Synthetic leather

Abstract

The present disclosure provides an article. In one embodiment, the article includes (A) a top layer comprised of a composition comprised of (i) 51 wt% to 90 wt% of a propylene-based polymer and (ii) 10 wt% to 49 wt% of an ethylene / octene multiblock copolymer having hard and soft segments. The ethylene / octene multiblock copolymer has a soft segment melting temperature (SS-Tm) of less than 2°C. The article also includes (B) a bottom layer comprised of a woven fabric.

Description

[Background technology]

[0001] The uses of synthetic leather continue to grow. Synthetic leather is used to manufacture clothing, footwear, bags and luggage, home upholstery, and automobile seats. Synthetic leather exhibits similar performance and feel when compared to natural leather. Synthetic leather offers the added benefits of being animal-friendly and inexpensive to manufacture compared to natural leather.

[0002] Conventional synthetic leather has drawbacks. The production of polyurethane-based synthetic leather (PU leather) requires the use of organic solvents, typically dimethyl formamide (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 plasticizers, which are each 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 its production 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 leather has excellent weather resistance and low-temperature flexibility, is resistant to hydrolysis, and resists yellowing. Furthermore, POE leather has a lower density compared to the respective densities of PU and PVC leathers, making it a popular choice in the current lightweighting drive in the luggage / bag, shoe, and automotive interior sectors.

[0005] Therefore, the art has recognized a need for POE leather. The art has further recognized a need for POE leather that has bally flex resistance and flexibility that meets or exceeds the bally flex resistance performance and flexibility of PU leather and / or PVC synthetic leather. Summary of the Invention

[0006] The present disclosure provides an article. In one embodiment, the article includes: (A) a top layer comprising a composition consisting of: (i) 51 wt% to 90 wt% of a propylene-based polymer; and (ii) 10 wt% to 49 wt% of an ethylene / octene multiblock copolymer having hard and soft segments. The ethylene / octene multiblock copolymer has a soft segment melting temperature (SS-Tm) of less than 2°C. The article also includes: (B) fabric The bottom layer consists of: [Brief explanation of the drawings]

[0007] [Figure 1] A scanning electron micrograph (SEM) of Example 7 (IE7) of the present invention is shown on the left, and an SEM of Comparative Sample 18 (CS18) is shown on the right. [Figure 2] SEM of IE1 (left) and CE6 (right) are shown. [Figure 3] SEM of CS9 is shown.

[0008] definition Any reference to the Periodic Table of the Elements is to that published by CRC Press, Inc., 1990-1991. References to element groups in this table are by the new notation for numbering groups.

[0009] For purposes of United States patent practice, the contents of any referenced patent, patent application, or publication are hereby incorporated by reference in their entirety (or the publication's equivalent United States patent application is likewise incorporated by reference), particularly with respect to the disclosure of definitions and general knowledge in the art (to the extent that they are in no way inconsistent with definitions specifically provided in this disclosure).

[0010] Numerical ranges disclosed herein include all values ​​between and including the lower and upper limits. Ranges containing explicit values ​​(e.g., 1 or 2, or 3-5, or 6, or 7) include every subrange between any two explicit values ​​(e.g., the 1-7 range above includes 1-2, 2-6, 5-7, 3-7, 5-6, etc.).

[0011] Unless otherwise stated or implicit from context, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

[0012] As used herein, the terms "blend" or "polymer blend" refer to a blend of two or more polymers. Such blends may or may not be miscible (not phase separated at the molecular level). Such blends may or may not be phase separated. Such blends may or may 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.

[0013] The term "composition" refers to a mixture of materials that comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0014] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether specifically disclosed or not. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless specifically stated otherwise. In contrast, the term "consisting essentially of" excludes from the scope of any succeeding description any other component, step, or procedure, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not expressly delineated or listed. The term "or," unless otherwise indicated, refers to the listed components individually as well as in any combination.

[0015] An "ethylene-based polymer" is a polymer that contains greater than 50 weight percent (wt%) polymerized ethylene monomer (based on the total amount of polymerizable monomers), and may optionally contain at least one comonomer. Ethylene-based polymers include ethylene homopolymers and ethylene copolymers (meaning units derived from ethylene and one or more comonomers). The terms "ethylene-based polymer" and "polyethylene" may be used interchangeably.

[0016] A "fabric" is a woven or non-woven (e.g., knit) structure formed from individual fibers or yarns.

[0017] "Fiber" and similar terms refer to an elongated column of intertwined filaments. Fiber diameter can be measured and reported in a variety of ways. Generally, fiber diameter is measured in denier per filament. Denier is defined as the number of grams of fiber per 9,000 meters of fiber length. fabricThe term monofilament generally refers to extruded strands having a denier per filament greater than 15, usually greater than 30. Fine denier fiber generally refers to fiber having a denier of 15 or less. Microdenier (also known as microfiber) generally refers to fiber having a diameter of 100 micrometers or less.

[0018] "Filament" and similar terms generally refer to a single continuous elongated strand of material having a circular cross-section and a length-to-diameter ratio of greater than 10.

[0019] As used herein, the term "foam" or "foam article" refers to a structure constructed from a polymer and containing a plurality of discrete gas pockets or foam cells completely surrounded by the polymer. As used herein, the term "foam cells" or "cells" refers to discrete spaces within a foam composition. The foam cells are separated or otherwise defined by membrane walls composed of the polymer of the foam composition.

[0020] An "interpolymer" is a polymer prepared by the polymerization of at least two different monomers. This generic term includes copolymers, which are commonly used to refer to polymers prepared from two different monomers, and polymers prepared from three or more different monomers, such as terpolymers, tetrapolymers, etc.

[0021] "Knitted fabrics" are formed from intertwining yarns or fibers into a series of connected loops by hand, with knitting needles, or on a machine. Fabrics may be formed by warp knitting or weft knitting, flat knitting, and circular knitting. Non-limiting examples of suitable warp knits include tricot, raschel powernet, and lace. Non-limiting examples of suitable weft knits include circular knitting, flat knitting, and seamless (which is often considered a subset of circular knitting).

[0022] "Nonwoven" refers to a web or fabric having a structure of individual fibers or strands that are interwoven randomly, but not in a discernible manner as in knitted fabrics.

[0023] An "olefin-based polymer" or "polyolefin" is a polymer that contains more than 50 weight percent polymerized olefin monomers (based on the total amount of polymerizable monomers), and may optionally contain at least one comonomer. Non-limiting examples of olefin-based polymers include ethylene-based polymers or propylene-based polymers.

