Synthetic leather

Abstract

An article is provided and includes (A) a top layer comprised of a composition consisting of (i) 70 wt% to 88 wt% of an ethylene-based polymer and (ii) 12 wt% to 30 wt% of an oil, based on the total weight of the top layer. The article also includes (B) a bottom layer comprised of a textile.

Description

BACKGROUND

[0001] The use of synthetic leather continues to grow. Synthetic leather is used to produce clothing, footwear, bags and luggage, home furnishings, and automotive seating. Synthetic leather exhibits similar performance and hand feel compared to natural leather. Synthetic leather offers the added advantage of being animal friendly and is less costly to produce compared to natural leather.

[0002] Conventional synthetic leather has drawbacks. Production of polyurethane-based synthetic leather (PU-leather) requires the use of an organic solvent, typically dimethylformamide (DMF), to form the polyurethane synthetic leather matrix. DMF is harmful to manufacturers, processors, consumers, and the environment.

[0003] Polyvinyl chloride synthetic leather (PVC-leather) requires halogenated polymers and plasticizers, typically phthalate-based plasticizers. Both halogenated polymers and phthalate-based plasticizers are harmful to manufacturers, processors, consumers, and the environment.

[0004] Polyolefin elastomer-based synthetic leather (POE-leather) is advantageous because it is halogen-free, phthalate-free, and production of POE-leather does not require the use of harmful solvents such as DMF. POE-leather has the added benefit of recyclability due to its thermoplastic nature. From a performance perspective, POE has excellent weatherability and low temperature flexibility, and is resistant to hydrolysis and yellowing. In addition, POE-leather is found to be advantageous to the light-weighting trend currently emerging in the luggage / bag, footwear, and automotive interior sectors because POE-leather has a lower density compared to the density of each of PU-leather and PVC-leather.

[0005] Accordingly, there is a recognized need in the art for POE-leather. There is further recognized need in the art for POE-leather having bally flex resistance performance and softness that meets or exceeds the bally flex resistance performance and softness of PU-leather and / or PVC-synthetic leather. SUMMARY

[0006] The present disclosure provides an article. In one embodiment, an article is provided and the article includes (A) a top layer comprised of a composition, the composition consisting of (i) 70 to 88 weight percent of an ethylene-based polymer and (ii) 12 to 30 weight percent of an oil, based on the total weight of the top layer. The article further includes (B) a bottom layer comprised of a textile. BRIEF DESCRIPTION OF DRAWINGS

[0007] Figure 1 is a dynamic mechanical spectrogram comparing Inventive Example 3 (IE3) to Comparative Sample 7 (CS7).

[0008] Definitions

[0009] Any reference to the Periodic Table of the Elements is to the Periodic Table of the Elements as published by CRC Press, Inc., 1990-1991. A group of elements in this table is referred to by its new notation.

[0010] For purposes of United States patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or its equivalent U.S. version is so incorporated by reference), especially with regard to the disclosure of definitions (to the extent not inconsistent with definitions specifically provided in the disclosure) and general knowledge in the art.

[0011] The numerical ranges recited herein include all values from and including the lower and upper values. For ranges containing explicit values (e.g., 1 or 2, or 3 to 5, or 6, or 7), any subrange between any two of the explicit values is included (e.g., the range 1 to 7 above includes a range from 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0012] Unless stated to the contrary, all parts and percentages are based upon weight and all test methods are current as of the filing hereof.

[0013] As used herein, the term "blend" or "polymer blend" is a blend of two or more polymers. This blend can or can not be miscible (not phase separated at a molecular level). The blend can or can not be phase separated. This blend can or can not contain one or more domain configurations as determined by transmission electron spectroscopy, light scattering, x-ray scattering, and other methods known in the art.

[0014] The term "composition" means a mixture of materials which comprises the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0015] The terms "comprising," "including," "having," and their derivatives, are not intended to exclude any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the terms "comprising," "including," "having" and their derivatives, are intended to include additional additives, adjuvants or compounds, whether polymeric or otherwise, in the compositions claimed, unless expressly excluded. Conversely, the term "consisting essentially of" excludes from the range of equivalents any additional component, step or procedure that is not specifically disclosed, except for components, steps or procedures that do not materially affect the operation of the composition. The term "consisting of" excludes any component, step or procedure not specifically named or listed. The term "or" as used in "or" as used in the context as used herein is to be interpreted as inclusive or, meaning there is at least one of the members in the list that is present.

[0016] As used herein, "ethylene-based polymer" is a polymer containing more than 50 wt% of polymerized ethylene monomer (based on the total amount of polymerizable monomers) and optionally can contain at least one comonomer.

[0017] "Fabric" is a woven or nonwoven (such as knitted) structure formed from individual fibers or yarns.

[0018] "Fiber" and like terms refer to an elongated column of entangled filaments. Fiber diameter can be measured and reported in a variety of ways. Typically, fiber diameter is measured in denier per filament. Denier is a textile term defined as the mass in grams of 9,000 meters of fiber length. Single filaments typically refer to extruded strands having a denier per filament greater than 15, typically greater than 30. Fine denier fibers typically refer to fibers having a denier of 15 or less. Microdenier (also referred to as "microfiber") typically refers to fibers having a diameter of no greater than 100 micrometers.

[0019] "Filament" and like terms refer to a single continuous strand of elongated material having a generally circular cross-section and an aspect ratio greater than 10.

[0020] As used herein, the term "foam" or "foam article" is a structure constructed from a polymer; the structure includes a plurality of discrete cells or foam cells completely surrounded by polymer. As used herein, the term "foam cell" or "cell" is a discrete space within a foam composition. Foam cells are separated or otherwise defined by a membrane wall composed of the polymer of the foam composition.

[0021] "Interpolymer" is a polymer prepared from the polymerization of at least two different monomers. This general term includes copolymers, typically used to refer to polymers prepared from two different monomers, as well as polymers prepared from more than two different monomers, such as terpolymers, tetrapolymers, etc.

[0022] "Knit" is formed by hand or on a machine with yarn or fiber wrapped in a series of connected loops with needles. Knits can be formed by warp knitting or weft knitting, flat knitting, and circular knitting. Non-limiting examples of suitable warp knit fabrics include Tereftal warp knit fabrics, Raschel power net, and laces. Non-limiting examples of suitable weft knit fabrics include circular, flat, and seamless (which is often considered a subset of circular knit fabrics).

