WO2021108608A1 - Crosslinked polyolefin foam having large core cells - Google Patents
Crosslinked polyolefin foam having large core cells Download PDFInfo
- Publication number
- WO2021108608A1 WO2021108608A1 PCT/US2020/062298 US2020062298W WO2021108608A1 WO 2021108608 A1 WO2021108608 A1 WO 2021108608A1 US 2020062298 W US2020062298 W US 2020062298W WO 2021108608 A1 WO2021108608 A1 WO 2021108608A1
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- WO
- WIPO (PCT)
- Prior art keywords
- foam
- foam sheet
- surface region
- closed cell
- crosslinked polyolefin
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/56—After-treatment of articles, e.g. for altering the shape
- B29C44/5627—After-treatment of articles, e.g. for altering the shape by mechanical deformation, e.g. crushing, embossing, stretching
- B29C44/5654—Subdividing foamed articles to obtain particular surface properties, e.g. on multiple modules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/34—Chemical features in the manufacture of articles consisting of a foamed macromolecular core and a macromolecular surface layer having a higher density than the core
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/026—Crosslinking before of after foaming
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
- C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
- C08J2331/04—Homopolymers or copolymers of vinyl acetate
Definitions
- the present disclosure relates in general to polyolefin foams, and more particularly, to high recovery and splittable large core cell polyolefin foams and methods of producing the same, wherein the foams comprise numerous improved structural and mechanical properties both as a single sheet of foam (prior to splitting) as well as after being split into two sheets of foam, for example.
- Conventional methods of producing polyolefin foams include extruding a foamable sheet comprising thermoplastic resins, foaming agents and additives. Prior to foaming the foamable sheet in an oven at an activation temperature of the foaming agent, the foamable sheet may be crosslinked via irradiation by passing it through an electron beam irradiator, for example.
- electron beam irradiators are configured to deliver a sufficient dose of electrons to each side of the foamable sheet such that the electrons pass all the way through the foamable sheet material and exit out the other side while providing an even level of crosslinking throughout the foamable sheet. As the electrons pass through the foamable sheet, they impart their energy to the material forming crosslinks between the polymer strands and thereby strengthen the bonds throughout the thickness of the foamable sheet.
- a foamable sheet may be passed through an electron beam irradiator such that a first side is first exposed with irradiation.
- the irradiator is configured to deliver a sufficient does of electrons such that they travel from the first side and through the foamable sheet to exit from the opposing, second side, but the electrons lose some energy as they pass through and interact with the polymer material to crosslink it.
- This means that the level of crosslinking and therefore gel content will be high in a first side surface region and progressively diminish through the thickness of the foamable sheet to a second side surface region, producing a gradient of crosslinking.
- the sheet is subsequently passed through the electron beam irradiator again, but such that the second side is exposed with the same level of irradiation, thereby balancing the dose through the thickness of the foam and achieving an even level of crosslinking throughout including in the intermediate region of the foamable sheet where the crosslinking levels overlap.
- a foamable sheet irradiated according to such method after being foamed in an oven, will have an even degree of crosslinking throughout the thickness of the material, including in both surface regions and an intermediate region therebetween, as well as a uniform cell size throughout.
- Patent publication number US20030082364A1 discloses a foam material with variable crosslinking, wherein one side of the foam is intentionally dosed with a higher irradiation than the other side. Such a foam will have a first side region having a higher amount of crosslinking and smaller cell size, and a second side region having a lower amount of crosslinking and larger cell size.
- the reference discloses that the greater cross-linking on one side allows the material to be used in combination with a wider range of materials than is possible with foamed materials having uniform cross-linking.
- the foamed material with a varied amount of cross-linking can have either two distinct levels of cross-linking across the material or a gradient of cross-linking across the material, thus allowing control of a range of properties such as heat resistance during molding, allowing use of plastics with higher melt temperatures, improved compression set properties in the final product, and improved high temperature performance of the final product. Additionally, the reference discloses it is also possible to cross-link a second time after foaming through irradiation or the like. This allows the foam sheet to be produced with lower density without compromising the heat resistance required during the end-use process (such as low-pressure molding, insert molding, compression molding, etc.).
- some end-use applications require a single sheet of foam that can be split apart in a controlled, even manner, to produce two sheets of foam.
- the tear does not propagate consistently through a core or intermediate region of the foam, but rather surfaces on one side or the other resulting in only a portion or chunk of the foam being pulled apart.
- a double-sided foam tape for example, when an adhered object is removed from a wall or other substrate surface, the entire foam sheet may end up being pulled off the wall surface, off the object surface, or more often, tom randomly such that uneven portions of the foam remain on both the wall and the object. In a worst-case scenario, portions of the substrate or object may also be damaged and pulled off.
- the present disclosure relates to closed cell crosslinked polyolefin foam sheets, a process for splitting the closed cell crosslinked polyolefin sheets, and the split crosslinked polyolefin foam having a closed cell skin side and an open cell split side.
- a closed cell crosslinked polyolefin foam sheet comprises an opposing first surface region and second surface region, and an intermediate region disposed therebetween, wherein a ratio of a gel content of the intermediate region versus an average gel content of the first surface region and the second surface region is about 75% or less, and wherein a ratio of the average cell size of the intermediate region versus an average cell size of the first surface region and the second surface region is about 125% or higher.
- a closed cell crosslinked polyolefin foam sheet comprises an opposing first surface region and second surface region, and an intermediate region disposed therebetween, wherein the intermediate region is configured to have a gel content lower than an average gel content of the first surface region and the second surface region to enable a controlled tear propagation within the intermediate region when a splitting force is applied to the closed cell crosslinked polyolefin foam sheet.
