WO2020158886A1 - 多層発泡体シート - Google Patents

多層発泡体シート Download PDF

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Publication number
WO2020158886A1
WO2020158886A1 PCT/JP2020/003509 JP2020003509W WO2020158886A1 WO 2020158886 A1 WO2020158886 A1 WO 2020158886A1 JP 2020003509 W JP2020003509 W JP 2020003509W WO 2020158886 A1 WO2020158886 A1 WO 2020158886A1
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Prior art keywords
layer
resin
resin layer
foam sheet
multilayer foam
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PCT/JP2020/003509
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English (en)
French (fr)
Japanese (ja)
Inventor
晶啓 浜田
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Priority to CN202080011075.3A priority Critical patent/CN113348072A/zh
Priority to KR1020217023847A priority patent/KR20210121049A/ko
Priority to JP2020516941A priority patent/JP7561616B2/ja
Publication of WO2020158886A1 publication Critical patent/WO2020158886A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/26—Porous or cellular plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material

Definitions

  • the present invention relates to a multilayer foam sheet comprising at least one layer of foam.
  • foam sheets made of foam are widely used as seal materials or shock absorbers.
  • the foamed sheet may be used as an adhesive tape by applying an adhesive on at least one surface inside an electronic device.
  • a foamed sheet used in these applications a crosslinked polyolefin resin foamed sheet obtained by foaming and crosslinking a foamable polyolefin resin sheet containing a thermal decomposition type foaming agent is known (for example, Patent Document 1). 1).
  • foam sheets used inside electronic devices have been required to be thinner as electronic devices have become smaller and thinner.
  • the mechanical strength such as tensile strength tends to be low, and therefore, for example, when the foamed sheet is used as an adhesive tape, the foamed sheet is easily damaged during reworking.
  • the foamed sheet if the foaming ratio is lowered to increase the mechanical strength, the compression strength becomes high, and the characteristics originally possessed by the foamed sheet such as impact absorption may be impaired.
  • a multilayer foam sheet having both properties is being studied.
  • the radius of curvature is different between the layer on the winding core side (inner layer) and the layer on the opposite side (outer layer). Therefore, the inner layer may be bent toward the base material layer side, and a defect due to a crease may occur.
  • the present invention has been made in view of the above problems, and provides a multilayer foam sheet that can suppress appearance defects such as folds and wrinkles while improving flexibility and mechanical strength. It is an issue.
  • the inventors of the present invention set the bending stress of at least one resin layer among the resin layers provided on both surfaces of the base material layer (foam) within a specific range in the multilayer foam sheet.
  • the inventors have found that the above-mentioned problems can be solved by the above and completed the following invention.
  • the present invention provides the following [1] to [15].
  • a first resin layer made of a resin film or a foam, a second resin layer made of a foam, and a third resin layer made of a resin film or a foam are provided in this order, and the radius of curvature (R) is A multilayer foam sheet in which the bending stress of the third resin layer defined by the following formula (1) when it is 152.4 mm is 1.6 MPa or less.
  • the total thickness of the first resin layer and the third resin layer is 50% or less of the total thickness of the multilayer foam sheet, according to any one of the above [1] to [4].
  • the bending stress of the third resin layer defined by the above formula (1) is 1.6 MPa or less when the radius of curvature (R) is 101.6 mm, and the above [1] to [5] The multilayer foam sheet according to any one of 1.
  • the bending stress of the third resin layer defined in the above (1) is 1.6 MPa or less when the radius of curvature (R) is 76.2 mm.
  • the bending stress of the first resin layer defined by the above formula (2) is 1.6 MPa or less when the radius of curvature (R2) is 76.2 mm, [8] or [9] above.
  • the multilayer foam sheet according to. [11] The multilayer foam sheet according to any one of the above [1] to [10], wherein the tensile strength of the first resin layer is 1.5 N or more.
  • the resin constituting the second resin layer is one or more selected from the group consisting of a polyolefin resin, a polyurethane resin, an acrylic resin, and a thermoplastic elastomer. ]
  • the present invention it is possible to provide a multilayer foam sheet that can suppress appearance defects such as folds and wrinkles while improving flexibility and mechanical strength.