[0023] "Nonwoven" refers to a web or fabric having a structure of individual fibers or threads which are interlaced, but not in an identifiable manner, as is the case of a knit.

[0024] "Olefin-based polymer" or "polyolefin" is a polymer containing more than 50 weight percent of polymerized olefin monomers (based on the total amount of polymerizable monomers) and optionally can contain at least one comonomer. A non-limiting example of an olefin-based polymer is an ethylene-based polymer.

[0025] "Polymer" is a compound prepared by polymerizing a plurality of and / or repeating "units" or "mer units", whether of the same or different type, monomers provided in polymeric form. Thus, the general term polymer encompasses the term homopolymer, which is generally used to refer to polymers prepared from only one type of monomer, and the term copolymer, which is generally used to refer to polymers prepared from at least two types of monomers. It also encompasses all forms of copolymers, such as random copolymers, block copolymers, and the like. The terms "ethylene / alpha-olefin polymer" and "propylene / alpha-olefin polymer" mean copolymers prepared by polymerizing ethylene or propylene, respectively, and one or more additional polymerizable alpha-olefin monomers, as described above. It should be noted that although polymers are often referred to as being "made from", "based on", "containing" a particular monomer or type of monomer, or a particular monomer content, and the like, in this context the term "monomer" is understood to refer to the polymerized residue of the particular monomer, and not the un-polymerized species. In general, polymers herein refer to "units" based on the corresponding monomers in polymeric form.

[0026] "Propylene-based polymer" is a polymer comprising more than 50 weight percent of polymerized propylene monomers (based on the total amount of polymerizable monomers) and optionally can contain at least one comonomer.

[0027] "Styrene" has the following structure A. "Styrene-based polymer" is a polymer containing polymerized styrene as a monomer.

[0028] Structure A

[0029]

[0030] “Woven” refers to a web or fabric having a structure of individual fibers or threads which are interwoven in an identifiable manner. A non-limiting example of a woven fabric is a knitted fabric.

[0031] Test Methods

[0032] Bally Flex Test was performed according to ASTM D6182 at 25 °C. The Bally Flex Test determines the durability of the coating applied to synthetic leather, leather, and fabric by repeatedly flexing the sample. The Bally Flexometer conforms to DIN 53351 and is operated at a rate of 100 cycles / minute. The end cycle is determined by the cycle at which the panel surface cracks and is reported as the Bally Flex result. Two specimens are tested for each sample and the average is reported as the Bally Flex value. The result is reported as the number of cycles. If no cracks / damage are found after 100,000 cycles for both specimens, the result is reported as “greater than 100,000” or “>100k”.

[0033] Density was measured according to ASTM D792 Method B. The result is reported in grams per cubic centimeter (g / cc).

[0034] Differential Scanning Calorimetry (DSC) Differential scanning calorimetry (DSC) can be used to measure the melting, crystallization, and glass transition behavior of a polymer over a wide temperature range. For example, this analysis is performed using a TA Instruments Q2000 DSC equipped with a refrigerated cooling system (RCS) and an autosampler. During testing, a nitrogen purge gas flow of 50 ml / min is used. Each sample is melt pressed into a thin film at about 175 °C; the melted sample is then air-cooled to room temperature (about 25 °C). A 3-10 mg, 6 mm diameter specimen is extracted from the cooled polymer, weighed, placed in a light aluminum pan (ca 50 mg), and crimped shut. Analysis is then performed to determine its thermal properties.

[0035] The thermal behavior of the sample is determined by ramping the sample temperature up and down to create a heat flow versus temperature curve. First, a sample is rapidly heated to 180 °C and held isothermal for 3 minutes in order to remove its thermal history. Next, the sample is cooled to -80 °C at a 10 °C / minute cooling rate and held isothermal at -80 °C for 3 minutes. The sample is then heated to 180 °C (this is the “second heat” ramp) at a 10 °C / minute heating rate. The cooling and second heating curves are recorded. The cooling curve is analyzed by setting baseline endpoints from the beginning of crystallization to -20 °C. The heating curve is analyzed by setting baseline endpoints from -20 °C to the end of melting. The values determined are the extrapolated onset of melting Tm and the extrapolated onset of crystallization Tc. The heat of fusion (Hf) and heat of crystallization (Hc) are calculated from the area under the curves. The degree of crystallinity is calculated as a ratio. f) and the calculated % crystallinity using the following equation: % crystallinity = ((H f ) / 292 J / g) x 100.

[0036] Heat of fusion (H f ) (also known as the enthalpy of fusion) and peak melting temperature are reported from the second heat curve.

[0037] The melting point, Tm, is determined from the DSC heating curve by first drawing a baseline between the start and end of the melting transition. A tangent line is then drawn to the data on the low temperature side of the melting peak. The point at which this tangent line intersects the baseline is the extrapolated onset of melting (Tm). This is as described in Bernhard Wunderlich, The Basis of Thermal Analysis in Thermal Characterization of Polymeric Materials 92, 277-278 (Edith A. Turi, ed., 2nd ed. 1997).

[0038] The glass transition temperature, Tg, is determined from the DSC heating curve where half of the sample has acquired the liquid heat capacity as described in Bernhard Wunderlich, The Basis of Thermal Analysis in Thermal Characterization of Polymeric Materials 92, 278-279 (Edith A. Turi, ed., 2nd ed. 1997). The baseline is drawn from below and above the glass transition region and extrapolated through the Tg region. The temperature at which the heat capacity of the sample is halfway between these baselines is Tg.

[0039] Dynamic mechanical spectra (DMS) were measured on compression molded plaques on a rheometer AR2000ex (TA Instruments) equipped with a dual cantilever clamp for torque testing, using a geometry of 25 mm parallel plates, frequency sweep, temperature: 160 °C, angular frequency: 1-628 rad / s, strain: 5%, in a hot press at 180 °C and 10 MPa pressure for 5 min, followed by water cooling on the press at 90 °C / min.

[0040] The melt index (MI or I2) (for ethylene-based polymers) is measured according to ASTM D 1238, condition 190 °C / 2.16 kg, with the result reported in grams / 10 minutes (g / 10 min).

[0041] Shore A hardness was measured according to ASTM D2240. Load 1 kg, duration 5 seconds. For testing, two 3 mm thick plaques were stacked together. DETAILED DESCRIPTION

[0042] The present disclosure provides an article. In one embodiment, the article includes (A) a top layer comprised of a composition consisting of (i) 70 to 88 weight percent of an ethylene-based polymer and (ii) 12 to 30 weight percent of an oil, based on the total weight of the top layer. The article also includes (B) a bottom layer comprised of a textile.

