Article having crosslinked foam layer adhered to substrate

Abstract

To provide an article in which a foam (having well-balanced toughness, heat resistance, water resistance and flexibility) is bonded to a hard molded substrate without delamination.SOLUTION: This article comprises a crosslinked foam composition, an adhesive layer, and a substrate comprising an olefin-based polymer. This crosslinked foam composition includes an ethylene / α-olefin multiblock copolymer, an ethylene / propylene / diene terpolymer (EPDM), an optional silicone rubber; an optional blend component selected from an ethylene / α-olefin random copolymer, an ethylene-vinyl acetate copolymer (EVA), a styrene-butadiene block copolymer, a hydrogenated styrene-butadiene block copolymer, and combinations thereof; an optional plasticizer, an optional filler, and an optional additive.SELECTED DRAWING: None

Description

[Background technology]

[0001] A bicycle saddle typically includes two components. The first component is a polypropylene The second component is a supporting substrate made of a rigid molded plastic such as polypropylene (PP). are typically constructed of polyurethane (PU) foam, and PU, polyvinyl chloride (PVC ), or soft padding protected by an artificial leather skin layer composed of other artificial leather materials. The problems with conventional PU foam-based saddles are low toughness and insufficient water resistance. The skin layer for the PU foam exposes the PU foam to the ambient environment. Low puncture resistance. If the skin is broken, the inner PU foam will collapse. PU foam readily absorbs water, resulting in collapse and foam decay.

[0002] Therefore, in the art, there is a need for a material that has a balance of toughness, heat and water resistance, and flexibility. The need for a bicycle saddle foam that can be easily detached without delamination has been recognized. A foam (with a good balance of toughness, heat resistance, water resistance, and flexibility) is bonded to a rigid molding substrate. There is also a recognition of the need for items that can be used to Summary of the Invention

[0003] The present disclosure provides an article, the article comprising a crosslinked foam composition, an adhesive layer, and an olefin The crosslinked foam composition includes a substrate composed of an ethylene / α-olefin polymer. Multiblock copolymer, ethylene / propylene / diene terpolymer (EPDM), Optional silicone rubber; ethylene / α-olefin random copolymer, ethylene-acetate Vinyl acetate copolymer (EVA), styrene-butadiene block copolymer, hydrogenated styrene an optional polymer selected from ethylene-butadiene block copolymers, and combinations thereof; blend components of the formula: . [Brief explanation of the drawings]

[0004] [Figure 1] 1 is a schematic diagram of an article comprising a foam, an adhesive layer, and a substrate according to an embodiment of the present disclosure. [Figure 2a] 1 is a photograph illustrating the cut resistance of foam for articles according to embodiments of the present disclosure. [Figure 2b] 1 is a photograph showing the cut resistance of a prior art polyurethane foam with a polyurethane leather skin.

[0005] definition All references herein to the Periodic Table of the Elements are to CRC Press, Inc. Therefore, the periodic table of elements was published and copyrighted in 2003. Any reference to a group (numbered) refers to that group using the IUPAC system for numbering groups. For the group(s) reflected in the Periodic Table of Elements. Unless otherwise indicated by context or customary in the art, all parts and percentages are used. For purposes of U.S. patent practice, any patents referenced herein, The contents of the patent application or publication are incorporated herein by reference in their entirety ( or their equivalent U.S. versions, which are so incorporated by reference).

[0006] The numerical ranges disclosed in this specification include all values ​​(including boundary values) from the lower limit to the upper limit. Ranges containing explicit values ​​(e.g., ranges of 1, or 2, or 3 to 5, or 6, or 7) range), any subrange between two explicit values ​​is included (for example, the range 1 above). ~7 includes the subranges 1~2, 2~6, 5~7, 3~7, 5~6, etc.).

[0007] Unless otherwise stated to the contrary, implicit from the context, or conventional in the art, Unless otherwise specified, all parts and percentages are by weight and all test methods are within the scope of the present disclosure. It is up to date as of the date.

[0008] As used herein, the term "composition" refers to a mixture of materials that comprises a composition; and reaction and decomposition products formed from the materials of the composition.

[0009] The words "comprising," "including," and "having" The words "additional," "components," and their derivatives are used interchangeably to refer to any additional component, step, or procedure specifically disclosed. It is not intended to exclude their existence, whether or not they exist. To avoid any doubt, the term "comprising" is used to refer to all of the claimed material. All compositions, whether polymeric or otherwise, are intended to be illustrative unless otherwise stated to the contrary. In contrast, "from" may include any additional additive, adjuvant, or compound. The term "essentially consisting" shall not be construed as limiting any following description except as is not essential to operability. The term "consisting of" excludes any other component, step, or procedure from its scope. This excludes any ingredient, step or procedure not delineated or listed in the preceding paragraph.

[0010] Terms such as "elastomer" refer to a material that can be stretched to at least twice its original length. and when the stretching force is released, it contracts very rapidly to nearly its original length. Elastomers are polymers with elastic properties below approximately 10,000 psi (68.95 MPa). and typically 200 in the uncrosslinked state at room temperature using the method of ASTM D638-72 It has an elongation of over %.

[0011] Terms such as "ethylene elastomer" refer to elastomers made up of ethylene-based polymers. Pointing to Ma.

[0012] As used herein, "ethylene-based polymer" refers to a polymer (based on the total amount of polymerizable monomers) that is (based on) greater than 50 weight percent polymerized ethylene monomer, and optionally, It is a polymer that may contain at least one comonomer.

[0013] As used herein, the term "foam" or "foam article" refers to a material made from a polymer. A structure constructed from multiple separate gas particles completely surrounded by a polymer. As used herein, "foam cell" or "cell" refers to a structure containing foam cells. The term "cell" refers to a discrete space within a foam composition. separated by a membrane wall made of a polymer of the composition, or otherwise It is defined as follows.

[0014] As used herein, "olefin-based polymer" or "polyolefin" refers to a polymer that is greater than 50 weight percent polymerized olefin monomers (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer. Non-limiting examples of ethylene-based polymers include ethylene-based polymers and propylene-based polymers. nothing.

[0015] A "polymer" is a group of multiple and / or repeating "units" or "structures" that make up the polymer. units in polymeric form, whether of the same or different types. It is a compound prepared by polymerizing a monomer. The term "polymer" is used to refer to polymers prepared from only one type of monomer. The commonly used term homopolymer refers to a polymer prepared from at least two types of monomers. The term copolymer is commonly used to refer to polymers that are The term "ethylene / copolymer" also includes copolymers of all types, for example, random and block copolymers. The terms "α-olefin polymer" and "propylene / α-olefin polymer" are used interchangeably herein. The copolymers described above prepared by polymerizing ethylene or propylene, respectively, and one or more The polymers often contain additional polymerizable α-olefin monomers. "Based on" the type of mer or monomer, "contains" a specified monomer content Although the term "made from" one or more specified monomers, such as In this context, the term "monomer" refers to the polymerized residue of a specified monomer, not the unpolymerized It should be noted that it is understood that no reference is made to species. Mers are referred to based on the "units" that are the polymerized form of the corresponding monomers.

[0016] "Propylene-based polymers" are 50% by weight (based on the total amount of polymerizable monomers) containing more than one polymerized propylene monomer, and optionally at least one comonomer It is a polymer that may contain

[0017] Test Method The Asker C hardness of the foam structure is 1.0, both before and after lamination. Plaque measuring 5cm (length) x 15cm (width) x 2cm (thickness) conforming to ASTM D22 Each sample was measured at least three times across the entire surface of the sample. The measurements were taken (with a 3-second waiting time between each measurement). The average of the measurements was taken as the Asker C hardness. and recorded it.

[0018] Bond strength was tested according to Dow's internal method. A foam slice having dimensions (length x width x thickness) is cut into an injection molded piece of the same size. The peeling speed was 100 mm / min, and the peeling angle was approximately 120 degrees (plastic sheet). The laminate was tested by a stretching machine at a temperature of at least 300°C (between the foam sheet and the foam slice). The bond strength was recorded as the average of the maximum forces of the three specimens.

[0019] Compression set was measured according to ASTM D395-B. Samples were 19±0 The specimens had a thickness of 0.5 mm, a diameter of 26 ± 0.5 mm, and a deflection of 50%. The incubation was carried out at 3°C ​​for 24 hours and at 50°C for 6 hours.

