. One sensor measures the total pressure drop across the detector, and the other sensor located between the two sides of the bridge measures the pressure difference. The specific viscosity (η s ) of the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity [η] at each point in the chromatogram is calculated by the following equation:

[0078] η s = c[η] + 0.3(c[η]) 2

[0079] where c is determined from the DRI output.

[0080] The branching index (g′, also known as g′(vis)) is calculated as follows using the output values of the SEC-DRI-LS-VIS method. The average intrinsic viscosity [η] of the sample avg is calculated as follows:

[0081]

[0082] where the sum is taken over all chromatogram slices i between the integration limits.

[0083] Here, various propylene-based elastomers having any combination of the above properties are considered.

[0084] Propylene-based elastomers can include copolymers prepared according to the procedures described in WO 02 / 36651, U.S. Patent No. 6,992,158, and / or WO00 / 01745, the contents of which are incorporated herein by reference. Preferred methods for preparing propylene-based elastomers can be found in U.S. Patent Nos. 7,232,871 and 6,881,800, the contents of which are incorporated herein by reference. The present invention is not limited to any particular polymerization method for preparing propylene-based elastomers, and the polymerization method is not limited by any particular type of reaction vessel.

[0085] Suitable propylene-based elastomers can be obtained under the trade name VISTAMAXX TM (available from ExxonMobil Chemical Company) (e.g., VISTAMAXX TM 3000, VISTAMAXX TM 3588FL, VISTAMAXX TM 6102, VISTAMAXX TM 8880), VERSIFY TM (available from The Dow Chemical Company), certain grades of TAFMER TM XM or NOTIO TM (available from Mitsui Company) and certain grades of SOFTEL TM (available from Basell Polyolefins). Specific grades of commercially available propylene-based elastomers suitable for use in the present invention can be readily determined using methods commonly known in the art.

[0086] The heavy layer composition of the present invention can contain one or more propylene-based elastomers at a total concentration of 5 wt% - 30 wt%, or 7 wt% - 20 wt%, or 10 wt% - 18 wt%, or 12 wt% - 15 wt%, based on the weight of the heavy layer composition.

[0087] Low density polyethylene

[0088] LDPE has a density of 0.915 g / cm 3 - 0.935 g / cm 3 or 0.920 g / cm 3 - 0.930 g / cm 3 of density.

[0089] LDPE has a melt flow index of 0.2 g / 10 min - 10 g / 10 min, or 0.5 g / 10 min - 7 g / 10 min, or 1 g / 10 min - 5 g / 10 min (ASTM D1238-13, 2.16 kg, 190 °C).

[0090] LDPE has a melt flow ratio of greater than 40, or 40 - 300, or 60 - 250, or 75 - 200 (ASTM D1238-13, 21.6 kg, 190 °C divided by ASTM D1238-13, 2.16 kg, 190 °C).

[0091] LDPE can be a polyethylene homopolymer. Alternatively, LDPE can be an ethylene copolymer containing C3-C 20 α-olefins. Examples of comonomers include propylene, 1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, 1-pentene, 1-pentene with one or more methyl, ethyl or propyl substituents, 1-hexene, 1-hexene with one or more methyl, ethyl or propyl substituents, 1-heptene, 1-heptene with one or more methyl, ethyl or propyl substituents, 1-octene, 1-octene with one or more methyl, ethyl or propyl substituents, 1-nonene, 1-nonene with one or more methyl, ethyl or propyl substituents, ethyl, methyl or dimethyl substituted 1-decene, 1-dodecene and styrene. Exemplary combinations of ethylene and comonomers include: ethylene 1-butene, ethylene 1-pentene, ethylene 4-methyl-1-pentene, ethylene 1-hexene, ethylene 1-octene, ethylene decene, ethylene dodecene, ethylene 1-butene 1-hexene, ethylene 1-butene 1-pentene, ethylene 1-butene 4-methyl-1-pentene, ethylene 1-butene 1-octene, ethylene 1-hexene 1-pentene, ethylene 1-hexene 4-methyl-1-pentene, ethylene 1-hexene 1-octene, ethylene 1-hexene decene, ethylene 1-hexene dodecene, ethylene propylene 1-octene, ethylene 1-octene 1-butene, ethylene 1-octene 1-pentene, ethylene 1-octene 4-methyl-1-pentene, ethylene 1-octene 1-hexene, ethylene 1-octene decene, ethylene 1-octene dodecene, and combinations thereof. It is understood that the above list of comonomers and comonomer combinations is merely exemplary and is not intended to be limiting. Preferably, the comonomer is 1-butene, 1-hexene or 1-octene. Most preferably, the comonomer is 1-hexene.