- a process for producing split crosslinked polyolefin foam sheets comprises producing a crosslinked polyolefin foam sheet having an opposing first surface region and second surface region, and an intermediate region disposed therebetween, wherein the intermediate region is configured to have a gel content lower than an average gel content of the first surface region and the second surface region, and an average cell size larger than an average cell size of the first surface region and the second surface region; and applying a splitting force to the crosslinked foam sheet such that a controlled tear propagation travels through the intermediate region until a first side of the crosslinked polyolefin foam sheet and a second side of the crosslinked polyolefin foam sheet are separated to produce two split polyolefin foam sheets.
- a split crosslinked polyolefin foam sheet comprises a skin side comprising a closed cell surface; and a split side comprising an open cell surface having peak heights of about 150 pm to about 550 pm.
- FIG. 1 is a schematic perspective view of a foamable sheet according to the present disclosure.
- FIG. 2 is a schematic perspective view of a foam sheet after foaming the foamable sheet of FIG. 1.
- FIG. 3 is a schematic side cross-sectional view of the foam sheet of FIG. 2.
- FIG. 4 is a schematic side view of the foam sheet of FIGS. 2 - 3 adhered to a substrate on one side and being split apart.
- FIGS. 5 A and 5B are schematic side views of the foam sheet of FIGS. 2 - 3 during splitting and after being split apart, respectively.
- FIG. 6 is a schematic view of an example production splitting process for the foam sheet of FIGS. 2 - 3 according to the present disclosure.
- FIGS. 7A - 7C are graphs of gel ratio versus foam density for foam sheets of the present disclosure.
- FIGS. 8A - 8C are graphs of cell size ratio versus foam density for foam sheets of the present disclosure.
- FIGS. 9A - 9C are graphs of 50% compression set versus foam density for foam sheets of the present disclosure.
- FIG. 10 is a schematic diagram of the splitting force strength testing apparatus according to the present disclosure.
- FIGS. 11 A - 11C are graphs of splitting force strength versus foam density for foam sheets according to the present disclosure.
- FIGS. 12A - 12C are graphs of T peel strength versus foam density for foam sheets according to the present disclosure.
- FIG. 13 is a graph of dent depth recovery for foam sheets according to the present disclosure.
- FIG. 14 is a graph of peak heights versus foam density for split foam sheets according to the present disclosure.
- FIG. 15 is a graph of surface roughness versus foam density for split foam sheets according to the present disclosure.
- FIG. 16A is a graph of the kinetic coefficient of friction versus foam density for split foam sheets according to the present disclosure.
- FIG. 16B is a graph of the static coefficient of friction versus foam density for split foam sheets according to the present disclosure.
- FIG. 17 is a graph of average sound reduction (transmittance acoustic) versus foam basis weight for split foam sheets according to the present disclosure.
- FIG. 18 is a graph of water mass gained (surface water retention) versus foam density for split foam sheets according to the present disclosure.
- FIG. 19 is a graph of peel strength versus test surface type for split foam sheets according to the present disclosure.
- the foam comprises numerous improved structural and mechanical properties both as a single sheet of foam, as well as after being split into two sheets of foam, for example.
- the foam comprises an intermediate region configured to allow controlled split tear propagation when a threshold splitting force is applied, such that a first side and second side of the foam split apart from one another in a consistent and even manner through only the intermediate region, and without undesired tears in the foam outside of that region.
- a manufacturing process for splitting the foam without the need for skiving.
- FIG. 1 is a perspective view of a foamable sheet 10, having a first side A, a second side B, an intermediate region 12 between sides A and B, as well as surface region 14A between intermediate region 12 and side A, and surface region 14B between intermediate region 12 and side B. Further represented are the machine direction MD (i.e. length dimension), the transverse direction TD (i.e. width dimension), and Z direction ZD (i.e. thickness dimension) of the foamable sheet 10, in reference to the direction of extrusion of the sheet.
- the foamable sheet may be made according to various processes common in the art, including extrusion, and may include one or more resins, a foaming agent, and suitable additives.
- Polymers or resins suitable for use in the foamable sheet include but are not limited to low density polyethylene (LDPE), linear low density polyethylene (LLDPE); medium density polyethylene (MDPE); high density polyethylene (HDPE); ethylene vinyl acetate (EVA); polypropylene (PP); ethylene propylene diene monomer (EPDM), thermoplastic olefin (TPO), thermoplastic elastomer (TPE), and rubber.
- LDPE low density polyethylene
- LLDPE linear low density polyethylene
- MDPE medium density polyethylene
- HDPE high density polyethylene
- EVA ethylene vinyl acetate
- PP polypropylene
- EPDM ethylene propylene diene monomer
- TPO thermoplastic olefin
- TPE thermoplastic elastomer
- Rubber Rubber
- each side A and B of foamable sheet 10 is irradiated at a lower energy configured based on the material and effective thickness of foamable sheet 10.
- the electrons entering each side in opposite directions penetrate a thickness of the foamable sheet that overlaps in the intermediate region 12 before losing energy and stopping their travel within the foamable sheet, rather than exiting the other side surface.
- the slowing down and eventual extinction of high energy electrons after travelling a certain distance through a material may be referred to as the practical range of those electrons.
- electron beam irradiators can be adjusted to change their voltage potential (kV) and current (mA) to affect the amount of dose (Mrads), for example, based on the effective thickness (ET) of the foamable sheet 10 and its material type. ET is calculated by the actual thickness of the foamable sheet (mils), multiplied by the density of the material (g/cm 3 ).
- Other variables that may be adjusted according to ordinary skill in the art are line speed (m/min) of the foamable sheet 10 traveling through the electron beam irradiation machine, and the scan beam width (in) of electrons. For example, if line speed is increased, then dose (Mrad) can be kept constant while the current (mA) must be adjusted accordingly.
- the foamable sheet 10 can then be foamed at or above an activation temperature of the foaming agent.
- foamable sheet 10 will expand in each direction TD, MD and Z to produce foam 10A (e.g., a foamed sheet).