[0020] Differential Scanning Calorimetry (DSC) Differential scanning calorimetry (DSC) is used to study the melting and freezing of polymers over a wide range of temperatures. Crystallization and glass transition behavior can be measured. A TA Instruments Q2000DSC equipped with a 3D sampler was used to measure this. During the test, a nitrogen purge gas flow rate of 50 mL / min was used. The sample was melt compressed at about 175°C into a thin film, and then the molten sample was cooled to room temperature (about 25°C). The polymer is cooled in air at 40°C. A 3-10 mg, 6 mm diameter specimen is extracted from the cooled polymer and weighed. , placed in a lightweight aluminum pan (approximately 50 mg) and crimped shut. An analysis is performed to determine:

[0021] The thermal behavior of the sample is measured by increasing and decreasing the sample temperature to generate a heat flow vs. temperature profile. First, the sample is rapidly heated to 180°C to remove its thermal history. The sample is then rapidly heated and held isothermally for 3 minutes. The sample is then cooled to -80°C at a rate of 10°C / min. The sample is then cooled to RT and held isothermally at -80°C for 3 minutes. The sample is then heated at a rate of 10°C / min. The temperature is then increased to 180°C (this is the "second heating" gradient). Record the heating curve. Record the cooling curve with a baseline endpoint at -20 °C, where crystallization begins. The heating curve is analyzed by setting a baseline interval from -20°C to the end of melting. The analysis is performed by setting the endpoint. The value obtained is the extrapolated melting onset Tm and extrapolated crystallization onset Tc, heat of fusion (H f ) (joules per gram), as well as The percent crystallinity of the polyethylene sample was calculated using the equation: Crystallinity % = ( (H f ) / 292J / g)×100.

[0022] From the second heating curve, the heat of fusion (H f ) (also known as enthalpy of fusion) and The peak melting temperature and the peak melting temperature are reported.

[0023] The melting point, Tm, is determined by first drawing a baseline between the start and end of the melting transition. It is obtained from the SC heating curve. Then, a tangent line is drawn to the data on the low temperature side of the melting peak. Where the line crosses the baseline is the extrapolated melting onset (Tm). hard Wunderlich,The Basis of Thermal Ana lysis,in Thermal Characterization of Pol ymeric Materials 92,277-278(Edith A.Turi ed.,2d ed.1997).

[0024] The glass transition temperature Tg is calculated by Bernhard Wunderlich, The Basis is of Thermal Analysis,in Thermal Charac terization of Polymeric Materials 92,278 -279 (Edith A. Turi ed., 2d ed. 1997) As can be seen from the DSC heating curve, half of the sample has acquired the heat capacity of a liquid. Baselines are drawn below and above the transition region and extrapolated through the Tg region. The temperature at which the heat capacity is midway between these baselines is the Tg.

[0025] The density of the foam article was measured according to ASTM D-1622-88 and the results were Kilograms per cubic meter (kg / m) at °C 3 ) or per cubic centimeter Report in grams of carbon dioxide (g / cc).

[0026] Polymer density is measured according to ASTM D792 and the results are in g / cc at 25°C. It is reported in.

[0027] Ultimate elongation was measured at a tensile speed of 500 mm / min according to ASTM D638 .

[0028] Melt flow rate (or MFR) measurements (for propylene-based polymers) are Tests are conducted according to ASTM D1238 at 30°C / 2.16 kilogram (kg) weight. Like the melt index, the melt flow rate is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt flow rate, although the relationship is not linear.

[0029] The melt index (MI or I2) (of ethylene-based polymers) is 190°C / 2. Measured according to ASTM D 1238 at 16 kg load, results are in grams per 10 minutes. Reported in grams per 10 minutes.

[0030] Melt viscosity was measured at 177°C (or other specified temperature) using a Brookfield viscometer model and Brookfield RV-DV-II-Pro viscometer using spindle 31 The sample is injected into the chamber, which is then measured using a Brookfield Thermo Insert the sample chamber into the osel and secure it in place. To ensure the chamber does not rotate when rotating, Brookfield The bottom has a notch that fits into the bottom of the Thermosel. Add sample (approximately 8-10 grams of tree root) until the sample is approximately 1 inch below the top of the sample chamber. Heat the viscometer (oil) to the required temperature. Lower the viscometer device and insert the spindle into the sample chamber. Continue lowering until the viscometer bracket is aligned on the Thermosel. Turn on the viscometer and adjust the torque to 40-60 percent of the total torque capacity based on the rpm output of the viscometer. Set the shear rate to operate at a shear rate that gives a torque reading within the range of 1 / 4 of the original value. Take a reading every minute for the duration of the test, or until the reading stabilizes, at which point Record the final reading.

[0031] Rebound is measured according to ASTM D3574. The test piece size is 100mm x 100mm x 100mm. The sample dimensions are 50 mm (width x length x thickness). The average of the median values ​​obtained from the three samples is used as the sample size. The pull is reported as a ball rebound value as a percentage.

[0032] Shore A hardness is measured according to ASTM D2240-05.

[0033] Tensile Strength. The compositions are characterized by their tensile strength at break (in MPa) and elongation at break (% Tensile strength and tensile elongation can be characterized according to ASTM D4703 Compression molded samples prepared according to ASTM D638 test procedure were measured. Elongation at break or Elongation to break is the strain of the sample at break, expressed as a percentage.

[0034] Heat shrinkage is used to measure the heat resistance of foams and is measured using Dow's internal method. The test piece size is 75mm x 75mm x 10mm (width x length x thickness). The mixture was heated in a heating oven at 65°C for 72 hours and at 70°C for 40 minutes, and then cooled to room temperature. Remove for 24 hours conditioning. Measure the sample size after heat treatment. The change in surface area (length x width) is recorded as a percentage of the heat shrinkage value. The average value obtained from the above is reported as the final heat shrinkage value. DETAILED DESCRIPTION OF THE INVENTION

[0035] The present disclosure provides an article, the article comprising a crosslinked foam composition, an adhesive layer, and an olefin The crosslinked foam composition includes a substrate composed of an ethylene / α-olefin polymer. Multiblock copolymer, ethylene / propylene / diene terpolymer (EPDM), Optional silicone rubber; ethylene / α-olefin random copolymer, ethylene-acetate Vinyl acetate copolymer (EVA), styrene-butadiene block copolymer, hydrogenated styrene an optional polymer selected from ethylene-butadiene block copolymers, and combinations thereof; blend components of the formula: .

[0036] A. Crosslinked Foam Composition The article comprises a crosslinked foam composition. As used herein, "crosslinked foam composition" The term refers to (i) ethylene / α-olefin multiblock copolymers, (ii) ethylene / α-olefin multiblock copolymers, (iii) an optional silicone; (iv) ethylene / α-olefin random copolymer, ethylene-vinyl acetate copolymer (EVA), styrene-butadiene block copolymer, hydrogenated styrene-butadiene an optional blend selected from adiene block copolymers, (v) an optional plasticizer; (vi) an optional filler; and (vii) an optional and any of the additives, wherein the foam is crosslinked. As used herein, the term "foamable composition" refers to a foamable article formed from a foamable composition. The term refers to (i) ethylene / α-olefin multiblock copolymers under compounding conditions. (ii) ethylene / propylene / diene terpolymer (EPDM); (iii) optional (iv) ethylene / α-olefin random copolymer, ethylene -Vinyl acetate copolymer (EVA), styrene-butadiene block copolymer, hydrogenated any one selected from styrene-butadiene block copolymers, and combinations thereof; optional blend components; (v) optional plasticizers; (vi) optional fillers; (vii) Mixing optional additives: (viii) crosslinking agents / coagents, and (ix) blowing agents / accelerators. The crosslinked foam composition is a product obtained from a foamable composition that has been subjected to a foaming process. It is a thing.

[0037] The foamable composition (and the resulting crosslinked foam composition) is an ethylene / α-olefin maltose copolymer. "Ethylene / α-olefin multiblock copolymer" includes two-block copolymers. The term refers to the polymerized form of ethylene and one copolymerizable C4-C8 α-olefin comonomer. Ethylene / C4-C8 α-olefin multibromide (and optionally additives) copolymers, which are polymers made of two polymerized monomers with different chemical or physical properties. It is characterized by multiple blocks or segments of mer units, the blocks being linearly joined (or is covalently bonded), i.e., the polymer has terminal ethylene groups to the polymerized ethylenic functional groups. It contains chemically distinct units in which the ends are joined together. Ethylene / α-olefin copolymers Multiblock copolymers are those with two blocks (diblock) and those with more than two blocks ( The C4 to C8 α-olefins include block copolymers having: butene, hexene, and octene. Ethylene / α-olefin multibromide The copolymers may be styrene (i.e., styrene-free), and / or vinyl aromatic monomers. does not contain or otherwise excludes monomers, and / or conjugated dienes. When referring to the amount of "ethylene" or "comonomer" in a polymer, this refers to the amount of polymerized units thereof. In some embodiments, ethylene / α-olefin multiblock copolymers are used. The copolymer can be represented by the following formula: (AB) n In the formula, n is at least Each of the numbers is 1, and preferably an integer greater than 1, for example, 2, 3, 4, 5, 10, 1 5, 20, 30, 40, 50, 60, 70, 80, 90, 100 or more; "A" represents a hard block or segment, and "B" represents a soft block or segment. A and B represent substantially branched or substantially star-shaped configurations. In another embodiment, the A blocks are linked or covalently bonded in a linear or non-linear fashion. The A and B blocks are randomly distributed along the polymer chain. Copolymers typically do not have the following structure: AAA-AA-BBB-BB. In this state, ethylene / α-olefin multiblock copolymers are produced by mixing different comonomers. In another embodiment, each of the blocks A and B does not have a third type of block. Each has monomers or comonomers substantially randomly distributed within the blocks. In other words, both block A and block B have a composition that is substantially different from the remaining blocks. The segment may include two or more sub-segments (or sub-blocks) of distinct composition, such as a tip segment. Not at all.