[0024] A "polymer" is a compound prepared by polymerizing monomers, whether of the same or different types, that provide multiple and / or repeating "units" or "mer units" that, in polymerized form, constitute the polymer. Thus, the general term polymer encompasses the term homopolymer, which is commonly used to refer to a polymer prepared from only one type of monomer, and the term copolymer, which is commonly used to refer to a polymer prepared from at least two types of monomer. It also encompasses all forms of copolymers, e.g., random, block, etc. The terms "ethylene / α-olefin polymer" and "propylene / α-olefin polymer" refer to the aforementioned copolymers prepared from polymerizing ethylene or propylene with one or more additional polymerizable α-olefin monomers, respectively. While polymers are often referred to as "made of" one or more specific monomers, "based on" a specific monomer or type of monomer, "containing" a specific monomer content, etc., it should be noted that in this context, the term "monomer" is understood to refer to the polymerized residue of a specific monomer, and not to the unpolymerized species. Generally, polymers herein are referred to in terms of "units" that are the polymerized form of the corresponding monomers.

[0025] A "propylene-based polymer" is a polymer that contains more than 50 weight percent polymerized propylene monomer (based on the total amount of polymerizable monomers) and may optionally contain at least one comonomer.

[0026] "Styrene" has the following structure A: A "styrenic polymer" is a polymer that contains polymerized styrene as a monomer.

[0027] [ka]

[0028] "Woven" refers to a web or fabric having a structure of individual fibers or strands interlaced and arranged in a pattern in a discernible manner. Non-limiting examples of woven fabrics include knit fabrics.

[0029] Test Method The Bally Flex Resistance Test is performed at 25°C according to ASTM D6182. The Bally Flex Test determines the durability of coatings applied to synthetic leather, leather, and fabrics by repeatedly flexing the test specimen. The Bally Flexometer complies with DIN 53351 and operates at a speed of 100 cycles per minute. The end cycle is determined by the cycle at which the plaque surface cracks and is reported as the Bally Flex result. Two specimens were tested for each sample, and the average value was reported as the Bally Flex Resistance value. The results are reported in number of cycles. If no cracks / damage are found after 100,000 cycles for two specimens, the result is reported as "More than 100,000" or ">100k."

[0030] 13 C NMR. 13 C nuclear magnetic resonance ( 13C nuclear magnetic resonance (NMR) samples are prepared by adding approximately 2.7 g of a 50 / 50 (w:w) mixture of tetrachloroethane-d2 / orthodichlorobenzene containing 0.025 M chromium acetylacetonate, Cr(AcAc)3 (or tetrachloroethane-d2 containing 0.025 M Cr(AcAc)3) to 0.2 g of polymer sample in a 10 mm NMR tube. Oxygen is removed from the sample by purging the tube headspace with nitrogen. The sample is then melted and homogenized by heating the tube and its contents to approximately 135 °C using a heating block and heat gun. Each molten sample is visually inspected to confirm homogeneity.

[0031] 13 C NMR data are collected using a 10 mm cryoprobe on either a Bruker 400 MHz or 600 MHz spectrometer. Data are acquired at a sample temperature of 120 °C using a 7.3 s pulse repetition delay, a 90 degree flip angle, and inverse gated decoupling. All measurements are performed in locked mode, without sample rotation. Samples are allowed to thermally equilibrate for 7 minutes before data acquisition. 13 C NMR chemical shifts are internally referenced to the EEE triad at 30.0 ppm.

[0032] Comonomer content was assigned from the literature (Liu, W., Rinaldi, PL, McIntosh, LH, and Quirk, RP, Macromolecules, 34, 2001, 4757-4767) and integrated. 13The C NMR spectrum is determined by solving the vector equation s = fM, where M is the assignment matrix, s is the row vector representation of the spectrum, and f is the mole fraction composition vector. The elements of f are the triads of ethylene (E) and octane (O) with all permutations of E and O. The assignment matrix M is created with one row for each triad in f and a column for each integrated NMR signal. The elements of the matrix are integer values ​​determined by referencing the assignment (Liu, W., Rinaldi, PL, McIntosh, LH, and Quirk, RP, Macromolecules, 34, 2001, 4757-4767). This equation is then calculated by dividing s by the integrated NMR signal for each sample. 13 Solve by varying the factors as necessary to minimize the error function between the C data. This is performed in Microsoft Excel by using the Solver function.

[0033] (i) the mole percent (%) of octene ("octene mol %) in the ethylene / octene multi-block copolymers of the present disclosure, and (ii) the mole % of octene comonomer in the soft segments of the ethylene / octene multi-block copolymers ("SS octene mol %), 13 C NMR spectroscopy and the methods described in U.S. Pat. No. 7,608,668, columns 60-63, which is incorporated herein by reference in its entirety.

[0034] Density is measured according to ASTM D792, Method B. Results are reported in grams per cubic centimeter (g / cc).

[0035] Differential scanning calorimetry (DSC) Differential Scanning Calorimetry (DSC) Differential scanning calorimetry (DSC) can be used to measure the melting, crystallization, and glass transition behavior of polymers over a wide temperature range. For example, a TA Instruments Discovery DSC equipped with a refrigerated cooling system (RCS) and an autosampler is used to perform this analysis. A nitrogen purge gas flow rate of 50 mL / min is used during testing. Each sample is melt-pressed into a thin film at approximately 190°C, and the molten sample is then air-cooled to room temperature (approximately 25°C). A 3-10 mg, 6 mm diameter specimen is extracted from the cooled polymer, weighed, placed in a lightweight aluminum pan (approximately 50 mg), and crimped shut. Analysis is then performed to determine its thermal properties.

[0036] The thermal behavior of the sample is determined by increasing and decreasing the sample temperature to create a heat flow versus temperature profile. First, the sample is rapidly heated to 180°C to remove its thermal history and held isothermally for 5 minutes. Next, the sample is cooled to -90°C at a cooling rate of 10°C / min and held isothermally at -90°C for 5 minutes. Next, the sample is heated to 150°C at a heating rate of 10°C / min (this is the "second heating" gradient). The cooling curve and the second heating curve are recorded.