[0043] A.J Top Layer

[0044] (i) Ethylene-based Polymer

[0045] The top layer is comprised of a composition comprising (i) 70 to 88 weight percent of an ethylene-based polymer and (ii) 12 to 30 weight percent of an oil. The weight percentages are based on the total weight of the top layer. The ethylene-based polymer is (i) an ethylene / C4-C8 alpha-olefin copolymer, (ii) an ethylene / C4-C8 alpha-olefin multi-block copolymer, and (iii) a combination of (i) and (ii).

[0046] The ethylene / C4-C8 alpha-olefin copolymer consists of (i) polymerized units of ethylene and (ii) polymerized units of a C4-C8 alpha-olefin comonomer. Non-limiting examples of suitable ethylene / C4-C8 alpha-olefin copolymers include ethylene / butene copolymers, ethylene / hexene copolymers, and ethylene / octene copolymers.

[0047] In one embodiment, the ethylene / C4-C8 alpha-olefin copolymer resin is an ethylene / octene copolymer having one, some, or all of the following properties:

[0048] (i) a density of 0.857 to 0.880 g / cc, or 0.865 to 0.875 g / cc; and / or

[0049] (ii) a melt index (I2) of 0.5 to 20 g / 10 min, or 1 to 15 g / 10 min, or 3 to 13 g / 10 min; and / or

[0050] (iii) a Shore A hardness value of less than 80, or less than 75, or 50 to 75, or 60 to 75.

[0051] In an embodiment, the ethylene-based polymer is an ethylene / C4-C8a-olefin multi-block copolymer. The term "ethylene / C4-C8a-olefin multi-block copolymer" refers to an ethylene / C4-C8a-olefin multi-block copolymer composed of ethylene and one copolymerizable C4-C8a-olefin comonomer (and optional additives) in polymerized form, the polymer being characterized by multiple blocks or segments of two polymerized monomer units differing in chemical or physical characteristics, the blocks being connected (or covalently bonded) in a linear fashion, i.e., a polymer comprising chemically distinguishable units joined end to end in relation to the polymerized ethylenic functionality. Ethylene / a-olefin multi-block copolymers include block copolymers having two blocks (diblocks) and more than two blocks (multiblocks). The C4-C8a-olefin is selected from butene, hexene, and octene. The ethylene / C4-C8a-olefin multi-block copolymer is free of, or otherwise does not contain, styrene (i.e., free of styrene), and / or an ethylene-based aromatic monomer, and / or a conjugated diene. When referring to the amount of "ethylene" or "comonomer" in the copolymer, it is understood that this refers to its polymerized units. In some embodiments, the ethylene / a-olefin multi-block copolymer can be represented by the following formula: (AB) n ; wherein n is an integer of at least 1, preferably greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or more, "A" represents a hard block or segment and "B" represents a soft block or segment. Preferably, A and B are connected or covalently bonded in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped fashion. In other embodiments, the A blocks and B blocks are randomly distributed along the polymer chain. In other words, the block copolymer does not typically have the following structure: AAA-AA-BBB-BB. In an embodiment, the ethylene / a-olefin multi-block copolymer does not have a third type of block comprising one or more different comonomers. In another embodiment, blocks A and B each have monomers or comonomers substantially randomly distributed within the block. In other words, neither block A nor block B contains two or more sub-segments (or sub-blocks) of different composition, such as end segments, having a composition substantially different from the remainder of the block.

[0052] In one embodiment, ethylene comprises the majority of the mole fraction of the entire ethylene / alpha-olefin multi-block copolymer, i.e., ethylene comprises at least 50 wt% of the entire ethylene / alpha-olefin multi-block copolymer. More preferably, ethylene comprises at least 60 wt%, at least 70 wt%, or at least 80 wt% of the substantially remainder of the entire ethylene / alpha-olefin multi-block copolymer comprises C4-C8 alpha-olefin comonomer. In one embodiment, the ethylene / alpha-olefin multi-block copolymer contains from 50 wt% to 90 wt% ethylene, or from 60 wt% to 85 wt% ethylene, or from 65 wt% to 80 wt% ethylene. For multi-block ethylene / octene copolymers, the composition comprises an ethylene content greater than 80 wt% of the entire ethylene / octene multi-block copolymer and an octene content of from 10 wt% to 15 wt%, or from 15 wt% to 20 wt% of the entire multi-block copolymer.

[0053] The ethylene / C4-C8 alpha-olefin multi-block copolymer includes various amounts of "hard" segments and "soft" segments. A "hard" segment is a block of polymerized units in which ethylene is present in an amount greater than 90 wt%, or 95 wt%, or greater than 95 wt%, or greater than 98 wt%, up to 100 wt% by weight of the polymer. In other words, the comonomer content (other than the monomer content of ethylene) in a hard segment is less than 10 wt%, or 5 wt%, or less than 5 wt%, or less than 2 wt%, and can be as low as zero by weight of the polymer. In some embodiments, a hard segment comprises all or substantially all units derived from ethylene. A "soft" segment is a block of polymerized units in which the comonomer content (content of monomers other than ethylene) is greater than 5 wt%, or greater than 8 wt%, greater than 10 wt%, or greater than 15 wt% by weight of the polymer. In one embodiment, the comonomer content in a soft segment is greater than 20 wt%, greater than 25 wt%, greater than 30 wt%, greater than 35 wt%, greater than 40 wt%, greater than 45 wt%, greater than 50 wt%, or greater than 60 wt% and can be as high as 100 wt%.

[0054] The soft segments can be present in the ethylene / alpha-olefin multi-block copolymer from 1 wt% to 99 wt% of the total weight of the ethylene / alpha-olefin multi-block copolymer, or from 5 wt% to 95 wt%, 10 wt% to 90 wt%, 15 wt% to 85 wt%, 20 wt% to 80 wt%, 25 wt% to 75 wt%, 30 wt% to 70 wt%, 35 wt% to 65 wt%, 40 wt% to 60 wt%, or 45 wt% to 55 wt% of the total weight of the ethylene / alpha-olefin multi-block copolymer. Conversely, the hard segments can be present in similar ranges. The soft segment weight percent and hard segment weight percent can be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed in, for example, USP 7,608,668 entitled "Ethylene / alpha-Olefin Block Inter-Polymers" filed on March 15, 2006 in the name of Colin L. P. Shan, Lonnie Hazlitt, et al., and assigned to Dow Global Technologies Inc., the disclosure of which is incorporated herein by reference in its entirety. Specifically, the hard segment weight percent and soft segment weight percent, as well as comonomer content, can be determined as described in columns 57-63 of USP 7,608,668.