[0092] In the copolymer, ethylene-derived units can account for 65 wt% - 99.9 wt% of LDPE, or 70 wt% - 99 wt%, or 85 wt% - 95 wt%, and the comonomer can account for 0.1 wt% - 35 wt% of LDPE, or 5 wt% - 15 wt%.

[0093] The LDPE that can be used in the present invention includes those that can be commercially purchased under the trade name EXXONMOBIL TM LDPEs commercially available from ExxonMobil Chemical Company, including but not limited to, those commercially available under the grade names: LD250, LD259, LD258, LD251, LD252, LD650, LD653, LD200.48, LD201.48 and LD202.48.

[0094] The LDPE described herein is not restricted to any particular preparation method and can be formed using any method known in the art. For example, LDPE can be formed by an autoclave or tubular reactor method.

[0095] The heavy layer composition of the present invention can contain one or more LDPEs at a total concentration of 5 wt% - 30 wt%, or 10 wt% - 20 wt%, or 5 wt% - 18 wt%, or 7 wt% - 15 wt%, based on the weight of the heavy layer composition.

[0096] Linear low density polyethylene

[0097] LLDPE has a density of 0.900 g / cm 3 - 0.955 g / cm 3 or 0.910 g / cm 3 - 0.950 g / cm 3 or 0.920 g / cm 3 - 0.945 g / cm 3 of density.

[0098] LLDPE has a melt flow index (ASTM D1238 - 13, 2.16 kg, 190 °C) of 0.2 g / 10 min - 30 g / 10 min, or 0.5 g / 10 min - 25 g / 10 min, or 1 g / 10 min - 20 g / 10 min.

[0099] LLDPE has a melt flow ratio (ASTM D1238 - 13, 21.6 kg, 190 °C divided by ASTM D1238 - 13, 2.16 kg, 190 °C) of 15 - 40, or 18 - 35, or 20 - 25.

[0100] LLDPE can be a polyethylene homopolymer. Alternatively, LLDPE can be a copolymer containing C3 - C 20Ethylene copolymers of α-olefins. Examples of comonomers include propylene, 1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, 1-pentene, 1-pentene with one or more methyl, ethyl or propyl substituents, 1-hexene, 1-hexene with one or more methyl, ethyl or propyl substituents, 1-heptene, 1-heptene with one or more methyl, ethyl or propyl substituents, 1-octene, 1-octene with one or more methyl, ethyl or propyl substituents, 1-nonene, 1-nonene with one or more methyl, ethyl or propyl substituents, ethyl, methyl or dimethyl substituted 1-decene, 1-dodecene and styrene. Exemplary combinations of ethylene and comonomers include: ethylene 1-butene, ethylene 1-pentene, ethylene 4-methyl-1-pentene, ethylene 1-hexene, ethylene 1-octene, ethylene decene, ethylene dodecene, ethylene 1-butene 1-hexene, ethylene 1-butene 1-pentene, ethylene 1-butene 4-methyl-1-pentene, ethylene 1-butene 1-octene, ethylene 1-hexene 1-pentene, ethylene 1-hexene 4-methyl-1-pentene, ethylene 1-hexene 1-octene, ethylene 1-hexene decene, ethylene 1-hexene dodecene, ethylene propylene 1-octene, ethylene 1-octene 1-butene, ethylene 1-octene 1-pentene, ethylene 1-octene 4-methyl-1-pentene, ethylene 1-octene 1-hexene, ethylene 1-octene decene, ethylene 1-octene dodecene, and combinations thereof. It is understood that the above list of comonomers and comonomer combinations is merely exemplary and is not intended to be limiting. Preferably, the comonomer is 1-butene, 1-hexene or 1-octene. Most preferably, the comonomer is 1-hexene.

[0101] In the copolymer, the ethylene-derived units can account for 65 wt% - 99.9 wt%, or 70 wt% - 99 wt%, or 85 wt% - 95 wt% of the LLDPE, and the comonomer can account for 0.1 wt% - 35 wt%, or 5 wt% - 15 wt% of the LLDPE.

[0102] The LLDPE that can be used in the present invention includes those that can be commercially purchased under the trade name EXCEED TM XP (available from ExxonMobil Chemical Company), EXXONMOBIL TM LLDPE (available from ExxonMobil Chemical Company) and EXXONMOBIL TM NTX LLDPE (available from ExxonMobil Chemical Company).

[0103] The LLDPE described herein is not restricted to any particular preparation method and can be formed using any method known in the art. For example, LLDPE can be formed by autoclave or tubular reactor methods.

[0104] The heavy layer composition of the present invention can contain one or more LDDPEs (when present) at a total concentration of 0.1 wt% - 15 wt%, or 1 wt% - 10 wt%, or 1 wt% - 5 wt%, or 0.1 wt% - 2 wt%, based on the weight of the heavy layer composition. The heavy layer composition of the present invention can be free of LLDPE.