[0037] The soft segment melting temperature (SS-Tm) is determined from the second heating curve of the DSC. Ethylene / octene multiblock copolymers typically have two melting peaks, one associated with the soft segment and one associated with the hard segment. SS-Tm is associated with the lower temperature peak. In some block copolymers, the peak associated with soft segment melting is a small hump on the baseline, making it difficult to assign the peak maximum. This difficulty can be overcome by converting the normal DSC profile to a weighted DSC profile using the following method. In other cases, the soft segment is amorphous and does not have a measurable melting enthalpy or melting temperature. In DSC, heat flow depends on the amount of material melting at a particular temperature and the specific heat capacity, which is dependent on temperature. The temperature dependence of the specific heat capacity in the melting regime of linear low-density polyethylene results in an increase in the heat of fusion, decreasing the comonomer content. That is, the heat of fusion value becomes progressively lower as crystallinity decreases with increasing comonomer content. See Wild, L., Chang, S., Shankernarayanan, M. J. Improved method for compositional analysis of polyolefins by DSC. Polym. Prep. 1990, 31:270-1, which is incorporated herein by reference in its entirety. For a given point on the DSC curve (defined by heat flow in watts per gram and temperature in degrees Celsius) by taking the ratio of the expected heat of fusion for a linear copolymer to the temperature-dependent heat of fusion (ΔH(T)), the DSC curve can be converted to a weight-dependent distribution curve. The second heating curve is baseline corrected by drawing a linear baseline between the heat flows at -30°C and 135°C. The temperature-dependent heat of fusion curve can then be calculated from the sum of the integrated heat flows between two consecutive data points, which can then be represented overall by a cumulative enthalpy curve. The expected relationship between the heats of fusion for linear ethylene / octene copolymers at a given temperature is shown by the heat of fusion versus melting temperature curve.Using random ethylene / octene copolymers, the expected heat of fusion, ΔH, of the linear copolymer. 直鎖状コポリマー , and the melting temperature T m The following relationship can be obtained for (units °C):

[0038]

number

[0039] For each integrated data point, a fractional weight can be assigned to each point on the DSC curve by taking the ratio of the enthalpy from the cumulative enthalpy curve at a given temperature to the expected heat of fusion of a linear copolymer at that temperature. This method is applicable to ethylene / octene copolymers but can be adapted to other polymers. The soft segment Tm is assigned as the location of the maximum in the enthalpy fractional weight vs. temperature curve.

[0040] Flexural modulus is measured according to ASTM D790. 3 mm thick plaques were cut into small bars for testing. Three specimens were tested for each sample, and the average value is reported as the flexural modulus value in megapascals (MPa).

[0041] The glass transition temperature, Tg, is determined from the second heating curve of a DSC where half of the sample has acquired a 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., 2d ed. 1997). Baselines are drawn below and above the glass transition region and extrapolated through the Tg region. The temperature at which the heat capacity of the sample is midway between these baselines is the Tg.

[0042] The melting temperature Tm of a polymer is determined as the temperature corresponding to the maximum heat flow in the DSC heating curve.

[0043] Melt flow rate (MFR) in g / 10 min (for propylene-based polymers) is measured according to ASTM D1238 (230° C. / 2.16 kg).

[0044] Melt index (MI) (I2) in g / 10 min (for ethylene-based polymers) is measured according to ASTM D1238 (190°C / 2.16 kg).

[0045] Shore A hardness is measured according to ASTM D2240. Two 3 mm thick plaques were stacked together for the test. For the POE leather compositions (Table 2A, Table 2B), a load of 1 kg and a duration of 5 seconds were used. For the ethylene / octene multiblock copolymers, a duration of 10 seconds was used (data in Table 1C). DETAILED DESCRIPTION OF THE INVENTION

[0046] The present disclosure provides an article. In one embodiment, the article includes: (A) a top layer comprising a composition consisting of: (i) 51 wt% to 90 wt% of a propylene-based polymer; and (ii) 10 wt% to 49 wt% of an ethylene / octene multiblock copolymer having hard segments and soft segments, the ethylene / octene multiblock copolymer having a soft segment melting temperature (SS-Tm) of less than 2°C. The article also includes: (B) fabric The bottom layer consists of:

[0047] A. Top layer (i) Propylene-based polymers The top layer is comprised of a composition including: (i) 51% to 90% by weight of a propylene-based polymer; and (ii) 10% to 49% by weight of an ethylene / octene multiblock copolymer having hard segments and soft segments, the ethylene / octene multiblock copolymer having a soft segment melting temperature (SS-Tm) of less than 2° C. The weight percentages are based on the total weight of the top layer.

[0048] Propylene-based polymers consist of (i) polymerized units of propylene, (ii) polymerized units of a C2 comonomer or a C4-C8 α-olefin comonomer, and (iii) optional additives. Non-limiting examples of suitable comonomers include ethylene, butene, hexene, and octene.

[0049] In one embodiment, the propylene-based polymer is a propylene / ethylene copolymer resin having one, some, or all of the following properties: (i) a density between 0.85 g / cc and 0.87 g / cc, and / or (ii) a melt flow rate (MFR) of 5.0 g / 10 min to 30 g / 10 min, or 8 g / 10 min to 25 g / 10 min, and / or (iii) a Shore A hardness value of 75 to 90 or 80 to 89, and / or (iv) 10% to 15% by weight ethylene, based on the total weight of the propylene / ethylene copolymer.

[0050] Non-limiting examples of suitable propylene / ethylene copolymers include VERSIFY 3300 and VERSIFY 4301 available from Dow, Inc.

[0051] (ii) Ethylene / octene multiblock copolymer The top layer comprises 10% to 49% by weight of an ethylene / octene multi-block copolymer. The weight percentage is based on the total weight of the top layer. The ethylene / octene multi-block copolymer has hard segments and soft segments. The ethylene / octene multi-block copolymer has a soft segment melting temperature (SS-Tm) of less than 2°C.