  • the multilayer foam sheet of the present invention includes a first resin layer made of a resin film or foam, a second resin layer (base material layer) made of foam, and a third resin layer made of resin film or foam.
  • first to third resin layers may be referred to as first to third layers for the sake of simplicity.
  • the multilayer foam sheet 10 is composed of three layers, and the first layer 11 and the third layer 13 may be directly laminated on both surfaces of the second layer 12. ..
  • the multilayer foam sheet 10 includes first to third layers 11, 12 and 13, and a first adhesive layer, an adhesive layer, and other adhesive layers 14 and 15 interposed therebetween.
  • Each of the first layer 11 and the third layer 13 may be laminated on both surfaces of the second layer 12.
  • the first and third layers 11 and 13 may be outermost layers in the multilayer foam sheet 10.
  • the bending stress of the third layer defined by the following formula (1) is 1.6 MPa or less when the radius of curvature (R) is 152.4 mm.
  • Bending stress of third layer D ⁇ S/R (1)
  • D Tensile elastic modulus (MPa) of the third layer in the MD direction
  • S Distance from the neutral point of the first layer to the surface of the third layer on the side opposite to the second layer (mm)
  • R radius of curvature Note that the neutral point is, as shown in FIGS. 1 and 2, an intermediate point C in the thickness direction of the first layer 11, and a distance S is from the intermediate point C to the surface of the third layer 13. It is the distance to 13A.
  • the multilayer foam sheet is generally wound around a core such as a paper core and stored, but at that time, a radius of curvature differs between the layer on the core side and the layer on the opposite side. Wrinkles will occur in the layer.
  • a radius of curvature differs between the layer on the core side and the layer on the opposite side. Wrinkles will occur in the layer.
  • the bending stress of one surface of the multilayer foam sheet is adjusted to a specific range, at least one surface of the multilayer foam sheet becomes sufficiently flexible and is wound around the winding core. Even if it is, it becomes possible to suppress the generation of creases.
  • "MD" means Machine Direction and means the direction which corresponds with the extrusion direction etc. of a film layer.
  • the above formula (1) means that the bending stress when the third layer is bent with a predetermined radius of curvature is 1.6 MPa or less. Therefore, the multilayer foam sheet of the present invention has a bending stress of only 1.6 MPa or less even when it is wound around a core such as a paper core having a radius of 152.4 mm (6 inches), thereby causing a crease. It is possible to suppress the occurrence of.
  • the paper core having a radius of 6 inches is generally used as a core for winding a foam sheet or the like.
  • the multilayer foam sheet of the present invention has a multilayer structure having three resin layers, it is easy to improve both flexibility and mechanical strength.
  • the bending stress of the third layer when the radius of curvature is 152.4 mm (6 inches) is more preferably 1.55 MPa or less, and further preferably 1.5 MPa or less from the viewpoint of sufficiently suppressing creases. It is 0 MPa or less, more preferably 0.6 MPa or less.
  • the bending stress when the radius of curvature is 152.4 mm (6 inches) is preferably 0.1 MPa or more, and more preferably 0.2 MPa or more, in order to give the third layer a certain tensile strength or more. ..
  • the bending stress of the third layer calculated by the formula (1) is preferably 1.6 MPa or less even when the radius of curvature (R) is 101.6 mm (4 inches).
  • a core such as a paper core having a radius of about 4 inches and a smaller diameter may be used.
  • the pressure is 1.6 MPa or less, a crease does not occur even when wound around a winding core having a small diameter.
  • the bending stress of the third layer calculated by the formula (1) is more preferably 1.6 MPa or less even when the radius of curvature is 76.2 mm (3 inches).
  • a core such as a paper core is generally used that has a minimum diameter of about 3 inches, but as described above, even when the radius of curvature is 76.2 mm.
  • the bending stress is 1.6 MPa or less, a crease does not occur even when wound on a winding core having an extremely small diameter.
