阅读说明：本技术 将乙烯类聚合物泡沫与硫化橡胶附接的粘合方法 (Method of bonding vinyl polymer foam to vulcanized rubber ) 是由 禹海洋 马万福 刘昕 于 2018-09-20 设计创作，主要内容包括：提供了一种将泡沫结构粘附到橡胶基材上的方法。所述泡沫结构由包含具有峰值熔融温度T-(E1)的第一乙烯类聚合物的第一组合物构成。将由包含具有熔体指数≤10克/10分钟和峰值熔融温度T-(E2)的第二乙烯类聚合物的第二组合物构成的膜施加到所述橡胶基材的表面,以形成橡胶基材/膜配置。在温度T-v(38℃≤T-(E2)＜T-v)下施加压缩力,以形成硫化橡胶/膜层压体。将所述泡沫结构施加到所述硫化橡胶/膜层压体的所述膜的表面上,以形成硫化橡胶-膜层压体/泡沫配置。在温度T-L下施加压缩力,其中T-(E2)＜T-L＜T-(E1),15℃≤(T-(E1)-T-L)≤40℃且10℃≤(T-L-T-(E2))≤70℃,以形成硫化橡胶-膜/泡沫层压体。(A method of adhering a foam structure to a rubber substrate is provided. The foam structure is made of a material having a peak melting temperature T E1 The first ethylene-based polymer of (1). Will consist of a melt index of 10 g/10 min or less and a peak melting temperature T E2 Is applied to a surface of the rubber substrate to form a rubber substrate/film arrangement. At a temperature T v (38℃≤T E2 ＜T v ) A compressive force is applied to form a vulcanized rubber/film laminate. Applying the foam structure onto a surface of the film of the vulcanized rubber/film laminate to form a vulcanized rubber-film laminate/foam configuration. At a temperature T L Applying a compressive force, wherein T E2 ＜T L ＜T E1 ，15℃≤(T E1 ‑T L ) Less than or equal to 40 ℃ and less than or equal to 10 ℃ (T) L ‑T E2 ) 70 ℃ or less to form a vulcanized rubber-film/foam laminate.)

1. A method of adhering a foam structure to a rubber substrate, wherein the foam structure is prepared by a process comprising a polymer having a peak melting temperature T_E1The first composition of the first ethylene-based polymer of (a), the process comprising the steps of:

a) applying a film formed from a second composition comprising a second ethylene-based polymer onto a surface of the rubber substrate to form a rubber substrate/film configuration, wherein the second ethylene-based polymer has a melt index and a peak melting temperature T of less than or equal to 10 grams/10 minutes_E2；

b) At a temperature T_vApplying a compressive force to the rubber substrate/film arrangement wherein T is 38 ℃ ≦ T_E2＜T_vTo form a vulcanized rubber/film laminate having an exposed surface of the film;

c) applying the foam structure to an exposed surface of the film to form a vulcanized rubber-film laminate/foam configuration; and

d) at a temperature T_LApplying a compressive force down to the vulcanized rubber-film laminate/foam configuration, wherein T_E2＜T_L＜T_E1，15℃≤(T_E1-T_L) Less than or equal to 40 ℃ and less than or equal to 10 ℃ (T)_L-T_E2) 70 ℃ or less to form a vulcanized rubber-film/foam laminate.

2. The process of claim 1, wherein the second ethylene-based polymer has a tensile strength greater than or equal to 3 MPa.

3. The process of any one of claims 1-2, wherein the second ethylene-based polymer is an ethylene/a-olefin interpolymer.

4. The process of claim 3, wherein the second ethylene-based polymer has a density of 0.860g/cm³To 0.885g/cm³And a melt index of 1.0 g/10 min to 5.0 g/10 min.

5. The process of any one of claims 1 to 4, wherein the first ethylene-based polymer is an ethylene/a-olefin multi-block copolymer.

6. The process of claim 5, wherein the first ethylene-based polymer has a melt index of from 0.5 g/10 min to 5.0 g/10 min.

7. The process of any one of claims 1 to 6, wherein the first composition comprises from 85 to 95 weight percent of the first ethylene-based polymer, based on the total weight of the first composition.

8. The method of any one of claims 1 to 7, wherein the second composition comprises 95 to 100 wt% of the second ethylene-based polymer, based on the total weight of the second composition.

9. The method of any one of claims 1 to 8, wherein the second composition comprises the second ethylene-based polymer, but not all other polymers.

10. The method of claim 9, wherein the vulcanized rubber-film/foam laminate has an adhesive strength of greater than or equal to 3N/mm.

11. The method of any one of claims 1-10, wherein the T is_L≤100℃。

Background

The shoe industry is a highly labor intensive industry due to the low degree of automation of many processes. In the production of footwear, the different parts or layers of the shoe must be glued manually. For example, midsoles, which are typically made of cross-linked foam materials, need to be bonded to an outsole, which is typically vulcanized rubber. The process of bonding the midsole to the outsole is referred to as "sole working". After sole processing, further bonding of the bonded midsole/outsole to the upper is required. The process of bonding the midsole/outsole to the upper is referred to as shoe molding. Both sole processing and shoe molding have steps that must be done manually.

Bottoming is a particularly labor intensive task, as many steps must be done manually. For example, the cross-linked foam midsole is not prepared by a 1: 1 foaming process. When injection molding a midsole, the material is injected into a mold that is much smaller than the final product size. The mold is kept closed at the desired temperature for a given period of time. When the mold is opened, the foam expands and the midsole jumps out of the mold. Because the resulting midsole is larger than the size of the mold (not 1: 1), it is not possible to pre-load the outsole into the midsole mold to over-mold the midsole onto the outsole of the shoe. This limits the possibilities for automating the bottom working process.

As another example, the phylon process may also be used for sole working by further compressing the midsole preform prior to bonding with the outsole. Because the compression of the midsole is only in the thickness direction, the length and width of the midsole are not affected. Thus, a thermal lamination between the mid-sole and the outsole is possible; however, the midsole must be prevented from shrinking, and the adhesive strength must not be sacrificed in the process.

Accordingly, the art recognizes a need for a bottom finishing process that addresses one or more of these deficiencies.

Disclosure of Invention

A method of adhering a foam structure to a rubber substrate, wherein the foam structure is formed from a polymeric material having a peak melting temperature T_E1The first composition of the first ethylene-based polymer of (a), the process comprising the steps of:

a) applying a film formed from a second composition comprising a second ethylene-based polymer onto a surface of the rubber substrate to form a rubber substrate/film configuration, wherein the second ethylene-based polymer has a melt index and a peak melting temperature T of less than or equal to 10 grams/10 minutes_E2；

b) At a temperature T_vApplying a compressive force downward to the rubber substrate/film arrangement, wherein T_E2＜T_vTo form a vulcanized rubber/film laminate having an exposed surface of the film;

c) applying a foam structure to the exposed surface of the film to form a vulcanized rubber-film laminate/foam configuration; and

d) applying a compressive force to the vulcanized rubber-film laminate/foam configuration at a temperature TL, wherein T_E2＜T_L＜T_E1，15℃≤(T_E1-T_L) Less than or equal to 40 ℃ and less than or equal to 10 ℃ (T)_L-T_E2)≤70℃。

Definition of

Any reference to the periodic Table of elements is to the periodic Table of elements as published by CRC Press, Inc., 1990-1991. A family of elements in the table is referred to by a new notation for numbering the families. For purposes of united states patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or the equivalent us version thereof is so incorporated by reference), especially with respect to the disclosure of definitions in the art (without inconsistent with any definitions specifically provided in this disclosure) and general knowledge. The numerical ranges disclosed herein include all values from the lower value to the upper value, and include both the lower value and the upper value. For ranges containing an exact value (e.g., 1 or 2; or 3 to 5; or 6; or 7), any subrange between any two exact values is included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6, etc.). Unless stated to the contrary, implied by context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

The term "composition" refers to a mixture of materials comprising the composition and reaction products and decomposition products formed from the materials of the composition.