[0105] Filler

[0106] Examples of fillers can include, but are not limited to, carbon black, fly ash, graphite, cellulose, starch, flour, wood flour, polymer fibers such as polyester-based, polyamide-based materials, calcium carbonate, aluminum trihydrate, talc, glass fibers, marble powder, cement powder, clay, feldspar, silica or glass, fumed silica, alumina, magnesia, antimony oxide, zinc oxide, barium sulfate, calcium sulfate, aluminum silicate, calcium silicate, titanium dioxide, titanates, clay, nanoclay, organically modified clay or nanoclay, glass microspheres, chalk, etc., and combinations thereof.

[0107] The heavy layer composition of the present invention can contain one or more fillers at a total concentration of 50 wt% - 90 wt%, or 60 wt% - 85 wt%, or 65 wt% - 80 wt%, or 75 wt% - 85 wt%, or 70 wt% - 75 wt%, based on the weight of the heavy layer composition.

[0108] Processing aids

[0109] Examples of processing aids include, but are not limited to, paraffinic oils, naphthenic oils, polyalpha-olefin (PAO) fluids, waxes, fatty acid salts such as calcium stearate or zinc stearate, alcohols including diols, diol ethers, alcohol ethers, polyesters, etc., and combinations thereof.

[0110] The heavy layer composition of the present invention can contain one or more processing aids at a total concentration of 0.1 wt% - 5 wt%, or 1 wt% - 4 wt%, or 3 wt% - 5 wt%, or 0.1 wt% - 3 wt%, based on the weight of the heavy layer composition.

[0111] Other additives

[0112] The heavy layer composition of the present invention can contain other additives. Examples of other additives include, but are not limited to, flame retardants, antioxidants, flow improvers, colorants, reinforcing materials, adhesion additives, etc., and combinations thereof.

[0113] The heavy layer composition may further contain an adhesion additive that can promote the adhesion of the extruded composition to the primary layer and the tufted carpet fibers. Useful binders include maleic anhydride functionalized EVA. When employed, the adhesion additive may be present in an amount of up to 10 wt%, or 0.1 wt% - 10 wt%, or 1 wt% - 8 wt%, or 1 wt% - 5 wt%, based on the weight of the heavy layer composition.

[0114] The heavy layer composition may contain a heat stabilizer and / or an antioxidant. Hindered amine stabilizers, such as CHIMASSORB available from Ciba Specialty Chemicals TM are exemplary heat and light stabilizers. Additionally, hindered phenols may be used as antioxidants. Some suitable hindered phenols include those available from Ciba Specialty Chemicals under the trade name IRGANOX TM When employed, the antioxidant and / or stabilizer may each be present in an amount of up to 20 wt%, or 0.1 wt% - 20 wt%, or 0.5 wt% - 15 wt%, or 1 wt% - 10 wt%, based on the weight of the heavy layer composition.

[0115] Manufacturing the heavy layer and the heavy layer mat

[0116] Figure 1 is an overview of the steps of an exemplary method 100 for forming the heavy layer and the heavy layer mat. First, the heavy layer composition according to the present disclosure can be compounded by any known method. For example, compounding can be carried out by mixing the components 102a, 102b, 102c, etc. of the heavy layer composition into a continuous mixer 104 such as a Brabender mixer, a grinder, or an internal mixer such as a Banbury mixer. Compounding can also be carried out in a continuous process such as in a twin-screw extruder 106. Optionally, a portion of the components of the heavy layer composition can be blended before blending with the remaining components.

[0117] After heating and compounding the components in the mixer 104 into a heavy layer melt, the heavy layer melt can be extruded via the extruder 106 into a heavy layer sheet 108 having a thickness of 0.1 mm - 5 mm, or 0.5 mm - 4 mm, or 1 mm - 3 mm, or 3 mm - 5 mm. During extrusion, rollers 110 can be used to bring the heavy layer sheet to the desired thickness. A cutter 112 then cuts the heavy layer sheet 108 into individual heavy layers 114.

[0118] Then, the heavy layer 114 can be molded. First, the heater 116 is used to preheat the heavy layer 114. Then, the preheated heavy layer 114 is placed in the mold 118, where a vacuum 120 and heat are applied to thermoform the heavy layer 114. When in the mold 118, there is a small amount of space available between the molded heavy layer 114 and the top of the mold, which provides space for the polyurethane foam 122 to be injected into the mold and forms a polyurethane foam layer 124 on one side of the heavy layer 114. A heavy layer pad 126 with two layers is obtained: the heavy layer 114 and the polyurethane foam layer 124. Optionally, additional steps known to those skilled in the art can be performed to apply a carpet or other fabric onto the polyurethane foam layer 124.

