Synthetic leather

Abstract

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

Description

[Background technology]

[0001] The uses of synthetic leather continue to increase. Synthetic leather is used in the manufacture of clothing, footwear, bags and suitcases, home furnishings, and car seats. Synthetic leather exhibits similar performance and feel to natural leather. It offers the advantages of being animal-friendly and is less expensive to manufacture compared to natural leather.

[0002] Conventional synthetic leather has drawbacks. The manufacture of polyurethane-based synthetic leather (PU leather) requires the use of organic solvents, 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, respectively.

[0004] Polyolefin elastomer-based synthetic leather (POE leather) is advantageous because it is halogen-free, phthalate-free, and its manufacture does not require the use of harmful solvents such as DMF. POE leather also has the additional advantage of being recyclable due to its thermoplastic properties. From a performance standpoint, POE has excellent weather resistance and low-temperature flexibility, is resistant to hydrolysis, and is resistant to yellowing. Furthermore, because POE leather has a lower density compared to PU leather and PVC leather, respectively, it has been found to be advantageous in the current trend towards lightweighting in the travel bag / bag, shoe, and automotive interior segments.

[0005] Therefore, the field of this technology recognizes the need for POE leather. Furthermore, the field of this technology recognizes the need for POE leather that has Bally flex resistance and flexibility that meets or exceeds those of PU leather and / or PVC synthetic leather. [Overview of the project]

[0006] This disclosure provides articles. In one embodiment, an article is provided which comprises an upper layer comprising a composition comprising (A) 70% to 88% by weight of an ethylene-based polymer and (ii) 12% to 30% by weight of an oil, based on the total weight of the upper layer. The article further comprises a lower layer comprising (B) a textile. [Brief explanation of the drawing]

[0007] [Figure 1] This is a dynamic machine spectroscopic graph comparing Example 3 (Inventive Example, IE3) of the present invention with comparative sample 7 (comparative sample, CS7). [Modes for carrying out the invention]

[0008] definition Any references to the periodic table refer to the edition published by CRC Press, Inc., 1990–1991. References to element groups in this table are based on a new notation for numbering groups.

[0009] For the purposes of U.S. patent practice, any referenced patent, patent application, or publication is incorporated by reference in its entirety (or an equivalent U.S. version thereof) particularly with respect to definitional disclosures (to the extent that they do not conflict with any definitions specifically provided in this disclosure) and general knowledge in the art.

[0010] Numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit (including boundary values). In the case of ranges containing explicit values ​​(e.g., ranges of 1, or 2, or 3 to 5, or 6, or 7), any subrange between two explicit values ​​is included (e.g., the above range 1 to 7 includes subranges 1 to 2, 2 to 6, 5 to 7, 3 to 7, 5 to 6, etc.).

[0011] Unless otherwise stated, implied by the context, or customary in the art, all parts and percentages are based on 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 a blend may or may not be miscible (i.e., not phase-separated at the molecular level). Such a blend may or may not be phase-separated. Such a blend 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 containing the composition, as well as reaction and decomposition products formed from the materials of the composition.

[0014] The terms “comprising,” “including,” and “having,” and their derivatives, are not intended to exclude the existence of any additional components, processes, or procedures, whether or not they are specifically disclosed. To avoid any doubt, all compositions claimed through the use of the term “comprising” may, unless otherwise stated, include any additional additives, adjuvants, or compounds, whether polymeric or otherwise. In contrast, the term “consisting essentially of” excludes any other components, processes, or procedures from the scope of any subsequent detail, except those not essential to operability. The term “consisting of” excludes any components, processes, or procedures not specifically described or enumerated. The term “or” refers to the enumerated items individually and in any combination, unless otherwise specified.

[0015] As used herein, “ethylene polymer” is a polymer containing more than 50 weight percent polymerized ethylene monomers (based on the total amount of polymerizable monomers) and optionally containing at least one comonomer.

[0016] "Fabric" is a woven or non-woven (such as knit) structure formed from individual fibers or threads.

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

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

[0019] As used herein, the term “foam” or “foam article” refers to a structure constructed from a polymer, the structure comprising a plurality of separate gas pockets or foam cells completely surrounded by the polymer. As used herein, the term “foam bubble” or “bubble” refers to a separate space within a foam composition. Foam bubbles 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 general term includes polymers prepared from two different monomers, and copolymers, which are commonly used to refer to polymers prepared from three or more different monomers, such as terpolymers and tetrapolymers.

[0021] "Knitted fabric" is formed by intertwining yarns or fibers into a series of connected loops by hand, with knitting needles, or on a machine. The fabric can be formed by warp knitting, weft knitting, plain knitting, and circular knitting. Non-limiting examples of suitable warp knitting include tricot, raschel power net, and lace. Non-limiting examples of suitable weft knitting include circular knitting, plain knitting, and seamless (which is often considered a subset of circular knitting).

[0022] "Non-woven" refers to a web or fabric having individual fibers or yarn-like structures that are randomly interlaced but not interlaced in a distinguishable pattern as in the case of knitted fabric.

[0023] "Olefin 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 may optionally contain at least one comonomer. Non-limiting examples of olefin polymers are ethylene-based polymers.

[0024] "Polymer" is a compound prepared by polymerizing monomers, whether of the same or different types, which provides the polymer with a plurality of and / or repeating "units" or "structural units" in a polymerized form. 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 monomers. It also encompasses all forms of copolymers, such as random and block copolymers. The terms "ethylene / α-olefin polymer" and "propylene / α-olefin polymer" refer to the above-mentioned copolymers prepared by polymerizing ethylene or propylene and one or more additional polymerizable α-olefin monomers, respectively. Polymers are often referred to as being "made from" one or more specified monomers, such as being "based on" a specified monomer or monomer type and "containing" a specified monomer content. In this context, it should be noted that the term "monomer" is understood to refer to the polymerized residue of the specified monomer and does not refer to non-polymerized species. Generally, polymers herein are referred to as being based on "units" that are the polymerized form of the corresponding monomers.

[0025] "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. "Styrene-based polymer" is a polymer that contains polymerized styrene as a monomer.