The terms "comprising", "including", "having" and derivatives thereof are not intended to exclude the presence of any additional component, step or procedure, whether or not the component, step or procedure is specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant or compound, whether polymeric or otherwise. In contrast, the term "consisting essentially of" excludes any other components, steps or procedures from any subsequently listed ranges, except for those that are not essential to operability. The term "consisting of" excludes any component, step or procedure not specifically recited or listed.

An "alpha-olefin (alpha-olefin)" or "alpha-olefin (alpha-olefin)" is a hydrocarbon molecule or a substituted hydrocarbon molecule (i.e., a hydrocarbon molecule containing one or more atoms in addition to hydrogen and carbon (e.g., halogen, oxygen, nitrogen, etc.)), the hydrocarbon molecule containing (i) only one ethylenically unsaturated bond, the unsaturated bond being located between a first carbon atom and a second carbon atom; and (ii) at least 2 carbon atoms, preferably 3 to 20 carbon atoms, in some cases preferably 4 to 10 carbon atoms, and in other cases preferably 4 to 8 carbon atoms. Non-limiting examples of alpha-olefins from which the elastomers are made include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-dodecene, and mixtures of two or more of these monomers.

An "ethylene-based polymer" or "ethylene polymer" is a polymer that contains a majority amount of polymerized ethylene by weight of the polymer and optionally may contain at least one comonomer. An "ethylene-based interpolymer" is an interpolymer that contains, in polymerized form, a majority amount of ethylene, based on the weight of the interpolymer, and at least one comonomer. Preferably, the ethylene-based interpolymer is a random interpolymer (i.e., comprising a random distribution of its monomeric constituents).

An "ethylene/α -olefin interpolymer" is an interpolymer that contains a majority amount of polymerized ethylene and at least one α -olefin, based on the weight of the interpolymer. An "ethylene/α -olefin copolymer" is an interpolymer that contains a majority amount of polymerized ethylene and α -olefin, based on the weight of the copolymer, as the only two monomer types.

"foam structure" refers to a formation formed by mixing a blowing agent and other necessary ingredients into a polymer at a temperature from 5 ℃ to 20 ℃ above the highest (peak) melting temperature of the polymer, and then foaming the composition at a suitable temperature at which the blowing agent and any other chemicals (e.g., crosslinking agents, etc.) are activated.

An "interpolymer" is a polymer prepared by polymerizing at least two different types of monomers. Thus, the generic term interpolymer includes copolymers (used to refer to polymers prepared from two different types of monomers), terpolymers (used to refer to polymers prepared from three different types of monomers), and polymers prepared from more than three different types of monomers.

An "olefin-based polymer" or "polyolefin" is a polymer that contains a majority amount of polymerized olefin monomer (e.g., ethylene or propylene) by weight of the polymer, and optionally may contain at least one comonomer. Non-limiting examples of the olefin-based polymer include ethylene-based polymers and propylene-based polymers.

An "olefin elastomer" or "polyolefin elastomer" or "POE" is an elastomeric polymer comprising at least 50 mole percent (mol%) of units derived from one or more olefins.

"peak melting temperature," "highest peak melting temperature," and similar terms refer to the Differential Scanning Calorimetry (DSC) melting peak of the polymer having the highest peak temperature, whether or not the other peaks are more prominent.

"polar ethylenic polymer" refers to an ethylenic polymer, as defined herein, containing one or more polar groups. A "polar group" is any group that imparts a bonded dipole moment to an otherwise nonpolar olefin molecule. Exemplary polar groups include carbonyl groups, carboxylic acid anhydride groups, carboxylic acid ester groups, epoxy groups, sulfonyl groups, nitrile groups, amide groups, silane groups, and the like, and these groups can be introduced into the olefin-based polymer by grafting or copolymerization. Non-limiting examples of polar ethylene-based polymers include ethylene/acrylic acid (EAA), ethylene/methacrylic acid (EMAA), and ethylene/acrylate or methacrylate, ethylene/vinyl acetate (EVA). Commercially available examples of polar ethylenic polymers include DuPontEthylene Vinyl Acetate (EVA) resin, AMPLIFY from Dow Chemical Company^TMEthylene Ethyl Acrylate (EEA) copolymer and PRIMCOR from Dow chemical^TMEthylene/acrylic acid copolymer.

A "polymer" is a polymeric compound prepared by polymerizing monomers, whether of the same type or a different type. The generic term polymer thus embraces the term "homopolymer" (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure) and the term "interpolymer" as defined below. Trace amounts of impurities, such as catalyst residues, may be incorporated into and/or within the polymer.

The terms "multi-block interpolymer," "multi-block copolymer," "segmented copolymer," and the like, refer to a polymer comprising two or more chemically distinct regions or segments (referred to as "blocks") preferably joined in a linear fashion rather than a pendant or grafted fashion, i.e., comprising chemically distinct units joined end-to-end with respect to a polymeric ethylenic functionality. In a preferred embodiment, the blocks differ in the following respects: amount or kind of comonomer incorporatedType, density, amount of crystallinity, crystallite size attributable to a polymer of such composition, type or degree of tacticity (isotactic or syndiotactic), regio-regularity or regio-irregularity, amount of branching (including long chain branching or hyper-branching), homogeneity, or any other chemical or physical property. Compared to block copolymers of the prior art, including copolymers produced by sequential monomer addition, stereo-labile catalysts, or anionic polymerization techniques, the multiblock copolymers can be characterized by polymer polydispersity (PDI or M)_w/M_nOr MWD), unique distribution of both block length distributions and/or block number distribution, in preferred embodiments due to the effect of one or more shuttling agents used in their preparation in combination with multiple catalysts. Representative olefin multi-block interpolymers include the olefin multi-block interpolymers sold by the Dow chemical company under the trade name INFUSE^TMOlefin multi-block interpolymers made and sold. In the context of the present disclosure, "multi-block interpolymer" and similar terms specifically exclude olefin-based polymers, vinyl halide-based polymers, and elastomeric rubbers.

"film", unless expressly having a specified thickness, includes when referring to a "film layer" in a thicker article, refers to any thin, flat extruded, cast, or molded article (e.g., sheet) up to about 1.0 millimeter in thickness that is substantially uniform and homogeneous.

Test method

The asker C-type hardness of the foam structure was measured before and after lamination on plaques having dimensions of 15cm (length) x 15cm (width) x 2cm (thickness) according to ASTM D2240. Each sample was measured at least 3 times across the surface of the sample (with a 5 second delay between each measurement). The average value is recorded.

The density of the polymer was measured according to ASTM D792, method B. Results are in grams (g) per cubic centimeter (g/cc or g/cm)³) Is recorded in units.

The melt index (I2) was measured at 190 ℃ under a load of 2.16kg according to ASTM D1238. Results are reported as grams eluted every 10 minutes (grams/10 minutes).