[0055] The ethylene / C4-C8 alpha-olefin multi-block copolymers comprise two or more chemically distinct regions or segments (referred to as "blocks") joined (or covalently bonded) in a linear fashion, i.e., a polymer that contains chemically distinguishable units joined end to end in a polymeric alkenyl functionality rather than in a pendent or grafted fashion. In one embodiment, the blocks differ in the amount or type of comonomer incorporated, the density, the amount of crystallinity, the crystallite size, the type or degree of stereoregularity (isotactic or syndiotactic), the tacticity (isotactic or syndiotactic), the amount of branching (including long chain branching or hyperbranching), the uniformity, or any other chemical or physical property attributable to the polymer of the composition. The ethylene / alpha-olefin multi-block copolymers of the present invention are characterized by a unique distribution of polymer polydispersity (PDI or Mw / Mn or MWD), polydisperse block length distribution, and / or polydisperse block number distribution, in one embodiment, due to the influence of one or more shuttling agents used in their preparation in combination with multiple catalysts, as compared to prior art block interpolymers, including interpolymers produced by sequential monomer addition, stereospecific catalysts, or anionic polymerization techniques.

[0056] In one embodiment, the ethylene / C4-C8a-olefin multi-block copolymer is produced in a continuous process and has a polydispersity index (Mw / Mn) of 1.7 to 3.5, or 1.8 to 3, or 1.8 to 2.5, or 1.8 to 2.2. When produced in a batch or semi-batch process, the ethylene / a-olefin multi-block copolymer has a Mw / Mn of 1.0 to 3.5, or 1.3 to 3, or 1.4 to 2.5, or 1.4 to 2.

[0057] Additionally, the ethylene / C4-C8a-olefin multi-block copolymer has a PDI (or Mw / Mn) that fits a Schultz-Flory distribution rather than a Poisson distribution. The ethylene / a-olefin multi-block copolymers of the present application have both a polydisperse block distribution as well as a polydisperse distribution of block sizes. This results in the formation of polymer products having improved and distinguishable physical properties. The theoretical benefits of a polydisperse block distribution have been previously modeled and discussed in Potemkin, Physical Review E (1998) 57(6), pp. 6902-6912 and Dobrynin, Journal of Chemical Physics (1997) 107(21), pp. 9234-9238. Physical Review E ) (1998) 57(6), pp. 6902-6912 and Dobrynin, Journal of Chemical Physics (1997) 107(21), pp. 9234-9238. J. Chem. Phys.

[0058] In one embodiment, the ethylene / a-olefin multi-block copolymers of the present application have a most probable distribution of block lengths.

[0059] In another embodiment, the ethylene / C4-C8a-olefin multi-block copolymers of the present disclosure, especially those made in a continuous solution polymerization reactor, have a most probable distribution of block lengths. In one embodiment of the present disclosure, the ethylene / C4-C8a-olefin multi-block copolymers are defined as having:

[0060] (A) a Mw / Mn of about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams / cubic centimeter, where the numerical values of Tm and d correspond to the relationship: 2 , and / or

[0061] (B) a Mw / Mn of about 1.7 to about 3.5, and is characterized by a heat of fusion, ΔH in J / g, and a delta quantity, ΔT, in degrees Celsius, defined as the temperature difference between the tallest DSC peak and the tallest Crystallization Analysis Fractionation ("CRYSTAF") peak, wherein the numerical values of ΔT and ΔH have the following relationships:

[0062] ​ΔT > -0.1299 ΔH + 62.81 for ΔH greater than zero and up to 130 J / g

[0063] ΔT > 48°C for ΔH greater than 130 J / g

[0064] where the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has a resolvable CRYSTAF peak, then the CRYSTAF temperature is 30 °C; and / or

[0065] (C) the elastic recovery Re, in percent, measured at 300 percent stress and 1 cycle using a compression-molded film of the ethylene / α-olefin interpolymer, and has a density d, in grams / cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when the ethylene / α-olefin interpolymer is substantially free of a cross-linked phase:

[0066] Re > 1481 - 1629(d); and / or

[0067] (D) when fractionated using TREF, has a molecular fraction which elutes between 40 °C and 130 °C, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable fraction eluting between the same temperatures of a comparable random ethylene interpolymer, wherein the comparable random ethylene interpolymer has the same comonomers and has a melt index, density, and molar comonomer content (based on the total polymer) within 10 percent of that of the ethylene / α-olefin interpolymer; and / or

[0068] (E) has a storage modulus G'(25 °C) and a storage modulus G'(100 °C), both measured at 25 °C, wherein the ratio of G'(25 °C) to G'(100 °C) is in the range of 1:1 to 9:1.

[0069] The ethylene / C4-C8 α-olefin multi-block copolymer can also have:

[0070] (F) when fractionated using TREF, a fraction which elutes at temperatures between 40 °C and 130 °C, characterized in that the fraction has a block index of at least 0.5 and up to 1, and a molecular weight distribution, Mw / Mn, greater than 1.3; and / or

[0071] (G) an average block index greater than zero and up to 1.0, and a molecular weight distribution, Mw / Mn, greater than 1.3.

[0072] It is understood that the ethylene / C4-C8a-olefin multi-block copolymers can have one, some, all, or any combination of properties (A)-(G). Block index can be determined as described in detail in USP 7,608,668, which is incorporated by reference herein for that purpose. Analytical methods for determining properties (A) through (G) are disclosed, for example, in USP 7,608,668, column 31, line 26 to column 35, line 44, which is incorporated by reference herein for that purpose.

[0073] In one embodiment, the ethylene / C4-C8a-olefin multi-block copolymer has hard segments and soft segments, is free of styrene, consists of only (i) ethylene and (ii) a C4-C8a-olefin or C8a-olefin (and optional additives), and is defined as having a Mw / Mn of 1.7 to 3.5, at least one melting point Tm, in degrees Celsius, and a density, in grams cubic centimeter, d, where the numerical values of Tm and d correspond to the relationship:

[0074] Tm > -2002.9 + 4538.5(d) - 2422.2(d) 2 ,

[0075] where the density d is 0.850 g / cc, or 0.860 g / cc, or 0.870 g / cc to 0.875 g / cc, or 0.877 g / cc, or 0.880 g / cc, or 0.890 g / cc; and the melting point Tm is 110 °C, or 115 °C, or 120 °C to 125 °C, or 130 °C, or 135 °C.