- Foam 10A will have a resulting gel content in the intermediate region 12 that is lower than the gel content of regions 14A and 14B, and will furthermore have a symmetrical cell size structure, with larger cells in the intermediate region 12 and proportionally smaller cells in the surface regions 14A and 14B, as described in more detail below. Importantly, this structure is achieved within the single sheet of foam 10A, and does not require lamination or co-extrusion of other foams or other post processing steps.
- FIG. 3 is a cross section of foam 10A of FIG. 2, showing that a larger cell structure in intermediate region 12 has resulted after foaming due to the lower degree of crosslinking (and lower gel content) in that region after utilizing the novel controlled depth crosslinking method.
- Cell formation may be influenced, for example, by the degree of crosslinking in the polymers around the foaming agent in the material, thereby restricting the expansion of gas from the foaming agent during the foaming process. If the degree of crosslinking is even throughout the foamable sheet, as well as the activation of foaming agent during the foaming process, then cells will normally expand to reach a similar restricted size throughout the material in relation to the degree of crosslinking.
- the gel content and cell size of the intermediate region 12 of foam 10A can be tightly controlled and configured for certain specifications versus surface regions 14A and 14B, including desired performance properties. These specifications and desired properties can not only be controlled for the single sheet of foam 10A, but also with respect to each sheet of foam produced after the foam has been split through controlled tear propagation, which is also enabled by the present methods.
- the foam may have a gel ratio configured to be between about 90% or less, preferably about 75% or less, more preferably about 50% or less.
- Gel ratio is calculated by comparing the gel content of the intermediate region 12 to the total average gel content of surface regions 14A and 14B, as further described in Example 1 of the present disclosure.
- the gel ratio may be between about 15% to about 90%, preferably between about 15% to about 75%, more preferably about 15% to about 50%.
- the thickness of the intermediate region 12 may also be adjusted to suit the needs of the foam application, but generally is between about 1/3 to about 2/3 of the overall foam thickness.
- the cell size ratio of the single sheet of foam 10A produced by the methods herein may be calculated as the difference in cell sizes between the intermediate region 12 divided by the total average of the surface regions 14A and 14B, as further described in Example 2 of the present disclosure.
- the cell size ratio may be configured to be about 125% or higher, preferably about 200% to about 400%, more preferably about 250% to about 400%.
- Suitable densities of foams produced according to the methods of the present disclosure may be between about 1.5 pcf to about 20 pcf, preferably about 1.5 pcf to about 15 pcf, more preferably about 2 pcf to about 10 pcf.
- the foam 10A may be tailored to have desirable properties suitable for a wide range of applications.
- foams produced according to the methods of the present disclosure may have a 50% compression set of under about 10%, preferably about 3% to about 10%, more preferably about 4% to about 9%, which is not achievable with standard irradiated foams.
- Foam 10A produced by the methods of the present disclosure may also be configured to have improved dent depth recovery versus standard foams, including recovery improvements of about 55% to about 80% versus the standard foams, as well as improvements of about 35% to about 65% versus standard foams even after post-crosslinking the foam to improve its heat resistance, as described in more detail with reference to Example 7 of the present disclosure.
- Foam 10A may, for example, have a dent depth of about 35% to about 45% of the original thickness at zero hours and about 4% to about 6% of the original thickness after 168 hours according to test standard VDA237-101-2.
- foam 10A may have dent depth recovery of about 50% to about 55% of the original thickness at zero hours and about 5% to about 10% of the original thickness after 168 hours according to test standard VDA237-101-2 after the polyolefin foam sheet has been post-crosslinked to have a gel content in the intermediate region of about 50% or higher.
- the lower degree of crosslinking or gel content in intermediate region 12 may be configured relative to surface regions 14A and 14B based on the irradiation and foamable sheet 10 conditions to enable a controlled split tear propagation along the intermediate region 12 of foam 10A when a threshold splitting force is applied to the foam sheet 10 A.
- the threshold splitting force may be determined based on the needs of the end-use application, for example, adjusting the degree of crosslinking such that it is sufficiently high enough to satisfy the holding strength of a foam tape application, while also being sufficiently low enough to enable the controlled, even split tear propagation along and within the bounds of intermediate region 12 and without damaging any substrate or object adhered to the foam 10 A.
- FIG. 4 shows an example of foam sheet 10A adhered on side B to substrate S, while a splitting force SF is represented by a few example vectors pulling on side A either in the Z direction or at some acute angle relative thereto.
- a splitting force SF is represented by a few example vectors pulling on side A either in the Z direction or at some acute angle relative thereto.
- new open cell surfaces 22A and 22B arise, with open cell surface 22A being opposite closed cell surface A, and open cell surface 22B being opposite closed cell surface B.
- split tear propagation line 16 which stays within intermediate region 12 in a controlled manner during splitting of foam 10 A, thereby allowing side A of foam 10A to be evenly peeled away from side B when a threshold splitting force SF is applied, such as by a user, ultimately producing two separate foam sheets from halves 20A and 20B.
- the relative degree of crosslinking of surface regions 14A and 14B and intermediate region 12 may be configured and tailored to meet the specific needs of an application, for example, to avoid damaging substrate S when an object bound to side A is pulled away at a threshold splitting force PF.
- a foam produced from a foamable sheet 10 according to the prior art methods when split lengthwise (MD) or across (TD) by applying a splitting force in the Z direction (ZD), for example, will not generate an even split tear propagation through the material. Rather, the tear 16 will propagate randomly through the material, outside of intermediate region 12, and may surface at either side A or B of foam 10A, at which point a chunk of the foam may tear off before the whole side has been peeled away. This is particularly troublesome for some foam tape applications where it is desired to evenly split one side of the foam away from the other, or methods where it is desirable to continuously peel side A away from side B to produce two foam sheets from one foam sheet.
- FIG. 5 A shows a similar concept of splitting foam 10A as shown in FIG. 4, except wherein neither side of foam 10A is anchored to a substrate, such that foam 10A may be pulled apart by two separate opposing splitting forces SF to produce two separate foams 20A’ and 20B’.