[0052] The term "ethylene / octene multiblock copolymer" refers to a copolymer of ethylene and octene comonomers (and optional additives) in polymerized form, characterized by multiple blocks or segments of two polymerized monomer units (i.e., ethylene and octene) with different chemical or physical properties, and the blocks are linked (or covalently linked) in a linear fashion, i.e., the polymer contains chemically distinct units linked end-to-end with respect to the polymerized ethylenic functional groups. Ethylene / octene multiblock copolymers include block copolymers having two blocks (diblock) and three or more blocks (multiblock). Ethylene / octene multiblock copolymers do not contain or otherwise exclude styrene (i.e., styrene-free), and / or do not contain or otherwise exclude vinyl aromatic monomers and / or conjugated dienes. When referring to the amount of "ethylene" or "octene" or "comonomer" in a copolymer, it is understood that it refers to the polymerized units thereof. The ethylene / octene multiblock copolymer can be represented by the following formula (AB)n, where n is at least 1 and preferably an integer greater than 1, e.g., 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or more, and "A" represents a hard block or segment and "B" represents a soft block or segment. A and B are linked or covalently bonded in a substantially linear or linear fashion, as opposed to a substantially branched or substantially star-shaped fashion. In other embodiments, the A and B blocks are randomly distributed along the polymer chain. In other words, the block copolymer typically does not have a structure such as: AAA-AA-BBB-BB. In one embodiment, the ethylene / octene multiblock copolymer does not have a third type of block containing different comonomer(s). In another embodiment, each of the A and B blocks has monomers or comonomers distributed substantially randomly within the block.In other words, neither block A nor block B includes two or more sub-segments (or sub-blocks) of distinct composition, such as a tip segment having a substantially different composition than the remainder of the block.

[0053] Ethylene constitutes the majority mole fraction of the total ethylene / octene multi-block copolymer. Ethylene constitutes at least 50 mole percent (mol%) of the total ethylene / octene multi-block copolymer. In one embodiment, the ethylene / octene multi-block copolymer contains 50 mole percent, or 60 mole percent, or 65 mole percent to 80 mole percent, or 85 mole percent, or 90 mole percent, or 95 mole percent ethylene and a relative amount of octene, or 5 mole percent, or 10 mole percent, or 15 mole percent, or 20 mole percent to 35 mole percent, or 40 mole percent, or less than 50 mole percent octene, based on the total moles of the ethylene / octene multi-block copolymer. In further embodiments, the ethylene / octene multiblock copolymer contains from 5 mol% to 30 mol% octene (and from 95 mol% to 70 mol% ethylene), or from greater than 16 mol% to 30 mol% octene, or from 17 mol% to 25 mol% octene (and from 83 mol% to 75 mol% ethylene).

[0054] Ethylene / octene multiblock copolymers contain varying amounts of "hard" and "soft" segments. The "hard" segments are blocks of polymerized units in which ethylene is present in an amount greater than 90%, or greater than 95%, or greater than 95%, or greater than 98%, up to 100% by weight based on the weight of the polymer. In other words, the comonomer content (content of monomers other than ethylene) in the hard segments is less than 10%, or less than 5%, or less than 5%, or less than 2% by weight based on the weight of the polymer, and can be as low as zero. In some embodiments, the hard segments contain all or substantially all units derived from ethylene. The "soft" segments are blocks of polymerized units in which the comonomer content (octene content) is greater than 5%, or greater than 8%, or greater than 10%, or greater than 15% by weight based on the weight of the polymer. In one embodiment, the comonomer content of the soft segment is greater than 20 weight percent, or greater than 25 weight percent, or greater than 30 weight percent, or greater than 35 weight percent, or greater than 40 weight percent, or greater than 45 weight percent, or greater than 50 weight percent, or greater than 60 weight percent, and can be up to 100 weight percent.

[0055] The soft segments in the ethylene / octene multiblock copolymer may be present at 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, or 99 wt% of the total weight of the ethylene / octene multiblock copolymer. Conversely, the hard segments may be present in a similar range. The weight percentages of the soft segments and the hard segments may be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed, for example, in U.S. Pat. No. 7,608,668, the disclosure of which is incorporated herein by reference in its entirety. In particular, the weight percentages of the hard and soft segments may be determined as described in US Pat. No. 7,608,668, columns 57-63, which are incorporated herein by reference.

[0056] Ethylene / octene multiblock copolymers contain two or more chemically distinct regions or segments (referred to as "blocks") linked (or covalently bonded) in a linear fashion, i.e., they contain chemically distinct units that are linked end-to-end with respect to polymerized ethylenic functional groups, rather than in a pendant or grafted fashion. The blocks differ in the amount or type of incorporated comonomer, density, amount of crystallinity, crystallite size attributable to polymers of such composition, type or degree of tacticity (isotactic or syndiotactic), regioregularity or regioirregularity, amount of branching (including long-chain branching or hyperbranching), homogeneity, or any other chemical or physical property. Compared to prior art block interpolymers, including those produced by continuous monomer addition, flow catalyst, or anionic polymerization techniques, the ethylene / octene multi-block copolymers of the present invention are, in one embodiment, characterized by a unique distribution of both polymer polydispersity (PDI or Mw / Mn or MWD), polydisperse block length distribution, and / or polydisperse block number distribution due to the effect of the shuttle agent(s) in combination with the multiple catalysts used in their preparation.

[0057] In one embodiment, the ethylene / octene multi-block copolymers are produced in a continuous process and have 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 / octene multi-block copolymers have 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.

[0058] It should be noted that the ethylene / octene multiblock copolymers have PDI (or Mw / Mn) values ​​that conform to a Schultz-Flory distribution rather than a Poisson distribution. The ethylene / octene multiblock copolymers of the present invention have both a polydisperse block distribution and a polydisperse distribution of block sizes. This results in polymer products with improved and identifiable physical properties. The theoretical advantages of a polydisperse block distribution have been previously modeled and discussed in Potemkin, Physical Review E (1998) 57(6), pp. 6902-6912, and Dobrynin, J. Chem. Phvs. (1997) 107(21), pp. 9234-9238.

[0059] In one embodiment, the ethylene / octene multi-block copolymers of the present invention have a most probable distribution of block lengths.

[0060] The ethylene / octene multiblock copolymers used in the compositions of the present invention are a distinct subset of ethylene / octene multiblock copolymers. The ethylene / octene multiblock copolymers of the present invention exhibit increased incorporation of soft segment octene when compared to the amount of octene present in the soft segments of other ethylene / octene multiblock copolymers. The SS-Tm of the ethylene / octene multiblock copolymers of the present invention of less than 2 ° C is the result of the increased incorporation of soft segment octene present therein. The ethylene / octene multiblock copolymers of the present invention with high octene in the soft segments, resulting in an SS-Tm of less than 2 ° C, enable the balance of flexibility and Bailey flex resistance required for the compositions of the present invention, compared to ethylene / octene multiblock copolymers with lower octene in the soft segments, resulting in an SS-Tm of greater than 2 ° C. The soft segments of the ethylene / octene multiblock copolymers of the present invention having an SS-Tm of less than 2°C, or an SS-Tm of -30°C to less than 2°C, or amorphous (without Tm) are hereinafter interchangeably referred to as "soft-OBC."