[0076] In one embodiment, the ethylene / C4-C8a-olefin multi-block copolymer is an ethylene / 1-octene multi-block copolymer (consisting of only ethylene and octene comonomer) and has one, some, or all of the following properties:

[0077] (i) Mw / Mn is 1.7, or 1.8 to 2.2, or 2.5, or 3.5; and / or

[0078] (ii) density is 0.857 g / cc, 0.860 g / cc, or 0.865 g / cc to 0.870 g / cc, or 0.877 g / cc, or 0.880 g / cc; and / or

[0079] (iii) melting point Tm is 115 °C, or 118 °C, or 119 °C, or 120 °C to 120 °C, or 123 °C, or 125 °C; and / or

[0080] (iv) a melt index (MI) of 0.1 g / 10 min, or 0.5 g / 10 min to 1.0 g / 10 min, or 2.0 g / 10 min, or 5 g / 10 min, or 10 g / 10 min; and / or

[0081] (v) 50 wt% to 85 wt% soft segments and 40 wt% to 15 wt% hard segments (based on the total weight of the ethylene / octene multi-block copolymer); and / or

[0082] (vi) 10 mol%, or 13 mol%, or 14 mol%, or 15 mol% to 16 mol%, or 17 mol%, or 18 mol%, or 19 mol%, or 20 mol%, or 25 mol% octene in the soft segments; and / or

[0083] (vii) 0.5 mol%, or 1.0 mol%, or 2.0 mol%, or 3.0 mol% to 4.0 mol%, or 5 mol%, or 6 mol%, or 7 mol%, or 9 mol% octene in the hard soft segments; and / or

[0084] (viii) an elastic recovery (Re) of 50%, or 60% to 70%, or 80%, or 90% at 300% min -1 deformation at 21 °C as measured according to ASTM D 1708; and / or

[0085] (ix) a polydispersity distribution of blocks and a polydispersity distribution of block sizes (hereinafter referred to as multi-block copolymer properties (i) to (ix)).

[0086] In one embodiment, the ethylene / C4-C8a-olefin multi-block copolymer is an ethylene / octene multi-block copolymer. Ethylene / octene multi-block copolymers are sold under the trade name INFUSE TM by The Dow Chemical Company, Midland, Michigan, USA.

[0087] Ethylene / C4-C8a-olefin multi-block copolymers can be produced via a chain shuttling process as described in USP 7,858,706, which is incorporated herein by reference. In particular, suitable chain shuttling agents and related information are listed in column 16, line 39 to column 19, line 44. Suitable catalysts are described in column 19, line 45 to column 46, line 19 and suitable co-catalysts are described in column 46, line 20 to column 51, line 28. The process is described throughout the document, but especially in column 51, line 29 to column 54, line 56. The process is also described in, for example: USP 7,608,668; USP 7,893,166; and USP 7,947,793.

[0088] In one embodiment, the ethylene / C4-C8a-olefin multi-block copolymer is an ethylene / octene multi-block copolymer having a density of 0.86 g / cc to 0.88 g / cc, a melt index of 0.5 g / 10 min to 20 g / 10 min or 1 g / 10 min to 15 g / 10 min, a Shore A hardness value of less than 80, or less than or equal to 75, or 60 to 75.

[0089] (ii) Oil

[0090] In addition to the ethylene-based polymer, the top layer also includes 12 wt% to 30 wt% of an oil. The weight percent is based on the total weight of the top layer. The oil can be a mineral oil, an aromatic oil, a naphthenic oil, a paraffinic oil, and a triglyceride-based vegetable oil such as castor oil or soybean oil, a synthetic hydrocarbon oil such as polypropylene oil, a silicone oil, and combinations thereof.

[0091] In one embodiment, the oil is a mineral oil. As used herein, "mineral oil" is a colorless, odorless oil that is a mixture of alkanes. The mineral oil is present in the top layer excluding aromatic oil, naphthenic oil, paraffinic oil, triglyceride-based vegetable oil, synthetic hydrocarbon oil, silicone oil, and any combination thereof. The mineral oil is present in the top layer in an amount of 12 wt% to 30 wt%, or 13 wt% to 27 wt%, or 15 wt% to 25 wt%, based on the total weight of the top layer. 15 -C 40 alkanes. The mineral oil is present in the top layer excluding aromatic oil, naphthenic oil, paraffinic oil, triglyceride-based vegetable oil, synthetic hydrocarbon oil, silicone oil, and any combination thereof. The mineral oil is present in the top layer in an amount of 12 wt% to 30 wt%, or 13 wt% to 27 wt%, or 15 wt% to 25 wt%, based on the total weight of the top layer.

[0092] B. Bottom Textile Layer

[0093] In addition to the top layer, the article of the present application also includes a bottom textile layer. A "textile" is a flexible material composed of a web of natural fibers, man-made fibers, and combinations thereof. Textiles include fabrics and cloths. The textile can be woven, nonwoven, knitted, plain, or spunbonded. Non-limiting examples of natural fibers include cotton, wool, hemp, silk, and combinations thereof. Non-limiting examples of man-made fibers include polyester (PET), polyamide (nylon), acrylic, polyolefin, polyurethane (e.g., spandex material), polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, and combinations thereof.

[0094] In one embodiment, the textile is a nonwoven textile.

[0095] In one embodiment, the textile is a microfiber nonwoven textile. A "microfiber" textile is a textile that contains fibers having a diameter of no greater than 100 microns.

[0096] In one embodiment, the textile has a density of 0.20 g / cc, or 0.25 g / cc to 0.27 g / cc, or 0.30 g / cc, or 0.31 g / cc, or 0.32 g / cc, or 0.35 g / cc, or 0.40 g / cc, or 0.50 g / cc.

[0097] In one embodiment, the textile contains fibers having a size of 0.1 denier, or 0.3 denier, or 1 denier, or 2 denier, or 3 denier to 4 denier, or 5 denier, or 6 denier, or 7 denier, or 8 denier, or 9 denier, or 10 denier. In another embodiment, the textile contains fibers having a size of 10 denier or less.

[0098] In one embodiment, the textile has a thickness of 0.5 mm, or 1.0 mm to 1.5 mm, or 2.0 mm.