- new open cell surfaces 22A and 22B arise, with open cell surface 22 A being opposite closed cell surface A in foam 20A’, and open cell surface 22B being opposite closed cell surface B in foam 20B’.
- Splitting force strength of foam 10A is measured as described in Example 4 of the present disclosure according to the splitting force strength test method, and may be configured to be between about 5 lbf to about 35 lbf, preferably about 8 lbf to about 33 lbf, more preferably about 9 lbf to about 30 lbf.
- the splitting force strength of foams of the present disclosure may be significantly reduced in comparison to standard foams having comparable densities, the reduction being between about 25% to about 80%, preferably between about 30% to about 70%, more preferably between about 40% to about 60%.
- T peel strength of foam 10A is measured as described in Example 5 of the present disclosure according to the T peel strength test method and may be configured to be between about 1 lbf to about 5 lbf, preferably about 1.5 lbf to about 4 lbf, more preferably about 1.6 lbf to about 3.1 lbf.
- the T peel strength of foams of the present disclosure may be significantly reduced in comparison to standard foams having comparable densities, the reduction being between about 20% to about 70%, preferably about 30% to about 60%, more preferably about 40% to about 50%.
- FIG. 6 is a schematic diagram of manufacturing process 100 showing an example of how the foam 10A according to the present disclosure may be continuously split.
- Feed roll F containing foam 10A may be fed to pairs of nip rollers Nl, N2 rotating in opposite directions, such as Nl in a counterclockwise and N2 in a clockwise direction as shown.
- a splitting force SF such as shown in FIG. 5A can be achieved mechanically from both sides A and B of foam 10A, thereby yielding two sheets of foam 20A’ and 20B’ that can be guided with the aid of guide rollers as needed and finally wound up by winding machines W1 and W2.
- the foam 10A can be split in half using only the nip rollers Nl, N2. Further, the rate at which the foam 10A may be split is sufficiently fast to enable it to be part of an in-line manufacturing process with the foam production itself.
- the controlled split tear propagation enabled by the present disclosure is so effective, it may be tailored to produce two split foams 20 A’ and 20B’ each having an average gauge of about 30% to about 70% of the original full gauge of the unsplit foam 10A, preferably about 40% to about 60%, more preferably about 45% to about 55%. Further, split foams 20A’ and 20B’ may also each have a mass of about 30% to about 70% of the original full mass of the unsplit foam 10A, preferably about 40% to about 60%, more preferably about 45% to about 55%.
- Split foams 20A’ and 20B’ may also each have a density of about 75% to about 125% of the original full density of the unsplit foam 10A, preferably about 85% to about 115%, more preferably about 90% to about 110%, as described further in Example 8 of the present disclosure.
- the method of the present disclosure may yield maximum variances of about 20% for gauge (from and ideal of 50%), about 10% for mass (from an ideal of 50%), and about 16% for density (from an ideal of 100%), as described further in Example 8 of the present disclosure.
- the method of the present disclosure may also yield maximum average variances of only about 5% for gauge (from and ideal of 50%), about 2% for mass (from an ideal of 50%), and about 6% for density (from an ideal of 100%), as described further in Example 8 of the present disclosure.
- foams 20 A’ and 20B’ may also be configured for numerous desirable properties.
- foams 20A’ and 20B’ may also comprise advantageous physical characteristics that provide for additional performance advantages as described herein.
- peak heights of surfaces 22A and 22B may range from about 150 pm to about 550 pm, preferably from about 200 pm to about 500 pm, and may comprise about a 12 fold increase in peak heights compared with standard foam skin (closed cell surface), and about a 4 fold increase compared with a standard foam skived surface (open cell surface), as described further in Example 9 of the present disclosure.
- Surface roughness (Sa) of surfaces 22A and 22B may range from about 70 pm to about 150 pm, preferably between about 75 pm to about 140 pm, more preferably between about 80 pm to about 135 pm, and may comprise about a 6 fold increase in surface roughness compared with standard foam skin (closed cell surface), and about a 1.8 fold increase compared with a standard foam skived surface (open cell surface), as described further in Example 10 of the present disclosure.
- the split foams 20 A’ and 20B’ may also be configured such that the coefficient of friction (COF) between surfaces 22 A and 22B ranges between about 1.0 lbf to about 4.5 lbf, preferably about 1.5 lbf to about 4.0 lbf, more preferably about 1.8 lbf to about 3.5 lbf for static COF, and for kinetic COF, between about 1.0 lbf to about 4.0 lbf, preferably about 1.5 lbf to about 3.5 lbf, more preferably about 1.5 lbf to about 3.0 lbf.
- COF coefficient of friction
- this may comprise about a 4.1 fold increase compared with standard foam skin (closed cell surface), and about a 3.3 fold increase compared with a standard foam skived surface (open cell surface); and for kinetic COF, may comprise about a 4.4 fold increase compared with standard foam skin (closed cell surface), and about a 3.7 fold increase compared with a standard foam skived surface (open cell surface), as described further in Example 11 of the present disclosure.
- the split foams 20 A’ and 20B’ may also be configured such that the average sound reduction achieved by surfaces 22A and 22B ranges between about 5 dB to about 25 dB, preferably about 5dB to about 20 dB, more preferably about 8 dB to about 17 dB according to the transmittance acoustic test method described in Example 12 of the present disclosure.
- Split foams surfaces 22A and 22B according to the present disclosure will perform better than any standard foam skin surface of comparable basis weight, and better than any standard foam skived surface for basis weights of about 7 g/sqft or above.