[0027]

Chemical formula

[0028] "Woven" refers to a web or fabric having a structure of individual fibers or twists arranged in an identifiable manner and in a specific pattern. A non-exclusive example of a woven fabric is knitted fabric.

[0029] Test method The Bailey flexure test is performed at 25°C according to ASTM D6182. The Bailey flexure test determines the durability of coatings applied to synthetic leather, leather, and fabric by repeatedly bending a test specimen. The Bailey flexure tester operates at a speed of 100 cycles / min in accordance with DIN 53351. The final cycle is determined by the cycle at which cracks appear on the plaque surface and is reported as the Bailey flexure result. Two test specimens are tested for each sample, and the average value is reported as the Bailey flexure resistance value. The results are reported in cycle count. If no cracks / damage are found after 100,000 cycles for two test specimens, the result is reported as "greater than 100,000" or ">100k".

[0030] The density is measured according to ASTM D792, Method B. The results are recorded in grams per cubic centimeter (g / cc).

[0031] 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 range of temperatures. For example, this analysis is performed using a TA Instruments Q2000 DSC equipped with a refrigerated cooling system (RCS) and autosampler. A nitrogen purge gas flow rate of 50 ml / min is used during the test. Each sample is melted and compressed into a thin film at approximately 175°C, and then the melted sample is air-cooled to room temperature (approximately 25°C). Test specimens of 3-10 mg, 6 mm in diameter are extracted from the cooled polymer, weighed, placed in a lightweight aluminum pan (approximately 50 mg), and pressed shut. Analysis is then performed to determine its thermal properties.

[0032] The thermal behavior of the sample is determined by raising and lowering the sample temperature to create a heat flow versus temperature profile. First, the sample is rapidly heated to 180°C and held isothermally for 3 minutes to remove thermal history. Next, the sample is cooled to -80°C at a cooling rate of 10°C / min and held isothermally at -80°C for 3 minutes. Then, the sample is heated to 180°C at a heating rate of 10°C / min (this is the "second heating" rise). The cooling curve and the second heating curve are recorded. The cooling curve is analyzed by setting the baseline endpoint from the start of crystallization to -20°C. The thermal curve is analyzed by setting the baseline endpoint from -20°C to the end of melting. The values ​​to be determined are the extrapolated melting start point Tm and the extrapolated crystallization start point Tc. Heat of fusion (H f ) (Joules per gram), and the degree of crystallinity % of the polyethylene sample calculated using the following formula: Degree of crystallinity % = ((H f ) / 292J / g)×100.

[0033] From the second heating curve, the heat of fusion (H f The enthalpy of melting (also known as the peak melting temperature) and the peak melting temperature are reported.

[0034] The melting point Tm is first determined from the DSC heating curve by drawing a baseline between the start and end of the melting transition. Next, a tangent line is drawn to the lower temperature data of the melting peak. The point where this line intersects the baseline is the extrapolated melting start point (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., 2d ed. 1997).

[0035] The glass transition temperature (Tg) is determined from the DSC heating curve, 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), where half of the sample has acquired the heat capacity of a liquid. 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 Tg.

[0036] Dynamic mechanical spectroscopy (DMS) was performed on compression-molded discs formed at a pressure of 10 MPa for 5 minutes in a 180°C hot press, followed by water cooling at 90°C / min in the press. The tests were performed using an AR2000ex rheometer (TA instruments, shape: 25 mm parallel plate, frequency sweep, temperature: 160°C, angular frequency: 1~628 rad / s, strain: 5%) fitted with a double cantilever fixture for torsion testing.

[0037] The melt index (MI or I2) of ethylene polymers is measured according to ASTM D 1238 under conditions of 190°C / 2.16 kg, and the results are reported in grams per 10 minutes (g / 10 min).

[0038] Shore A hardness was measured according to ASTM D2240. Load: 1 kg, duration: 5 seconds. Two 3 mm thick plaques were stacked together for the test.

[0039] Detailed explanation This disclosure provides articles. In one embodiment, the article comprises an uppermost layer comprising a composition consisting of (A) 70% to 88% by weight of an ethylene-based polymer and (ii) 12% to 30% by weight of an oil, based on the total weight of the uppermost layer. The article also comprises a lowermost layer comprising (B) a textile.

[0040] A. Top floor (i) Ethylene polymers The top layer consists of a composition comprising (i) 70% to 88% by weight of an ethylene-based polymer and (ii) 12% to 30% by weight of oil. The weight percentages are based on the total weight of the top layer. The ethylene-based polymers are (i) ethylene / C4-C8α-olefin copolymer, (ii) ethylene / C4-C8α-olefin multiblock copolymer, and (iii) combinations of (i) and (ii).

[0041] Ethylene / C4-C8α-olefin copolymers consist of (i) polymerization units of ethylene and (ii) polymerization units of C4-C8α-olefin comonomers. Non-limiting examples of preferred ethylene / C4-C8α-olefin copolymers include ethylene / butene copolymers, ethylene / hexene copolymers, and ethylene / octen copolymers.

[0042] In one embodiment, the ethylene / C4-C8α-olefin copolymer resin is an ethylene / octen copolymer having one, some, or all of the following properties: (i) Densities of 0.857 g / cc to 0.880 g / cc or 0.865 g / cc to 0.875 g / cc, and / or (ii) Melt index (I2) of 0.5g / 10 min to 20g / 10 min, or 1g / 10 min to 15g / 10 min, or 3g / 10 min to 13g / 10 min, and / or (iii) Shore A hardness values ​​of less than 80, or less than 75, or between 50 and 75, or between 60 and 75.