[0061] In one embodiment, the ethylene / octene multi-block copolymer has hard segments and soft segments and consists solely of ethylene monomer and octene comonomer (and optional additives), and the ethylene / octene multi-block copolymer (soft-OBC) has one, some, or all of the following properties: (i) an SS-Tm of less than 2°C, or an SS-Tm of between -30°C and less than 2°C, or an amorphous soft segment; and / or (ii) 21 mol% to 35 mol%, or 22 mol% to 30 mol% of octene in the soft segment, and / or (iii) greater than 16 mol% to 25 mol% octene and 84 mol% to 75 mol% ethylene in an ethylene / octene multiblock copolymer; and / or (iv) a Tg of -70°C to -60°C, or -70°C to -66°C, and / or (v) a density between 0.855 g / cc and 0.880 g / cc, and / or (vi) a Tm of 115°C to 125°C, and / or (vii) a melt index (I2) of 0.1 g / 10 min to 6.0 g / 10 min, and / or (viii) Mw / Mn between 1.7 and 3.5, and / or (ix) Polydisperse distribution of blocks and polydisperse distribution of block sizes.

[0062] B. fabric bottom layer The article of the present invention may further comprise a top layer fabric Including the bottom layer. fabric " is a flexible material composed of a network of natural fibers, man-made fibers, and combinations thereof. fabric Examples include fabrics and cloth. fabricThe fibers may be woven, nonwoven, knitted, plain weave, or spunbonded. Non-limiting examples of natural fibers include cotton, wool, linen, silk, and combinations thereof. Non-limiting examples of man-made fibers include polyesters (PET), polyamides (nylon), acrylics, polyolefins, polyurethanes (e.g., spandex materials), polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, and combinations thereof.

[0063] In one embodiment, fabric is nonwoven fabric is.

[0064] In one embodiment, fabric Made of microfiber nonwoven fabric "Microfiber" fabric is a fabric containing fibers with a diameter of 100 micrometers or less.

[0065] In one embodiment, fabric 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.

[0066] In one embodiment, fabric 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. fabric contains fibers having a size of 10 denier or less.

[0067] In one embodiment, fabric has a thickness of 0.2 mm, 0.5 mm, or 1.0 mm to 1.5 mm, or 2.0 mm.

[0068] In one embodiment, fabricis a nonwoven having one, some, or all of the following characteristics: fabric is. (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 (b) a fiber size of 1 denier or 3 denier to 5 denier, and / or (c) A thickness of 0.2 mm, 0.5 mm, or 1.0 mm to 1.5 mm, or 2.0 mm.

[0069] In one embodiment, fabric is a fabric composed of polyester, polyethylene, and / or polypropylene. The fabric is subjected to a pre-lamination treatment, such as corona surface treatment, impregnation, etc., and the top layer is heat laminated to the fabric such that the top layer is in direct contact with the bottom layer, with no intervening layer or structure between the top and bottom layers.

[0070] fabric may include two or more embodiments disclosed herein.

[0071] In one embodiment, the article comprises (A) a top layer and (B) fabricThe top layer is in direct contact with the bottom layer. The top layer (A) contains (i) 51 wt% to 90 wt%, or 55 wt% to 80 wt%, or 55 wt% to 65 wt% of a propylene / ethylene copolymer. The propylene / ethylene copolymer has a density of 0.85 g / cc to 0.87 g / cc and a melt flow rate of 5 g / 10 min to 30 g / 10 min, or 8 g / 10 min to 30 g / 10 min. The top layer (A) also contains (ii) 49 wt% to 10 wt%, or 45 wt% to 20 wt%, or 45 wt% to 35 wt% of a soft-OBC or amorphous soft segment having a SS-Tm of less than 2°C, or a SS-Tm of -30°C to less than 2°C. The soft-OBC contains 21 mol% to 35 mol% octene, or 22 mol% to 30 mol% octene in the soft segment. The top layer has a Bailey flex resistance value of greater than 60,000, or 65,000 to 150,000, or 75,000 to 150,000, or 80,000 to 150,000, or 87,000 to 150,000, or 90,000 to 140,000. The top layer composition has a Shore A hardness value of less than 80, or 55 to 75.

[0072] In one embodiment, the article comprises (A) a top layer and (B) fabric The top layer is in direct contact with the bottom layer. The top layer (A) contains (i) 51 wt % to 90 wt %, or 55 wt % to 80 wt %, or 55 wt % to 65 wt % of a propylene / ethylene copolymer. The propylene / ethylene copolymer has a density of 0.85 g / cc to 0.87 g / cc and a melt flow rate of 5 g / 10 min to 30 g / 10 min, or 8 g / 10 min to 30 g / 10 min. The top layer (A) also contains (a) a first soft-OBC having an SS-Tm of less than 2°C, or an SS-Tm of between -30°C and less than 2°C, or an amorphous soft segment; and (b) A second soft-OBC different from the first soft-OBC, the second soft-OBC having an SS-Tm of less than 2°C, or an SS-Tm of between -30°C and less than 2°C, or an amorphous soft segment. The first soft-OBC and the second soft-OBC each contain 21 mol% to 35 mol%, or 22 mol% to 30 mol% of octane in the soft segment. The combined amount of component (a) and component (b) is present in an amount of 49 wt% to 10 wt%, or 45 wt% to 20 wt%, or 45 wt% to 35 wt% of the top layer (A). The weight percentages are based on the total weight of the top layer (A). The top layer (A) has a Bailey flex resistance value of greater than 60,000, or from 65,000 to 150,000, or from 75,000 to 150,000, or from 80,000 to 150,000, or from 87,000 to 150,000, or from 90,000 to 140,000. The top layer composition has a Shore A hardness value of less than 80, or from 55 to 75.

[0073] C. Middle foam layer In one embodiment, the article includes an intermediate foam layer (C) in addition to the top layer (A) and the bottom layer (B). The intermediate layer (C) is disposed between the top layer (A) and the bottom layer (B). The intermediate foam layer (C) is in direct contact with the top layer (A) and / or the bottom layer (B). In one embodiment, the intermediate foam layer (C) is in direct contact with the top layer (A) and the bottom layer (B). The intermediate foam layer (C) is comprised of a composition including: (i) 51 wt% to 90 wt% of a propylene-based polymer; and (ii) 10 wt% to 49 wt% of a soft-OBC having an SS-Tm of less than 2°C. The weight percentages are based on the total weight of the intermediate foam layer (C).