  • the multilayer foam sheet in which the resin film or the foam is provided on both sides of the base material layer (second layer) is any one of the resin films or the foam provided on both sides. Is the first layer, and the other is the third layer. Therefore, in the present invention, it is preferable that one of the resin film or the foam provided on both surfaces has a bending stress calculated by the formula (1) of 1.6 MPa or less. This is because if the bending stress of one layer (that is, the third layer) is 1.6 MPa or less, creases will not occur if the third layer is wound so as to be on the winding core side (inside). ..
  • both the resin film and the foam provided on both surfaces have a bending stress of 1.6 MPa or less. That is, when the radius of curvature (R2) is 152.4 mm, the bending stress of the first layer defined by the following formula (2) is preferably 1.6 MPa or less.
  • the bending stress of both the first and third layers is 1.6 MPa or less, so that both the first and third layers are wound so as to be on the winding core side (inner side). Since wrinkles do not occur even when taken, the multilayer foam sheet can be wound without limitation.
  • the bending stress of the first layer when the radius of curvature is 152.4 mm (6 inches) is more preferably 1.55 MPa or less, and further preferably 1.5 MPa or less from the viewpoint of sufficiently suppressing creases. It is 0 MPa or less, more preferably 0.6 MPa or less. Further, when the radius of curvature is 152.4 mm (6 inches), the bending stress of the first layer is preferably 0.1 MPa or more in order to give the first layer a certain tensile strength or more, 2 MPa or more is more preferable.
  • the bending stress of the first layer calculated by the equation (2) has a radius of curvature (R2) of 101 even from the viewpoint that the winding of the multilayer foam sheet can be performed without limitation on a winding core having a small diameter. Even when it is 0.6 mm (4 inches), it is more preferably 1.6 MPa or less. Further, from the viewpoint that the multi-layer foam sheet can be wound around the winding core having an extremely small diameter without limitation, the bending stress of the first layer calculated by the formula (2) has a radius of curvature of 76. Even in the case of 0.2 mm (3 inches), the pressure is more preferably 1.6 MPa or less.
  • the tensile elastic modulus (D) of the third layer in the MD direction is preferably 40 to 500 MPa, more preferably 60 to 450 MPa, still more preferably 150 to 400 MPa.
  • the tensile elastic modulus (D2) in the MD direction of the first layer is preferably 40 to 500 MPa, more preferably 60 to 450 MPa, still more preferably 150 to 400 MPa.
  • the tensile elastic moduli of the first layer and the third layer in the MD direction may be obtained by measuring as described in the examples.
  • the tensile strength of the third layer in the MD direction is 1.5 N or more, and preferably 2.5 N or more.
  • the tensile strength of the third layer is 2.5 N or more, it is possible to improve the mechanical strength without causing creases and maintaining the flexibility of the multilayer foam sheet.
  • the tensile strength in the MD direction of the third layer is more preferably 4N or more.
  • the tensile strength is, for example, 200 N or less, and preferably 100 N or less, from the viewpoint of keeping the bending stress constant or less.
  • the tensile strength in the MD direction of the first layer is 1.5 N or more, but from the viewpoint of improving mechanical strength while maintaining flexibility, 2.5 N or more is preferable. It is also preferable that the tensile strengths in the MD direction of both the first and third layers are 2.5 N or more. When the tensile strengths of both the first and third layers are 2.5 N or more, it becomes easier to improve the mechanical strength of the multilayer foam sheet.
  • the tensile strength in the MD direction of the first layer is more preferably 4N or more, and further preferably, the tensile strength in the MD direction of both the first and third layers is 4N or more. Further, the tensile strength may be, for example, 200 N or less, and preferably 100 N or less, from the viewpoint of keeping the bending stress below a certain level. The tensile strength can be measured according to JIS K6767.
  • the 25% compressive strength of the multilayer foam sheet of the present invention is preferably 800 kPa or less.
  • the 25% compressive strength of the multilayer foam sheet is 800 kPa or less, the flexibility of the multilayer foam sheet is improved, and the impact absorbency and the like are also improved.
  • the adhesive strength of the adhesive tape is easily improved when it is used as a base material of the adhesive tape. From these viewpoints, the 25% compressive strength of the multilayer foam sheet is preferably 700 kPa or less, more preferably 300 kPa or less, and further preferably 100 kPa or less.