[0043] In one embodiment, the ethylene-based polymer is an ethylene / C4-C8α-olefin multiblock copolymer. The term "ethylene / C4-C8α-olefin multiblock copolymer" refers to an ethylene / C4-C8α-olefin multiblock copolymer consisting of ethylene in its polymer form and one copolymerizable C4-C8α-olefin comonomer (and an optional additive), wherein the polymer is characterized by multiple blocks or segments of two polymerized monomer units with different chemical or physical properties, and the blocks are linearly joined (or covalently bonded). That is, the polymer contains chemically distinct units whose ends are joined to a polymerized ethylenically functional group. Ethylene / α-olefin multiblock copolymers include block copolymers having two blocks (diblocks) and more than two blocks (multiblocks). The C4-C8α-olefin is selected from butene, hexene, and octene. Ethylene / C4-C8 α-olefin multiblock copolymers do not contain styrene (i.e., styrene-free) and / or vinyl aromatic monomers and / or conjugated dienes, or otherwise exclude them. When referring to the amount of "ethylene" or "comonomer" in the copolymer, this is understood to refer to its polymerization units. In some embodiments, the ethylene / α-olefin multiblock copolymer is given by the following formula: (AB) nIt can be represented by the formula, where n is at least 1, preferably an integer greater than 1, for example, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or more, where "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 manner, or in a linear style, as opposed to a substantially branched or substantially star-shaped arrangement. In other embodiments, A blocks and B blocks are randomly distributed along the polymer chain. In other words, block copolymers do not typically have a structure such as: AAA-AA-BBB-BB. In one embodiment, the ethylene / α-olefin multiblock copolymer does not have a third type of block containing different comonomers. In another embodiment, each of block A and block B has monomers or comonomers substantially randomly distributed within the block. In other words, neither Block A nor Block B contains two or more subsegments (or subblocks) of distinct compositions, such as a tip segment, which has a substantially different composition from the rest of the block.

[0044] In one embodiment, ethylene constitutes a majority mole fraction of the total ethylene / α-olefin multiblock copolymer, i.e., ethylene constitutes at least 50% by weight of the total ethylene / α-olefin multiblock copolymer. More preferably, ethylene, together with the substantially remaining portion of the whole ethylene / α-olefin multiblock copolymer containing C4-C8 α-olefin comonomers, constitutes at least 60% by weight, at least 70% by weight, or at least 80% by weight. In one embodiment, the ethylene / α-olefin multiblock copolymer contains 50% to 90% by weight of ethylene, or 60% to 85% by weight of ethylene, or 65% to 80% by weight of ethylene. In many ethylene / octene multiblock copolymers, the composition contains an ethylene content of more than 80% by weight of the total ethylene / octene multiblock copolymer and an octene content of 10% to 15% by weight or 15% to 20% by weight of the total multiblock copolymer.

[0045] Ethylene / C4-C8α-olefin multiblock copolymers contain varying amounts of “hard” and “soft” segments. “Hard” segments are blocks of polymerization units in which ethylene is present in amounts of more than 90% by weight, or 95% by weight, or more than 95% by weight, or more than 98% by weight, up to a maximum of 100% by weight, based on the weight of the polymer. In other words, the comonomer content (content of monomers other than ethylene) in hard segments is less than 10% by weight, or 5% by weight, or less than 5% by weight, or less than 2% by weight, based on the weight of the polymer, and can be as low as zero. In some embodiments, hard segments contain all or substantially all units derived from ethylene. “Soft” segments are blocks of polymerization units in which the comonomer content (content of monomers other than ethylene) is more than 5% by weight, or more than 8% by weight, more than 10% by weight, or more than 15% by weight, based on the weight of the polymer. In one embodiment, the comonomer content in the soft segment is greater than 20% by weight, greater than 25% by weight, greater than 30% by weight, greater than 35% by weight, greater than 40% by weight, greater than 45% by weight, greater than 50% by weight, or greater than 60% by weight, and can be up to 100% by weight.

[0046] Soft segments may be present in the ethylene / α-olefin multiblock copolymer at concentrations of 1% to 99% by weight of the total weight, or at concentrations of 5% to 95%, 10% to 90%, 15% to 85%, 20% to 80%, 25% to 75%, 30% to 70%, 35% to 65%, 40% to 60%, or 45% to 55% by weight. Conversely, hard segments may be present in similar ranges. The weight percentages of soft segments and hard segments can be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed, for example, in U.S. Patent No. 7,608,668, titled "Ethylene / α-Olefin Block Inter-polymers," filed on March 15, 2006, in the names of Colin LPShan, Lonnie Hazlitt, et al., and assigned to Dow Global Technologies Inc., the disclosure is incorporated herein by reference in its entirety. In particular, the weight percentages of the hard and soft segments and the comonomer content may be determined as described in columns 57–63 of U.S. Patent No. 7,608,668.

[0047] Ethylene / C4~C8α-olefin multiblock copolymers contain two or more linearly bonded (or covalently bonded) chemically distinct regions or segments (referred to as "blocks"), that is, chemically distinct units whose ends are bonded to the polymeric ethylenically functional groups rather than being pendanted or grafted. In one embodiment, the blocks differ in the amount or type of incorporated comonomers, density, degree of crystallinity, microcrystalline size which may result from polymers of such composition, type or degree of stereoregularity (isotactic or syndiotactic), positional regularity or positional irregularity, amount of branching (including long-chain branching or hyperbranching), uniformity, or any other chemical or physical properties. Compared to conventional block interpolymers, which include interpolymers produced by continuous monomer addition, fluid catalysts, or anionic polymerization techniques, the ethylene / α-olefin multiblock copolymers of the present invention are characterized in one embodiment 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 shuttle agents combined with multiple catalysts used in their preparation.

[0048] In one embodiment, the ethylene / C4-C8α-olefin multiblock copolymer is produced in a continuous process and has a polydispersity index (Mw / Mn) of 1.7-3.5, or 1.8-3, or 1.8-2.5, or 1.8-2.2. When produced in a batch or semi-batch process, the ethylene / α-olefin multiblock copolymer has an Mw / Mn of 1.0-3.5, or 1.3-3, or 1.4-2.5, or 1.4-2.

[0049] Furthermore, the ethylene / C4-C8α-olefin multiblock copolymer has a PDI (or Mw / Mn) that conforms to a Schultz-Flory distribution rather than a Poisson distribution. This ethylene / α-olefin multiblock copolymer has both a polydisperse block distribution and a polydisperse block size distribution. This results in polymer products with improved, identifiable physical properties. The theoretical advantages of the polydisperse block distribution have already been 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.