[0074] In one embodiment, the intermediate foam layer (C) can be prepared by blending or compounding the individual components together in any conventional mixing equipment, such as a Banbury kneader or any suitable extruder, under conditions and for a time to produce a substantially homogeneous mixture, calendering the mixture using conventional equipment and conditions to form a sheet, and then laminating the sheet using conventional lamination equipment and conditions to form a top layer and / or fabricThe intermediate foam layer is typically prepared by heat laminating it to the top layer (A) and fabric It is not exposed to foaming conditions until after it is laminated to the bottom layer (B). The foaming conditions are such that very fine, regular cells are formed throughout the layer. Typical foaming conditions include oven temperatures of 200°C or higher and oven residence times of 60 to 120 seconds. The foam efficiency (i.e., the ratio of foamed volume to original (unfoamed) volume), based on the thickness ratio, is typically 1.5 to 5, or 2 to 3.

[0075] In one embodiment, the article comprises (A) a top layer and (B) fabric The foam layer (C) is a bottom layer containing the top layer (A) and an intermediate foam layer (C). fabric The top layer (A) is in direct contact with the middle foam layer (C), which is located between the bottom layer (B) and the top layer (A). fabricIt is in direct contact with the bottom layer (B). The top layer (A) and the intermediate foam layer (C) each contain (i) 51% to 90% by weight, or 55% to 80% by weight, or 55% to 65% by weight of a propylene / ethylene copolymer. The propylene / ethylene copolymer in the top layer (A) and the propylene / ethylene copolymer in the intermediate foam layer (C) may be the same or different. The propylene / ethylene copolymer in the top layer (A) and the propylene / ethylene copolymer in the intermediate foam layer (C) each have a density of 0.85 g / cc to 0.87 g / cc and a melt flow rate of 5 g / 10 min to 30 g / 10 min, or 8 g / 10 min to 30 g / 10 min. The top layer (A) and the intermediate foam layer (C) each contain (ii) 49 wt% to 10 wt%, or 45 wt% to 20 wt%, or 45 wt% to 35 wt% of soft-OBC. The soft-OBC in layer (A) and the soft-OBC in the intermediate foam layer (C) may be the same or different. The soft-OBC in the top layer (A) and the soft-OBC in the intermediate foam layer (C) each have an SS-Tm of less than 2°C, or an SS-Tm of -30°C to less than 2°C, or an amorphous soft segment. The soft-OBC in the top layer (A) and the soft-OBC in the intermediate foam layer (C) each contain 21 mol% to 35 mol%, or 22 mol% to 30 mol% of octene in the soft segment.

[0076] In one embodiment, the article comprises: (A) a top layer; (B) fabric and (C) an intermediate foam layer. The foam layer (C) is a layer that is in contact with the top layer (A). fabricThe top layer (A) is in direct contact with the intermediate foam layer (C), and the intermediate foam layer (C) is in direct contact with the bottom layer. The top layer (A) and the intermediate foam layer (C) each contain (i) 51% to 90% by weight, or 55% to 80% by weight, or 55% to 65% by weight of a propylene / ethylene copolymer. The propylene / ethylene copolymer in the top layer (A) and the propylene / ethylene copolymer in the intermediate foam layer (C) may be the same or different. The propylene / ethylene copolymer in the top layer (A) and the intermediate foam layer (C) each have a density of 0.85 g / cc to 0.87 g / cc and a melt flow rate of 5 g / 10 min to 30 g / 10 min. The top layer (A) also comprises (ii) 10% to 49% by weight of a soft-OBC having a SS-Tm of less than 2° C. or a SS-Tm of −30° C. to less than 2° C. The intermediate foam layer (C) also comprises: (a) a first soft-OBC having an SS-Tm of less than 2°C, or an SS-Tm of between -30°C and less than 2°C, or an amorphous soft segment; and (b) A second soft-OBC different from the first soft-OBC, the second soft-OBC having an SS-Tm of less than 2°C, or an SS-Tm of between -30°C and less than 2°C, or an amorphous soft segment. The soft-OBC in the top layer (A), the first soft-OBC in the intermediate foam layer (C), and the second soft-OBC in the intermediate foam layer (C) each contain 21 mol% to 35 mol%, or 22 mol% to 30 mol% of octene in the soft segment. The combined components (a) and (b) are present in the intermediate foam layer (C) in an amount of 49 wt% to 10 wt%, or 45 wt% to 20 wt%, or 45 wt% to 35 wt% of the top layer. The weight percentages are based on the total weight of the intermediate foam layer (C).

[0077] D. Additives The top layer and / or intermediate foam layer may include one or more optional additives. Non-limiting examples of suitable additives include antioxidants, curing agents, crosslinking coagents, enhancing solvents and inhibitors, processing aids, UV absorbers or stabilizers, antistatic agents, nucleating agents, slip agents, plasticizers, lubricants, viscosity modifiers, tackifiers, antiblocking agents, surfactants, extender oils, acid scavengers, pigments and / or dyes, and metal deactivators. When present, the additive(s) are present in an amount of from 0.01% to less than 10% by weight, or from 0.1% to less than 5% by weight, or from 0.1% to less than 1.0% by weight, based on the total weight of each respective individual layer—top layer and intermediate foam layer.

[0078] In one embodiment, the top layer (A) and fabric a two-layer article having a bottom layer (B) and / or a top layer (A); fabric The three-layer article having a bottom layer (B) and an intermediate foam layer (C) further comprises a primer layer and a top coating layer. The primer layer is in direct contact with the top layer, and the top coating layer is in direct contact with the primer layer, such that the top coating 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. Subsequently, polyurethane is applied to the primer layer. fabric The bottom layer maintains the shape of the article (ie, synthetic leather) and provides the article with mechanical properties. fabric The bottom layer also provides foam stability for the intermediate foam layer (if present). The intermediate foam layer, if present, provides flexibility, cushioning, softness, thermal insulation, lightness, and hand feel to the multi-layer structure of the article. The top layer provides protection against UV rays, heat, and other weathering factors. The top layer may also have visible functionality such as printing, embossing, color, and / or gloss. The purpose of the top coating layer is to provide protection for the top layer and to protect the article from scratches, mars, and abrasions, provide a surface for text and designs, and impart an aesthetically pleasing finish to the article. The purpose of the primer layer is to facilitate adhesion of the top coating layer to the top layer.