- the split foams 20 A’ and 20B’ may also be configured such that the surface water retention of surfaces 22A and 22B ranges between about 0.010 grams to about 0.050 grams, preferably about 0.015 grams to about 0.045 grams, more preferably about 0.017 grams to about 0.043 grams according to the surface water retention test method described further in Example 13 of the present disclosure, and may comprise about a 3.9 fold improvement compared with a standard foam skin surface, and about a 1.5 fold improvement compared with a standard foam skived surface.
- the split foams 20 A’ and 20B’ may also exhibit superior adhesive properties on surfaces 22A and 22B, having beter adhesive anchorage than a standard foam skived surface, and comparable performance to a standard foam skin surface.
- the skin peel strength of the split foam surface may be about 0.95 N/mm or greater, preferably about 1.00 N/mm or greater, more preferably about 1.10 N/mm or greater, according to the adhesive test method and results described further in Example 14 of the present disclosure.
- EVA is ethylene-vinyl-acetate
- PE is polyethylene
- PP is polypropylene
- LDPE low-density polyethylene
- LLDPE linear low-density polyethylene
- AO antioxidant
- h-PP is a homopolymer of PP
- TPE is a thermoplastic elastomer
- AR denotes “as required” to achieve the target density of the foam as is known in the art.
- foamable sheets were then foamed at an activation temperature of the foaming agent to produce foam samples having varying densities for testing according to the procedures below.
- A-side and B-side results were averaged to generate an outside gel content value, and then the measured gel content value of the core region was divided by the averaged outside gel content value to create a ratio of core to outside.
- the results are shown in TABLES 2A, 2B, and 2C below, and corresponding FIGS. 7A, 7B, and 7C, respectively.
- surface region 14 A and surface B were measured for each irradiated sample of foam produced according to the experimental method above.
- a perpendicular cut to the foam was made using a sharp razor blade to make sure the sliced surface was pristine.
- a microscope Keyance 3D microscope VHX-6000 with measurement capability, cross- sections were observed from each region of foam. In particular, five cells were selected from the A-side and five cells from the B-side, close to the surface, and then cell sizes were measured in the z-direction, with the average cell sizes determined. Further, ten cells from the core region were selected and measured in the z-direction, and the average determined.
- the cell size ratio for the control samples all hovered around 100%, indicating an even level of cell size throughout the samples.
- the cell size ratios for the controlled depth crosslinking samples were all consistently much higher than the controls, meaning the cell size in the cores was much larger than the cell size in the surface regions. These cell size ratios were achieved from about 220% to about 365% according to the methods of the present disclosure.
- the 50% compression set was improved (lowered) for all the samples versus the standard control foams.
- the 50% compression set was at least as good or comparable to standard PP foams, such that performance was not sacrificed.
- Splitting force strength was measured for each irradiated sample of foam produced according to the experimental method above. Splitting force strength was measured according to the fabricated apparatus shown in FIG. 10 using the splitting force strength test method as follows. Each foam sample was corona treated on both sides, then a strong pressure sensitive adhesive was applied to both sides of the foam 10A to convert it into a double-sided foam tape. The foam tape was then cut down to 2 inch x 1 inch specimens. Making sure the stainless steels of the jig were clean, the double-sided foam tape 10A was applied on to the small stainless-steel plate (“S.S. Small Plate” of FIG. 10), on the end without the slit and on the side without the indentation.
- S.S. Small Plate small stainless-steel plate
- the small stainless steel and foam assembly was placed into the 2 inch wide slot of the placement jig, and then the placement jig's hook was placed at the end of the big stainless steel plate (“S.S. Big Plate” of FIG. 10).
- the small plate was pressed firmly onto the big plate and the placement jig was removed.
- the small stainless steel and foam assembly was located 1 inch away from the end of the big plate.
- the tape was allowed to cure for 24 hours.
- the big plate was slid into the table, and the post under the table was inserted into an instron machine.
- the horizontal rod was slid under the small plate, into the indented area, and the vertical rod was allowed to rise up into the slit.
- MD machine direction
- CM cross-machine direction
- FIGS. 11 A, 11B, and 11C respectively.
- splitting force strength set was reduced (improved) in each PP, PE and EVA sample compared with the controls of a given density, the % reduction ranging from about 25% to about 80%.
- T peel strength was measured for each irradiated sample of foam produced according to the experimental method above.
- the T peel strength test method was performed as follows. A 1 inch x 6 inch specimen was cut out from each foam sample. The samples were partially split by splitting apart approximately 1 inch of the sample material by hand in the case of the foam samples produced by controlled depth crosslinking (having large cell size in core region), or by using a razor in the case of the control samples. The two ends from the partial split were pinched by the instron grips, and the instron was run in extension mode at 10 inches/min for 3 inches, measuring the max force to split the foam in half in pounds. It was observed that the foam samples produced with controlled depth crosslinking continued to split consistently and evenly over the entire 3 inches, while the control samples ripped unevenly shortly after the extension started.
- FIGS. 12 A, 12B, and 12C respectively. TABLE 6 A
- T peel strength was calculated for each control sample of a same density based on the trend data from FIGS. 9A and 9B respectively, and compared in TABLE 6D below. As shown, T peel strength was reduced (improved) in each PP, PE and EVA sample compared with the controls of a given density, the % reduction ranging from about 25% to about 70%.
- Example 6 Post-crosslinking: Heat Resistance [0085] Heat resistance was measured for each irradiated sample of foam produced according to the experimental method above. EVA foam samples were produced with the controlled depth crosslinking method, and post-crosslinking (post-XL) samples were produced by subjecting the EVA foam samples to post-foaming irradiation until their core regions had a gel content of at least 50%. These samples were both compared against standard EVA control foams of comparable density to determine their ability to withstand 21 seconds of extreme heat in a thermal former such that the surface temperature of the foams reached around 225C. The results are shown in TABLE 7 below. TABLE 7
- the EVA control foam showed areas of surface degradation, signifying the heat was above the foam's maximum process temperature.