[0050] In one embodiment, the ethylene / α-olefin multiblock copolymer has a most probable distribution of block lengths.

[0051] In further embodiments, the ethylene / C4-C8α-olefin multiblock copolymer of the present disclosure, particularly those produced in a continuous solution polymerization reactor, has a most probable distribution of block lengths. In one embodiment of the present disclosure, the ethylene / C4-C8α-olefin multiblock copolymer is (A) The values ​​of Mw / Mn between approximately 1.7 and 3.5, at least one melting point Tm expressed in degrees Celsius, and density d, Tm, and d expressed in grams per cubic centimeter correspond to the following relationship: Tm>-2002.9+4538.5(d)-2422.2(d) 2 , and / or (B) Characterized by a Mw / Mn of approximately 1.7 to 3.5, the heat of fusion, ΔH (J / g), and delta amount ΔT are degrees Celsius defined as the temperature difference between the highest DSC peak and the highest crystallization analysis fractionation ("CRYSTAF") peak, and ΔT and ΔH have the following relationship: ΔT > -0.1299ΔH + 62.81 (for ΔH greater than 0 and with a maximum of 130 J / g) ΔT ≥ 48℃ (in the case of ΔH exceeding 130 J / g) If the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and less than 5 percent of the polymer has a discernible CRYSTAF peak, then the CRYSTAF temperature is 30°C, and / or (C) Defined as having a 300 percent strain and an elastic recovery rate Re (percent) in one cycle, measured using a compression-molded film of ethylene / α-olefin interpolymer, and having a density d (grams / cubic centimeter), and if the ethylene / α-olefin interpolymer substantially contains no crosslinking phase, the values ​​of Re and d satisfy the following relationship: Re>1481-1629(d); and / or (D) Having a molecular fraction that elutes at 40°C to 130°C when fractionated using TREF, characterized in that the fraction has a comonomer molar content at least 5 percent higher than an equivalent random ethylene interpolymer fraction that elutes at the same temperature, the equivalent random ethylene interpolymer having the same comonomers and having a melt index, density, and comonomer molar content (based on the entire polymer) within 10 percent of that of the ethylene / α-olefin interpolymer, and / or (E) It has a storage modulus of G'(25°C) at 25°C and G'(100°C) at 100°C, and the ratio of G'(25°C) to G'(100°C) is in the range of 1:1 to 9:1.

[0052] Ethylene / C4~C8α-olefin multiblock copolymer is also (F) A molecular fraction that elutes at 40°C to 130°C when fractionated using TREF, characterized by having a block index of at least 0.5 and a maximum of 1 and a molecular weight distribution Mw / Mn greater than 1.3, and / or (G) It has an average block index greater than 0 and a maximum of 1.0, and a molecular weight distribution Mw / Mn greater than 1.3.

[0053] It is understood that ethylene / C4-C8α-olefin multiblock copolymers may have one, some, all, or any combination of properties (A) to (G). The block index may be determined as detailed in U.S. Patent No. 7,608,668, which is incorporated herein by reference for that purpose. Analytical methods for determining properties (A) to (G) are disclosed, for example, in columns 31, line 26 to 35, line 44 of U.S. Patent No. 7,608,668, which is incorporated herein by reference for that purpose.

[0054] In one embodiment, an ethylene / C4-C8α-olefin multiblock copolymer is defined as having hard and soft segments, being styrene-free, and consisting only of (i) ethylene and (ii) C4-C8α-olefin or C8α-olefin (and optional additives), having a Mw / Mn of 1.7 to 3.5, at least one melting point Tm (temperature in degrees Celsius), and density d (grams / cubic centimeter), where the values ​​of Tm and d correspond to the following relationship: Tm>-2002.9+4538.5(d)-2422.2(d) 2 , In the formula, 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 melting point Tm is 110°C, or 115°C, or 120°C to 125°C, or 130°C, or 135°C.

[0055] In one embodiment, the ethylene / C4-C8α-olefin multiblock copolymer is an ethylene / 1-octene multiblock copolymer (consisting only of ethylene and octene comonomers) having one, some, or all of the following properties: (i) Mw / Mn in 1.7 or 1.8 to 2.2, or 2.5, or 3.5, and / or (ii) densities of 0.857, 0.860 g / cc or 0.865 g / cc to 0.870 g / cc, 0.877 g / cc or 0.880 g / cc, and / or (iii) a melting point Tm of 115°C, or 118°C, or 119°C, or 120°C to 120°C, or 123°C, or 125°C, and / or (iv) 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 (v) 50-85% by weight of soft segments and 40-15% by weight of hard segments (based on the total weight of the ethylene / octene multiblock copolymer), and / or (vi) 10 mol%, 13 mol%, 14 mol%, 15 mol%, to 16 mol%, 17 mol%, 18 mol%, 19 mol%, 20 mol%, or 25 mol% of octene in the soft segment, and / or (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%, of octene in the hard segment, and / or (viii) When measured according to ASTM D 1708, 300% / min at 21°C 1 Elastic recovery (Re) of 50%, 60%, 70%, 80%, or 90% in the deformation rate, and / or (ix) Polydispersive distribution of the blocks and polydispersive distribution of the block size (hereinafter referred to as properties (i) to (ix) of the multiblock copolymer).

[0056] In one embodiment, the ethylene / C4-C8α-olefin multiblock copolymer is an ethylene / octene multiblock copolymer. The ethylene / octene multiblock copolymer is available from The Dow Chemical Company (Midland, Michigan, USA) and is sold under the trade name INFUSE®.

[0057] Ethylene / C4-C8α-olefin multiblock copolymers can be produced via chain shuttle processes, such as those described in U.S. Patent No. 7,858,706, which is incorporated herein by reference. Particularly preferred chain shuttles and related information are listed in columns 16, lines 39 to 19, line 44. Preferred catalysts are described in columns 19, lines 45 to 46, line 19, and preferred co-catalysts are described in columns 46, lines 20 to 51, line 28. The process is described throughout this document, but in particular in columns 51, lines 29 to 54, line 56. The process is also described, for example, in U.S. Patents No. 7,608,668, 7,893,166, and 7,947,793.