[0038] In embodiments, the ethylene is an all ethylene / α-olefin multi-block copolymer. ethylene constitutes the majority mole fraction of the total ethylene / α-olefin monomers. More preferably, ethylene constitutes at least 50% by weight of the multiblock copolymer. is an ethylene / α-olefin multiblock copolymer containing C4-C8 α-olefin comonomers. At least 60% by weight, at least 70% by weight, with substantially the remainder of the total copolymer In an embodiment, the ethylene / α-olefin copolymer comprises at least 80% by weight of the ethylene / α-olefin copolymer. The multiblock copolymer may be 50% to 90% by weight of ethylene, or 60% to 85% by weight of % by weight of ethylene, or 65% to 80% by weight of ethylene. In the case of ethylene / octene multiblock copolymers, the composition is the total ethylene / octene multiblock copolymer. The ethylene content of the block copolymer is greater than 80% by weight and the ethylene content of the total multi-block copolymer is greater than 1% by weight. The octene content is between 0% and 15% by weight or between 15% and 20% by weight.

[0039] Ethylene / α-olefin multiblock copolymers are available with varying amounts of "hard" segments. The "hard" segments are those in which ethylene is bonded to the polymer. More than 90% by weight, or 95% by weight, or more than 95% by weight, or 98% by weight, based on the weight of the %, up to 100% by weight. The comonomer content (content of monomers other than ethylene) in a segment is determined by the weight of the polymer. Based on the amount, less than 10% by weight, or less than 5% by weight, or less than 5% by weight, or less than 2% by weight In some embodiments, the hard segments are ethylene. The "soft" segment includes all or substantially all units derived from The monomer content (content of monomers other than ethylene) is 5 times higher than the polymer weight. %, or more than 8 wt. %, or more than 10 wt. %, or more than 15 wt. % of the blocks of polymerized units. In an embodiment, the comonomer content in the soft segment is greater than 20% by weight, greater than 25% by weight. More than 30% by weight, more than 35% by weight, more than 40% by weight, more than 45% by weight, more than 50% by weight, or is more than 60% by weight and can be up to 100% by weight.

[0040] The soft segment is the total weight of the ethylene / α-olefin multiblock copolymer. 1% by weight to 99% by weight of the ethylene / α-olefin multiblock copolymer, or the total 5% to 95% by weight, 10% to 90% by weight, 15% to 85% by weight, 20 Weight% ~ 80% by weight, 25% by weight ~ 75% by weight, 30% by weight ~ 70% by weight, 35% by weight ~ 65 wt%, 40 wt% to 60 wt%, or 45 wt% to 55 wt% of ethylene / α-olefin copolymer Conversely, hard segments may be present in similar multi-block copolymers. The weight percentage of the soft segment and the weight percentage of the hard segment can be in the range. The percentage of the amount can be calculated based on data obtained from DSC or NMR. Such methods and calculations are described, for example, in Colin LPShan, Lonnie Ha Filed on March 15, 2006 in the name of Zlitt et al., and filed with Dow Global Tec "Ethylene / α-Olefin" was transferred to hnologies Inc. U.S. Patent No. 7,608,668 entitled "Block Inter-polymers" No. 6,239,593, the disclosure of which is incorporated herein by reference in its entirety. The weight percent of the hard and soft segments and the comonomer content are as described in U.S. Pat. No. 7,608 This can be determined as described in columns 57 to 63 of Publication No. 668.

[0041] Ethylene / α-olefin multiblock copolymers are linearly bonded (or covalently bonded) ) containing two or more chemically distinct regions or segments (called "blocks"). i.e., to polymerized ethylenic functional groups, rather than pendant or grafted. In embodiments, the bridging group contains chemically distinct units joined end to end. The lock can be determined by the amount or type of comonomer incorporated, the density, the amount of crystallinity, and so on. The crystallite size, type or degree of stereoregularity (isotacticity) that can be attributed to the polymer of the composition regioregular or regioirregular, branched (long chain The amount, uniformity, or any other chemical or physical property of the branched or hyperbranched structure may differ. Interpolymers produced by sequential monomer addition, fluid catalyst, or anionic polymerization techniques Compared to prior art block interpolymers, including ethylene / α-octadecyl copolymers, The olefin multi-block copolymers may, in embodiments, be prepared by mixing the olefin multi-block copolymers with the olefin multi-block copolymers. Due to the effect of the shuttle agent in combination with the catalyst, the polydispersity (PDI or M w / Mn or MWD), polydisperse block length distribution, and / or polydisperse block It is characterized by the distribution of the number of blocks.

[0042] In embodiments, the ethylene / α-olefin multi-block copolymers are produced in a continuous process. Produced in a process of 1.7 to 3.5, or 1.8 to 3, or 1.8 to 2.5, or 1.8 to 2 It has a polydispersity index (Mw / Mn) of 0.2 and is produced in a batch or semi-batch process. When the ethylene / α-olefin multiblock copolymer is It has an Mw / Mn of 1.3 to 3, or 1.4 to 2.5, or 1.4 to 2.

[0043] Furthermore, ethylene / α-olefin multiblock copolymers do not follow a Poisson distribution. It has a PDI (or Mw / Mn) that conforms to the Schultz-Flory distribution. α-olefin multi-block copolymers have polydisperse block distribution and block size This allows for the production of polymers with improved and distinguishable physical properties. The theoretical advantages of polydisperse block distribution are discussed by Potemkin, P Hysical Review E(1998)57(6),pp.6902-6912 , and Dobrynin, J. Chem. Phvs. (1997) 107(21), pp. This has already been modeled and discussed in 9234-9238.

[0044] In embodiments, the ethylene / α-olefin multi-block copolymer comprises a block copolymer. It has the most probable distribution of length.

[0045] In a further embodiment, the ethylene / α-olefin multi-block copolymers of the present disclosure Polymers, especially those made in continuous solution polymerization reactors, have a most probable distribution of block lengths. In one embodiment of the disclosure, the ethylene / α-olefin multi-block copolymer comprises: Defined to have: (A) Mw / Mn of about 1.7 to about 3.5, at least one melting point Tm (in degrees Celsius); and density d (grams / cubic centimeter), the values ​​of Tm and d being related by the following relationship: Tm>-2002.9+4538.5(d)-2422.2(d) 2 Corresponding to; and / or (B) having a Mw / Mn of about 1.7 to about 3.5, a heat of fusion ΔH (J / g), and a maximum D Defined as the temperature difference between the SC peak and the highest crystallization analytical fraction ("CRYSTAF") peak. The values ​​of ΔT and ΔH are related by the following relationship: If ΔH is greater than zero and up to 130 J / g, ΔT>-0.1299ΔH +62.81, If ΔH is greater than 130 J / g, ΔT ≥ 48°C and The CRYSTAF peak was determined using at least 5 percent of the cumulative polymer. If less than 5 percent of the polymer has an identifiable CRYSTAF peak, the CR The YSTAF temperature is 30°C, and / or (C) Measured on compression molded films of ethylene / α-olefin interpolymers It has a strain of 300 percent and an elastic recovery Re (percent) at one cycle, and d (grams / cubic centimeter), and ethylene / α-olefin interpolymer When the polymer is substantially free of crosslinked phases, the values ​​of Re and d satisfy the following relationship: Re>1481-1629(d) and / or (D) Molecular fractions eluting between 40°C and 130°C when fractionated using TREF. However, the fractions tend to be more soluble than comparable random ethylene interpolymer fractions eluting between the same temperatures. and having a molar comonomer content at least 5 percent higher than that of the copolymer, Random ethylene interpolymers such as ethylene / α-olefin copolymers have the same comonomer and are Melt index, density, and other properties within 10 percent of Finn Interpolymer and / or having a Mermol content (based on the whole polymer) (E) Storage modulus G' at 25°C (25°C) and storage modulus G at 100°C G'(100°C) and the ratio of G'(25°C) to G'(100°C) is about 1:1 to about 9: The range is 1.