- the EVA foam sample (having lower gel content core) not only had surface degradation, but severe cases of blistering all over the surface. Blistering was caused by the large core cells rupturing, combining multiple cells into larger cells that appear as blisters under the surface. This happened to the EVA foam sample because the gel in the core area was low and too weak to be heat stable.
- the post- crosslinked (post-XL) EVA foam sample received an additional dose of irradiation, strengthening the foam in the core area and increasing gel content there, while preserving the large cell structure.
- the foam surprisingly no longer blistered, but only exhibited surface degradation from the excessive heat, much like the standard EVA control foam. Accordingly, the controlled tear propagation and other performance benefits of the foam samples may be preserved while also imparting heat resistance features to the foam through post-crosslinking.
- Example 7 Post-crosslinking: Dent Depth Recovery
- EVA foam samples were produced with the controlled depth crosslinking method, and post-crosslinking (post-XL) samples were produced by subjecting the EVA foam samples to post-foaming irradiation until their core regions had a gel content of at least 50%.
- post-XL samples were both compared against standard EVA control foams of comparable density to determine their dent depth recovery performance as measured by automotive test standard VDA237-101-2 after 24, 48 and 168 hours. The results are shown in TABLE 8A below.
- FIG. 13 is a graph of the 2kg dent depth recovery shown in TABLE 8.
- both EVA samples including the post-crosslinked one display superior dent depth recovery to the standard EVA control foam, while the post-crosslinked sample only suffers a marginal performance reduction compared with the EVA sample that wasn’t post-crosslinked. Accordingly, the mechanical and performance features of the foam samples produced according to the method of the present disclosure can largely be preserved even after the benefits of post-crosslinking are imparted on such samples.
- Example 8 Split Foam Gauge. Mass and Density
- Foam samples produced according to the experimental method above for controlled depth crosslinking were measured for gauge and mass before and after splitting them apart using controlled tear propagation down the intermediate/core region of the foam such as described previously with reference to FIGS. 4 - 6, such that the resulting split foam samples could be evaluated for their consistency in gauge, mass and calculated density. Mass was measured using a calibrated scale, and gauge was measured using a calibrated micrometer.
- ten 4 inch x 4 inch specimens were cut from the center of the foam sheet sample at 1 inch spacing. The gauge and mass were measured and used to calculate the density of each specimen. Then, each specimen was split using controlled tear propagation into an A-side and B-side. The gauge and mass of each A-side and B-side split foam sample was then measured and corresponding density was calculated. Since some deformation of the foam specimens would occur from the force of splitting it, the gauge measurements were taken from non-deformed areas of the split foam sides.
- the gauge, mass and density were then averaged across all the specimens from each foam sample, and each value was compared before and after splitting the foam.
- the machine direction (MD) comparison is provided in TABLE 9A below, while the cross-machine (CM) comparison is provided in TABLE 9B below.
- Each value is expressed as a percentage of the original unsplit foam sample, such that a perfectly and evenly split foam would yield, for each side, an ideal A-side average as well as a B-side average gauge and mass as close as possible to 50% of the original unsplit sample, as well as a density as close as possible to 100%.
- the maximum amount of variance for the samples from the ideal values was also determined and is shown in the TABLES 9A, 9B below, as well as the average variance of the samples from ideal.
- the maximum amount of gauge variance of a split foam specimen was 16%, but on average, was only 5% at most.
- the maximum amount of variance of a split foam specimen was 7%, but on average, was only 2% at most.
- density the maximum amount of variance of a split foam specimen was 14%, but on average, was only 6% at most. Therefore, the foam samples produced by the experimental method had a tear propagation that was highly consistent through the core of the foam, leading to A-sides and B-sides having very little average variance in gauge, mass and density, making this method of the present disclosure highly suitable for mass production of foam such as described with reference to FIG. 6.
- Foam samples produced according to the experimental method above for controlled depth crosslinking were measured under a 3D microscope to assess surface peak heights.
- split foam samples that were tom apart using controlled tear propagation down the intermediate/core region of the foam such as described previously with reference to FIGS. 4 - 6 were measured for peak heights on the new open cell surface (such as 22 A and 22B as shown in FIGS. 5A and 5B) as well as measuring the same surface for standard foam samples that had been skived apart using a blade.
- peak heights were also measured on the skin side surface (closed cell surface, such as side A and B in FIGS. 5A and 5B) as a control.
- a Keyence 3D microscope VHX-6000 was used to determine peak heights by placing each specimen under the microscope, and using the built-in function, scanning a 5mm x 5mm area. The base-height was established by taking the average of the entire heights within the scanned area. Local high peaks were selected, and the peak heights were measured relative to the established base-height using the microscope's function. The results are shown in TABLES 10A, 10B and IOC below for each density of foam sample measured, and were further graphed as shown in FIG. 14. TABLE 10A
- the split foam open cell surfaces of each sample had much higher average peak heights than either the skived or the skin surface of comparable foams. Comparing average peak heights, the split foam surface was about 11.8 times higher than skin, and about 4.1 times higher than skived foam surfaces.
- Foam samples produced according to the experimental method above for controlled depth crosslinking were measured under a 3D microscope to assess surface roughness.
- split foam samples that were tom apart using controlled tear propagation down the intermediate/core region of the foam such as described previously with reference to FIGS. 4 - 6 were measured for surface roughness on the new open cell surface (such as 22A and 22B as shown in FIGS. 5A and 5B) as well as measuring the same surface for standard foam samples that had been skived apart using a blade.
- surface roughness was also measured on the skin side surface (closed cell surface, such as side A and B in FIGS. 5A and 5B) as a control.
- a Keyence 3D microscope VHX-6000 was used to determine surface roughness by placing each specimen under the microscope, and using the built-in function, scanning a 5mm x 5mm area, with surface areas measured by the microscope to calculate a roughness value Sa.
- Sa is the arithmetic average of the surface roughness, and is the extension of Ra arithmetical mean height of a line. It expresses, as an absolute value, the difference in height of each point compared to the arithmetical mean of the surface.