[0099] In one embodiment, the textile is a nonwoven textile having one, some, or all of the following properties:

[0100] (a) a density of 0.20 g / cc, or 0.25 g / cc to 0.32 g / cc, or 0.35 g / cc; and / or

[0101] (b) a fiber size of 1 denier, or 3 denier to 5 denier; and / or

[0102] (c) a thickness of 0.5 mm, or 1.0 mm to 1.5 mm, or 2.0 mm.

[0103] In one embodiment, the textile is a fabric composed of polyester, polyethylene, and / or polypropylene. The fabric is subjected to a lamination pre-treatment, such as a corona surface treatment, impregnation, and the like, and a top layer is heat laminated to the fabric such that the top layer directly contacts the bottom layer, such that there is no intermediate layer or no intermediate layer structure between the top layer and the bottom layer.

[0104] The textile can include two or more embodiments disclosed herein.

[0105] In one embodiment, the article includes (A) a top layer and (B) a bottom layer containing a textile. The top layer directly contacts the bottom layer. The top layer contains (i) 80 wt% to 88 wt% of an ethylene / C4-C8 alpha-olefin copolymer, and (ii) 12 wt% to 20 wt% of an oil. The ethylene / C4-C8 alpha-olefin copolymer has a density of 0.86 g / cc to 0.88 g / cc, a melt index of 0.5 g / 10 min to 20 g / 10 min, and a Shore A value of less than 75. The oil is a mineral oil, excluding any other type of oil. The top layer has a Bailey Flex value of greater than 86,000, or 87,000 to 150,000, or 90,000 to 140,000. In another embodiment, the top layer (A) has a melt index of 2 g / 10 min to 10 g / 10 min, and a Shore A hardness value of 60 to less than 75.

[0106] In one embodiment, the article includes (A) a top layer and (B) a bottom layer containing a textile. The top layer directly contacts the bottom layer. The top layer contains (i) 80 wt% to 88 wt% of an ethylene / C4-C8 alpha-olefin copolymer, and (ii) 12 wt% to 20 wt% of an oil. The ethylene / C4-C8 alpha-olefin copolymer has a density of 0.86 g / cc to 0.88 g / cc, a melt index of 0.5 g / 10 min to 20 g / 10 min, and a Shore A value of less than 75. The oil is a mineral oil, excluding any other type of oil. The top layer has a Bailey Flex value of greater than 86,000, or 87,000 to 150,000, or 90,000 to 140,000. In another embodiment, the top layer (A) has a melt index of 2 g / 10 min to 10 g / 10 min, and a Shore A hardness value of 60 to less than 75.

[0107] C. Middle Foam Layer

[0108] In one embodiment, the article includes an intermediate foam layer in addition to the top and bottom layers. The intermediate layer is positioned between the top and bottom layers. The intermediate foam layer is in direct contact with the top layer and / or the bottom layer. In one embodiment, the intermediate foam layer is in direct contact with the top layer and in direct contact with the bottom layer. The intermediate foam layer is composed of a composition including (i) 70 wt% to 90 wt%, or 70 wt% to 88 wt%, of an ethylene-based polymer, and (ii) 10 wt% to 30 wt%, or 12 wt% to 30 wt%, of an oil, based on the total weight of the intermediate foam layer.

[0109] In one embodiment, the intermediate foam layer is prepared by blending or compounding the components with one another in any conventional mixing equipment (e.g., a Banbury mixer or any suitable extruder) for a period of time under conditions which result in a substantially uniform mixture, calendaring the mixture using conventional equipment and conditions to form a sheet, and then hot laminating the sheet to the top and / or bottom textile layers using conventional lamination equipment and conditions. The intermediate foam layer is typically not subjected to foaming conditions until after it is laminated to the top layer (A) and bottom textile layer (B). Foaming conditions are such that very fine and regular cells are formed throughout the intermediate foam layer. Typical foaming conditions include oven temperatures of 200 °C or higher and oven residence times of 60-120 seconds. The foam efficiency [i.e., the ratio of the expanded volume to the original (unexpanded) volume] is based on the thickness ratio, and it is typically 1.5 to 5, or 2 to 3.

[0110] In one embodiment, the article includes (A) a top layer and (B) a bottom layer containing a textile, and (C) a middle foam layer. The middle foam layer (C) is positioned between the top layer (A) and the bottom textile layer (B). The top layer (A) directly contacts the middle foam layer (C) and the middle foam layer (C) directly contacts the bottom layer. The top layer (A) and the middle foam layer (C) each contain (i) 70 wt% to 90 wt%, or 80 wt% to 88 wt%, of an ethylene / C4-C8a-olefin copolymer, and (ii) 10 wt% to 30 wt%, or 12 wt% to 20 wt%, of an oil. The ethylene / C4-C8a-olefin copolymer in the top layer (A) and the middle foam layer (C) can be the same or can be different. The ethylene / C4-C8a-olefin copolymer in the top layer (A) and the middle foam layer (C) each has a density of 0.86 g / cc to 0.88 g / cc, a melt index of 0.5 g / 10 min to 20 g / 10 min, and a Shore A value of less than or equal to 75. The oil in the top layer (A) and the oil in the middle foam layer (C) is a mineral oil, excluding any other type of oil. The amount of oil in the top layer and the amount of oil in the middle foam layer can be the same or different. The top layer (A) and the foam layer (C) each has a Ballistic Flexibility value of greater than 86,000, or 87,000 to 150,000, or 90,000 to 140,000. In another embodiment, the composition of the top layer (A) and the foam in the middle layer (C) each has a melt index of 2 g / 10 min to 10 g / 10 min, and a Shore A hardness value of 60 to less than 75.