[0046] The ethylene / α-olefin multi-block copolymer may also have: (F) Molecular fractions eluting at 40°C to 130°C when fractionated using TREF. The fraction has a block index of at least 0.5 and at most 1 and a molecular weight greater than 1.3. characterized by a distribution Mw / Mn, and / or (G) an average block index greater than zero and up to 1.0 and a molecular weight distribution Mw greater than 1.3 / Mn.

[0047] Ethylene / α-olefin multiblock copolymers have the following characteristics (A) to (G): It is understood that a block may have one, some, all, or any combination of the following: The Q index is disclosed in U.S. Pat. No. 7,608,608, which is incorporated herein by reference for that purpose. The characteristics (A) to (G) can be calculated as detailed in No. 668. Analytical methods are described, for example, in U.S. Pat. No. 7,447,493, which is incorporated herein by reference for that purpose. This is disclosed in column 31, line 26 to column 35, line 44 of Patent Application No. 608,668.

[0048] In embodiments, the ethylene / α-olefin multi-block copolymer comprises hard segments. It has a styrene-free polymer containing (i) ethylene and (ii) a soft segment. C4-C8 α-olefins or C8 α-olefins (and optional additives) only and a Mw / Mn of 1.7 to 3.5, at least one melting point Tm (in degrees Celsius), and a density The values ​​of Tm and d are defined as follows: Respond to: Tm>-2002.9+4538.5(d)-2422.2(d) 2 , where density d is 0.850 g / cc, 0.860 g / cc, or 0.870 g / cc~0.875g / cc, or 0.877g / cc, or 0.880g / cc, or 0.890g / cc, and the melting point Tm is 110°C, 115°C, or 120°C to 12 5°C, or 130°C, or 135°C.

[0049] In embodiments, the ethylene / α-olefin multi-block copolymer is an ethylene / α-olefin multi-block copolymer. 1-octene multiblock copolymer (consisting only of ethylene and octene comonomers) ) and have one, some, or all of the following properties: (i) Mw / from 1.7 or 1.8 to 2.2, or 2.5, or 3.5 Mn, and / or (ii) 0.860 g / cc or 0.865 g / cc to 0.870 g / cc; or a density of 0.877 g / cc or 0.880 g / cc, and / or (iii) from 115°C, 118°C, 119°C, or 120°C a melting point Tm of 120°C, or 123°C, or 125°C, and / or (iv) 0.1 g / 10 min or 0.5 g / 10 min to 1.0 g / 10 min, or 2.0g / 10min, 5g / 10min, or 10g / 10min melt index (MI), and / or (v) (based on the total weight of the ethylene / octene multiblock copolymer) 50 to 85% by weight of a soft segment and 40 to 15% by weight of a hard segment, and / or (iv) 10 mol%, 13 mol%, or 14 mol% in the soft segment , or 15 mol % to 16 mol %, or 17 mol %, or 18 mol %, or or less than 19 mol %, or 20 mol % octene, and / or (vii) 0.5 mol %, or 1.0 mol % in the hard segment, or 2.0 mol%, or 3.0 mol% to 4.0 mol%, or 5 mol%, or or 6 mol%, or 7 mol%, or 9 mol% octene, and / or (viii) 300% / min at 21°C when measured in accordance with ASTM D 1708 ‐1 Deformation rate of 50% or 60% to 70%, or 80%, or 90 % Elastic Recovery (Re), and / or (ix) Polydisperse distribution of blocks and polydisperse distribution of block sizes (hereinafter referred to as multiblock The properties of the copolymer are referred to as (i) to (ix).

[0050] In embodiments, the ethylene / α-olefin multi-block copolymer is an ethylene / α-olefin multi-block copolymer. Octene multi-block copolymer. Ethylene / octene multi-block copolymer The Dow Chemical Company (Midland, Michigan) It is sold under the trade name INFUSE™ available from Igan, USA.

[0051] Ethylene / α-olefin multiblock copolymers are incorporated herein by reference. Chain shuttling processes such as those described in incorporated U.S. Pat. No. 7,858,706 Particularly suitable chain shuttling agents and related information can be found in Suitable catalysts are listed in column 19, line 45-46. Suitable cocatalysts are listed in column 46, line 20 to column 51, line 28. The process is described throughout the document, particularly in column 51, paragraph 29. This process is described in lines 54 to 56 of column 54. See U.S. Patent Nos. 7,608,668, 7,893,166, and 7,944. No. 7,793.

[0052] The base ethylene / α-olefin multiblock copolymer is a copolymer of more than one ethylene The polymer may include an olefin / α-olefin multi-block copolymer.

[0053] In embodiments, the ethylene / α-olefin multi-block copolymer is a crosslinked foam. 50% by weight, or 52% by weight, or 54% by weight, or 56% by weight, based on the total weight of the composition % by weight, or 58% to 62% by weight, or 64% by weight, or 66% by weight, or 68% by weight %, or 70% by weight, in the crosslinked foam composition.

[0054] The foamable composition (and the resulting crosslinked foam composition) is an ethylene / propylene / diene Contains terpolymer (EPDM). EPDM) is a polymer that contains a majority weight percent (i.e., greater than 50 weight percent) of units derived from ethylene. a polymer having units derived from a propylene comonomer and units derived from a diene comonomer; EPDM is a polymerized form of ethylene, propylene, and one diene copolymer. It is composed of or otherwise consists of nomomers.

[0055] EPDM terpolymers contain units derived from diene monomers. The diene is a monomer with 6 to 15 units. The hydrocarbon diene may be a conjugated, non-conjugated, straight chain, branched chain, or cyclic hydrocarbon diene having carbon atoms of Non-limiting examples of suitable dienes include 1,4-hexadiene; 1,6-octadiene; 1,7-octadiene; 1,9-decadiene; branched acyclic dienes, e.g., 5-methyl 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,4-hexadiene 1,7-octadiene and mixed isomers of dihydromyricene and dihydroocinene Monocyclic alicyclic dienes, such as 1,3-cyclopentadiene, 1,4-cyclohexadiene cyclohexene, 1,5-cyclooctadiene, and 1,5-cyclododecadiene; and polycyclic alicyclic Fused and bridged ring dienes, such as astetrahydroindene, methyltetrahydroindene dicyclopentadiene, and bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl, and cycloalkylidene norbornenes; For example, 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene Norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene norbornadiene, 5-ethylidene-2-norbornene (ENB), 5-vinylidene -2-norbornene (VNB), 5-methylene-2-norbornene (MNB), dicyclo pentadiene (DCPD); and combinations thereof. Further suitable dienes include Non-limiting examples include 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, octadiene, 5,7-dimethyl-1,6-octadiene, 3,7,11-trimethyl-1, 6,10-octatriene, 6-methyl-1,5-heptadiene, 1,3-butadiene, 1,6-heptadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene Diene, 1,5-cyclododecadiene, bicyclo[2.2.1]hepta-2,5-diene (norbornadiene), tetracyclododecene, butadiene, dicyclopentadiene, bicyclopentadiene Nylnorbornene, mixed isomers of dihydromyricene and dihydroocinene, tetrahydro Indene, methyltetrahydroindene, 5-propenyl-2-norbornene, 5-isopropyl Propylene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-Cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and Examples include combinations of these.

[0056] EPDM terpolymer is 40% by weight to 80% by weight, or 60% by weight to 80% by weight, or 65% by weight to 75% by weight of ethylene, 0.2% by weight to 1.5% by weight, or 0 0.3 wt.% to 0.8 wt.%, or 0.4 to 0.7 wt.%, the diene content being ENB, and weight percents are based on the total weight of the EPDM terpolymer. - Polymers have a density of 0.865g / cc to 0.885g / cc and a Mooney of 15 to 25 The EPDM terpolymer has a viscosity of 125°C, ML1+4. is present in the crosslinked foam composition in an amount of 16% to 36% by weight based on the total weight of the composition.

[0057] In an embodiment, the EPDM terpolymer is an ethylene / propylene / ENB terpolymer. and has one, some, or all of the following properties: (i) 0.860g / cc~0.890g / cc or 0.865g / cc~0. a density of 885 g / cc, and / or (ii) a Mooney viscosity (1 25°C, ML1+4), and / or (iii) 45% to 80% by weight, or 60% to 80% by weight, or 6 an ethylene content of 0% to 75% by weight, or 65% to 75% by weight, and / or (iv) 0.2% by weight to 9.5% by weight, or 0.3% by weight to 8.0% by weight, or 0.4% to 6.0% by weight, or 0.4% to 5.0% by weight, or 0. 4% by weight to 3.5% by weight, or 0.4% by weight to 2% by weight, or 0.4% by weight to 1 % by weight, or 0.2% by weight to 1.5% by weight, or 0.3% by weight to 0.9% by weight, or 0.3 wt.% to 0.7 wt.% ENB content, where the weight percentage is EPD M based on the total weight of the terpolymer (hereafter referred to as EPDM properties (i) to (iv)).