Differential Scanning Calorimetry (DSC)

Differential Scanning Calorimetry (DSC) can be used to measure the melting, crystallization and glass transition behavior of polymers over a wide temperature range. For example, a TA instrument Q1000 DSC (TA Instruments Q1000 DSC) equipped with an RCS (refrigerated cooling system) and an autosampler was used for this analysis. During the test, a nitrogen purge flow of 50 ml/min was used. Melt pressing each sample into a film at about 190 ℃; the molten sample was then air cooled to room temperature (25 ℃). From the cooled polymer, 3-10mg of a 6mm diameter specimen was taken, weighed, placed in a light aluminum pan (50mg), and allowed to curl closed. And then analyzed to determine its thermal properties.

The thermal behavior of the sample is determined by ramping the sample temperature up and down to produce a heat flow versus temperature curve. First, the sample was rapidly heated to 180 ℃ and held isothermally for 3 minutes to remove its thermal history. Next, the sample was cooled to-80 ℃ at a cooling rate of 10 ℃/min and held isothermally at-80 ℃ for 3 minutes. The sample was then heated to 180 ℃ at a 10 ℃/minute heating rate (this is a "second heating" ramp). The cooling and second heating profiles were recorded. The determined value is the extrapolated onset temperature of melting T_mAnd extrapolated crystallization onset temperature T_c. Heat of fusion (H) for polyethylene samples_f) (in joules per gram) and the calculated% crystallinity were calculated using the following equation: degree of crystallinity = ((H)_f)/292J/g)×100。

Heat of fusion (H)_f) (also known as the enthalpy of fusion) and the peak melting temperature are reported by the second thermal profile.

Melting point T was determined from the DSC heating curve by first drawing a baseline between the beginning and end of the melting transition_m. A tangent line is then drawn for the data on the low temperature side of the melting peak. The intersection of this line with the baseline is the extrapolated onset of melting temperature (T)_m). This is as described in Bernhard Wunderlich, The Basis of Thermal Analysis in The Thermal Characterization of Polymeric Materials (The Basis of Thermal Analysis, in Thermal Characterization of Polymeric Materials) 92, 277-278(Edith A. Turi edition, 2 nd edition, 1997).

Peak melting temperature (T)_E) From the DSC heating curve, by determining the temperature corresponding to the position of the highest melting peak.

Hardness as compared to control foam is H₁/H₀Relative percentage calculated by 100%, wherein H₀Is the hardness of the foam before lamination with the adhesive film, and H₁Is the foam hardness of the same foam measured after final lamination to produce a vulcanized rubber-film/foam laminate.

The adhesive strength was measured by T-peel testing using INSTRON 5566 and a sample having the structure shown in figure 1. The unattached ends of the bonded sample were clamped in the top and bottom grips of INSTRON, respectively. The initial clamping distance was 1 inch. The bonded samples were peeled at a crosshead speed of 100 mm/min. The peel force was recorded and the average peel force was calculated. The peel strength (N/mm) was calculated as follows: average peel force (N)/sample width (mm). In fig. 1, the foam layer is 1, the adhesive layer is 2, and the rubber layer is 3, and the non-adhesive ends 4,5 belong to the foam layer 1 and the rubber layer 3, respectively.

Tensile strength was measured according to D638 and reported in MPa.

Detailed Description

Disclosed herein is a method of adhering a foam structure to a rubber substrate. A method of adhering a foam structure to a rubber substrate, wherein the foam structure is formed by a foam comprising a polymer having a peak melting temperature T_E1The first composition of the first ethylene-based polymer of (a), the process comprising the steps of:

a) applying a film formed from a second composition comprising a second ethylene-based polymer onto a surface of the rubber substrate to form a rubber substrate/film configuration, wherein the second ethylene-based polymer has a melt index and a peak melting temperature T of less than or equal to 10 grams/10 minutes_E2；

b) Applying a compressive force to the rubber substrate/film arrangement at a temperature Tv, wherein T is 38 ℃ ≦ T_E2＜T_vTo form a vulcanized rubber/film laminate having an exposed surface of the film;

c) applying a foam structure to the exposed surface of the film to form a vulcanized rubber-film laminate/foam configuration; and

d) applying a compressive force to the vulcanized rubber-film laminate/foam configuration at a temperature TL, wherein T_E2＜T_L＜T_E1，15℃≤(T_E1-T_L) Less than or equal to 40 ℃ and less than or equal to 10 ℃ (T)_L-T_E2) 70 ℃ or less to form a vulcanized rubber-film/foam laminate.

The process of adhering the foam structure to the rubber substrate may comprise a combination of two or more embodiments described herein.

Each component of the process of adhering the foam structure to the rubber substrate may comprise a combination of two or more embodiments as described herein.

Ethylene polymer

Ethylene-based polymers are polymers that comprise, in polymerized form, a majority amount (greater than 50 wt%) of units derived from ethylene, based on the total weight of the polymer. In one embodiment, the ethylene-based polymer is an ethylene homopolymer or an ethylene-based copolymer, such as an ethylene/alpha-olefin copolymer or a polar ethylene-based copolymer. Non-limiting examples of suitable ethylene/alpha-olefin copolymers include copolymers of ethylene and one or more alpha-olefins having from 3 to 12 carbon atoms. Non-limiting examples of suitable polar ethylene-based copolymers include Ethylene Vinyl Acetate (EVA), Ethylene Ethyl Acrylate (EEA), and chain-links. Suitable ethylene homopolymers and ethylene-based copolymers may be heterogeneous or homogeneous.

Typical catalyst systems for the preparation of suitable ethylene homopolymers and ethylene/alpha-olefin copolymers are magnesium/titanium based catalyst systems, which can be exemplified by the catalyst systems described in USP 4,302,565 (heterogeneous polyethylene); vanadium-based catalyst systems, such as those described in USP 4,508,842 (heterogeneous polyethylene) and 5,332,793; 5,342,907, respectively; and 5,410,003 (homogeneous polyethylene); chromium-based catalyst systems such as those described in USP 4,101,445; metallocene catalyst systems such as those described in UPS 4,973,299, 5,272,236, 5,278,272, and 5,317,036; or other transition metal catalyst systems. Many of these catalyst systems are often referred to as Ziegler-Natta catalyst systems (Ziegler-Natta catalysts systems) or Phillips catalyst systems (Phillips catalysts systems). Catalyst systems employing chromium or molybdenum oxides on silica-alumina supports may be included herein. Processes for preparing suitable ethylene homopolymers and ethylene/alpha-olefin copolymers are also described in the above documents. In-situ blends of polyethylene homopolymers and/or ethylene/alpha-olefin copolymers, and processes and catalyst systems for providing the same, are described in USP 5,371,145 and 5,405,901.

Non-limiting examples of suitable ethylene homopolymers and ethylene/alpha-olefin copolymers include low density homopolymers of ethylene (HP-LDPE), Linear Low Density Polyethylene (LLDPE), Very Low Density Polyethylene (VLDPE), Medium Density Polyethylene (MDPE), High Density Polyethylene (HDPE) having a density greater than 0.940g/cc, and metallocene copolymers having a density less than 0.900g/cc prepared by a high pressure process.

The VLDPE can be a copolymer of ethylene and one or more alpha-olefins having from 3 to 12 carbon atoms. The density of the VLDPE may be from 0.870g/cc to 0.915 g/cc. LLDPE can include VLDPE and MDPE, which are also linear, but generally have a density of 0.916 to 0.925 g/cc. The LLDPE can be a copolymer of ethylene and one or more alpha-olefins having 3 to 12 carbon atoms.

In one embodiment, the ethylene-based polymer is an ethylene-based copolymer. In one embodiment, the ethylene-based copolymer is selected from the group consisting of ethylene/alpha-olefin copolymer and EVA.