  • the 25% compressive strength of the multilayer foam sheet is preferably 20 kPa or more, more preferably 30 kPa or more, still more preferably 40 kPa or more.
  • the 25% compressive strength can be measured according to JIS K6767.
  • the total thickness of the multilayer foam sheet is not particularly limited, but is preferably 50 to 2000 ⁇ m, more preferably 80 to 1800 ⁇ m, and further preferably 150 to 1200 ⁇ m. By making the total thickness of the multilayer foam sheet within such a range, it becomes possible to make the multilayer foam sheet thin and it becomes easy to obtain a multilayer foam sheet having good flexibility and mechanical strength.
  • the total thickness of the first layer and the third layer is preferably 50% or less, more preferably 30% or less, and further preferably 25% or less of the total thickness of the multilayer foam sheet. preferable.
  • the total thickness is preferably 2% or more, more preferably 4% or more, still more preferably 7% or more of the total thickness of the multilayer foam sheet.
  • the total thickness of the multilayer foam sheet 10 is the total of the three layers in the case of the three-layer structure of the first layer 11, the second layer 12, and the third layer 13. Is T1.
  • FIG. 1 the total thickness of the multilayer foam sheet 10 is the total of the three layers in the case of the three-layer structure of the first layer 11, the second layer 12, and the third layer 13. Is T1.
  • the total thickness is equal to that between the first layer 11 and the second layer 12 or between the second layer 12 and the third layer 13 (adhesive layers 14 and 15).
  • the thickness T2 is the total thickness of the first to third layers 11 to 13 plus the thickness of the adhesive layers 14 and 15.
  • each of the first layer and the third layer is preferably 1 to 500 ⁇ m, more preferably 5 to 250 ⁇ m, and further preferably 10 to 90 ⁇ m. Within such a range, the multilayer foam sheet can be made thinner. Moreover, it becomes easy to adjust the tensile strength of the first layer and the third layer and the 25% compressive strength of the multilayer foam sheet within the above range.
  • the thicknesses of the first layer and the third layer may be the same or different.
  • the thickness of the second layer is not particularly limited, but is preferably 40 to 1900 ⁇ m, more preferably 70 to 1600 ⁇ m, and further preferably 100 to 1000 ⁇ m. By setting the thickness of the second layer within such a range, it becomes possible to make the multilayer foam sheet thin and it is easy to obtain a multilayer foam sheet having good flexibility.
  • the thickness of the second layer is typically larger than the thickness of each of the first and third layers. By making the thickness of the second layer larger than that of each of the first and third layers, it becomes easy to increase the flexibility of the multilayer foam sheet.
  • the second layer of the present invention is made of resin foam.
  • the type of resin forming the second layer is not particularly limited, but examples thereof include polyolefin-based resin, acrylic resin, polyurethane-based resin, and thermoplastic elastomer. These may be used alone or in combination of two or more. Of these, polyolefin resins and thermoplastic elastomers are preferable, and polyolefin resins are more preferable. By using the polyolefin resin and the thermoplastic elastomer, it becomes easy to secure the flexibility and mechanical strength of the second layer while improving the foamability and the like.
  • the resin used in the second layer may be used alone or in combination of two or more.
  • the polyolefin resin is a thermoplastic resin, and specific examples thereof include polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer, and the like, and among these, polyethylene resin is preferable.
  • the polyethylene resin include polyethylene resins polymerized with a polymerization catalyst such as a Ziegler-Natta compound, a metallocene catalyst and a chromium oxide compound, and preferably a polyethylene resin polymerized with a metallocene catalyst is used.
  • metallocene catalyst examples include compounds such as a bis(cyclopentadienyl) metal complex having a structure in which a transition metal is sandwiched by ⁇ -electron unsaturated compounds. More specifically, tetravalent transition metals such as titanium, zirconium, nickel, palladium, hafnium, and platinum have one or more cyclopentadienyl rings or their analogs as ligands. The compound can be mentioned. Such a metallocene catalyst has uniform properties of active sites and each active site has the same activity. Polymers synthesized using a metallocene catalyst have high homogeneity in molecular weight, molecular weight distribution, composition, composition distribution, etc.