[0058] Non-limiting examples of suitable EPDM terpolymers include The Dow Chemical The NORDEL™ IP3720P is available from the Company.

[0059] The crosslinked foam composition includes an optional silicone rubber. When silicone rubber is present, the silicone rubber may be a polysiloxane, polydimethylsiloxane, or the like. The silicone rubber is selected from the group consisting of 1.00g / cc to 1 The crosslinked foam composition has a density of 0.20 g / cc and a Shore A hardness of 40 to 65. from 0 wt. %, or 0 wt. %, or 2 wt. %, based on the total weight of the bridge foam composition; or more than 4% by weight, up to 7% by weight, or 9% by weight, or 11% by weight Contains carbon rubber.

[0060] In embodiments, the silicone rubber may have one, some, or all of the following properties: Having: (i) 1.00 g / cc, or 1.04 g / cc, or 1.08 g / cc; or 1.12 g / cc to 1.16 g / cc, or 1.18 g / cc, or Density up to 1.20 g / cc, and / or (ii) 40, or 45, or 50 to 55, or 60, or 65 Shore A hardness up to (hereinafter referred to as SiR characteristics (i) to (ii)).

[0061] Non-limiting examples of suitable silicone rubbers include those available from The Dow Chemical Co. The compound is XIAMETER™ RBB-2003-50 available from the company.

[0062] The crosslinked composition includes optional blend components. When present, the blend components are ethylene / α-olefin random copolymer, ethylene -Vinyl acetate copolymer, styrene-butadiene block copolymer, hydrogenated styrene- butadiene block copolymers, and combinations thereof.

[0063] In an embodiment, the blend component is an ethylene / α-olefin random copolymer. Ethylene / α-olefin random copolymers are polymerized together to form the individual repeating units. are present in a random or statistical distribution in the polymer chain, forming a polymer of ethylene and one or more α-olefin monomers. The foam composition may comprise from 0 wt. % to more than 0 wt. % based on the total weight of the crosslinked foam composition. , or more than 10 wt.%, or more than 20 wt.%, or more than 30 wt.%, to 40 wt.% %, or 50% by weight, or 60% by weight, or 70% by weight of ethylene / α-olefin Contains a random copolymer.

[0064] Non-limiting examples of suitable ethylene / α-olefin random copolymers include those listed in The D ENGAGE™ trade name available from Now Chemical Company It is a polyolefin elastomer sold by

[0065] In an embodiment, the blend component is an ethylene-vinyl acetate copolymer. - Vinyl acetate copolymer is composed of ethylene and vinyl acetate in polymerized form or The crosslinked foam composition is a crosslinked foam composition. from 0% by weight, or more than 0% by weight, or more than 10% by weight, or From more than 20% by weight, or more than 30% by weight, to 40% by weight, or 50% by weight, or 60% by weight %, or up to 70% by weight of ethylene-vinyl acetate copolymer.

[0066] In an embodiment, the blend component is a styrene-butadiene block copolymer. The styrene block copolymers are composed of at least one block segment of butadiene comonomer. having at least one block segment of styrene monomer in combination with The presence of styrene-butadiene block copolymer in the foam composition In this case, the styrene-butadiene block copolymer is styrene / butadiene / styrene. Block copolymer (SBS), α-methylstyrene / butadiene / α-methylstyrene Block copolymer (mSBmS), α-methylstyrene / butadiene / styrene block copolymer copolymer, styrene / butadiene / styrene / butadiene / styrene block copolymer The crosslinked foam composition is selected from the group consisting of crosslinked styrenesulfonic acid (SBSBS), ... and combinations thereof. From 0 wt. % or more than 0 wt. %, or more than 10 wt. % based on the total weight of the foam composition or more than 20% by weight, or more than 30% by weight, to 40% by weight, or 50% by weight, or contains up to 60% or 70% by weight of styrene-butadiene block copolymer Has.

[0067] In an embodiment, the blend component is a hydrogenated styrene-butadiene block copolymer. Hydrogenated styrene-butadiene block copolymer is a styrene-butadiene block copolymer. At least 90% of the double bonds present in the styrene block of the copolymer are hydrogenated. at least 95% of the double bonds present in the butadiene block are saturated or % is a hydrogenated or saturated copolymer. From 0 wt. % or greater than 0 wt. % or 10 wt. % based on the total weight of the foam composition or more than 20% by weight, or more than 30% by weight, to 40% by weight, or 50% by weight, or up to 60% by weight, or up to 70% by weight of hydrogenated styrene-butadiene block copolymer It contains mers.

[0068] The crosslinked foam composition includes an optional plasticizer. In this case, the plasticizer is aromatic oil, mineral oil, naphthenic oil, paraffinic oil, triglyceride-based vegetable oil. The crosslinked foaming agent is selected from the group consisting of oils, synthetic hydrocarbon oils, silicone oils, and combinations thereof. The foam composition may contain from 0% by weight to more than 0% by weight, or less than 10% by weight, based on the total weight of the crosslinked foam composition. or more than 5% by weight, or more than 10% by weight, or more than 15% by weight, to 20% by weight, or contains plasticizer in an amount of up to 25% or 30% by weight.

[0069] In embodiments, the plasticizer is mineral oil and is present in an amount of 0 wt. % based on the total weight of the crosslinked foam composition. or more than 5% by weight, or more than 10% by weight, or more than 15% by weight to 20% by weight, or It is present in an amount up to 25% or 30% by weight.

[0070] A non-limiting example of a suitable mineral oil is SUNPAR, available from Sunoco Inc. (trademark) 2280.

[0071] The crosslinked foam composition includes an optional filler. In this case, the filler is talc, silicon dioxide (SiO2), calcium carbonate (CaCO3 ), mica, glass fiber, carbon black (CB), and combinations thereof. The crosslinked foam composition may contain from 0 wt. % or more of the polyisoprene copolymer, based on the total weight of the crosslinked foam composition. greater than 0% by weight, or greater than 1% by weight, or greater than 2% by weight, or greater than 3% by weight, or from more than 4% by weight to 5% by weight, or 6% by weight, or 7% by weight, or 8% by weight; or up to 9% by weight, or up to 20% by weight of filler.

[0072] In an embodiment, the filler is talc and is present in an amount of 0.05 wt., based on the total weight of the crosslinked foam composition. More than 20% by weight, or 1% to 9% by weight, or 2% to 7% by weight, or 3% by weight % to 6% by weight, or 4% to 5% by weight.

[0073] The crosslinked foam composition includes optional additives. If additives are present, suitable additives Non-limiting examples of agents include pigments (carbon black, titanium dioxide), antioxidants, acid scavengers, UV stabilizers (e.g., N,N'-bisformyl-N,N'-bis(2,2,6 ,6-tetramethyl-4-piperidinyl)-hexamethylenediamine and other hindered light stabilizers), flame retardants, processing aids, extrusion aids, antistatic agents, UV inhibitors, colorants, and In embodiments, the additives include processing aids, UV inhibitors, colorants, and combinations thereof. coloring agents, and combinations thereof.

[0074] In embodiments, the additives may range from 0 wt. % or is more than 0% by weight, or more than 1% by weight, or more than 2% by weight, or more than 3% by weight, to 4 % by weight, or 5% by weight, or 6% by weight, or 7% by weight, or 8% by weight, or up to 9% by weight is present in the crosslinked foam composition in an amount of

[0075] In embodiments, the additives include processing aids, UV inhibitors, colorants, and combinations thereof. and is selected from 0 wt % to 9 wt %, or 0 wt %, based on the total weight of the crosslinked foam composition. % to 9% by weight, or 1% to 8% by weight, or 2% to 7% by weight, or 2% to 6% by weight % by weight, or 3% to 6% by weight, or 3% to 5% by weight, or 2% to 4% by weight exists in quantity.

[0076] In embodiments, the additives in the crosslinked foam composition are present in an amount of about 100% by weight based on the total weight of the crosslinked foam composition. hand, (i) 0.3 wt% to 5.0 wt% polyethylene glycol (PEG), (ii) 0.5 wt% to 5.0 wt% TiO2; (iii) 0.3 to 5.0 wt. % of a color masterbatch (MB); Includes:

[0077] In embodiments, the additives in the crosslinked foam composition are present in an amount of about 100% by weight based on the total weight of the crosslinked foam composition. hand, (i) 0.5% to 2.0% by weight of polyethylene glycol (PEG); (ii) 1.0 wt% to 5.0 wt% TiO2; (iii) 0.5 to 2.0 wt. % of a color masterbatch (MB); Includes:

[0078] Non-limiting examples of suitable additives include those available from The Dow Chemical Company Polyethylene Glycol 8000, available from The Chemours Com TiO2 available from the Company and Cabot Corporation It is a highly functional carbon black.