In one embodiment, the ethylene-based polymer or further ethylene/alpha-olefin copolymer is a polyolefin elastomer (POE). POE is prepared using at least one metallocene catalyst. POE may also be prepared with more than one metallocene catalyst, or may be a blend of multiple elastomeric resins prepared with different metallocene catalysts. In one embodiment, the POE is a Substantially Linear Ethylene Polymer (SLEP). SLEPs and other metallocene catalyzed elastomers are described, for example, in U.S. patent No. 5,272,236, which is incorporated herein by reference. Non-limiting examples of suitable POEs include ENGAGE, available from the Dow chemical company^TMElastomeric resins, or fromEXACT by Exxon^TMPolymer or TAFMER from Mitsui Chemical^TMA polymer.

In one embodiment, the POE is an ethylene-based polymer, and further an ethylene-based copolymer. Ethylene-based copolymers comprise ethylene and an alpha-olefin comonomer in polymerized form. Non-limiting examples of alpha-olefin comonomers include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-dodecene, and mixtures of these or other comonomers. In one embodiment, the POE is an ethylene/1-octene copolymer or an ethylene/1-butene copolymer.

The POE has a density of 0.850g/cc, or 0.860g/cc, or 0.870g/cc to 0.880g/cc, or 0.890g/cc, or 0.900g/cc, or 0.910g/cc, as measured according to ASTM D792.

The melt index of POE is 0.25 g/10 min, or.5 g/10 min, or 1 g/10 min, or 5 g/10 min to 10 g/10 min, or 15 g/10 min, or 20 g/10 min, or 25 g/10 min, or 30 g/10 min, as measured according to ASTM D1238(190 ℃, 2.16 kg).

In one embodiment, the ethylene-based polymer or further ethylene/α -olefin copolymer is an ethylene/α -olefin multi-block interpolymer. In one embodiment, the ethylene/α -olefin multi-block interpolymer is an ethylene/α -olefin multi-block copolymer.

The term "ethylene/α -olefin multi-block interpolymer" refers to a copolymer made from, in polymerized form, ethylene and one or more copolymerizable C' s₄-C₈ethylene/C of alpha-olefin comonomer (and optional additives)₄-C₈Alpha-olefin multi-block copolymers, said polymers being characterized by multiple blocks or segments of two polymerized monomer units differing in chemical or physical properties, said blocks being joined (or covalently bonded) in a linear manner, i.e. polymers comprising chemically distinguishable units joined end-to-end in terms of polymerized ethylenic functionality. In one embodiment, the ethylene/α -olefin multi-block interpolymer is an ethylene/α -olefin multi-block copolymer. The term "ethylene/alpha-olefin multi-block copolymer" refers to a copolymer made from ethylene and a copolymerizable monomer in polymerized formC₄-C₈ethylene/C of alpha-olefin comonomer₄-C₈Alpha-olefin multi-block copolymers, said polymers being characterized by multiple blocks or segments of two polymerized monomer units differing in chemical or physical properties, said blocks being joined (or covalently bonded) in a linear manner, i.e. polymers comprising chemically distinguishable units joined end-to-end in terms of polymerized ethylenic functionality. Ethylene/a-olefin multi-block copolymers include block copolymers having two blocks (diblock) and more than two blocks (multiblock). C₄-C₈The alpha-olefin is selected from the group consisting of butene, hexene and octene. The ethylene/α -olefin multi-block copolymer is free or otherwise free of styrene (i.e., free of styrene), and/or vinyl aromatic monomers, and/or conjugated dienes. When referring to the amount of "ethylene" or "comonomer" in a copolymer, it is understood that this refers to the polymerized units thereof. In some embodiments, the ethylene/α -olefin multi-block copolymer may be represented by the formula: (AB) n; wherein n is at least 1, preferably an integer greater than 1, such as 2, 3, 4,5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or more, "a" represents a hard block or segment and "B" represents a soft block or segment. Preferably, a and B are linked or covalently bonded in a substantially linear manner, or in a linear manner, relative to a substantially branched or substantially star-shaped manner. In other embodiments, the a and B blocks are randomly distributed along the polymer chain. In other words, block copolymers generally do not have the following structure: AAA-AA-BBB-BB. In one embodiment, the ethylene/α -olefin multi-block copolymer does not have a third type of block, which comprises one or more different comonomers. In another embodiment, block a and block B each have a monomer or comonomer substantially randomly distributed within the block. In other words, neither block a nor block B comprises two or more sub-segments (or sub-blocks) of different compositions, such as end segments, which have a composition that is substantially different from the rest of the block.

Preferably, the ethylene comprises the majority of the molar fraction of the total base ethylene/alpha-olefin multi-block copolymer, i.e. the ethylene comprises the total base ethylene/alpha-olefin multi-block copolymerAt least 50 wt% of the block copolymer. More preferably, the ethylene comprises at least 60 wt%, at least 70 wt%, or at least 80 wt%, with the substantial remainder of the entire ethylene/α -olefin multi-block copolymer comprising C₄-C₈An alpha-olefin comonomer. In one embodiment, the ethylene/α -olefin multi-block copolymer contains 50 wt%, or 60 wt%, or 65 wt% to 80 wt%, or 85 wt%, or 90 wt% ethylene. For a plurality of ethylene/octene multi-block copolymers, the composition comprises an ethylene content greater than 80 wt% of the total ethylene/octene multi-block copolymer and an octene content from 10 wt% to 15 wt%, or from 15 wt% to 20 wt%, of the total ethylene/octene multi-block copolymer.

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

The soft segment can be present in the base ethylene/α -olefin multiblock copolymer at 1 wt%, or 5 wt%, or 10 wt%, or 15 wt%, or 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt% to 55 wt%, or 60 wt%, or 65 wt%, or 70 wt%, or 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 99 wt% of the total weight of the ethylene/α -olefin multiblock copolymer. Conversely, hard segments may be present in similar ranges. The soft segment weight percent and hard segment weight percent can be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed, for example, in USP 7,608,668, the disclosure of which is incorporated herein by reference in its entirety. Specifically, the hard segment weight percent and soft segment weight percent and comonomer content can be determined as described in column 57 to column 63 of USP 7,608,668.

Ethylene/α -olefin multi-block copolymers comprise two or more chemically distinct regions or segments (referred to as "blocks") joined (or covalently bonded) in a linear fashion, i.e., polymers that contain chemically distinguishable units joined end-to-end in terms of polymerized ethylenic functionality rather than in a pendant or grafted fashion. In one embodiment, the blocks differ in the following respects: the amount or type of comonomer incorporated, the density, the crystallinity, the crystallite size attributable to the polymer of such composition, the type or degree of stereoisomerism (isotactic or syndiotactic), regio-regularity or regio-irregularity, the amount of branching (including long chain branching or hyper-branching), homogeneity or any other chemical or physical property. Compared to prior art block interpolymers, including interpolymers produced by continuous monomer addition, stereo-labile catalysts, or anionic polymerization techniques, the ethylene/α -olefin multiblock copolymers of the present invention are characterized by a unique distribution of polymer polydispersity (PDI or Mw/Mn or MWD), polydispersity block length distribution, and/or polydispersity block number distribution, in one embodiment, due to the effect of one or more shuttling agents used in their preparation in combination with multiple catalysts.

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

In addition, the ethylene/α -olefin multi-block copolymer has a PDI (or Mw/Mn) that fits a Schultz-Flory distribution rather than a Poisson distribution. Ethylene of the inventionThe/α -olefin multi-block copolymer has both a polydisperse block distribution as well as a polydisperse distribution of block sizes. This results in the formation of a polymer product having improved and distinguishable physical properties. Physical comments E (previously described in Potemkin;)Physical Review E)57 (1998), page 6902-6912 and Dobrynin, journal of chemico-physical (J.chem.Phys.) (1997)107(21), page 9234-9238.