[0119] The polyurethane foam layer 124 can have a thickness of 0.1 mm - 5 mm, or 0.5 mm - 4 mm, or 1 mm - 3 mm, or 3 mm - 5 mm.

[0120] Exemplary heavy layer pads include a heavy layer composed of the heavy layer composition described herein; and a polyurethane layer on the surface of the heavy layer.

[0121] Another exemplary heavy layer pad includes a heavy layer composed of the heavy layer composition described herein; a polyurethane layer on the surface of the heavy layer; and multiple fibers on the polyurethane foam layer such that the polyurethane foam layer is between the heavy layer and the multiple fibers.

[0122] Yet another exemplary heavy layer pad includes a heavy layer composed of the heavy layer composition described herein; a polyurethane foam layer on the surface of the heavy layer; and a multi-layer adhesive film on the polyurethane foam layer such that the polyurethane foam layer is between the heavy layer and the multi-layer adhesive film, wherein the multi-layer adhesive film includes a polar layer and a non-polar layer.

[0123] Advantageously, the heavy layer composition of the present invention has improved melt strength, which enables the preheating and thermoforming of the heavy layers while maintaining their integrity and thickness. Additionally, the heavy layer composition described herein preferably contains substantially no EVA copolymer and thus has no associated vinegar odor.

[0124] Example Embodiment

[0125] The first embodiment of the present invention is a composition comprising: 5 wt% - 30 wt% propylene-based elastomer; 5 wt% - 30 wt% low density polyethylene; 0 wt% - 15 wt% linear low density polyethylene; 50 wt% - 90 wt% filler; and 0.1 wt% - 5 wt% processing aid. Optionally, the composition may include one or more of the following elements: Element 1: wherein the composition does not contain linear low density polyethylene; Element 2: wherein the composition does not contain ethylene-vinyl acetate copolymer; Element 3: wherein the low density polyethylene is a homopolymer of polyethylene; Element 4: wherein the low density polyethylene has 65 wt% - 99.9 wt% ethylene-derived units and 0.1 wt% - 35 wt% units derived from at least one of C3-C 12 α-olefins; Element 5: wherein the linear low density polyethylene is a homopolymer of polyethylene; Element 6: wherein the linear low density polyethylene has 65 wt% - 99.9 wt% ethylene-derived units and 0.1 wt% - 35 wt% units derived from at least one of C3-C 12 α-olefins; Element 7: wherein the composition further comprises 0.1 wt% - 20 wt% stabilizer and / or antioxidant; and Element 8: wherein the composition further comprises ethylene-vinyl acetate copolymer at 0.1 wt% - 10 wt%. Examples of combinations include, but are not limited to, the combination of Element 1 and 2 optionally further combined with one of Element 3 and 4; the combination of Element 7 and 8 optionally further combined with one of Element 3 and 4; one of Element 3 and 4 combined with Element 1; one of Element 3 and 4 combined with Element 2; one of Element 3 and 4 combined with Element 7; one of Element 3 and 4 combined with Element 8; one of Element 3 and 4 combined with one of Element 5 or 6 optionally further combined with Element 2; and one of Element 5 or 6 combined with Element 2.

[0126] Another embodiment is a heavy laminated mat comprising: a heavy layer made of the composition of the first embodiment (optionally including one or more of the above optional elements); and a polyurethane layer on the surface of the heavy laminated mat.

[0127] Yet another embodiment is a heavy laminated mat comprising: a heavy layer made of the composition of the first embodiment (optionally including one or more of the above optional elements); a polyurethane foam layer on the surface of the heavy layer; and a plurality of fibers on the polyurethane foam layer such that the polyurethane foam layer is between the heavy layer and the plurality of fibers.

[0128] Another embodiment is a heavy-duty laminated mat, comprising: a heavy-duty layer composed of the composition of the first embodiment (optionally including one or more of the above optional elements); a polyurethane foam layer on the surface of the heavy-duty layer; and a multi-layer adhesive film on the polyurethane foam layer such that the polyurethane foam layer is between the heavy-duty layer and the multi-layer adhesive film, wherein the multi-layer adhesive film includes a polar layer and a non-polar layer.

[0129] In the three foregoing embodiments of the heavy-duty laminated mat, the heavy-duty layer may optionally have a thickness of 0.1 mm - 5 mm and / or the polyurethane foam layer may optionally have a thickness of 0.1 mm - 5 mm.

[0130] Another exemplary embodiment is a method, comprising: thermoforming a polymer sheet having a front surface and a back surface with a mold to prepare a molded polymer sheet, the polymer sheet comprising: the composition of the first embodiment (optionally including one or more of the above optional elements); and injecting a polyurethane foam into the mold such that the polyurethane foam is on the back surface of the molded polymer sheet.