[0079] The foamable composition includes a blowing agent. In embodiments, the blowing agent is a chemical blowing agent. The blowing agent generates one or more physical blowing agents by thermal decomposition during the foaming process. Swelling agents include sodium bicarbonate, sodium borohydride, azodicarbonamide, Azodiisobutyronitrile, Barium azodicarboxylate, N,N'-dimethyl-N,N '-Dinitrosoterephthalamide, and benzenesulfonhydrazide, 4,4-oxybenzyl Benzenesulfonyl semicarbazide, 4,4'-oxybis(benzenesulfonic acid) dihydroxide azide, and p-toluenesulfonylsemicarbazide, trihydrazinotriazine, and Mixtures such as (but not limited to) citric acid and sodium bicarbonate do not have).

[0080] In an embodiment, the chemical expanding agent is azodicarbonamide.

[0081] In embodiments, the additives in the foamable composition include: (i) 0.3% to 3.0% by weight of polyethylene glycol (PEG); (ii) 0.5 wt% to 5.0 wt% TiO2; (iii) 0.3 wt% to 5.0 wt% of a color masterbatch (MB); (iv) 0.5 wt% to 5.0 wt% azodicarbonamide, (v) 0.05% by weight to 0.5% by weight of 1,3,5-triallyl-1,3,5-tri Azine-2,4,6(1H,3H,5H)-trione (TAIC), (vi) 0.3% by weight to 1.5% by weight of bis(tert-butyldioxyisopropyl) Benzene (BIPB), (vii) 0.3 wt% to 1.5 wt% zinc oxide (ZnO); (viii) 0.1% to 0.7% by weight of stearic acid; (ix) 0.1 to 0.7 wt. % zinc stearate, Includes:

[0082] In embodiments, the additives in the foamable composition include: (i) 0.5% to 2.0% by weight of polyethylene glycol (PEG); (ii) 1.0 wt% to 3.0 wt% TiO2; (iii) 0.5 wt% to 2.0 wt% of a color masterbatch (MB); (iv) 1.0 wt% to 2.5 wt% azodicarbonamide, (v) 0.05% by weight to 0.3% by weight of 1,3,5-triallyl-1,3,5-tri Azine-2,4,6(1H,3H,5H)-trione (TAIC), (vi) 0.6% by weight to 1.0% by weight of bis(tert-butyldioxyisopropyl) Benzene (BIPB), (vii) 0.6 wt% to 1.2 wt% zinc oxide (ZnO); (viii) 0.3% to 0.6% by weight of stearic acid; (ix) 0.3% to 0.6% by weight of zinc stearate; Includes:

[0083] A foamable composition ((i) an ethylene / α-olefin multiblock copolymer, (ii) ) ethylene / propylene / diene terpolymer (EPDM), (iii) optional silicone Corn rubber, (iv) ethylene / α-olefin random copolymer, ethylene-vinyl acetate Ethylene vinyl copolymer (EVA), styrene-butadiene block copolymer, hydrogenated styrene -butadiene block copolymers, and combinations thereof. (v) optional plasticizer; (vi) optional filler; (vii) optional (viii) crosslinking agents / coagents, and (ix) blowing agents / accelerators) in the foaming process. The foamable composition is melt-mixed in an internal mixer to dissolve the polymer. The crosslinking agent / coagent, blowing agent / accelerator, filler, and additives are blended into the molten mixture. The molten mixture is then crushed in a roll mill for further mixing and then fed into an extruder. Pellets are prepared. The pellets are poured into an injection mold. The compound is then completely injected into the mold. After hardening, the mold is quickly opened, thereby reducing the pressure within the mold and releasing the melt mixture. The crosslinked foam is formed by inducing expansion of the foamable composition. or else formed from it.

[0084] In embodiments, the crosslinked foam composition comprises: (A) 50% by weight to 70% by weight or 55% by weight to 65% by weight of ethylene / α-olefin multiblock copolymers (having multiblock properties (i) to (ix)), (B) 16% by weight to 36% by weight or 20% by weight to 30% by weight of EPDM (EPDM specific) having properties (i) to (iv) (C) 0% by weight, or 2% by weight to 12% by weight, or 5% by weight to 10% by weight of silicone rubber (having SiR properties (i) to (ii)); (D) 0% by weight, or 10% by weight to 70% by weight, or 30% by weight to 50% by weight Styrene / α-olefin random copolymer, ethylene-vinyl acetate copolymer, styrene styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, and combinations thereof; (E) 0% by weight, or 5% by weight to 30% by weight, or 10% by weight to 20% by weight of a plasticizer , (F) 0% by weight, or 1% by weight to 20% by weight, or 3% by weight to 9% by weight of a filler, and and (G) 0% by weight or 1% by weight to 9% by weight of an additive, and The total amount of the crosslinked foam composition is 100% by weight, and the crosslinked foam composition has the following characteristics: Having one, some, or all of the following: (i) 0.10g / cc to 0.30g / cc, or 0.15g / cc to 0.2 Density of 0 g / cc, and / or (ii) 20 to 40 degrees, or 25 to 38 degrees, or 32 to 38 degrees, or or Asker C hardness of 34 to 38 degrees, and / or (iii) 1.0 MPa to 3.0 MPa, or 1.5 MPa to 2.0 MPa, Or tensile strength of 1.0MPa to 1.8MPa, or 1.2MPa to 1.6MPa and / or (iv) 300% to 600%, or 400% to 500%, or 400% or more 600%, or 450% to 550% ultimate elongation, and / or (v) 50% to 75%, or 60% to 70%, or 63% to 67% rebound and / or (vi) 23°C / 24 hours: 5% to 25%, or 10% to 25%, or 1 Compression set of 5% to 20%, and / or (vii) 3% to 10% or 4% to 7% heat shrinkage at 65°C / 72 hours (hereinafter, (hereinafter referred to as Foam 1).

[0085] B. Adhesive layer The article includes an adhesive layer. As used herein, the term "adhesive layer" refers to a crosslinked a layer positioned between the crosslinked foam composition and the substrate, the adhesive layer being The adhesive layer is made of (i) an ethylene elastomer, (ii) a tacky adhesive, and and (iii) a wax.

[0086] The adhesive layer includes an ethylene elastomer. The ethylene elastomer is an ethylene-α -Different from olefin multi-block copolymers. Ethylene elastomers are polymerized in of ethylene and one copolymerizable α-olefin comonomer or polar comonomer The α-olefin comonomer may be butene, The polar comonomer is selected from vinyl acetate, methyl acetate, hexene, and octene. Ethyl acetate, butyl acetate, acrylic acid, methylacrylic acid, maleic anhydride monoester and combinations thereof.

[0087] In an embodiment, the ethylene elastomer is an ethylene / octene copolymer, Possess one, some, or all of the following characteristics: (i) 0.850g / cc to 0.895g / cc, or 0.860g / cc to 0 Density between 0.885g / cc or 0.865g / cc and 0.875g / cc, and / or teeth (vi) Melting at 50°C to 90°C, or 60°C to 80°C, or 65°C to 75°C temperature Tm, and / or (iii) 1,000 mPa·s to 50,000 mPa·s, or 5,000 m Pa·s to 30,000mPa·s, or 10,000mPa·s to 20,000m Melt viscosity (at 177°C) in Pa·s (hereafter referred to as elastomer properties (i) to (iii)) ).

[0088] In an embodiment, the ethylene elastomer is an ethylene / vinyl acetate copolymer; Possess one, some, or all of the following characteristics: (i) 0.930g / cc~0.970g / cc or 0.940g / cc~0. a density of 960 g / cc, and / or (ii) a melting temperature Tm of 45°C to 100°C or 55°C to 90°C, and / or (iii) 1,000 mPa·s to 50,000 mPa·s or 10,000 m Melt viscosity (at 177°C) of Pa·s to 40,000 mPa·s (hereafter referred to as elastomer) -Characteristics (iv)~(vi)).

[0089] Non-limiting examples of suitable ethylene elastomers include The Dow Chemical AFFINITY™ GA 1950 and E available from Cal Company LVAX™ 210W is an example.