In one embodiment, the ethylene/α -olefin multi-block copolymer has the most likely distribution of block lengths.

Non-limiting examples of suitable ethylene/a-olefin multi-block copolymers are disclosed in U.S. patent No. 7,608,668, which is incorporated herein by reference.

In one embodiment, the ethylene/α -olefin multi-block copolymer has a hard segment and a soft segment; styrene is not contained; only from (i) ethylene and (ii) C₄-C₈Alpha-olefin (and optional additives); and is defined as having a Mw/Mn from 1.7 to 3.5, at least one melting point, Tm, in degrees celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship: tm > -2002.9+4538.5(d) -2422.2(d)²Wherein the density d is 0.850g/cc, or 0.860g/cc, or 0.870g/cc to 0.875g/cc, or 0.877g/cc, or 0.880g/cc, or 0.890 g/cc; and a melting point Tm of 110 ℃ or 115 ℃ or 120 ℃ to 122 ℃ or 125 ℃ or 130 ℃ or 135 ℃.

In one embodiment, the ethylene/α -olefin multi-block copolymer is an ethylene/1-octene multi-block copolymer (consisting only of ethylene and octene comonomers) and has one, some, or all of the following attributes: (i) Mw/Mn is 1.7, or 1.8 to 2.2, or 2.5, or 3.5; and/or (ii) a density of 0.850g/cc, or 0.860g/cc, or 0.865g/cc or 0.870g/cc to 0.877g/cc, or 0.880g/cc or 0.900 g/cc; and/or (iii) a melting point Tm of 115 ℃ or 118 ℃ or 119 ℃ or 120 ℃ to 121 ℃ or 122 ℃ or 125 ℃; and/or (iv) a melt index (I2) 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 or 50 g/10 min; and/or (v)50 to 85 wt% soft segment and 40 to 15 wt% hard segment; and/or (vi) soft segment10 mol%, or 13 mol%, or 14 mol% or 15 mol% to 16 mol%, or 17 mol%, or 18 mol%, or 19 mol% or 20 mol% C₄-C₁₂An alpha-olefin; 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% octene in the hard segment; and/or (viii) elastic recovery (Re) at 21 ℃ at 300% min as measured according to ASTM D1708¹50% or 60% to 70% or 80% or 90% at deformation; and/or (ix) a polydisperse distribution of blocks and a polydisperse distribution of block sizes; and/or (x) a shore a hardness of 50, or 60, or 65, or 70, or 75 to 80, or 85, or 90. In further embodiments, the ethylene/1-octene multi-block copolymer has all of the attributes (i) - (x) described above.

In one embodiment, the ethylene/α -olefin multi-block copolymer is an ethylene/octene multi-block copolymer. Ethylene/octene multi-block copolymer is under the trade name INFUSE^TMCommercially available from The Dow Chemical Company of Midland, Michigan, USA.

The ethylene-based polymer may comprise two or more embodiments discussed herein.

Foaming structure

In one embodiment, the method comprises applying a foam structure to an exposed surface of a film, wherein the foam is formed from a first composition comprising a first ethylenic polymer.

The first ethylene-based polymer may comprise any embodiment or combination of embodiments discussed herein.

In one embodiment, the first ethylene-based polymer is an ethylene/a-olefin multi-block interpolymer, or further an ethylene/a-olefin multi-block copolymer, as discussed herein. In one embodiment, the ethylene/α -olefin multi-block interpolymer is an ethylene/octene multi-block copolymer, such as that sold under the trade name INFUSE^TMCommercially available ethylene/octene multi-block copolymers are available from The Dow Chemical Company, Midland, Michigan, USA, Midland, Mich.

In one embodiment, the first ethylene-based polymer has a peak melting temperature (T)_E1) At 115 deg.C, or 120 deg.C, or 125 deg.C to 130 deg.C, or 135 deg.C. Peak melting temperature (T) if there is more than one peak melting temperature in the DSC curve_E1) The peak temperature is the highest temperature. In one embodiment, the first ethylene-based polymer has a single melting temperature.

In one embodiment, the first ethylene-based polymer has a density of 0.850g/cc, or 0.860g/cc, or 0.870g/cc to 0.875g/cc, or 0.877g/cc, or 0.880g/cc, or 0.890 g/cc.

In one embodiment, the first ethylene-based polymer has a melt index of from 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 or 50 g/10 min;

in one embodiment, the first ethylenic polymer has a shore a hardness of 50, or 60, or 65, or 70, or 75 to 80, or 85, or 90.

In one embodiment, the first ethylene-based polymer is an ethylene/α -olefin multi-block interpolymer or a further ethylene/α -olefin multi-block copolymer and has one, some, or all of the following attributes: (i) peak melting temperature (T)_E1) At 115 ℃, or 120 ℃, or from 125 ℃ to 130 ℃, or 135 ℃; and/or (ii) a density of 0.850g/cc, or 0.860g/cc, or 0.870g/cc to 0.875g/cc, or 0.877g/cc, or 0.880g/cc, or 0.890 g/cc; and/or (iii) a melt index 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 or 50 g/10 min; and/or (iv) a shore a hardness of 50, or 60, or 65, or 70, or 75 to 80, or 85, or 90. In one embodiment, the first ethylene-based polymer has one, two, three, or all four of attributes (i) - (iv).

In one embodiment, the first composition comprises 85 wt%, or 87 wt%, or 90 wt% to 92 wt%, or 95 wt%, or 97 wt%, or 99 wt%, or 100 wt% of the first ethylene-based polymer, based on the total weight of the first composition.

In one embodiment, the first composition comprises a first ethylene-based polymer, but does not comprise all other polymers.

The first composition further comprises a blowing agent. A "blowing agent" is a substance that is capable of creating a cellular structure in a composition through a foaming process. Non-limiting examples of suitable blowing agents are chemical blowing agents, i.e. substances which form gaseous products. Non-limiting examples of suitable chemical blowing agents include sodium bicarbonate, azodicarbonamide, 4' -oxydiphenylsulfonyl hydrazide, and carbazide.

The blowing agent is present in an amount of greater than 0.0 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt% to 2.0 wt%, or 3.0 wt%, or 5.0 wt%, or 10.0 wt%, based on the total weight of the first composition.

The first composition optionally includes a crosslinking agent. A crosslinking agent and optionally a blowing agent are added to the ethylene-based polymer and used to crosslink the ethylene-based polymer with itself.

Non-limiting examples of suitable crosslinking agents include azido and vinylic functional silanes, organic peroxides, and polyfunctional vinyl monomers. Non-limiting examples of azido-functional silane compounds include azidotrialkoxysilanes, such as 2- (trimethoxysilyl) ethylphenylsulfonyl azide and (triethoxysilyl) hexylsulfonyl azide. Non-limiting examples of vinyl functional silane compounds include vinyl functional alkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane. Non-limiting examples of organic peroxides include dicumyl peroxide (DCP). Non-limiting examples of the polyfunctional vinyl monomer include trimethylolpropane triacrylate (TMPTA) and pentaerythritol triacrylate (PETA). The crosslinking agent is present in an amount of 0 wt% or greater than 0 wt% or 0.1 wt% or 0.5 wt% or 1.0 wt% to 2.0 wt% or 3.0 wt% or 5.0 wt% or 10.0 wt% based on the total weight of the first composition.