[0131] Optionally, the exemplary method may include one or more of the following: the method further comprises: attaching a plurality of fibers to the polyurethane foam via thermocompression; attaching a multi-layer adhesive film to the polyurethane foam via thermocompression, wherein the multi-layer adhesive film includes a polar layer and a non-polar layer; the heavy-duty layer may optionally have a thickness of 0.1 mm - 5 mm; and / or the polyurethane foam layer may optionally have a thickness of 0.1 mm - 5 mm.

[0132] Unless otherwise indicated, all numerical values used in the specification and the appended claims to indicate amounts of ingredients, properties such as molecular weight, reaction conditions, etc. should be understood in all instances to be modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties sought to be obtained by the embodiments of the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0133] This document presents one or more illustrative embodiments incorporating the inventive embodiments disclosed herein. For clarity, not all features of physical implementations are described or shown in this application. It should be understood that in developing physical embodiments incorporating the inventive embodiments, numerous implementation-specific decisions must be made to achieve the developer's goals, such as compliance with system-related, business-related, government-related, and other constraints, which depend on the circumstances and change from time to time. Although the efforts of developers may be time-consuming, such efforts are still routine tasks for those of ordinary skill in the art and are benefited by this disclosure.

[0134] Although the compositions and methods are described herein in terms of "comprising" various components or steps, the compositions and methods may also "consist essentially of" or "consist of" the various components and steps.

[0135] To facilitate a better understanding of the embodiments of the present invention, the following examples of preferred or representative embodiments are given. The following examples should in no way be construed as limiting or defining the entire scope of the present invention. Examples

[0136] Example 1. Prepare blends according to the formulations in Table 1.

[0137] Table 1

[0138]

[0139] Measure the extensional viscosity of each sample. The extensional rheological properties of polymers play an important role in the processing process and final properties. First, press all samples into sheets. Conduct extensional viscosity tests on an ARES EFV instrument at 200 °C using the STC-EM-RHE-05.00 test method, using a nitrogen atmosphere to avoid oxidative degradation. Test all samples at a series of strain rates: 0.01 s -1 , 0.1 s -1 , 1 s -1 , 10 s -1 . Sample 1 (a market benchmark sample) exhibits strain hardening, indicating good melt strength. Samples 2 and 3 (control samples without LDPE) do not show strain hardening, indicating poor melt strength. Samples 4 - 7 (inventive samples) show strain hardening, indicating good melt strength.

[0140] Example 2. Prepare samples with a polymer blend: filler (CaCO3) weight ratio of 40:60. The polymer blends used are provided in Table 2. The properties of each polymer in the blends are provided in Table 3. The thermal properties of the samples (i.e., the polymer blends with fillers) are provided in Table 4.

[0141] Table 2

[0142]

[0143] *Available from Dow Chemical

[0144] Table 3

[0145]

[0146] Table 4

[0147] Sample Tc Tm Tg ΔHc <![CDATA[40:60 wt% Sample 8: CaCO3]]> 110.4 123.4 -30.5 9.5 <![CDATA[40:60 wt% Sample 9: CaCO3]]> 96.1 110.1 -30.2 16.3 <![CDATA[40:60 wt% Sample 10: CaCO3]]> 96.7 109.8 -31.1 17.6 <![CDATA[40:60 wt% Sample 11: CaCO3]]> 97.9 109.5 -31.4 10.9

[0148] Measure the extensional viscosity of each of Samples 8 - 11 as described in Example 1. Figures 2 - 5 Provide separately the extensional viscosity measurements at 0.01 s -1 , 0.1 s -1 , 1 s -1 and 10 s -1 . Figure 6 is the maximum elongational viscosity of each sample at each strain rate. Samples 9 - 11 (each containing LDPE but not LLDPE) obtained higher elongational viscosities than Sample 8 which contained LLDPE but not LDPE.

[0149] The tensile strength of Samples 8 - 11 is provided in Figure 7 . Tensile bars were prepared by injection molding. The flexural modulus of Samples 8 - 11 is provided in Figure 8 . Flexural modulus sample bars were prepared by injection molding. The tensile strength and stiffness of the samples could not be elucidated by the presence of LDPE or LLDPE.

[0150] Samples 8 - 11 were subjected to room temperature (20 °C) and low temperature (-40 °C) Izod tests; the results are shown in Figure 9 . For Samples 9 and 10 which included VISTAMAXX TM 6102 and LDPE, the impact resistance at low temperature was inferior to that at room temperature. Additionally, no breakage was observed for all samples, which indicates that the formulations based on VISTAMAXX TM 6102 have good impact resistance.