[0090] The adhesive layer includes a tackifier. Non-limiting examples of suitable tackifiers include: (1) Natural and modified rosins (e.g., gum rosin, wood rosin, tall oil rosin, distilled rosin) , hydrogenated rosin, dimerized rosin, and polymerized rosin), (2) glycerols of natural and modified rosins ol and pentaerythritol esters (e.g., glycerol from pale wood rosin) Esters, glycerol esters of hydrogenated rosin, glycerol esters of polymerized rosin, Pentaerythritol ester of hydrogenated rosin and phenol-modified pentaerythritol ester of rosin thritol esters), (3) copolymers and terpolymers of natural terpenes (e.g., sucralose, (4) Polyterpene resin and hydrogen (5) phenol-modified terpene resins and their hydrogenated derivatives (e.g., , a resin product obtained from the condensation of a bicyclic terpene with a phenol in an acidic medium), (6 ) Aliphatic or alicyclic hydrocarbon resins and their hydrogenated derivatives (e.g., mainly olefins and diolefins) (7) resins obtained by polymerization of olefin-based monomers, and (8) aromatic hydrocarbon resins. (8) Aromatically modified aliphatic or alicyclic hydrocarbon resins and their hydrogenated derivatives Derivatives, as well as combinations thereof.

[0091] In embodiments, the tackifier is a hydrogenated alicyclic hydrocarbon resin having the following properties: Having one, some, or all of: (i) 400 g / mol, or 500 g / mol, or 570 g / mol, or 600g / mol, or 620g / mol, or 650g / mol 690g / mol, or 720g / mol, or 770g / mol, or 1 Mw of 1000 g / mol, or 1200 g / mol, or 1500 g / mol; and / or (ii) 200 mPa·s, or 400 mPa·s, or 700 mPa·s , or 750 mPa·s to 850 mPa·s, or 900 mPa·s, or is a melt viscosity at 160°C of 1500 mPa·s or 2000 mPa·s (hereafter , tackifier properties (i)~(ii)).

[0092] Non-limiting examples of suitable tackifiers include ExxonMobil Chemical C The preferred acrylic acid ester is Escorez™ 5400 available from the company Escorez.

[0093] The adhesive layer comprises a wax. Non-limiting examples of suitable waxes include propylene glycol, propylene glycol acrylate ... Polymer wax, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, oxidized Fischer-Tropsch wax, and hydro These include functionalized waxes such as roxystearamide wax and fatty acid amide wax. do.

[0094] In an embodiment, the wax is a Fischer-Tropsch wax having the following properties: Having one, some, or all of the following: (i) a freezing point of 80°C or 90°C to 100°C or 120°C, and / or or (ii) 1 mPa·s, or 5 mPa·s, or 7 mPa·s to 10 m Pa·s, or 20mPa·s, or 40mPa·s, or 50mPa·s or Brookfield viscosity at 135°C up to 100 mPa·s, and / or teeth (iii) 1 mPa·s to 100 mPa·s, or 5 mPa·s to 20 mPa·s s, or 6 mPa·s to 10 mPa·s melt viscosity at 135°C (hereinafter referred to as wax) characteristics (i) to (iii)).

[0095] A non-limiting example of a suitable wax is Sasolwax H available from Sasol It is 1.

[0096] In an embodiment, the adhesive layer comprises: (A) 20% by weight to 60% by weight, or 30% by weight to 50% by weight, or 35% by weight to 4 5% by weight of ethylene elastomer (elastomer properties (i) to (iii) or elastomer (iv) to (vi) (B) 20% by weight to 60% by weight, or 30% by weight to 50% by weight, or 35% by weight to 4 a tackifier (having tackifier properties (i) to (ii)) in an amount of 5 wt. %; and (C) 5% by weight to 30% by weight, or 5% by weight to 25% by weight, or 10% by weight to 25% by weight % by weight of wax, where the weight percent is based on the total weight of the adhesive layer ( It has wax properties (i) to (iii) (hereinafter referred to as Adhesive 1).

[0097] C. Base material The article includes a substrate. The substrate may be an olefin-based polymer, an engineering plastic, or the like. The olefin polymer is composed of a component selected from the group consisting of olefins, ... , an ethylene-based polymer or a propylene-based polymer.

[0098] In embodiments, the olefin-based polymer is a propylene impact copolymer. Ethylene / propylene impact copolymer is a rubber with separate domains of ethylene / propylene copolymer. The phase (or discontinuous phase) is distributed throughout the matrix phase (or continuous phase) of propylene homopolymer. Propylene impact copolymer is a two-phase polymer in which propylene impact copolymer is dispersed. 0.1 wt % to 15 wt %, or 0.5 wt % to 10 wt %, based on the total weight of the copolymer % by weight, or 3% to 8% by weight of an ethylene / propylene rubber phase.

[0099] In embodiments, the propylene impact copolymer has one or more of the following properties: or have all of: (i) 1% by weight to 10% by weight or 3% by weight to 8% by weight of ethylene / propylene glycol Mu phase, and / or (ii) 0.89g / cc to 0.92g / cc or 0.89g / cc to 0.91 density in g / cc, and / or (iii) 0.5g / 10min to 5.0g / 10min, or 0.5g / 10min to 3. MFR of 5g / 10min or 0.5g / 10min to 1.0g / 10min.

[0100] Non-limiting examples of suitable propylene impact copolymers include SINOPEC Yans K8303 available from Han Petrochemical Company .

[0101] In embodiments, the substrate is an engineering plastic. "Engineering plastics" are acrylonitrile-butadiene-styrene (AB S) copolymers, high impact polystyrene (HIPS) copolymers, and combinations thereof The polymer material is selected from the group consisting of:

[0102] D.Goods The article comprises (A) a crosslinked foam composition, (B) an adhesive layer, and (C) a substrate. The adhesive layer bonds the crosslinked foam composition to the substrate.

[0103] In an embodiment, the article comprises: (C) a substrate comprised of an impact propylene copolymer; (B) adhesive layer of Adhesive 1, which is in direct contact with (A) foam 1 frame, which is in direct contact with (B) adhesive layer of Adhesive 1. a bridge foam composition.

[0104] In an embodiment, the article comprises: (1) A crosslinked foam composition, (A) 50% by weight to 70% by weight or 55% by weight to 65% by weight of ethylene / α-olefin multiblock copolymers (having multiblock properties (i) to (ix)), (B) 16% by weight to 36% by weight or 20% by weight to 30% by weight of EPDM (EPDM specific) having properties (i) to (iv) (C) 5% by weight to 10% by weight of silicone rubber (SiR) having properties (i) to (ii) ( (F) 3% to 9% by weight of a filler, and (G) 1% to 5.0% by weight of (i) polyethylene glycol (PEG), (i (iii) an additive selected from the group consisting of a color masterbatch (MB); Including, Components (A), (B), (C), (F), and (G) together account for 100% by weight of crosslinking. The foam composition will have the following properties: (i) 0.10g / cc to 0.30g / cc, or 0.15g / cc to 0.2 Density of 0 g / cc, and / or (ii) 20 to 40 degrees, or 25 to 38 degrees, or 32 to 38 degrees, or or Asker C hardness of 34 to 38 degrees, and / or (iii) 1.0 MPa to 3.0 MPa, or 1.5 MPa to 2.0 MPa, Or tensile strength of 1.0MPa to 1.8MPa, or 1.2MPa to 1.6MPa and / or (iv) 300% to 600%, or 400% to 500%, or 400% or more 600%, or 450% to 550% ultimate elongation, and / or (v) 50% to 75%, or 60% to 70%, or 63% to 67% rebound and / or (vi) 23°C / 24 hours: 5% to 25%, or 10% to 25%, or 1 Compression set of 5% to 20%, and / or (vii) One of the following: 3% to 10% or 4% to 7% thermal shrinkage at 65°C / 72 hours a crosslinked foam composition having one, some, or all of the (2) an adhesive layer, (A) ethylene elastomer in an amount of 30% by weight to 50% by weight or 35% by weight to 45% by weight Elastomer (elastomer properties (i) to (iii) or elastomer properties (iv) to (vi) have), (B) a tackifier (adhesive) in an amount of 30% by weight to 50% by weight or 35% by weight to 45% by weight having the properties (i) to (ii) of the additive; and (C) wax in an amount of 5% by weight to 25% by weight or 10% by weight to 25% by weight (wax (having properties (i) to (iii)), and the sum of components (A), (B), and (C) an adhesive layer, which becomes a 100% adhesive layer by weight when (3) a substrate comprising a propylene impact copolymer; Including, The item has a strength of more than 113N / 30mm to 133N / 30mm or 120N / 30mm to 130N / 30mm, or over 120N / 30mm to 125N / 30mm It has strength.

[0105] In embodiments, the article is a bicycle saddle, a moped seat, a motorcycle seat, Other outdoor seating (for boats, wagons, strollers, dollies, trailers, etc.), outdoor furniture and any combination thereof.

[0106] By way of example and not limitation, some embodiments of the present disclosure are illustrated in the following examples. This will be explained in detail. [Example]

[0107] Preparation of the crosslinked foam composition, adhesive layer, and substrate in the examples of the present invention ("IE") The raw materials used in the preparation are provided in Table 1 below.