The first composition may further comprise an activator. An activator is a substance that activates or helps initiate or sustain a blowing agent chemical reaction. Non-limiting examples of suitable activators include zinc oxide, zinc stearate, and combinations thereof. In one embodiment, the activator is present in an amount of 0 wt% or greater than 0 wt%, or 0.1 wt%, or 0.2 wt%, or 0.3 wt%, or 0.4 wt% to 0.5 wt%, or 0.6 wt%, or 0.8 wt%, or 1.0 wt%, or 1.5 wt%, or 2.0 wt%, based on the total weight of the first composition.

The first composition may also include a filler. Non-limiting examples of fillers include calcium carbonate, titanium dioxide, tac, and combinations thereof. In one embodiment, the filler is present in an amount of 0 wt% or greater than 0 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt%, or 1.5 wt%, or 2.0 wt% to 2.5 wt%, or 3.0 wt%, or 3.5 wt%, or 4.0 wt%, or 5.0 wt%, or 6.0 wt%, or 10.0 wt%, based on the total weight of the first composition.

The first composition may comprise two or more embodiments as disclosed herein.

A first composition comprising a first ethylene-based polymer is foamed to form a foamed structure.

To form the foam structure, the first ethylenic polymer is melted prior to adding any additional components (e.g., crosslinking agents or additives) to form a molten polymer mass. The blowing agent and (optionally) the crosslinking agent, the activator, and any filler are then added. The molten polymer mass is further heated to a peak melting temperature (T) greater than the first ethylene-based polymer_E1) A temperature of 5 ℃, or 10 ℃, or 15 ℃ to 20 ℃ higher.

In one embodiment, the first ethylenic polymer is melted prior to adding any additional components (e.g., blowing agent or crosslinking agent) to form a molten polymer mass. The molten polymer mass is then heated in a foam mold (e.g., a slabstock foam mold) and placed in a foam press at a selected temperature and pressure for a period of time to initiate reaction of the blowing agent and crosslinking agent, if present. Upon release of the pressure and removal of the article from the mold, the molten polymer mass expands to form a foamed article.

In one embodiment, the molten polymer mass is pressed at a foaming temperature of 100 ℃, or 110 ℃, or 120 ℃, or 130 ℃, or 140 ℃, or 150 ℃ to 160 ℃, or 170 ℃, or 180 ℃, or 190 ℃, or 200 ℃.

In one embodiment, the molten polymer mass is compressed at a pressure of 90 bar or 95 bar or 100 bar to 105 bar or 110 bar or 115 bar or 120 bar.

In one embodiment, the molten polymer mass is pressed for a period of 6 minutes, or 8 minutes, or 10 minutes, or 12 minutes to 14 minutes, or 16 minutes, or 18 minutes or 20 minutes.

The foam structure may comprise two or more embodiments as disclosed herein.

Rubber substrate

The present disclosure provides a method of adhering a foam structure to a rubber substrate. The substrate is typically in sheet form and may comprise any natural or synthetic rubber. Synthetic rubbers include, but are not limited to, polyacrylate rubbers, vinyl acrylate rubbers, polyester urethanes, polybutadiene, polychloroprene, Ethylene Propylene (EP), Ethylene Propylene Diene Monomer (EPDM), polyether urethanes, perfluorocarbon rubbers, polyisoprene, acrylonitrile butadiene (NBR), polysiloxanes, styrene-ethylene-butylene-styrene (SEBS), styrene-butadiene (SBR), and the like.

In one embodiment, the rubber substrate is formed from a composition comprising rubber and one or more additives including, for example, one or more accelerators, curing additives and/or processing aids.

In one embodiment, the rubber substrate comprises, consists essentially of, or consists of EPDM.

The rubber substrate is formed by melt compounding a rubber-containing composition and forming the molten compound into a sheet-like substrate. In one embodiment, the molten compound is rolled into a rubber substrate having a thickness of about 2mm, 3mm, 5mm to 6mm, 8mm, or 10 mm.

In one embodiment, the rubber substrate is cold pressed.

In one embodiment, the rubber substrate is cold pressed at a temperature of 90 ℃ or 95 ℃ to 100 ℃ or 105 ℃ or 110 ℃.

In one embodiment, the rubber substrate is cold pressed at a force of 150kN, 180kN to 200kN, 220kN, or 250 kN.

In one embodiment, the rubber substrate is cold pressed for a duration of 5 minutes, or 6 minutes, or 7 minutes to 8 minutes, or 9 minutes, or 10 minutes, or 12 minutes.

In one embodiment, the rubber substrate is further cold pressed at a temperature of 90 ℃, or 95 ℃ to 100 ℃, or 105 ℃, or 110 ℃ with a force of 150kN, or 180kN to 200kN, or 220kN, or 250kN for a duration of 5 minutes, or 6 minutes, or 7 minutes to 8 minutes, or 9 minutes, or 10 minutes, or 12 minutes to form the rubber substrate, which is a sheet.

In one embodiment, the rubber substrate is a sheet having a thickness of 0.2mm, or 0.4mm, or 0.5mm to 0.6mm, or 0.8mm, or 1.0 mm.

The rubber substrate may comprise two or more embodiments disclosed herein.

Adhesive film

A method of adhering a foam structure to a rubber substrate includes applying a film formed from a second composition comprising a second ethylene-based polymer to a surface of the rubber substrate.

The second ethylene-based polymer may comprise any embodiment or combination of embodiments discussed herein.

In one embodiment, the second ethylene-based polymer is an ethylene-based homopolymer or an ethylene-based interpolymer, or further an ethylene-based copolymer. In one embodiment, the ethylene-based copolymer is POE. In one embodiment, the second ethylene-based polymer is a random ethylene-based copolymer. In one embodiment, the random ethylene-based copolymer is an ethylene/α -olefin copolymer or EVA. In one embodiment, the ethylene-based copolymer is a random ethylene/octene copolymer or a random ethylene/butene copolymer.

In another embodiment, the second ethylene-based polymer is an ethylene/α -olefin random copolymer. In another embodiment, the second ethylene-based polymer is selected from the group consisting of ethylene/octene random copolymers and ethylene/butene random copolymers.

In one embodiment, the second ethylene-based polymer has a peak melting temperature T_E2Is 30 ℃, or 35 ℃, or 40 ℃, or 45 ℃, or 50 ℃ to 55 ℃, or 60 ℃, or 65 ℃, or 70 ℃, or 75 ℃, or 80 ℃. Peak melting temperature (T) if there is more than one melting temperature in the DSC curve_E2) Is the peak maximum temperature. In one embodiment, the second ethylene-based polymer has a single melting temperature.

In one embodiment, the second ethylene-based polymer has a peak melting temperature (T)_E2) Lower than the peak melting temperature (T) of the first ethylene-based polymer_E1)。

In one embodiment, the second ethylene-based polymer has a peak melting temperature (T)_E2) Is 30 ℃, or 35 ℃, or 40 ℃, or 45 ℃, or 50 ℃ to 55 ℃, or 60 ℃, or 65 ℃, or 70 ℃, or 75 ℃, or 80 ℃, and the peak melting temperature (T) of the second ethylene-based polymer_E2) Lower than the peak melting temperature of the first ethylenic polymer_E1)。

In one embodiment, the second ethylene-based polymer has a density of 0.850g/cc, or 0.860g/cc, or 0.870g/cc to 0.875g/cc, or 0.877g/cc, or 0.880g/cc, or 0.890 g/cc.

In one embodiment, the second ethylene-based polymer has a melt index 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 less than or equal to 10 g/10 min.