[0151] Example 3. Prepare Samples 12 - 17 according to Table 5. Measure the extensional viscosity of Samples 12 - 17 as described in Example 1, except that the measurement is carried out at 190 °C. Figures 10 - 13 Provide separately Samples 12 - 17 at 0.01 s -1 , 0.1 s -1 , 1 s -1 and 10 s-1 Tensile viscosity measurement values under Figure 14 Show the maximum elongational viscosity of each of Samples 12 - 17 at various strain rates. Samples 14 - 17, which contain LDPE but not LLDPE, have better elongational viscosities than both EVA-based Sample 12 and LLDPE-based Sample 13, indicating that the addition of LDPE in high filler loading formulations is associated with improved melt strength.

[0152] Table 5

[0153]

[0154] * Thermoplastic elastomer

[0155] Example 4. Prepare a comparative heavy layer with a heavy layer composition containing 10 wt% - 15 wt% VISTAMAXX TM , 10 wt% - 15 wt% LLDPE, 65 wt% - 75 wt% calcium carbonate and barium sulfate, and 2 wt% - 5 wt% processing oil. Prepare the heavy layer of the present invention with a heavy layer composition containing 10 wt% - 15 wt% VISTAMAXX TM , 10 wt% - 15 wt% LDPE, 65 wt% - 75 wt% calcium carbonate and barium sulfate, and 2 wt% - 5 wt% processing oil.

[0156] Thermoform these heavy layers into molded heavy layers. Figure 15 Is a picture of cracks in the molded comparative heavy layer. Figure 16 Is a photograph of the molded heavy layer of the present invention without cracks.

[0157] Accordingly, the present invention is well suited to attain the advantages mentioned as well as those inherent therein. The specific embodiments disclosed above are merely illustrative, as the present invention may be modified and practiced in different but equivalent ways that are obvious to those skilled in the art benefiting from the teachings herein. Additionally, there is no intention to limit the details of the construction or design shown herein other than as described in the following claims. Thus, it is evident that the specific illustrative embodiments disclosed above may be altered, combined, or modified, and all such variations are considered to be within the scope and spirit of the present invention. The present invention disclosed illustratively herein may be suitably practiced without any element not specifically disclosed herein and / or any non-essential element disclosed herein. While compositions and methods are described in terms of "comprising," "containing," or "including" various components or steps, the compositions and methods may also "consist essentially of" or "consist of" the various components and steps. All of the numerical values and ranges disclosed above may vary slightly. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within that range are expressly disclosed. In particular, each range of values disclosed herein (of the form "from about a to about b" or equivalently "from approximately a to b" or equivalently "from approximately a - b") should be understood to list every number and range subsumed within the broader range of values. Additionally, the terms in the claims have their ordinary and normal meanings unless the patentee has otherwise defined them explicitly and clearly. Further, the indefinite article "a" or "an" used in the claims is defined herein to mean one or more of the elements introduced by it.

Claims

1. A composition comprising: 5 wt%-30 wt% propylene-based elastomer having at least 75% triad tacticity of three propylene units measured by 13 13C NMR, a heat of fusion of 75 J / g or less and a melting point temperature of 105 °C or less, wherein the propylene-based elastomer contains at least 60 wt% propylene-derived units, based on the weight of the propylene-based elastomer; 5 wt%-30 wt% low density polyethylene having a density of 0.915 g / cm 3 -0.935 g / cm 3 , a melt flow index measured according to ASTM D1238-13 at 2.16 kg and 190 °C of 0.2 g / 10min - 10 g / 10min and a melt flow ratio greater than 40, where the melt flow ratio is the melt flow index measured according to ASTM D1238-13 at 21.6 kg and 190 °C divided by the melt flow index measured according to ASTM D1238-13 at 2.16 kg and 190 °C; 0 wt%-15 wt% linear low density polyethylene; 50 wt%-85 wt% filler; and 0.1 wt%-5 wt% processing aid.

2. The composition of claim 1, wherein the low density polyethylene is a homopolymer of polyethylene.

3. The composition of claim 1, wherein the low density polyethylene has 65 wt%-99.9 wt% of units derived from ethylene and 0.1 wt%-35 wt% of units derived from at least one of C3-C 12 α-olefins.

4. The composition according to any one of claims 1-3, wherein the linear low density polyethylene has 65 wt%-99.9 wt% of ethylene-derived units and 0.1 wt%-35 wt% of units derived from at least one of C3-C 12 α-olefins.

5. A composition comprising: 5 wt%-30 wt% propylene-based elastomer having at least 75% triad tacticity of three propylene units measured by 13 13C NMR, a heat of fusion of 75 J / g or less, and a melting point temperature of 105 °C or less, wherein the propylene-based elastomer contains at least 60 wt% propylene-derived units, based on the weight of the propylene-based elastomer; 5 wt% - 30 wt% low density polyethylene having a density of 0.915 g / cm 3 - 0.935 g / cm 3 and a melt flow index measured according to ASTM D1238 - 13 at 2.16 kg and 190 °C of 0.2 g / 10 min - 10 g / 10 min and a melt flow ratio greater than 40, where the melt flow ratio is the melt flow index measured according to ASTM D1238 - 13 at 21.6 kg and 190 °C divided by the melt flow index measured according to ASTM D1238 - 13 at 2.16 kg and 190 °C; 0 wt%-15 wt% linear low density polyethylene; 50 wt%-85 wt% filler; 0.1 wt%-5 wt% processing aid; and 0.1 wt%-20 wt% stabilizer and / or antioxidant.