[0108] [Table 1]

[0109] 1. Foam Preparation (1) Formulation: The ingredients were added to the mixer in the following order: INFUSE™ 9507 (ethylene / octene multiblock copolymer), NORDEL™ 3720P (EPDM) , and XIAMETER RBB-2003-50 (silicone rubber), followed by ZnO , ZnSt, and talc (filler). Ethylene / octene multiblock copolymer, E After the PDM and silicone rubber are melted, a peroxide / blowing agent is added to form the foamable composition. The total mixing time was 10-15 minutes, with the melt temperature controlled below 130°C. The rotor speed was 30-50 rpm. The resulting batch was then mixed in a two-roll mill. Drip quickly onto the mill to thoroughly remove any ingredients remaining on the surface as they drip from the mixer. The roll mill was set at 80-120°C and 7-8 rpm. The compound is dropped into a single screw extruder connected to a pelletizer to produce pellets for compression or injection molding. A let was created.

[0110] (2) Foaming Pellets (of the foamable composition) are injected into an injection molding machine with the screw temperature set to 110°C. The molten pellets were then injected into a mold set at a temperature of 175°C. The mold was then opened and the bun foam (this crosslinked foam composite) was removed. Using different mold designs, foams with various shapes (foamed foam) were obtained. The foamable compositions (body slab, foam saddle pad) were produced. The formulations of the foamable compositions are provided in Table 2A below. The formulation of the resulting crosslinked foam composition in the form of a crosslinked foam pad is provided below in Table 2B. do.

[0111] [Table 2]

[0112] [Table 3]

[0113] 2. Heat resistance / heat shrinkage Heat resistance of the crosslinked foam composition when treated under various heat conditions (65°C and 70°C) The heat shrinkage is listed in Table 2B. Table 2B shows a sample with a heat shrinkage of 5.4% at 65°C for 72 hours (h). The crosslinked foam composition has a heat shrinkage resistance of less than 8% at 65°C / 72 hours. Meets general industry standards (foam saddles).

[0114] 3. Substrate Preparation A substrate made of a propylene impact copolymer having a designed structure was applied to the substrate. The resin was produced by an injection molding process using a screw temperature of 20°C and a mold temperature of 23°C. .

[0115] 4. Preparation of Adhesive Layer Affinity GA 1950 or Elvax 210W (ethylene elastomer) ), Escorez 5400 (tackifier), and Sasolwax H1 (wax) The mixture was weighed into an iron container and preheated in an oven at 177°C for 1 hour. Mix the ingredients in the container at 177°C using a Paravisc-style mixer head. Mixed in a heat block for 30 minutes. The adhesive formulation is provided in Table 3 below.

[0116] [Table 4]

[0117] 5. Fabrication of Foam / Adhesive Layer / Substrate Article During the assembly process, adhesive formulation 1 or 2 is completely melted (above 160°C). temperature), and then directly onto the surface of a propylene impact copolymer substrate without surface pretreatment. A crosslinked foam composition (from Table 2B) in the form of a foam pad was applied to the adhesive formulation. (A) a crosslinked foam composition layer, (B) an adhesive layer, and (C) a crosslinked foam composition layer. C) An article composed of the substrate was formed. The article was set at 100 to 140°C (from the inlet to the outlet). The article was subjected to a high temperature oven line equipped with a multi-stage heating unit for 30 minutes. This process causes the foam pad to shrink slightly. A schematic diagram of the article is shown in FIG. The article is referred to as having a crosslinked foam composition / adhesive / substrate layer.

[0118] 6. Properties of Articles Having Crosslinked Foam Composition / Adhesive / Substrate Layers Heat absorption resistance PU foam saddle (comparative sample ("CS")) and crosslinked foam / adhesive / of the present invention The heat absorption resistance of the foam saddles with the substrate layer structure was tested as shown in Table 4 below. The sample is a black PU foam saddle and is designated as CS-1. IE-1 is a A black foam saddle containing article having a crosslinked foam composition / adhesive / substrate layer. 2 is a white foam saddle containing article having the crosslinked foam composition of the present invention / adhesive / substrate layer is.

[0119] [Table 5]

[0120] Table 4 shows the surface of CS-1, IE-1, and IE-2 after exposure to sunlight for a certain period of time. The temperature is shown in Figure 1. White foam containing article having a crosslinked foam composition of the present invention / adhesive / substrate layer The saddle (IE-2) was exposed to sunlight at an ambient temperature of 34°C for 2 hours, and the PU foam ( The surface temperature was up to 8°C lower than that of the adhesive (CS-1). / The black foam saddle (IE-1) containing the article having the substrate layer was exposed to sunlight at an environmental temperature of 36°C. After 2 hours under light, the surface temperature was at least 5°C lower than that of the PU foam (CS-1). showed.

[0121] 7. Water resistance of articles having the crosslinked foam composition of the present invention / adhesive / substrate layer The crosslinked foam composition of the crosslinked foam composition / adhesive / substrate layer article of the present invention is unique It has an open-cell structure and is water-resistant. PU foam has an open-cell structure and is generally polymeric in nature. It is water-based.

[0122] Cut resistance of the foam of the present invention An article having a crosslinked foam composition / adhesive / substrate layer of the present invention may be formed as shown in FIG. 2a. After being cut, the PU foam showed an integrated structure without any separated skin layers. As shown in Figure 1, the PU leather skin layer was destroyed after being cut.

[0123] 8. Bond strength of articles having the crosslinked foam composition of the present invention / adhesive / substrate layer Table 5 shows the thermal conductivity of the crosslinked foam composition / adhesive / substrate layer of the present invention measured at various environmental temperatures. IE-3 indicates the bond strength of an article that has a foam / adhesive layer / substrate structure. and the adhesive layer is made from Formulation 1 in Table 3. IE-4 is foam / adhesive layer / substrate The adhesive layer is made from Formulation 2 in Table 3. Bond strengths exceeding 0 N / 30 mm were obtained, and in this case, substrate failure mode was observed (development The foam was destroyed. At 23°C, 113N / 30mm to 133N / 30mm (122 to 1 A bond strength of 23 N / 30 mm was obtained, and again the substrate failure mode was observed.

[0124] [Table 6]

[0125] The present disclosure is not limited to the embodiments and examples contained herein, but includes some of the embodiments and examples. Variations of those embodiments, including combinations of elements of different embodiments, are listed below. It is specifically intended to encompass within the scope of the following claims.

Claims

1. An article, (A) A crosslinked foam composition, (i) ethylene / α-olefin multi-block copolymers; (ii) ethylene / propylene / diene terpolymers (EPDM); (iii) an optional silicone rubber; (iv) Ethylene / α-olefin random copolymer, ethylene-vinyl acetate copolymer Polymers, styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers Optional blends selected from the group consisting of ethylenediaminetetraacetic acid copolymers, ... component, (v) an optional plasticizer; (vi) optional fillers, and (vii) optional additives; a crosslinked foam composition comprising: (B) an adhesive layer; (C) Olefin polymers, engineering plastics, and combinations thereof a base material comprising a component selected from the group consisting of a mixture of Including, goods.

2. The article according to claim 1, wherein the crosslinked foam composition (A) is Based on the total weight of the ingredients (i) 50% by weight to 70% by weight of the ethylene / α-olefin multiblock copolymer With Rimmer, (ii) 16% to 36% by weight of said ethylene / propylene / diene terpolymer (EPDM), Including, goods.

3. 3. The article according to claim 1, wherein the crosslinked foam composition (A) is (iii) greater than 0% to 12% by weight of silicone rubber; Including, goods.

4. The article according to any one of claims 1 to 3, wherein the crosslinked foam composition (A) is (C) greater than 0 wt. % to 20 wt. % of a filler; Including, goods.

5. The article according to any one of claims 1 to 4, wherein the crosslinked foam composition (A) is (v) from greater than 0% to 9% by weight of processing aids, UV inhibitors, colorants, and combinations thereof one or more additives selected from the group consisting of Including, goods.

6. The article according to any one of claims 1 to 5, wherein the foam composition (A) is a density of 0.1 g / cc to 0.3 g / cc; A compression set of 5% to 25% at 23°C / 24 hours, and 3% to 10% heat shrinkage at 65°C for 72 hours An article having:

7. The article according to any one of claims 1 to 6, wherein the adhesive layer (B) is (i) an ethylene elastomer; (ii) a tackifier; and (iii) a wax; and Including, goods.

8. 8. The article according to claim 7, wherein the adhesive layer (B) is Based on quantity, (i) 20% to 60% by weight of said ethylene elastomer; (ii) 20% to 60% by weight of the tackifier; (iii) 5% to 30% by weight of said wax; Including, goods.

9. The article according to any one of claims 1 to 8, wherein the substrate (C) is a propylene-based polymer. An item made of limer.

10. 10. The article of claim 9, having a strength of 113 N / 30 mm to 133 N / 30 mm at 23°C. The article has a bond strength of

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