  • the crosslinking is uniform. Proceed to. Since the uniformly crosslinked sheet is uniformly foamed, it becomes easy to stabilize the physical properties. Further, since the film can be stretched uniformly, the thickness of the foam can be made uniform.
  • Examples of the ligand include a cyclopentadienyl ring and an indenyl ring. These cyclic compounds may be substituted with a hydrocarbon group, a substituted hydrocarbon group or a hydrocarbon-substituted metalloid group.
  • Examples of the hydrocarbon group include a methyl group, an ethyl group, various propyl groups, various butyl groups, various amyl groups, various hexyl groups, 2-ethylhexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups. , Various cetyl groups, phenyl groups and the like.
  • cyclic compound as an oligomer may be used as a ligand.
  • monovalent anion ligands such as chlorine and bromine or divalent anion chelate ligands, hydrocarbons, alkoxides, arylamides, aryloxides, amides, arylamides, phosphides, aryls. You may use phosphide etc.
  • the metallocene catalyst containing a tetravalent transition metal or a ligand examples include cyclopentadienyl titanium tris(dimethylamide), methylcyclopentadienyl titanium tris(dimethylamide), bis(cyclopentadienyl)titanium dichloride, and dimethyl. Examples thereof include silyltetramethylcyclopentadienyl-t-butylamide zirconium dichloride.
  • the metallocene catalyst when combined with a specific co-catalyst (co-catalyst), exhibits an action as a catalyst during the polymerization of various olefins.
  • cocatalysts include methylaluminoxane (MAO) and boron compounds.
  • the ratio of the cocatalyst used to the metallocene catalyst is preferably 100 to 1,000,000 mol times, more preferably 50 to 5,000 mol times.
  • linear low density polyethylene is preferable.
  • the linear low-density polyethylene is obtained directly by copolymerizing ethylene (for example, 75% by mass or more, preferably 90% by mass or more with respect to the total amount of monomers) and a small amount of ⁇ -olefin as necessary. Chain low density polyethylene is more preferable.
  • Specific examples of the ⁇ -olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene and the like. Of these, ⁇ -olefins having 4 to 10 carbon atoms are preferable.
  • Polyethylene resin for example the density of the above-mentioned linear low density polyethylene, from the viewpoint of flexibility, preferably 0.870 ⁇ 0.925g / cm 3, more preferably 0.890 ⁇ 0.925g / cm 3, 0 It is more preferably 0.910 to 0.925 g/cm 3 .
  • the polyethylene resin a plurality of polyethylene resins may be used, and a polyethylene resin having a density outside the above range may be added.
  • Examples of the ethylene-vinyl acetate copolymer used as the polyolefin resin include an ethylene-vinyl acetate copolymer containing 50% by mass or more of ethylene.
  • Examples of the polypropylene resin include homopolypropylene and a propylene- ⁇ -olefin copolymer containing 50% by mass or more of propylene. These may be used alone or in combination of two or more.
  • ⁇ -olefin constituting the propylene- ⁇ -olefin copolymer examples include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1- Examples thereof include octene, and of these, ⁇ -olefin having 6 to 12 carbon atoms is preferable.
  • thermoplastic elastomer examples include olefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, polyester-based thermoplastic elastomer, and polyamide-based thermoplastic elastomer.
  • these components may be used alone or in combination of two or more.
  • olefin-based thermoplastic elastomers and styrene-based thermoplastic elastomers are preferable, and styrene-based thermoplastic elastomers are more preferable.
  • thermoplastic elastomer examples include blend type, dynamically cross-linking type, and polymerization type. More specifically, a thermoplastic crystalline polyolefin such as polypropylene or polyethylene is used for the hard segment and a soft segment is used for the soft segment. Thermoplastic elastomers using fully vulcanized or partially vulcanized rubber are mentioned. Examples of the thermoplastic crystalline polyolefin include homopolymers of ⁇ -olefins having 1 to 4 carbon atoms or copolymers of two or more types of ⁇ -olefins, with polyethylene or polypropylene being preferred. Examples of the soft segment component include butyl rubber, halobutyl rubber, EPDM, EPM, acrylonitrile/butadiene rubber, NBR and natural rubber, and among these, EPDM is preferable.