[0111] In one embodiment, the article includes (A) a top layer and (B) a bottom layer containing a textile, and (C) an intermediate foam layer. The intermediate foam layer (C) is positioned between the top layer (A) and the bottom textile layer (B). The top layer (A) directly contacts the intermediate foam layer (C) and the intermediate foam layer (C) directly contacts the bottom layer. The top layer (A) and the intermediate foam layer (C) each contain (i) 30 wt% to 50 wt%, or 35 wt% to 45 wt%, of an ethylene / C4-C8a-olefin multi-block copolymer, (ii) 30 wt% to 50 wt%, or 35 wt% to 45 wt%, of an ethylene / C4-C8a-olefin copolymer, and (iii) 10 wt% to 30 wt%, or 12 wt% to 30 wt%, or 15 wt% to 25 wt%, of an oil. It is understood that the ethylene / C4-C8a-olefin multi-block copolymer, the ethylene / C4-C8a-olefin copolymer, and the oil total 100 wt% of the top layer (A). It is understood that the ethylene / C4-C8a-olefin multi-block copolymer, the ethylene / C4-C8a-olefin copolymer, and the oil total 100 wt% of the intermediate foam layer (C). The ethylene / C4-C8a-olefin multi-block copolymer in the top layer (A) and the ethylene / C4-C8a-olefin multi-block copolymer in the intermediate foam layer (C) can be the same or can be different. The amount of oil in the top layer and the amount of oil in the intermediate foam layer can be the same or different. The ethylene / C4-C8a-olefin multi-block copolymer in the top layer (A) and the ethylene / C4-C8a-olefin multi-block copolymer in the intermediate layer (C) each have a density of 0.86 g / cc to 0.88 g / cc, a melt index of 0.5 g / 10 min to 20 g / 10 min, and a Shore A value of 60 to less than or equal to 75. The top layer (A) has a Baril Flex value of greater than 86,000, or 87,000 to 150,000, or 90,000 to 140,000. In another embodiment, the composition of the top layer (A) and the foam in the intermediate layer (C) each have a melt index of 2 g / 10 min to 10 g / 10 min and a Shore A hardness value of 60 to less than 75.

[0112] D. Additives

[0113] The top layer and / or the intermediate foam layer can include one or more optional additives. Non-limiting examples of suitable additives include antioxidants, curing agents, crosslinking co-agents, accelerators and retarders, processing aids, ultraviolet absorbers or stabilizers, antistatic agents, nucleating agents, slip agents, plasticizers, lubricants, viscosity control agents, tackifiers, anti-block agents, surfactants, acid scavengers, pigments and / or dyes, and metal deactivators. When present, the additives are present in an amount of 0.01 wt% to less than 10 wt%, or 0.1 wt% to less than 5 wt%, or 0.1 wt% to less than 1.0 wt%, based on the total weight of each respective individual layer - the top layer and / or the intermediate foam layer.

[0114] In one embodiment, the two-layer article having a top layer (A) and a bottom textile layer (B) and / or the three-layer article having a top layer (A), a bottom textile layer (B), and a middle foam layer (C) further includes a primer layer and a topcoat layer. The primer layer directly contacts the top layer, and the topcoat layer directly contacts the primer layer, such that the topcoat layer is the outermost layer of the article. The primer layer is formed by applying a primer (e.g., chlorinated polypropylene (CPP)) to the top layer. Polyurethane is subsequently applied to the primer layer. The bottom textile layer maintains the shape of the article (i.e., synthetic leather) and provides mechanical properties to the article. The bottom textile layer also provides stability to the foaming of the middle foam layer (when present). The middle foam layer (when present) provides flexibility, cushioning, softness, thermal insulation, light weight, and hand feel to the multi-layer structure of the article. The top layer provides protection from UV radiation, heat, and other weather factors. The top layer can also carry visible functions such as printing, embossing, color, and / or gloss. The purpose of the topcoat layer is to provide protection to the top layer and to protect the article from scratches, damage, and wear; to provide a surface for text and design; and to impart an aesthetically pleasing smoothness to the article. The purpose of the primer layer is to promote adhesion of the topcoat layer to the top layer.

[0115] Bally Flex is an important feature of synthetic leather products; Bally Flex is a characterization of durability and mechanical fatigue during cyclic flexural stress. Applicants have found that the addition of 12 wt% to 30 wt% mineral oil to (i) ethylene / C4-C8 alpha-olefin copolymer and / or (ii) ethylene / C4-C8 alpha-olefin multi-block copolymer in the top layer of a synthetic leather article and / or the addition of 10 wt% to 30 wt% or 12 wt% to 30 wt% oil in the middle foam layer unexpectedly improves (increases) the Bally Flex value of the POE synthetic leather to a value that meets or exceeds the Bally Flex value of comparable PU synthetic leather structures and / or PVC synthetic leather structures. The addition of 12 wt% to 30 wt% mineral oil to (i) ethylene / C4-C8 alpha-olefin copolymer and / or to (ii) ethylene / C4-C8 alpha-olefin multi-block copolymer in the top layer also maintains the melt index of the composition in the range of 2 g / 10 min to 10 g / 10 min, which is necessary to maintain a melt viscosity suitable for processing operations such as calendering and extrusion casting; a MI of 2-10 g / 10 min enables surface smoothness and high production efficiency.

[0116] The articles of the present invention are found to have many useful applications as synthetic leather (i.e., POE-leather). Accordingly, non-limiting examples of the present invention include clothing (shirts, blouses, slacks, skirts, dresses, coats, jackets, shoes, boots, hats), wallets, luggage, automotive interiors (car seats, interior door panels, instrument panels), and furniture (chairs, sofas).

[0117] By way of example, and without limitation, certain embodiments of the disclosure will now be described in detail in the following Examples.

[0118] Examples

[0119] The materials used in the inventive examples and comparative samples are provided in Table 1 below.

[0120] Table 1. Materials

[0121]

[0122]

[0123] Brabender mixing and compression molding.

[0124] For examples without chemical blowing agent (CBA): POE resin was fed into the Brabender mixer at a set temperature of 150 °C with a rotor speed of 30 rpm. After two minutes, the resin was uniformly heated and melted. Then, all other ingredients were weighed and gradually added to the container. Mixing was continued for another six minutes at 50 rpm.

[0125] For samples containing CBA, the container temperature was set to 130 °C. Mixing was performed at 35 rpm for about 6 minutes. The final melt temperature was controlled and kept below 145 °C. The compounds were collected and compression molded into flat cake shapes for later use.

[0126] The compounds from Brabender mixing were compression molded into plaques in 1.1 mm thick molds. The compounds were preheated at 150 °C for 5 minutes, then degassed, followed by a compression molding process at 150 °C for another two minutes. After being brought down to room temperature, the plaques were removed from the molds. The obtained plaques were further cut into shapes and sizes required for the Barus Flex Test and DMS analysis, or cut into pellets for melt index measurements.

[0127] For samples containing CBA: 0.5 mm thick films were first compression molded, then foamed in an air-circulating oven at 220 °C for 90 seconds to form foam plaques for the Barus Flex Test.