[0058] In one embodiment, the ethylene / C4-C8α-olefin multiblock copolymer is an ethylene / octene multiblock 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, and a Shore A hardness of less than 80, or 75 or less, or 60 to 75.

[0059] (ii) oil The top layer contains 12% to 30% by weight of oil in addition to ethylene-based polymers. The weight percentage is based on the total weight of the top layer. The oil may be mineral oil, aromatic oil, naphthenic oil, paraffinic oil, triglyceride-based vegetable oil (such as castor oil or soybean oil), synthetic hydrocarbon oil (such as polypropylene oil), silicone oil, or a combination thereof.

[0060] In one embodiment, the oil is mineral oil. As used herein, "mineral oil" is a colorless and odorless oil that is a mixture of C 15 ~C 40 alkanes. Mineral oil is present in the uppermost layer, excluding aromatic oils, naphthenic oils, paraffin oils, triglyceride-based vegetable oils, synthetic hydrocarbon oils, silicone oils, and any combination thereof. Mineral oil is present in the uppermost layer in an amount of 12 to 30 wt%, 13 to 27 wt%, or 15 to 25 wt% based on the total weight of the uppermost layer.

[0061] B. Lowermost textile layer The article of the present invention includes a lowermost textile layer in addition to the uppermost layer. "Textile" is a flexible material composed of a network of natural fibers, artificial fibers, and combinations thereof. Textiles include fabrics and cloths. The textile may be woven, non-woven, knitted, plain-woven, or spunbonded. Non-limiting examples of natural fibers include cotton, wool, linen, and combinations thereof. Non-limiting examples of artificial fibers include polyester (PET), polyamide (nylon), acrylic, polyolefin, polyurethane (e.g., spandex material), polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, and combinations thereof.

[0062] In one embodiment, the textile is a non-woven textile.

[0063] In one embodiment, the textile is a microfiber non-woven textile. A "microfiber" textile is a fabric containing fibers with a diameter of 100 micrometers or less.

[0064] 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.

[0065] In one embodiment, the textile contains fibers having a size of 0.1 denier, 0.3 denier, 1 denier, 2 denier, 3 to 4 denier, 5 denier, 6 denier, 7 denier, 8 denier, 9 denier, or 10 denier. In another embodiment, the textile contains fibers having a size of 10 denier or less.

[0066] In one embodiment, the textile has a thickness of 0.5 mm, or 1.0 mm to 1.5 mm, or 2.0 mm.

[0067] In one embodiment, the textile is a nonwoven textile having one, some, or all of the following characteristics: (a) Densities of 0.20 g / cc, or 0.25 g / cc to 0.32 g / cc, or 0.35 g / cc, and / or (b) Fiber size of 1 denier, or 3 to 5 denier, and / or (c) Thickness of 0.5 mm, or 1.0 mm to 1.5 mm, or 2.0 mm.

[0068] In one embodiment, the textile is a fabric made of polyester, polyethylene and / or polypropylene. The fabric undergoes pre-lamination treatment such as corona surface treatment and impregnation, and the top layer is heat-laminated to the fabric such that the top layer is in direct contact with the bottom layer, so that there is no intervening layer or structure between the top layer and the bottom layer.

[0069] The textile may include two or more embodiments disclosed herein.

[0070] In one embodiment, the article comprises (A) an uppermost layer and (B) a bottom layer containing a textile. The uppermost layer is in direct contact with the bottom layer. (A) The uppermost layer contains (i) 80% to 88% by weight of ethylene / C4-C8α-olefin copolymer and (ii) 12% to 20% by weight of oil. The ethylene / C4-C8α-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 mineral oil, excluding any other type of oil. The uppermost layer has a Bailey flexure resistance value greater than 86,000, or 87,000 to 150,000, or 90,000 to 140,000. In a further embodiment, the top layer (A) composition 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.

[0071] In one embodiment, the article comprises (A) an uppermost layer and (B) a bottom layer containing a textile. The uppermost layer is in direct contact with the bottom layer. The uppermost layer contains (i) 30% to 50% by weight, or 35% to 45% by weight of ethylene / C4-C8α-olefin multiblock copolymer, (ii) 30% to 50% by weight, or 35% to 45% by weight of ethylene / C4-C8α-olefin copolymer, and (iii) 12% to 30% by weight, or 15% to 25% by weight of oil. It is understood that the sum of the amounts of ethylene / C4-C8α-olefin multiblock copolymer, ethylene / C4-C8α-olefin copolymer, and oil equals 100% by weight of the uppermost layer. The ethylene / C4-C8α-olefin multiblock 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 60 to 75 or less. The top layer has a Bailey flexure resistance value greater than 86,000, or 87,000 to 150,000, or 90,000 to 140,000. In further embodiments, the top layer has a melt index of 2 g / 10 min to 10 g / 10 min, and a Shore A hardness value less than 80, or 60 to 75.

[0072] C. Intermediate foam layer In one embodiment, the article includes an intermediate foam layer in addition to the top layer and the bottom layer. The intermediate layer is positioned between the top layer and the bottom layer. 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 comprising (i) 70% to 90% by weight, or 70% to 88% by weight, of an ethylene-based polymer, and (ii) 10% to 30% by weight, or 12% to 30% by weight, of an oil, based on the total weight of the intermediate foam layer.

[0073] In one embodiment, the intermediate foam layer is prepared by blending or compounding individual components with each other under conditions and for a period of time that produce a substantially homogeneous mixture in any conventional mixing apparatus, e.g., a Banbury kneader or any suitable extruder; calendering the mixture using conventional apparatus and conditions to form a sheet; and then thermal laminating the sheet to the top and / or bottom textile layer using conventional laminating apparatus and conditions. The intermediate foam layer is typically not subjected to foaming conditions until after it has been laminated to the top (A) and bottom textile layer (B). The foaming conditions are such that very fine and regular bubbles are formed throughout the intermediate foam layer. Typical foaming conditions include an oven temperature of 200°C or higher and an oven residence time of 60–120 seconds. The foaming efficiency [i.e., the ratio of expanded volume to the original (unexpanded) volume] is typically 1.5–5 or 2–3, based on the thickness ratio.