  • a block copolymer type may be mentioned as the olefinic thermoplastic elastomer.
  • the block copolymer type include those having a crystalline block and a soft segment block, and more specifically, a crystalline olefin block-ethylene/butylene copolymer-crystalline olefin block copolymer (CEBC) is exemplified.
  • CEBC crystalline olefin block-ethylene/butylene copolymer-crystalline olefin block copolymer
  • the crystalline olefin block is preferably a crystalline ethylene block
  • examples of commercially available products of such CEBC include "DYNARON 6200P" manufactured by JSR Corporation.
  • styrene-based thermoplastic elastomer examples include a block copolymer having a polymer or copolymer block of styrene and a polymer or copolymer block of a conjugated diene compound.
  • conjugated diene compound examples include isoprene and butadiene.
  • the styrene-based thermoplastic elastomer used in the present invention may or may not be hydrogenated. When hydrogenating, hydrogenation can be performed by a known method.
  • the styrene-based thermoplastic elastomer is usually a block copolymer, such as styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer.
  • SEBS styrene-ethylene/butylene-styrene block copolymer
  • SEPS styrene-ethylene/propylene-styrene block copolymer
  • SEB styrene-ethylene/butylene block copolymer
  • SEP block copolymers
  • SEBC styrene-ethylene/butylene-crystalline olefin block copolymers
  • styrene-based thermoplastic elastomers are manufactured by JSR Co., Ltd., product name “DYNARON 8600P” (styrene content 15% by mass), product name “DYNARON 4600P” (styrene content 20% by mass), product name Examples include “DYNARON 1321P” (styrene content 10% by mass).
  • the second layer used in the present invention is preferably obtained by foaming a foamable composition containing the above resin and a foaming agent.
  • a foaming agent a thermal decomposition type foaming agent is preferable.
  • an organic foaming agent or an inorganic foaming agent can be used.
  • the organic foaming agent include azodicarbonamide, metal salts of azodicarboxylic acid (barium azodicarboxylic acid), azo compounds such as azobisisobutyronitrile, nitroso compounds such as N,N'-dinitrosopentamethylenetetramine, and hydra.
  • Examples thereof include hydrazine derivatives such as zodicarbonamide, 4,4′-oxybis(benzenesulfonylhydrazide) and toluenesulfonylhydrazide, and semicarbazide compounds such as toluenesulfonylsemicarbazide.
  • Examples of the inorganic foaming agent include ammonium carbonate, sodium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, anhydrous monosodium citrate and the like.
  • an azo compound is preferable, and an azodicarbonamide is more preferable, from the viewpoints of obtaining fine bubbles, economical efficiency, and safety.
  • the thermal decomposition type foaming agents may be used alone or in combination of two or more.
  • the blending amount of the foaming agent in the foamable resin composition is preferably 1 to 20 parts by mass, more preferably 1.5 to 15 parts by mass, and even more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the resin.
  • a decomposition temperature adjusting agent may be added to the foamable resin composition.
  • the decomposition temperature adjusting agent is added to lower the decomposition temperature of the thermal decomposition type foaming agent or to accelerate or control the decomposition rate, and specific compounds include zinc oxide, zinc stearate and urea. Etc.
  • the decomposition temperature adjusting agent is mixed, for example, in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin in order to adjust the surface condition of the second layer and the like.
  • An antioxidant may be added to the foamable resin composition.
  • the antioxidant include phenolic antioxidants such as 2,6-di-t-butyl-p-cresol, sulfur antioxidants, phosphorus antioxidants, amine antioxidants and the like.
  • the antioxidant is mixed, for example, in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin.
  • the resin is the main component, and the content of the resin is, for example, 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, based on the total amount of the second layer.
  • the foamable resin composition if necessary, contains additives generally used in foams such as heat stabilizers, colorants, flame retardants, antistatic agents, and fillers in addition to the above. Good.