6. A composition comprising: 5 wt%-30 wt% propylene-based elastomer having at least 75% triad tacticity of three propylene units measured by 13 13C NMR, a heat of fusion of 75 J / g or less, and a melting point temperature of 105 °C or less, wherein the propylene-based elastomer contains at least 60 wt% propylene-derived units, based on the weight of the propylene-based elastomer; 5 wt%-30 wt% low density polyethylene having a density of 0.915 g / cm 3 -0.935 g / cm 3 , a melt flow index measured according to ASTM D1238-13 at 2.16 kg and 190 °C of 0.2 g / 10min - 10 g / 10min, and a melt flow ratio greater than 40, where the melt flow ratio is the melt flow index measured according to ASTM D1238-13 at 21.6 kg and 190 °C divided by the melt flow index measured according to ASTM D1238-13 at 2.16 kg and 190 °C; 0 wt%-15 wt% linear low density polyethylene; 50 wt%-85 wt% filler; 0.1 wt%-5 wt% processing aid; and 0.1 wt%-10 wt% ethylene-vinyl acetate copolymer.

7. A composition comprising: 5 wt%-30 wt% propylene-based elastomer having at least 75% triad tacticity of three propylene units measured by 13 13C NMR, a heat of fusion of 75 J / g or less, and a melting point temperature of 105 °C or less, wherein the propylene-based elastomer contains at least 60 wt% propylene-derived units, based on the weight of the propylene-based elastomer; 5 wt% - 30 wt% low density polyethylene having a density of 0.915 g / cm 3 - 0.935 g / cm 3 , a melt flow index measured according to ASTM D1238 - 13 at 2.16 kg and 190 °C of 0.2 g / 10 min - 10 g / 10 min, and a melt flow ratio greater than 40, where the melt flow ratio is the melt flow index measured according to ASTM D1238 - 13 at 21.6 kg and 190 °C divided by the melt flow index measured according to ASTM D1238 - 13 at 2.16 kg and 190 °C; 0 wt%-15 wt% linear low density polyethylene; 50 wt%-85 wt% filler; 0.1 wt%-5 wt% processing aid; 0.1 wt%-20 wt% stabilizer and / or antioxidant; and 0.1 wt%-10 wt% ethylene-vinyl acetate copolymer.

8. A heavy-duty laminated mat comprising: a heavy-duty layer composed of the composition according to any one of claims 1-7; and a polyurethane layer on the surface of the heavy-duty layer.

9. A heavy-duty laminated mat comprising: a heavy-duty layer composed of the composition according to any one of claims 1-7; a polyurethane foam layer on the surface of the heavy-duty layer; and a layer on the polyurethane foam layer such that the polyurethane foam layer is between the heavy-duty layer and the layer.

10. The heavy-duty laminated mat of claim 9, wherein the layer comprises a plurality of fibers.

11. The heavy-duty laminated mat of claim 9, wherein the layer comprises a multi-layer adhesive film, and the multi-layer adhesive film comprises a polar layer and a non-polar layer.

12. The heavy-duty laminated mat according to any one of claims 9-11, wherein the heavy-duty layer has a thickness of 0.1 mm-5 mm.

13. The heavy-duty laminated mat according to any one of claims 9-11, wherein the polyurethane foam layer has a thickness of 0.1 mm-5 mm.

14. A method for preparing a molded polymer sheet, comprising: thermoforming a polymer sheet having a front surface and a back surface with a mold to prepare a molded polymer sheet, the polymer sheet comprising: 5 wt%-30 wt% propylene-based elastomer having at least 75% triad tacticity of three propylene units measured by 13 13C NMR, a heat of fusion of 75 J / g or lower, and a melting point temperature of 105 °C or lower, wherein the propylene-based elastomer contains at least 60 wt% propylene-derived units, based on the weight of the propylene-based elastomer; 5 wt%-30 wt% low density polyethylene, having a density of 0.915 g / cm 3 -0.935 g / cm 3 and a melt flow index measured according to ASTM D1238-13 at 2.16 kg and 190 °C of 0.2 g / 10 min - 10 g / 10 min and a melt flow ratio greater than 40, where the melt flow ratio is the melt flow index measured according to ASTM D1238-13 at 21.6 kg and 190 °C divided by the melt flow index measured according to ASTM D1238-13 at 2.16 kg and 190 °C; 0 wt%-15 wt% linear low density polyethylene; 50wt%-85wt% filler; and 0.1 wt%-5 wt% processing aid; and injecting polyurethane foam into the mold such that the polyurethane foam is on the back surface of the molded polymer sheet.