[0128] Table 2 Composition and properties of inventive examples (IE) and comparative samples (CS)

[0129] Table 2A - Composition of Top Layer

[0130]

[0131] Table 2B - Composition of Middle Foam Layer

[0132]

[0133]

[0134] Table 2A shows Inventive Examples (IE) IE1-IE6 of top layer compositions consisting of (i) one or more ethylene-based polymers and (ii) 12 wt% to 30 wt% mineral oil. Table 2A also shows Comparative Samples (CS) CS1-CS9 consisting of one or more ethylene-based polymers and containing no oil. In Table 2A, IE1-IE6 show that the addition of 12 wt% to 30 wt% mineral oil (to 100 wt%) to a supplemental amount (88 wt% to 70 wt%) of one or more ethylene / C4-C8a-olefin copolymers unexpectedly results in compositions having improved Ball Indentation Flexibility and improved MI, with Ball Indentation Flexibility values greater than 86,000; i.e., MIs greater than 2.0 g / 10 min. Compositions with MIs greater than 2.0 g / 10 min are necessary for suitable flexibility during extrusion or calendering processing. CS1 to CS9 are not able to achieve both Ball Indentation Flexibility values greater than 86,000 and MIs greater than 2.0. DMS is further used to characterize the flowability of the examples over a wide range of shear rates, as shown in Table 2A. As shown in Table 2A, IE3 has a lower viscosity (i.e., higher flowability) compared to CS7. In addition, IE3 also has a greater Ball Indentation Flexibility value (100k) compared to CS7 (58k), which indicates that the addition of oil is more effective than blending a high MI resin to achieve both a good Ball Indentation Flexibility value (greater than 86,000) and high flowability for processability (MI greater than 2.0 g / 10 min). Figure 1 Figure 1

[0135] In Table 2B, IE7-IE8 and CS10 chemical blowing agents are added to the compositions to make foamed sheet materials, which can be used to simulate the middle foam layer of a typical synthetic leather structure. Ball Indentation Flexibility values of foamed sheet materials with similar expansion ratios (ER) indicate that the addition of 10 wt% to 30 wt%, or 12 wt% to 30 wt% mineral oil maintains the Ball Indentation Flexibility value compared to foamed sheet materials without oil. Thus, the addition of 10 wt% to 30 wt% oil to the middle foam layer composition of a synthetic leather can be used to maintain Ball Indentation Flexibility and improve processability by increasing the MI of the foam composition to greater than 2.0 g / 10 min.

[0136] It is especially advantageous to include in the present disclosure, not only the embodiments herein specifically recited, but also modifications and equivalents of the embodiments included within the spirit and scope of the description.​​

Claims

1. A product comprising: A. A top layer composed of a composition comprising, based on the total weight of the top layer: (i) 70 wt% to 88 wt% of an ethylene-based polymer consisting of (i) ethylene and (ii) a C4-C8 α-olefin comonomer, (ii) 12% to 30% by weight of oil; (iii) optional additives, and (i), (ii) and (iii) total 100% by weight of the top layer; wherein the composition has a melt index (MI) greater than 2.0 g / 10 min; and B. A base layer comprising a textile.

2. The article of claim 1, wherein the ethylene-based polymer is selected from the group consisting of ethylene / C4-C8 α-olefin copolymers, ethylene / C4-C8 α-olefin multi-block copolymers, and combinations thereof.

3. The article of claim 2, wherein the ethylene-based polymer is an ethylene / C4-C8 α-olefin copolymer having the following properties: Density of 0.857 g / cc to 0.88 g / cc; A melt index of 0.5 g / 10 min to 20 g / 10 min; and A Shore A value of 75 or less.

4. The article of claim 2, wherein the ethylene-based polymer is an ethylene / C4-C8 α-olefin multi-block copolymer having the following properties: Density of 0.857 g / cc to 0.88 g / cc; A melt index of 0.5 g / 10 min to 20 g / 10 min; and A Shore A value of 75 or less.

5. The article according to any one of claims 1 to 4, comprising: 80 to 87 wt% of the ethylene / C4-C8 α-olefin copolymer; 13% to 20% by weight of said oil; and The top layer has a Balley Flex Resistance value greater than 86,000.

6. The article according to any one of claims 1 to 4, comprising: 30 to 50 wt% of an ethylene / C4-C8 alpha-olefin multi-block copolymer; 30 to 50 wt% of an ethylene / C4-C8 alpha-olefin copolymer; 13% to 30% by weight of said oil; and The top layer has a Balley Flex Resistance value greater than 86,000.

7. The article of any one of claims 1-4, wherein the composition of the top layer has a Shore A value of less than 80.

8. The article according to any one of claims 1 to 4, comprising: C. An intermediate foam layer composed of a composition, based on the total weight of the intermediate foam layer, the composition comprising: (i) an ethylene-based polymer consisting of (i) ethylene and (ii) a C4-C8 α-olefin comonomer; and (ii) 10 to 30 wt% oil.

9. The article of claim 8, wherein the ethylene-based polymer in the middle foam layer is selected from the group consisting of ethylene / α-olefin copolymers, ethylene / α-olefin multi-block copolymers, and combinations thereof.

10. The article of claim 9, wherein the ethylene-based polymer in the middle foam layer is an ethylene / C4-C8 alpha-olefin copolymer having the following properties: Density of 0.857 g / cc to 0.88 g / cc; A melt index of 0.5 g / 10 min to 20 g / 10 min; and A Shore A value of 75 or less.

11. The article of claim 9, wherein the ethylene-based polymer in the middle foam layer is an ethylene / C4-C8 α-olefin multi-block copolymer having the following properties: Density of 0.857 g / cc to 0.88 g / cc; A melt index of 0.5 g / 10 min to 20 g / 10 min; and A Shore A value of 75 or less.

12. The article of claim 9, wherein the intermediate foam layer comprises: 80 to 87 wt% of the ethylene / C4-C8 α-olefin copolymer; 10% to 20% by weight of said oil; and The middle foam layer has a Balley Flex Resistance value greater than 60,000.

13. The article of claim 9, wherein the middle foam layer comprises: 30 to 50 wt% of an ethylene / C4-C8 alpha-olefin multi-block copolymer; 30 to 50 wt% of an ethylene / C4-C8 alpha-olefin copolymer; 10% to 30% by weight of said oil; and The middle foam layer has a Balley Flex Resistance value greater than 86,000.

14. The article of claim 1, wherein the oil is mineral oil, to the exclusion of any other type of oil.

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