In one embodiment, the second ethylene-based polymer has a shore a hardness of 50, or 60, or 65, or 70, or 75 to 80, or 85, or 90.

In one embodiment, the second ethylene-based polymer has a tensile strength greater than or equal to 3MPa, or greater than or equal to 4MPa, or greater than or equal to 5MPa to 6MPa, or 7MPa, or 8MPa, or 9MPa, or 10MPa, or 15MPa, or 20 MPa.

In one embodiment, the second ethylene-based polymer is a POE, or further an ethylene/α -olefin random copolymer, and has one, some or all of the following attributes: (i) the peak melting temperature is 30 ℃, or 35 ℃, or 40 ℃, or 45 ℃, or 50 ℃ to 55 ℃, or 60 ℃, or 65 ℃At 70 deg.C, or at 75 deg.C, or at 80 deg.C; and/or (ii) peak melting temperature (T)_E2) Lower than the peak melting temperature (T) of the first ethylene-based polymer_E1) (ii) a And/or (iii) a density of 0.850g/cc, or 0.860g/cc, or 0.870g/cc to 0.875g/cc, or 0.877g/cc, or 0.880g/cc, or 0.890 g/cc; and/or (iv) a melt index 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 less than or equal to 10 g/10 min; and/or (v) a shore a hardness of 50, or 60, or 65, or 70, or 75 to 80, or 85, or 90; and/or (vi) a tensile strength of greater than or equal to 3MPa, or greater than or equal to 4MPa, or greater than or equal to 5MPa to 6MPa, or 7MPa, or 8MPa, or 9MPa, or 10MPa, or 15MPa, or 20 MPa. In one embodiment, the first ethylene-based polymer has one, two, three, four, five, or all six of attributes (i) - (vi).

In one embodiment, the second ethylene-based polymer has at least attributes (i), (ii), and (iv).

In one embodiment, the second composition comprises 90 wt%, or 95 wt% to 96 wt%, or 97 wt%, or 98 wt%, or 99 wt%, or 99.5 wt%, or 99.9 wt%, or 100 wt% of the second ethylene-based polymer, based on the total weight of the second composition.

In one embodiment, the second composition comprises a second ethylene-based polymer, but does not comprise all other polymers. In one embodiment, the second composition consists essentially of or consists of the second ethylene-based polymer.

In one embodiment, the second composition optionally comprises one or more additives including, for example, processing aids, tackifiers, fillers, and other such additives useful in the adhesive layer.

The second composition may comprise two or more embodiments described herein.

In one embodiment, the second composition forms a film. The film may be formed by casting, extruding, or molding the second composition into a substantially flat article (e.g., a sheet) having a uniform thickness. Suitable membranes have a thickness of 10 microns, or 50 microns, or 100 microns to 0.2mm, or 0.4mm, or 0.6mm, or 0.8mm, or 1.0 mm.

In one embodiment, the film is prepared by compressing the second composition.

In one embodiment, the second composition is compressed at a temperature of 60 ℃, or 70 ℃, or 80 ℃ to 90 ℃, or 100 ℃, or 110 ℃, or 120 ℃.

In one embodiment, the second composition is compressed at a compressive force of 200kN, or 250kN to 300kN, or 350kN, or 400 kN.

In one embodiment, the second composition is compressed for a duration of 1 minute, or 3 minutes, or 5 minutes to 7 minutes, or 10 minutes.

In a particular embodiment, the film is prepared by compressing the second composition at a temperature of 60 ℃, or 70 ℃, or 80 ℃ to 90 ℃, or 100 ℃, or 110 ℃, or 120 ℃ with a compressive force of 200kN, or 250kN to 300kN, or 350kN, or 400kN for 1 minute, or 3 minutes, or 5 minutes to 7 minutes, or 10 minutes.

The membrane may comprise two or more embodiments described herein.

Vulcanized rubber/film laminate

The process of adhering the foam structure to the rubber substrate comprises applying a film to a surface of the rubber substrate to form a rubber substrate/film arrangement. The rubber substrate/film arrangement includes an unvulcanized rubber substrate having at least a portion of a facial surface in contact with at least a portion of a facial surface of the film. Pressure is applied to the rubber substrate/film arrangement at a temperature to form a vulcanized rubber/film laminate.

The foam structure may comprise any embodiment or combination of embodiments disclosed herein.

The rubber substrate may comprise any embodiment or combination of embodiments disclosed herein.

The membrane may comprise any embodiment or combination of embodiments disclosed herein.

The step of applying the film to the surface of the rubber substrate comprises contacting the surface of the film with the surface of the rubber substrate.

The compressive force is 200kN, or 240kN, or 300kN to 340kN, or 400kN, or 440kN, or 500 kN.

Compression temperature T_V(vulcanization temperature) is higher than the peak melting temperature (T) of the second ethylene-based polymer_E2). In one embodiment, the Tv is 130 ℃, or 140 ℃, or 150 ℃ to 160 ℃, or 170 ℃, or 180 ℃, or 190 ℃, or 200 ℃.

The compression time (cure time) is 10 minutes, or 12 minutes, or 15 minutes to 18 minutes, or 20 minutes.

In one embodiment, the vulcanized rubber/film laminate has a shore a hardness of 50, or 55, or 60, or 65 to 70, or 75, or 80, or 85, or 90.

In one embodiment, the vulcanized rubber/film laminate has a density of 1.0g/cc, or 1.1g/cc, or 1.2g/cc to 1.3g/cc, or 1.4g/cc, or 1.5 g/cc.

Vulcanized rubber-film/foam laminate

The process of adhering the foam structure to the rubber substrate further comprises the steps of: after forming the vulcanized rubber/film laminate to form the vulcanized rubber-film laminate/foam configuration, the foam is applied to the exposed surface of the film and a compressive force is applied at a temperature to form the vulcanized rubber-film/foam laminate.

The vulcanized rubber/film laminate can be any embodiment or combination of embodiments disclosed herein.

The foam structure may be any embodiment or combination of embodiments disclosed herein.

After forming the vulcanized rubber/film laminate to form the vulcanized rubber-film laminate/foam configuration, the step of applying the foam to the exposed surface of the film comprises contacting a surface of the foam with a surface of the vulcanized rubber/film laminate.

The pressure is 20kN, or 25kN, or 30kN to 35kN, or 40kN, or 45 kN.

The compression temperature TL (lamination temperature) is 80 deg.C or 85 deg.C, or 90 deg.C to 95 deg.C, or less than or equal to 100 deg.C.

At one isIn embodiments, T of the second ethylene-based polymer_LNot less than the peak melting temperature (T)_E2)。

In one embodiment, T of the first ethylene-based polymer_LPeak melting temperature (T)_E1)。

In one embodiment, T_LThe following relationship is satisfied:

T_E2≤T_L≤T_E1

in one embodiment, T_LThe following relationship is satisfied:

15℃≤(T_E1-T_L)≤40℃

that is, in one embodiment, the peak melting temperature (T) of the first ethylene-based polymer_E1) And lamination temperature (T)_L) The difference between them is greater than or equal to 15 ℃ or 20 ℃, or 25 ℃ to 30 ℃, or 35 ℃, or 40 ℃.

In one embodiment, T_LThe following relationship is satisfied:

10℃≤(T_L-T_E2)≤70℃

that is, in one embodiment, the lamination temperature (T) of the second ethylene-based polymer_L) And peak melting temperature (T)_E2) The difference between 10 ℃, or 15 ℃, or 20 ℃, or 25 ℃, or 30 ℃, or 35 ℃, or 40 ℃ to 45 ℃, or 50 ℃, or 55 ℃, or 60 ℃, or 65 ℃, or 70 ℃.