[0074] In one embodiment, the article comprises (A) an uppermost layer, (B) a bottom layer containing textile, and (C) an intermediate foam layer. The intermediate foam layer (C) is located between the uppermost layer (A) and the bottom textile layer (B). The uppermost 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 uppermost layer (A) and the intermediate foam layer (C) each contain (i) 70% to 90% by weight, or 80% to 88% by weight, of ethylene / C4-C8α-olefin copolymer, and (ii) 10% to 30% by weight, or 12% to 20% by weight, of oil. The ethylene / C4-C8α-olefin copolymer in the upper layer (A) and the intermediate foam layer (C) may be the same or different. The ethylene / C4-C8α-olefin copolymers in the uppermost layer (A) and the intermediate foam layer (C) have densities of 0.86 g / cc to 0.88 g / cc, melt indexes of 0.5 g / 10 min to 20 g / 10 min, and Shore A values ​​of 75 or less, respectively. The oil in the upper layer (A) and the oil in the intermediate foam layer (C) is mineral oil, excluding any other types of oil. The amounts of oil in the uppermost layer and the intermediate foam layer may be the same or different. The uppermost layer (A) and the foam layer (C) have Bailey flexure resistance values ​​greater than 86,000, or 87,000 to 150,000, or 90,000 to 140,000, respectively. In further embodiments, the composition of the uppermost 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.

[0075] In one embodiment, the article comprises (A) an uppermost layer, (B) a bottom layer containing textile, and (C) an intermediate foam layer. The intermediate foam layer (C) is located between the uppermost layer (A) and the bottom textile layer (B). The uppermost 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 uppermost layer (A) and the intermediate foam layer (C) each contain (i) 30% to 50% by weight, or 35% to 45% by weight of ethylene / C4-C8α-olefin multiblock copolymer, (ii) 30% to 50% by weight, or 35% to 45% by weight of ethylene / C4-C8α-olefin copolymer, and (iii) 10% to 30% by weight, or 12% to 30% by weight, or 15% to 25% by weight of oil. It is understood that the sum of the amounts of ethylene / C4~C8α-olefin multiblock copolymer, ethylene / C4~C8α-olefin copolymer, and oil equals 100% by weight of the top layer (A). It is understood that the sum of the amounts of ethylene / C4~C8α-olefin multiblock copolymer, ethylene / C4~C8α-olefin copolymer, and oil equals 100% by weight of the intermediate foam layer (C). The amounts of ethylene / C4~C8α-olefin multiblock copolymer in the top layer (A) and the ethylene / C4~C8α-olefin multiblock copolymer in the intermediate foam layer (C) may be the same or different. The amounts of oil in the top layer and the intermediate foam layer may be the same or different. The ethylene / C4-C8α-olefin multiblock copolymer in the uppermost layer (A) and the ethylene / C4-C8α-olefin multiblock 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 75 or less. The uppermost layer (A) has a Bailey flexure resistance value greater than 86,000, or 87,000 to 150,000, or 90,000 to 140,000. In further embodiments, the composition of the uppermost 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.

[0076] D. Additives The top layer and / or intermediate foam layer may contain one or more optional additives. Non-limiting examples of suitable additives include antioxidants, curing agents, crosslinking aids, enhancing solvents and inhibitors, processing aids, UV absorbers or stabilizers, antistatic agents, nucleating agents, slip agents, plasticizers, lubricants, viscosity modifiers, tackifiers, anti-tackifiers, surfactants, acid scavengers, pigments and / or dyes, and metal deactivators. If present, additives are present in amounts of 0.01% to less than 10% by weight, or 0.1% to less than 5% by weight, or 0.1% to less than 1.0% by weight, based on the total weight of each individual layer—the top layer and / or intermediate foam layer.

[0077] In one embodiment, a two-layer article having an uppermost layer (A) and a bottommost textile layer (B), and / or a three-layer article having an uppermost layer (A), a bottommost textile layer (B), and an intermediate foam layer (C), further include a primer layer and a top coating layer. The primer layer is in direct contact with the uppermost 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. The bottom textile layer maintains the shape of the article, i.e., synthetic leather, and provides the article with mechanical properties. The bottom textile layer also provides foaming stability to the intermediate foam layer (if present). The intermediate foam layer, if present, provides flexibility, cushioning, suppleness, heat insulation, lightness, and tactile feel to the multilayer structure of the article. The top layer provides protection against ultraviolet radiation, heat, and other weathering factors. The top layer may also have visible functionalities such as printing, embossing, color, and / or gloss. The purpose of the top coating layer is to provide protection to the top layer, as well as to protect the article from scratches, abrasions, and wear, to provide a surface for text and design, and to give the article an aesthetically pleasing finish. The purpose of the primer layer is to facilitate the adhesion of the top coating layer to the top layer.

[0078] Bailey flexure resistance is an important characteristic for synthetic leather products, and it is a characteristic of durability and mechanical fatigue under repeated bending stress. The applicant has found that the addition of 12% to 30% by weight of mineral oil to (i) ethylene / C4~C8α-olefin copolymer and / or (ii) ethylene / C4~C8α-olefin multiblock copolymer in the top layer of a synthetic leather article, and / or the addition of 10% to 30% by weight or 12% to 30% by weight of oil in the intermediate foam layer, unexpectedly improves (increases) the Bailey flexure resistance of POE synthetic leather to meet or exceed the Bailey flexure resistance values ​​of comparable PU synthetic leather structures and / or PVC synthetic leather structures. When 12% to 30% by weight of mineral oil is added in the top layer to (i) ethylene / C4-C8α-olefin copolymer and / or (ii) ethylene / C4-C8α-olefin multiblock copolymer, the melt index of the composition is also maintained in the range of 2 g / 10 min to 10 g / 10 min, which is necessary to maintain a melt viscosity suitable for process operations such as calendering and extrusion casting, and an MI of 2 to 10 g / 10 min allows for surface smoothness and efficient production rate.