15. The method for preparing a molded polymer sheet of claim 14, further comprising: adhering a plurality of fibers to the polyurethane foam via thermocompression.

16. The method for preparing a molded polymer sheet of claim 14, further comprising: adhering a multi-layer adhesive film comprising a polar layer and a non-polar layer to the polyurethane foam via thermocompression.

17. A method for preparing a molded polymer sheet, comprising: thermoforming a polymer sheet having a front surface and a back surface with a mold to prepare a molded polymer sheet, the polymer sheet comprising: 5 wt%-30 wt% propylene-based elastomer having at least 75% triad tacticity of three propylene units measured by 13 13C NMR, a heat of fusion of 75 J / g or lower, and a melting point temperature of 105 °C or lower, wherein the propylene-based elastomer contains at least 60 wt% propylene-derived units, based on the weight of the propylene-based elastomer; 5 wt%-30 wt% low density polyethylene having a density of 0.915 g / cm 3 - 0.935 g / cm 3 , a melt flow index measured according to ASTM D1238-13 at 2.16 kg and 190 °C of 0.2 g / 10 min - 10 g / 10 min and a melt flow ratio greater than 40, where the melt flow ratio is the melt flow index measured according to ASTM D1238-13 at 21.6 kg and 190 °C divided by the melt flow index measured according to ASTM D1238-13 at 2.16 kg and 190 °C; 0 wt%-15 wt% linear low density polyethylene; 50wt%-85wt% filler; 0.1 wt%-5 wt% processing aid; and 0.1 wt%-20 wt% stabilizer and / or antioxidant; and injecting a polyurethane foam into the mold such that the polyurethane foam is on the back surface of the molded polymer sheet.

18. A method for preparing a molded polymer sheet, comprising: thermoforming a polymer sheet having a front surface and a back surface with a mold to prepare a molded polymer sheet, the polymer sheet comprising: 5 wt%-30 wt% propylene-based elastomer having at least 75% triad tacticity of three propylene units measured by 13 13C NMR, a heat of fusion of 75 J / g or less, and a melting point temperature of 105 °C or less, wherein the propylene-based elastomer contains at least 60 wt% propylene-derived units, based on the weight of the propylene-based elastomer; 5 wt% - 30 wt% low density polyethylene, having a density of 0.915 g / cm 3 - 0.935 g / cm 3 , a melt flow index measured according to ASTM D1238 - 13 at 2.16 kg and 190 °C of 0.2 g / 10 min - 10 g / 10 min, and a melt flow ratio greater than 40, where the melt flow ratio is the melt flow index measured according to ASTM D1238 - 13 at 21.6 kg and 190 °C divided by the melt flow index measured according to ASTM D1238 - 13 at 2.16 kg and 190 °C; 0 wt%-15 wt% linear low density polyethylene; 50wt%-85wt% filler; 0.1 wt%-5 wt% processing aid; and 0.1 wt%-10 wt% ethylene-vinyl acetate copolymer; and injecting a polyurethane foam into the mold such that the polyurethane foam is on the back surface of the molded polymer sheet.

19. A method for preparing a molded polymer sheet, comprising: thermoforming a polymer sheet having a front surface and a back surface with a mold to prepare a molded polymer sheet, the polymer sheet comprising: 5 wt%-30 wt% propylene-based elastomer having at least 75% triad tacticity of three propylene units measured by 13 13C NMR, a heat of fusion of 75 J / g or less, and a melting point temperature of 105 °C or less, wherein the propylene-based elastomer contains at least 60 wt% propylene-derived units, based on the weight of the propylene-based elastomer; 5 wt%-30 wt% low density polyethylene having a density of 0.915 g / cm 3 -0.935 g / cm 3 , a melt flow index measured according to ASTM D1238-13 at 2.16 kg and 190 °C of 0.2 g / 10 min - 10 g / 10 min and a melt flow ratio greater than 40, where the melt flow ratio is the melt flow index measured according to ASTM D1238-13 at 21.6 kg and 190 °C divided by the melt flow index measured according to ASTM D1238-13 at 2.16 kg and 190 °C; 0 wt%-15 wt% linear low density polyethylene; 50wt%-85wt% filler; 0.1 wt%-5 wt% processing aid; 0.1 wt%-20 wt% stabilizer and / or antioxidant; and 0.1 wt%-10 wt% ethylene-vinyl acetate copolymer; and injecting a polyurethane foam into the mold such that the polyurethane foam is on the back surface of the molded polymer sheet.

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