- TABLES 11 A, 11B and 11C below for each density of foam sample measured, and were further graphed as shown in FIG. 15.
- Foam samples produced according to the experimental method above for controlled depth crosslinking were assessed according to ASTM D1894 to measure their coefficient of friction (COF), both kinetic COF and static COF.
- COF coefficient of friction
- split foam samples that were tom apart using controlled tear propagation down the intermediate/core region of the foam such as described previously with reference to FIGS. 4 - 6 were measured for COF on the new open cell surface against the opposing open cell surface (such as 22A against 22B as shown in FIGS. 5A and 5B) as well as measuring the same opposing surfaces for standard foam samples that had been skived apart using a blade.
- COF was also measured on opposing skin side surface (closed cell surface, such as side A against side B in FIGS. 5A and 5B) as a control.
- the results are shown in TABLES 12A, 12B and 12C below for each density of foam sample measured, and were further graphed as shown in FIGS. 16A and 16B.
- the split foam open cell surfaces of each sample had a much higher COF, both static and kinetic, than either the skived or the skin surfaces of comparable foams. Comparing average static COF, the split foam surface was about 4.1 times higher than skin, and about 3.3 times higher than skived foam surfaces. Comparing average kinetic COF, the split foam surface was about 4.4 times higher than skin, and about 3.7 times higher than skived foam surfaces.
- Foam samples produced according to the experimental method above for controlled depth crosslinking were assessed for their transmittance acoustic properties to determine the average sound reduction achieved by the foam.
- split foam samples that were tom apart using controlled tear propagation down the intermediate/core region of the foam such as described previously with reference to FIGS. 4 - 6 were measured for average sound reduction across the new open cell surface (such as 22A or 22B as shown in FIGS. 5 A and 5B) as well as measuring the same for standard foam samples that had been skived apart using a blade.
- average sound reduction was also measured on skin side surfaces (closed cell surface, such as side A or side B in FIGS. 5A and 5B) as a control.
- the transmittance acoustic test method was performed as follows. Two 4-inch- long x 12 inch diameter PVC pipes were prepared. One end of both pipes with closed with 1- inch thick wood pieces. A 3/4-inch diameter hole was drilled in the center of one of the wood pieces. The pipe without the drilled hole was placed on the table, wood end down. A bluetooth speaker was placed in the center of the first pipe, facing up. A 12-inch x 12-inch foam specimen was placed on the first PVC pipe opening with the tested surface facing the speaker. The second PVC pipe with the drilled hole was used to sandwich the specimen, with wood facing up. A decibel meter was inserted through the hole on top, approximately 3 inches above the foam specimen.
- a tone generator software application was used to play a tone ranging from 1000 Hz to 20,000Hz at 1000 Hz intervals, and the resulting decibels passing through the foam specimen were recorded, making sure the volume was not too loud to avoid maxing out the decibel meter's functional range. The process was then repeated without the foam specimen to generate the baseline control measurement. Once data was collected, a best fit linear line was generated through the data to find the equation. Using the equation, the dB at 1000Hz and 20000Hz was calculated, and then the specimen values were subtracted from the baseline values to generate the sound reduction value. Then, the average sound reduction value was calculated to generate one value to describe the level of sound reduction from the specimen tested. The average sound reduction value was then graphed relative to the calculated basis weight of each foam specimen.
- the split foam open cell surface samples had superior average sound reduction performance compared with standard skin surfaces of foam for all basis weights of foam.
- the split foam surface had superior average sound reduction performance for basis weights of foam at about 7 g/sqft or above.
- Foam samples produced according to the experimental method above for controlled depth crosslinking were assessed for their surface water retention properties.
- split foam samples that were tom apart using controlled tear propagation down the intermediate/core region of the foam such as described previously with reference to FIGS. 4 - 6 were measured for surface water retention properties on the new open cell surfaces (such as 22A or 22B as shown in FIGS. 5A and 5B) as well as measuring the same for standard foam samples that had been skived apart using a blade.
- surface water retention was also measured on skin side surfaces (closed cell surface, such as side A or side B in FIGS. 5A and 5B) as a control.
- the surface water retention test method was performed as follows. 4-inch x 4- inch foam specimens and a shallow vat of water were prepared. Each specimen was dry weighed, then the specimen's side of interest was placed onto the water so it floated. The specimens were allowed to float for 45 seconds. During that time, forceps were used to glide each specimen over the surface of the water to make sure any trapped air under the specimen escaped while making sure no water got on the dry side. After 45 seconds, the specimen was picked up from the water and placed on a scale, dry side down, to weigh the new mass including any water that was retained by the specimen. The before and after masses were compared to calculate the amount of water retained on the surface of each specimen.
- the split foam retained more water on its surface than either the standard skin or skived foam surfaces. This result is interesting in part because even a skived foam will present an open cell surface, however, the particular surface characteristics of the split foam open cell surface made it superior at retaining water, potentially due to the increase in peak heights and surface roughness as described with respect to previous examples. Comparing the total average water retention, the split foam surface retained about 3.9 times more water than the skin surfaces, and about 1.5 times more water than the skived foam surfaces.
- Foam samples produced according to the experimental method above for controlled depth crosslinking were assessed for their adhesive properties.
- split foam samples that were tom apart using controlled tear propagation down the intermediate/core region of the foam such as described previously with reference to FIGS. 4 - 6 were measured for adhesive properties on the new open cell surfaces (such as 22 A or 22B as shown in FIGS. 5A and 5B) as well as measuring the same for standard foam samples that had been skived apart using a blade.
- adhesive properties were also measured on skin side surfaces (closed cell surface, such as side A or side B in FIGS. 5A and 5B) as a control.
- the adhesive test method was performed as follows. Across the width of the foam samples, 3 specimens were cut in the MD direction, 350 mm x 50 mm. Both sides were then corona treated. Samples with a density lower than 3.2 pcf did not need to be treated. Samples with densities greater than 12.5 pcf were not tested.