[0079] This article, as synthetic leather, or POE leather, finds many useful applications. Therefore, non-limiting examples of this article include clothing (shirts, blouses, slacks, skirts, dresses, coats, jackets, shoes, boots, hats), wallets, travel bags, automotive interiors (car seats, interior door panels, dashboards), and furniture (chairs, sofas).

[0080] Rather than being limiting, some embodiments of the present disclosure are described in detail below in the following examples. [Examples]

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

[0082] [Table 1]

[0083] Brabender mixing and compression molding.

[0084] In the example without a chemical blowing agent (CBA), POE resin was supplied to a Brabender mixer at a set temperature of 150°C and a rotor speed of 30 rpm. After 2 minutes, the resin was uniformly heated and melted. Then, all other components were weighed and gradually added to the chamber. Mixing was continued at 50 rpm for a further 6 minutes.

[0085] For samples containing CBA, the chamber temperature was set to 130°C. Mixing was performed at 35 rpm for approximately 6 minutes. The final melting temperature was controlled and maintained below 145°C. The compound was collected and pressed into a flat pie shape for subsequent use.

[0086] The compound from the Brabender mixture was compression-molded in a 1.1 mm thick mold to form a plaque. The compound was preheated at 150°C for 5 minutes, then degassed, and subsequently pressed at 150°C for a further 2 minutes. After cooling to room temperature, the plaque was removed from the mold. The resulting plaque was further cut into the shape and size required for Bailey flexion testing and DMS analysis, or into pellets for melt index measurement.

[0087] For samples containing CBA, a first compression-molded film with a thickness of 0.5 mm was prepared, and then this film was foamed in an air-circulating oven at 220°C for 90 seconds to create a foamed plaque for the Bailey flexure test.

[0088] Table 2. Composition and performance of the embodiment (IE) and comparative sample (CS) of the present invention

[0089] [Table 2]

[0090] [Table 3]

[0091] Table 2A shows examples (IE) IE1 to IE6 of the present invention for a top layer composition comprising (i) one or more ethylene polymers and (ii) 12% to 30% by weight of mineral oil. Table 2A also shows comparative samples (CS) CS1 to CS9, which consist of one or more ethylene polymers and not oil. In Table 2A, IE1 to IE6 show that the addition of 12 to 30% by weight of mineral oil to one or more ethylene / C4-C8α-olefin copolymers (up to 100% by weight) in supplementary amounts (88 to 70% by weight) unexpectedly results in a composition having improved Bailey flexure resistance, a Bailey flexure resistance value greater than 86,000, and improved MI, i.e., MI greater than 2.0 g / 10 min. A composition having MI greater than 2.0 g / 10 min is necessary for proper flexure during extrusion or calendering. CS1 to CS9 fail to achieve both a Bailey flexural resistance value exceeding 86,000 and an MI exceeding 2.0. DMS was further used to characterize the fluidity of the examples over a wide shear rate range, as shown in Figure 1. As shown in Figure 1, IE3 has a lower viscosity (i.e., higher fluidity) compared to CS7. Furthermore, IE3 also has a higher Bailey flexural resistance value (100k) compared to CS7 (58k), indicating that adding oil is more effective than blending high MI resins in simultaneously achieving both a good Bailey flexural resistance value (over 86,000) and high fluidity (MI over 2.0 g / 10 min) for processability.

[0092] In Table 2B, IE7-IE8 and CS10 chemical blowing agents were added to compositions to create thin foamed plaques that can be used to mimic the intermediate foam layer of a typical synthetic leather structure. The Bailey flexure resistance values ​​of the foamed plaques with similar expansion ratios (ER) demonstrated that the addition of 10%-30% or 12%-30% by weight of mineral oil maintained the Bailey flexure resistance values ​​compared to foamed plaques without oil. As a result, the addition of 10-30% by weight of oil to the intermediate foam layer composition of synthetic leather can maintain flexure resistance and improve processability (by increasing the MI of the foam composition to more than 2.0 g / 10 min).

[0093] This disclosure is not limited to the embodiments and examples contained herein, but is particularly intended to include modified forms of these embodiments, including some embodiments and combinations of elements of different embodiments, as falling within the scope of the following claims. This application also relates to the following aspects. 〔1〕 Articles, A. The top floor, (i) 70% to 88% by weight of an ethylene-based polymer, (ii) Based on the total weight of the uppermost layer, 12% to 30% by weight of oil, (iii) A composition comprising an optional additive, The sum of (i), (ii), and (iii) amounts to 100% by weight of the top layer, B. Articles including the lowest layer containing textiles. 〔2〕 The ethylene-based polymer is ethylene / C 4 ~C 8 α-olefin copolymer, ethylene / C 4 ~C 8 The article described in (1) above, selected from the group consisting of α-olefin multiblock copolymers and combinations thereof. 〔3〕 The aforementioned ethylene polymer Density of 0.857 g / cc to 0.88 g / cc Melt index for 0.5g / 10 min to 20g / 10 min, and Ethylene / C with a Shore A value of 75 or less 4 ~C 8 The article described in (2) above, which is an α-olefin copolymer. 〔4〕 The aforementioned ethylene polymer Density of 0.857 g / cc to 0.88 g / cc Melt index for 0.5g / 10 min to 20g / 10 min, and Ethylene / C with a Shore A value of 75 or less 4 ~C 8 The article described in (2) above, which is an α-olefin multiblock copolymer. 〔5〕 80% to 87% by weight of the ethylene / C 4 ~C 8 α-olefin copolymer and The oil comprises 13% to 20% by weight, The article according to any one of (1) to (4) above, wherein the uppermost layer has a Bailey flexural resistance value greater than 86,000. 〔6〕 30% to 50% by weight of ethylene / C 4 ~C 8 α-olefin multiblock copolymer and 30% to 50% by weight of ethylene / C 4 ~C 8 α-olefin copolymer and The oil comprises 13% to 30% by weight, The article according to any one of (1) to (4) above, wherein the uppermost layer has a Bailey flexural resistance value greater than 86,000. 〔7〕 The article according to (5) or (6), wherein the composition of the uppermost layer has a melt index of more than 2 g / 10 min to 10 g / 10 min. 〔8〕 The article according to any one of (5) to (7), wherein the uppermost layer of the composition has a Shore A value of less than 80. 〔9〕 C. Intermediate foam layer, (i) Ethylene-based polymers, (ii) An article according to any one of (1) to (8) above, comprising an intermediate foam layer, wherein the intermediate foam layer is composed of a composition comprising 10% to 30% by weight of oil, based on the total weight of the intermediate foam layer. 〔10〕 The article according to (9), wherein the ethylene-based polymer in the intermediate foam layer is selected from the group consisting of ethylene / α-olefin copolymer, ethylene / α-olefin multiblock copolymer, and combinations thereof. 〔11〕 The ethylene-based polymer in the intermediate foam layer is Density of 0.857 g / cc to 0.88 g / cc Melt index for 0.5g / 10 min to 20g / 10 min, and Ethylene / C with a Shore A value of 75 or less 4 ~C 8 The article described in (10) above, which is an α-olefin copolymer. 〔12〕 The ethylene-based polymer in the intermediate foam layer is Density of 0.857 g / cc to 0.88 g / cc Melt index for 0.5g / 10 min to 20g / 10 min, and Ethylene / C with a Shore A value of 75 or less 4 ~C 8 The article described in (10) above, which is an α-olefin multiblock copolymer. 〔13〕 The aforementioned intermediate foam layer 80% to 87% by weight of the ethylene / C 4 ~C 8 α-olefin copolymer and The oil comprises 10% to 20% by weight, The article according to any one of (9) to (12), wherein the intermediate foam layer has a Bailey flexural resistance value of over 60,000. 〔14〕 The aforementioned intermediate foam layer 30% to 50% by weight of ethylene / C 4 ~C 8 α-olefin multiblock copolymer and 30% to 50% by weight of ethylene / C 4 ~C 8 α-olefin copolymer and The oil comprises 10% to 30% by weight, The article according to any one of (9) to (12), wherein the intermediate foam layer has a Bailey flexural resistance value greater than 86,000. 〔15〕 The article according to any one of (1) to (14) above, wherein the oil is mineral oil excluding any other type of oil.