[0079] The article finds many useful applications as a synthetic leather (i.e., POE leather), and thus, non-limiting examples of the article include clothing (shirts, blouses, slacks, skirts, dresses, coats, jackets, shoes, boots, hats), wallets, luggage, automotive interiors (car seats, interior door panels, dashboards), and furniture (chairs, sofas).

[0080] By way of example and not limitation, several embodiments of the present disclosure are detailed in the following examples. [Example]

[0081] The materials used in the examples of the present invention and the comparative samples are shown in Tables 1A to 1C below.

[0082] [Table 1]

[0083] [Table 2]

[0084] [Table 3] * Amorphous Soft Segment

[0085] Brabender Mixing and Compression Molding The POE resin was fed into a Brabender mixer at a set temperature of 180°C and a rotor speed of 30 rpm. After 2 minutes, the rotor speed was increased to 50 rpm. Mixing continued at 50 rpm for an additional 6 minutes. The compound was collected and pressed into a flat pie shape for further use.

[0086] The compound from the Brabender mix was compression molded into 1.1 mm thick plaques. The compound was preheated at 180°C for 5 minutes, then degassed, followed by a pressing process at 180°C for another 5 minutes. After cooling to room temperature, the plaques were removed from the mold. The resulting plaques were cut into shapes and sizes required for further testing.

[0087] Tables 2A-2B provide the compositions and performance of inventive examples (IE) and comparative samples (CS).

[0088] [Table 4]

[0089] [Table 5]

[0090] Tables 2A-2B provide the compositions and properties of Inventive Examples 1-7 (IE1-IE7) and Comparative Samples 1-19 (CS1-CS19). Each Inventive Example includes a propylene / ethylene copolymer (Versify resin) and a soft-OBC. Comparative samples include pure propylene / ethylene copolymer (Versify resin), blends of propylene / ethylene copolymer (Versify resin) with other ethylene / octene multiblock copolymers (INFUSE resin), ethylene / octene copolymer (ENGAGE resin), and an EPDM (NORDEL resin), and blends of propylene / ethylene copolymer (Versify 4301 resin) with 50 wt.% or more of a soft-OBC.

[0091] Pure Versify 3300 resin (CS1) and pure Versify 4301 resin (CS2) each have acceptable Bailey Flex Resistance values ​​(each resin has a Bailey Flex Resistance value >100k). However, pure Versify 3300 resin and pure Versify 4301 each have a Shore A hardness value of over 80, which exceeds the upper Shore A hardness value suitable for synthetic leather applications, making pure Versify 3300 and pure Versify 4301 unsuitable for synthetic leather applications.

[0092] In IE1-IE7, three different soft-OBCs were blended with Versify 3300 resin and Versify 4301 resin. The soft-OBC content in IE1-IE7 ranged from 20% to 45% by weight based on the total weight of the composition. Tables 2A-2B show that the Bailey Flex Resistance values ​​for IE1-IE7 were the same as or similar to the Bailey Flex Resistance values ​​for pure Versify 3300 resin (CS1) and pure Versify 4301 resin (CS2). However, Tables 2A-2B show that IE1-IE7 exhibit improved flexibility (Shore A values ​​less than 80 and flexural modulus less than 30 MPa) compared to Versify 3300 resin (CS1) and pure Versify 4301 resin (CS2). The improved flexibility of IE1-IE7 is attributed to the presence of the soft-OBC.

[0093] In CS17 and CS18, the soft-OBC1 (INFUSE 9077 resin) content was increased to 50% and 60%, respectively, resulting in insufficient Bailey Flex Resistance values, i.e., values ​​less than 60,000 (CS17-19k, CS18-17k). When the soft-OBC is less than 50 wt%, the soft-OBC is the discontinuous phase and the propylene / ethylene copolymer is the continuous phase, whereby the propylene / ethylene copolymer (Versify resin) is primarily responsible for resisting Bailey Flex. Without being bound by theory, it is believed that phase inversion occurs when the composition contains 50 wt% or more soft-OBC, whereby the soft-OBC becomes the continuous phase, as shown in Figure 1. Figure 1 (left) shows an SEM of IE7 (40 wt% soft-OBC1), and Figure 1 (right) shows an SEM of CE18 (60 wt% soft-OBC1), each containing a complementary amount of Versify 4301 (light areas) resin up to 100 wt%. When the soft-OBC is the continuous phase (dark areas) (CS18, Figure 1 right), the Bailey Flex Resistance value is reduced (17,000 for CS18) because the continuous soft-OBC is more susceptible to flex cracking than the propylene / ethylene copolymer (Versify resin).

[0094] Table 2B shows other ethylene / octene multiblock copolymers (INFUSE resins) and ethylene / octene copolymers (ENGAGE resins) blended with a propylene / ethylene copolymer (Versify 3300 resin) (see CS3-CS16), each of which exhibits unacceptably low Bailey Flex Resistance values, i.e., values ​​less than 60,000.

[0095] Without being bound by any particular theory, it is believed that the soft-OBC results in smaller domain sizes at the same loading in the propylene / ethylene copolymer compared to the domain sizes of other ethylene / octene multiblock copolymers. Figure 2 shows a soft-OBC (IE1 with 40 wt% soft-OBC1) with smaller domain sizes compared to the domain sizes of other ethylene / octene multiblock copolymers (CS6 with 40 wt% INFUSE9107 resin).

[0096] In summary, it has been unexpectedly discovered that blends of propylene / ethylene copolymers (Versify resins) with 10 to 49 weight percent soft-OBC provide compositions having Bailey Flex Resistance values ​​greater than 60,000 and Shore A hardness values ​​less than 80. Conversely, blends of propylene / ethylene copolymers (Versify resins) with other ethylene / octene multiblock copolymers (INFUSE resins) or ethylene / octene copolymers (ENGAGE resins) resulted in reduced Bailey Flex Resistance values ​​(less than 60,000).