- a pressure sensitive double-sided tape was prepared using a Coatema coating machine with KS900 as the release liner. 65g/m2 of Collano T2 1434 was applied at 160°C. The foam specimen was coated on both sides with the prepared double-sided tape while avoiding trapping any air. The adhesive was rolled down twice with a 5kg roller and a uniform speed of 600 mm/min.
- the specimens were die cut to 300 mm x 25 mm. Release liner was removed on one side and a MYLAR PET film was placed, 0.019mm thick, and then rolled twice with a roller as above.
- a plane chromium-nickel plate 50mm x 210mm was cleaned with 600 grit paper (in length direction only) and any shavings, grease, etc. were removed with a lint free paper soaked in benzene. About 11 cm of the other release liner was removed from the specimen and placed so the opened adhesive side was on the cleaned metal plate. Starting with the edge of the specimen at the cleaned edge of the metal plate, a roller was used to roll it down four times with a roller as above.
- foam tear referred to a situation where the foam itself tore
- adhesive foam failure referred to a situation where the foam-adhesive tape interface failed, which is a sign that the adhesive is not getting a good anchorage to the foam.
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CN202080081508.2A CN114765983A (en) | 2019-11-28 | 2020-11-25 | Crosslinked polyolefin foam having large core pores |
EP20892318.5A EP4065363A4 (en) | 2019-11-28 | 2020-11-25 | Crosslinked polyolefin foam having large core cells |
JP2022530752A JP2023503983A (en) | 2019-11-28 | 2020-11-25 | Crosslinked polyolefin foam with large core cells |
AU2020394440A AU2020394440A1 (en) | 2019-11-28 | 2020-11-25 | Crosslinked polyolefin foam having large core cells |
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US16/699,062 US11332590B2 (en) | 2019-11-28 | 2019-11-28 | Crosslinked polyolefin foam having large core cells |
US16/699,063 | 2019-11-28 | ||
US16/699,062 | 2019-11-28 | ||
US16/699,063 US11976175B2 (en) | 2019-11-28 | 2019-11-28 | Split crosslinked polyolefin foam composition and method |
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PCT/US2020/062306 WO2021108615A1 (en) | 2019-11-28 | 2020-11-25 | Split crosslinked polyolefin foam composition and method |
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EP (1) | EP4065363A4 (en) |
JP (1) | JP2023503983A (en) |
CN (1) | CN114765983A (en) |
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JPH0912762A (en) * | 1995-06-29 | 1997-01-14 | Sekisui Chem Co Ltd | Cross-linked polyolefinic resin foam, laminate and molded article |
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JP2001138422A (en) * | 1999-11-15 | 2001-05-22 | Sekisui Chem Co Ltd | Foamed sheet and method of manufacturing the same |
JP2004204154A (en) * | 2002-12-26 | 2004-07-22 | Sekisui Chem Co Ltd | Crosslinked polyolefin resin foam and production method thereof |
JP2010031137A (en) * | 2008-07-29 | 2010-02-12 | Sekisui Chem Co Ltd | Closed cell foam sheet |
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WO2002002316A1 (en) * | 2000-06-30 | 2002-01-10 | Mitsui Chemicals, Inc. | Layered product of olefin foam and use |
JP6449768B2 (en) * | 2012-08-29 | 2019-01-09 | ダウ グローバル テクノロジーズ エルエルシー | Ethylene-based polymer composition and foam |
EP3053948A4 (en) * | 2013-09-30 | 2017-05-24 | Sekisui Chemical Co., Ltd. | Crosslinked polyolefin resin foam sheet |
EP3317333A1 (en) * | 2015-06-30 | 2018-05-09 | Sekisui Voltek, LLC | Physically crosslinked foamable particle, method of making in-situ foam and laminated foam therefrom |
US11738492B2 (en) * | 2016-03-31 | 2023-08-29 | Toray Plastics (America), Inc. | Methods of producing polyolefin foam sheets and articles made thereof |
JPWO2018025343A1 (en) * | 2016-08-03 | 2019-05-23 | 東レ株式会社 | Laminate |
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2020
- 2020-11-25 CN CN202080081508.2A patent/CN114765983A/en active Pending
- 2020-11-25 AU AU2020394440A patent/AU2020394440A1/en active Pending
- 2020-11-25 EP EP20892318.5A patent/EP4065363A4/en active Pending
- 2020-11-25 JP JP2022530752A patent/JP2023503983A/en active Pending
- 2020-11-25 WO PCT/US2020/062298 patent/WO2021108608A1/en unknown
- 2020-11-25 WO PCT/US2020/062306 patent/WO2021108615A1/en active Application Filing
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US5883144A (en) * | 1994-09-19 | 1999-03-16 | Sentinel Products Corp. | Silane-grafted materials for solid and foam applications |
JPH0912762A (en) * | 1995-06-29 | 1997-01-14 | Sekisui Chem Co Ltd | Cross-linked polyolefinic resin foam, laminate and molded article |
JP2001138422A (en) * | 1999-11-15 | 2001-05-22 | Sekisui Chem Co Ltd | Foamed sheet and method of manufacturing the same |
JP2004204154A (en) * | 2002-12-26 | 2004-07-22 | Sekisui Chem Co Ltd | Crosslinked polyolefin resin foam and production method thereof |
JP2010031137A (en) * | 2008-07-29 | 2010-02-12 | Sekisui Chem Co Ltd | Closed cell foam sheet |
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EP4065363A1 (en) | 2022-10-05 |
AU2020394440A1 (en) | 2022-06-23 |
CN114765983A (en) | 2022-07-19 |
WO2021108615A1 (en) | 2021-06-03 |
EP4065363A4 (en) | 2023-12-27 |
JP2023503983A (en) | 2023-02-01 |
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