Claims

1. Synthetic leather, A. The top floor, (i) 70% to 88% by weight of an ethylene-based polymer selected from the group consisting of ethylene / octene copolymer, ethylene / octene multiblock copolymer, and combinations thereof, (ii) Based on the total weight of the uppermost layer, 12% to 30% by weight of an oil selected from the group consisting of mineral oil, aromatic oil, naphthenic oil, paraffin oil, triglyceride-based vegetable oil, synthetic hydrocarbon oil, silicone oil, and combinations thereof, (iii) A composition comprising an optional additive, The sum of the amounts of (i), (ii), and (iii) equals 100% by weight of the top layer, B. The bottom layer including textiles, Synthetic leather.

2. The aforementioned ethylene polymer Density of 0.857 g / cc to 0.88 g / cc, Melt index of 0.5g / 10 min to 20g / 10 min, and The synthetic leather according to claim 1, which is an ethylene / octen copolymer having a Shore A value of 75 or less.

3. The aforementioned ethylene polymer Density of 0.857 g / cc to 0.88 g / cc, Melt index of 0.5g / 10 min to 20g / 10 min, and The synthetic leather according to claim 1, which is an ethylene / octene multiblock copolymer having a Shore A value of 75 or less.

4. 80% to 87% by weight of the ethylene-based polymer, The oil comprises 13% to 20% by weight, The synthetic leather according to any one of claims 1 to 3, wherein the uppermost layer has a Bailey flexure resistance value of over 86,000.

5. 30% to 50% by weight of ethylene / octene multiblock copolymer, A 30% to 50% by weight ethylene / octene copolymer different from the aforementioned ethylene / octene multiblock copolymer, The oil comprises 13% to 30% by weight, The synthetic leather according to any one of claims 1 to 3, wherein the uppermost layer has a Bailey flexure resistance value of over 86,000.

6. The synthetic leather according to claim 4 or 5, wherein the composition of the uppermost layer has a melt index of more than 2 g / 10 min to 10 g / 10 min.

7. The synthetic leather according to any one of claims 4 to 6, wherein the composition of the uppermost layer has a Shore A value of less than 80.

8. C. Intermediate foam layer, (i) Ethylene-based polymers and (ii) A synthetic leather according to any one of claims 1 to 7, comprising an intermediate foam layer, wherein the intermediate foam layer is composed of a composition comprising 10% to 30% by weight of oil, based on the total weight of the intermediate foam layer.

9. The synthetic leather according to claim 8, wherein the ethylene-based polymer in the intermediate foam layer is selected from the group consisting of ethylene / octene copolymer, ethylene / octene multiblock copolymer, and combinations thereof.

10. The ethylene-based polymer in the intermediate foam layer is Density of 0.857 g / cc to 0.88 g / cc, Melt index of 0.5g / 10 min to 20g / 10 min, and The synthetic leather according to claim 9, which is an ethylene / octen copolymer having a Shore A value of 75 or less.

11. The ethylene-based polymer in the intermediate foam layer is Density of 0.857 g / cc to 0.88 g / cc, Melt index of 0.5g / 10 min to 20g / 10 min, and The synthetic leather according to claim 9, which is an ethylene / octene multiblock copolymer having a Shore A value of 75 or less.

12. The aforementioned intermediate foam layer 80% to 87% by weight of the ethylene-based polymer, The oil comprises 10% to 20% by weight, The synthetic leather according to any one of claims 8 to 11, wherein the intermediate foam layer has a Bailey flexural resistance value of over 60,000.

13. The aforementioned intermediate foam layer 30% to 50% by weight of ethylene / octene multiblock copolymer, A 30% to 50% by weight ethylene / octene copolymer different from the aforementioned ethylene / octene multiblock copolymer, The oil comprises 10% to 30% by weight, The synthetic leather according to any one of claims 8 to 11, wherein the intermediate foam layer has a Bailey flexural resistance value of over 86,000.

14. The synthetic leather according to any one of claims 1 to 13, wherein the oil is mineral oil.

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