[0097] The present disclosure is not limited to the embodiments and examples contained herein, but is expressly intended to include portions of the embodiments and modified forms of those embodiments, including combinations of elements of different embodiments, to the extent that they fall within the scope of the following claims. The present specification includes the following aspects. Section 1. An article, A. The top layer, (i) 51% by weight to 90% by weight of a propylene-based polymer; (ii) a top layer comprising a composition comprising 10 wt% to 49 wt% of an ethylene / octene multi-block copolymer having hard segments and soft segments, wherein the ethylene / octene multi-block copolymer has a soft segment melting temperature (SS-Tm) of less than 2°C; B. a bottom layer comprising fabric. Section 2. Item 1. The article according to item 1, wherein the ethylene / octene multiblock copolymer contains 21 mol% to 35 mol% octene in the soft segment. Section 3. The composition of the top layer is (i) a Bailey flexural resistance value of greater than 60,000; and (ii) The article according to paragraph 2, having a Shore A hardness of less than 80. Section 4. The propylene-based polymer is With a density of 0.85g / cc~0.87g / cc, Item 4. The article according to any one of items 1 to 3, which is a propylene / ethylene copolymer having a melt flow rate of 5 g / 10 min to 30 g / 10 min. Section 5. The composition of the top layer is 10% to 49% by weight a first ethylene / octene multi-block copolymer, the first ethylene / octene multi-block copolymer having hard segments and soft segments and a soft segment melting temperature (SS-Tm) of less than 2°C; and a second ethylene / octene multi-block copolymer different from the first ethylene / octene multi-block copolymer, wherein the second ethylene / octene multi-block copolymer has hard segments and soft segments, and the second ethylene / octene multi-block copolymer has a soft segment melting temperature (SS-Tm) of less than 2 ° C. The article of any one of items 1 to 4, comprising a second ethylene / octene multi-block copolymer. Section 6. C. An intermediate foam layer, (i) 51% by weight to 90% by weight of a propylene-based polymer; (ii) 10% to 49% by weight of an ethylene / octene multiblock copolymer having a hard segment and a soft segment, wherein the ethylene / octene multiblock copolymer has a soft segment melting temperature (SS-Tm) of less than 2 ° C. The article according to any one of items 1 to 5, comprising an intermediate foam layer composed of a composition comprising an ethylene / octene multiblock copolymer. Section 7. Item 7. The article according to item 6, wherein the ethylene / octene multiblock copolymer in the intermediate foam layer contains 21 mol% to 35 mol% octene in the soft segment. Section 8. The propylene-based polymer in the intermediate foam layer is With a density of 0.85g / cc~0.87g / cc, Item 8. The article according to item 7, which is a propylene / ethylene copolymer having a melt flow rate of 5 g / 10 min to 30 g / 10 min. Section 9. The composition of the intermediate foam layer is 10% to 49% by weight a first ethylene / octene multi-block copolymer, the first ethylene / octene multi-block copolymer having hard segments and soft segments and a soft segment melting temperature (SS-Tm) of less than 2°C; and a second ethylene / octene multi-block copolymer different from the first ethylene / octene multi-block copolymer, wherein the second ethylene / octene multi-block copolymer has hard segments and soft segments, and the second ethylene / octene multi-block copolymer has a soft segment melting temperature (SS-Tm) of less than 2 ° C. The article of any one of items 6 to 8, comprising a second ethylene / octene multi-block copolymer. Section 10. the first ethylene / octene multiblock copolymer in the intermediate foam layer contains 21 mol % to 35 mol % octene in the soft segment; Item 10. The article according to item 9, wherein the second ethylene / octene multiblock copolymer in the intermediate foam layer contains 21 mol% to 35 mol% octene in the soft segment.

Claims

1. An article, A. A top layer, (i) 51% to 90% by weight of a propylene-based polymer; (ii) a top layer comprising a composition comprising: an ethylene / octene multi-block copolymer having hard segments and soft segments, the ethylene / octene multi-block copolymer comprising at least 50 mol% ethylene, the ethylene / octene multi-block copolymer having a soft segment comprising 21 mol% to 35 mol% octene, and a soft segment melting temperature (SS-Tm) of −30° C. to less than 2° C.; B. a bottom layer comprising fabric.

2. The composition of the top layer is (i) a Bailey flex resistance value of greater than 60,000; and (ii) the article of claim 1 having a Shore A hardness of less than 80.

3. The propylene-based polymer is a density of 0.85 g / cc to 0.87 g / cc; 3. The article of claim 1, wherein the polymer is a propylene / ethylene copolymer having a melt flow rate of from 5 g / 10 min to 30 g / 10 min.

4. The composition of the top layer is 10% to 49% by weight a first ethylene / octene multi-block copolymer having hard segments and soft segments, the first ethylene / octene multi-block copolymer having a soft segment melting temperature (SS-Tm) of less than 2°C; and a second ethylene / octene multi-block copolymer different from the first ethylene / octene multi-block copolymer, the second ethylene / octene multi-block copolymer having a different octene mole % than the octene mole % in the first ethylene / octene multi-block copolymer, the second ethylene / octene multi-block copolymer having hard segments and soft segments, and a soft segment melting temperature (SS-Tm) of less than 2°C. The article of any one of claims 1 to 3.

5. C. An intermediate foam layer, (i) 51% to 90% by weight of a propylene-based polymer; (ii) 10% to 49% by weight of an ethylene / octene multi-block copolymer having hard segments and soft segments, wherein the ethylene / octene multi-block copolymer has a soft segment melting temperature (SS-Tm) of less than 2°C. The article of any one of claims 1 to 4, comprising an intermediate foam layer composed of a composition comprising:

6. 6. The article of claim 5, wherein the ethylene / octene multi-block copolymer in the intermediate foam layer comprises 21 mol% to 35 mol% octene in the soft segment.

7. The propylene-based polymer in the intermediate foam layer is a density of 0.85 g / cc to 0.87 g / cc; 7. The article of claim 6, which is a propylene / ethylene copolymer having a melt flow rate of from 5 g / 10 min to 30 g / 10 min.

8. The composition of the intermediate foam layer is 10% to 49% by weight a first ethylene / octene multi-block copolymer having hard segments and soft segments, the first ethylene / octene multi-block copolymer having a soft segment melting temperature (SS-Tm) of less than 2°C; and a second ethylene / octene multi-block copolymer different from the first ethylene / octene multi-block copolymer, the second ethylene / octene multi-block copolymer having a different octene mole % than the octene mole % in the first ethylene / octene multi-block copolymer, the second ethylene / octene multi-block copolymer having hard segments and soft segments, and a soft segment melting temperature (SS-Tm) of less than 2°C. The article of any one of claims 5 to 7.

9. the first ethylene / octene multi-block copolymer in the intermediate foam layer comprises 21 mol% to 35 mol% octene in the soft segments; 9. The article of claim 8, wherein the second ethylene / octene multi-block copolymer in the intermediate foam layer comprises 21 mol% to 35 mol% octene in the soft segment.

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