In one embodiment, T_LEach of the following relationships is satisfied:

T_E2≤T_L≤T_E1

15℃≤(T_E1-T_L)≤40℃

10℃≤(T_L-T_E2)≤70℃

in another embodiment, T_LAlso satisfies the relation of T being not less than 10 DEG C_L-T_E2Less than or equal to 65 ℃, or less than or equal to 10 ℃ and less than or equal to T_L-T_E2≤60℃。

The compression time (lamination time) is 1 minute, or 2 minutes, or 5 minutes to 6 minutes, or 8 minutes, or 10 minutes.

In one embodiment, the asker C hardness of the foam layer of the vulcanized rubber-film/foam laminate is 40, or 42, or 44, or 46 to 48, or 50, or 51, or 52.

In one embodiment, the foam has a hardness of less than 110%, or less than or equal to 109%, or less than or equal to 108%, or less than or equal to 107%, or less than or equal to 106% to 105%, or 104%, or 103%, or 102%, or 101%, or 100%, or 99%, or 98%, or 97%, or 96%, or 95% after lamination, relative to the hardness of the foam before lamination, wherein the relative foam hardness is in ((H) hardness₁/H₀) 100% of calculation, wherein H₀Is the hardness of the foam before lamination and H₁Is the hardness of the foam after lamination.

In one embodiment, the foam structure has an adhesion strength to the rubber substrate of greater than or equal to 3N/mm, or greater than 3N/mm. In one embodiment, the bond strength of the foam structure to the rubber substrate is greater than 3N/mm, or 3.5N/mm, or 4.0N/mm to 4.5N/mm, or 5.0N/mm, or 5.5N/mm.

In one embodiment, the failure mode after peel testing of the foam structure/rubber substrate bond is caused by foam tearing.

The vulcanized rubber-film foam laminate may comprise two or more embodiments disclosed herein.

By way of example, and not limitation, some embodiments of the disclosure will now be described in detail in the following examples.

Examples of the invention

Material

The materials used in this study are listed in tables 1-3 below. The compositions of the foam structure and the rubber substrate are also provided in tables 2-3 below.

Table 1: adhesive film material

Table 2: material and composition of foam structure

Table 3: material and composition of rubber substrate

Preparation of foam structures

The OBC was added to a 1.5 liter Branbury mixer. ZnO, ZnSt and CaCO were added after melting of OBC (about 5 minutes)₃. Finally, the blowing agent and peroxide were added and mixed for an additional 3-5 minutes for a total mixing time of 15 minutes. The rolled blanket was cut into squares and placed into a preheated slab foam mold. Preheating was carried out at 120 ℃ for 9 minutes and pressurization was carried out at 100kN for 4 minutes. The preheated material was transferred to the foaming press and heated at 100kg/cm²And held at 180 ℃ for 10 minutes. Once the pressure was released, the slab foam was quickly removed from the tray and placed on several non-stick sheets in a fume hood. It was cooled overnight and then cut into sheets ready for lamination with rubber substrates.

Preparation of unvulcanized rubber substrate

The ingredients listed in table 3 above were melt compounded using an internal mixer (3000cc volume, 72% fill factor) and a 6 "reliable roll mill to give sheets of 5mm thickness.

Preparation of adhesive film (second composition)

The POE or OBC pellets were placed in a 0.5mm mold (15cm square) which was further subjected to thermal compression at 130 ℃ for 5 minutes at a compressive force of 270 kN. The thickness of the adhesive film was 0.5 mm.

Preparation of vulcanized rubber/film laminate

The uncured rubber substrate was cold-pressed into 1mm sheets by a two-roll mill at 100 ℃ with a compression force of 200kN for 10 minutes. The adhesive film was stacked with a rubber substrate and then placed in a rubber vulcanization mold (15cm square). The mold was subjected to hot compression at 160 ℃ for 15 minutes at a compressive force of 300kN to form a vulcanized rubber/film laminate.

Preparation of vulcanized rubber-film/foam laminate

The foam structure (one sheet) was stacked on the exposed adhesive film side of the vulcanized rubber/film laminate to form a pre-structure. A one inch piece of release paper was inserted at one end of the pre-structure to prevent the film from adhering to the rubber substrate at that point, forming an unattached end, as shown in fig. 1. The structures were laminated in a hot press at different temperatures as shown in table 4 below at a compressive force of 30kN for 5 minutes. In this step, the compression force was set low to avoid deformation of the foam sample during compression. The final articles were all three-layer structures with a vulcanized rubber-film laminate/foam configuration. The thickness of the foam layer is about 3-5mm, the thickness of the adhesive film layer is less than 0.5mm, the thickness of the rubber layer is about 1mm, and the total thickness is about 5 mm. The total length of the final article was 15cm and the total width of the final article was 7.5 cm.

Table 4: lamination temperature and properties of vulcanized rubber-film laminate/foam structure

Adhesive strength of less than 3N/mm

The ratio of hardness to control foam structure at failure 2%

Acceptable adhesive strength greater than 3N/mm

Preferably, the bond strength is greater than 3N/mm, and foam tearing (material rupture) occurs when the bond fails

As the results in table 4 show, lamination temperatures above 100 ℃ resulted in shrinkage of the foam structure during lamination as evidenced by increased hardness. The vulcanized rubber-film laminate/foam structure laminated at a temperature above 100 ℃ has a foam hardness greater than 110% relative to the foam hardness of the control. It was also found that the adhesive film layer of the OBC resulted in a vulcanized rubber-film laminate/foam structure with an unacceptable foam hardness (greater than 110% foam hardness relative to the control) due to its higher melting point. POE has a lower melting point and a lower lamination temperature, and thus is useful as an adhesive film.

For the samples using POE as the adhesive film, a density of less than 0.858g/cm was used in the adhesive film as compared to other vulcanized rubber-film laminates/foam structures³Those vulcanized rubber-film laminate/foam structures of POE exhibited lower adhesive strength. Using a density in the adhesive film of greater than 0.890g/cm³The POE of (2) requires the use of higher lamination temperatures, resulting in increased foam shrinkage. The use of POE with a melt index between 1 g/10 min and 5 g/10 min in the adhesive layer also improved the bond strength in the samples.

In summary, it has surprisingly been found that when a thermoplastic polymer composition is prepared having a peak melting temperature (T)_E2) Is laminated on a rubber substrate serving as an adhesive layer between the rubber substrate and the foam structure first, and has a peak melting temperature (T)_E1) The first composition of the first ethylene-based polymer of (1) when the second ethylene-based polymer has a melt index of 10 g/10 min or less, and (2) the rubber substrate is adhered to each other by heating at a temperature T_vLaminating the substrate and film by applying a compressive force to a rubber substrate/film arrangement wherein T is 38 ℃ ≦ T_E2＜T_v(formation of a vulcanized rubber/film laminate), (3) by heating at a temperature T_LLaminating the foam to the vulcanized rubber/film laminate by applying a compressive force down to the vulcanized rubber-film laminate/foam configuration, wherein T_E2＜T_L＜T_E1，(4)15℃≤(T_E1-T_L) Not more than 40 ℃, and (4) not more than 10 ℃ (T)_L-T_E2) Less than or equal to 70 ℃. As shown in table 4 above, each of the above requirements (1) - (4) results in insufficient bond strength of the structure (less than 3N/mm) and/or an unacceptable increase in foam hardness of the structure (greater than 110% hardness to control foam structure).