  • the expansion ratio of the second layer is not particularly limited, but is preferably 1.1 to 20 cm 3 /g. By setting the expansion ratio to 1.1 cm 3 /g or more, the flexibility of the multilayer foam sheet is increased, and the expansion ratio is set to 20 cm 3 /g or less. The strength of the multilayer foam sheet is improved.
  • the expansion ratio of the second layer is more preferably 2.5 to 18 cm 3 /g, and further preferably 7.5 to 16 cm 3 /g.
  • the expansion ratio of the second layer is represented by the reciprocal of the apparent density of the second layer.
  • the degree of crosslinking of the second layer is not particularly limited, but is, for example, 5 to 65%, preferably 10 to 55%, more preferably 20 to 50%.
  • the degree of crosslinking of the second layer is set to the lower limit value or more, it is possible to prevent the flexibility from increasing more than necessary and to secure a certain mechanical strength.
  • the content is not more than the above upper limit, the flexibility and the impact absorption are improved.
  • the first layer and the third layer are resin films or foams, respectively, as described above, and preferably resin films.
  • the resin film is a non-foamed resin layer.
  • both the first layer and the third layer are resin films will be described in more detail.
  • the kind of the resin constituting the resin film is not particularly limited as long as it satisfies the relations of the above formulas (1) and (2).
  • the resin include polyolefin resin, acrylic resin, polyurethane resin, and thermoplastic elastomer.
  • vinyl chloride resin, styrene resin, polyester resin, polyamide resin, ionomer resin, etc. may be used.
  • the resin may be used alone or in combination of two or more.
  • the resin used for the first layer and the resin used for the third layer may be the same kind of resin or different resins, but from the viewpoint of productivity and both layers. From the viewpoint of easily making the physical properties of the same or similar, it is preferable that they are the same kind.
  • the resin constituting each of the first layer and the third layer is preferably a thermoplastic resin, and by using the thermoplastic resin, the first layer and the third layer are easily bonded to the second layer. It is possible to in addition, as the resin used for each of the first layer and the third layer, a polyolefin resin is preferable among the above. By using the polyolefin-based resin, it becomes easy to increase the mechanical strength of the multilayer foam sheet while reducing the bending stress. Further, when a polyolefin resin or a thermoplastic elastomer is used for the second layer, the adhesion of the first and third layers to the second layer can be made particularly good.
  • polystyrene resin examples include polyethylene resin and polypropylene resin. Further, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer and the like may be used.
  • polyethylene resin examples include polyethylene resins polymerized with a polymerization catalyst such as a Ziegler-Natta compound, a metallocene catalyst and a chromium oxide compound, and preferably a polyethylene resin polymerized with a metallocene catalyst is used.
  • Examples of the polyethylene resin include low-density polyethylene (density: less than 0.930 g/cm 3 ), medium-density polyethylene (density: 0.930 g/cm 3 or more and less than 0.942 g/cm 3 ), high-density polyethylene ( Density: 0.942 g/cm 3 or more).
  • examples of the low-density polyethylene include linear low-density polyethylene. Since the details of the linear low-density polyethylene are as described in the description of the second layer, the details are omitted. Further, since the details of the polypropylene resin are as described in the description of the second layer, the details thereof will be omitted.
  • the ethylene-vinyl acetate copolymer used in the first and third layers includes, for example, an ethylene-vinyl acetate copolymer containing 50% by mass or more of a constitutional unit derived from ethylene.
  • the ethylene-ethyl acrylate copolymer includes an ethylene-ethyl acrylate copolymer containing 50% by mass or more of constituent units derived from ethylene.
  • ethylene resin particularly linear low-density polyethylene is preferable.
  • ethylene-vinyl acetate copolymer is also preferable.
  • the resin is the main component, and the resin content is, for example, 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, based on the total amount of each layer.
  • the first layer and the third layer may contain additives such as an antioxidant, a heat stabilizer, a colorant, a flame retardant, an antistatic agent and a filler, in addition to the above resins.
  • the first and third layers may be crosslinked.
  • the first and third layers may be cross-linked at the same time as the second layer is cross-linked, as described in the production method 1 described later, and thus are preferably cross-linked by ionizing radiation.
  • Each of the first and third layers may be foam, as described above.
  • the resin that can be used in the first and third layers is mixed with a foaming agent or the like as described in the second layer. Then, the first and third layers may be foamed.
  • the expansion ratio is low and the bubble ratio indicating the ratio of bubbles contained in each layer is low from the viewpoint of ensuring a certain mechanical strength.
  • the bubble ratio of each of the first layer and the third layer is preferably 66% or less, more preferably 33% or less, and further preferably 0%.
  • the bubble ratio is 0%.
  • the bubble ratio can be obtained, for example, by observing the cross section of the first layer and the third layer and calculating the ratio of the area occupied by the bubbles to the area of each layer. Specifically, a cross section is cut out along the thickness direction, and the cross section is photographed with an optical microscope. After that, the air bubbles and the resin portion may be binarized to be divided, and the area of the air bubbles/total area may be calculated.
  • the first layer and the second layer, or the second layer and the third layer may be directly adhered, but another layer (that is, an adhesive layer) is used. May be bonded together.
  • the adhesive layer a known adhesive or pressure-sensitive adhesive may be used. Further, it may be a double-sided pressure-sensitive adhesive tape in which a pressure-sensitive adhesive layer is provided on both sides of the base material.
  • the adhesive layer may have a thickness that does not significantly affect physical properties such as mechanical strength and flexibility in the multilayer foam sheet. Therefore, the thickness of the adhesive layer for bonding the first layer and the second layer is preferably thinner than that of the first layer, and more preferably 1/2 or less of the thickness of the first layer. Similarly, the thickness of the adhesive layer that bonds the second layer and the third layer is preferably thinner than that of the third layer, and more preferably 1/2 or less of the thickness of the third layer.
  • the multilayer foam sheet of the present invention is not particularly limited, but for example, a method of obtaining a multilayer laminate sheet by laminating a plurality of layers made of a resin composition, and then foaming the multilayer laminate sheet ( Hereinafter, it can be manufactured by "manufacturing method 1").
  • resin composition also includes a case where it is composed of one type of resin alone.
  • the manufacturing method 1 includes the following steps I to II.
  • (I) Multilayer laminate comprising a layer made of a foamable resin composition, a first layer formed on one surface of the layer, and a third layer formed on the other surface of the layer Step of obtaining a sheet
  • the method for obtaining the multilayer laminate sheet in step (I) is not particularly limited, but coextrusion molding is preferable. Specifically, a resin for forming the first layer and the third layer, and other additives to be blended as necessary are supplied to the first and third extruders respectively and melt-kneaded. , To obtain a resin composition for forming the first and third layers. Further, a resin for forming the second layer, a foaming agent such as a thermal decomposition type foaming agent, and an additive to be blended as necessary are supplied to the second extruder and melt-kneaded, A foamable resin composition for forming the layer is obtained.
  • the resin compositions supplied from the first to third extruders are merged so that the composition supplied from the second extruder becomes an intermediate layer, and the mixture is extruded into a sheet by a T-die or the like.
  • a multilayer laminate sheet having a three-layer structure can be obtained.
  • either the feed block method or the multi-manifold method may be used, but the feed block method is preferable.
  • the step (I) it is preferable to further crosslink the multilayer laminate sheet obtained above.
  • a cross-linking method there is also a method of previously blending an organic peroxide and heating the multi-layer laminate sheet obtained in the step (I) to cross-link, but the multi-layer laminate sheet is irradiated with ionizing radiation. It is preferable to crosslink.
  • the ionizing radiation include electron beams and ⁇ rays, but electron beams are preferable.
  • the dose of ionizing radiation is preferably 1 to 10 Mrad, more preferably 1.5 to 5 Mrad.
  • the multilayer laminate sheet obtained in the step (I) is subjected to a foaming treatment to foam a layer made of the foamable resin composition.
  • the layer made of the foamable resin composition may be treated so that the foaming agent foams.
  • the foaming agent is a pyrolytic foaming agent
  • the multilayer laminate sheet is heated to foam.
  • the heating temperature may be equal to or higher than the temperature at which the pyrolytic foaming agent decomposes, and is, for example, about 150 to 320°C.
  • the method for heating the multilayer laminate sheet is not particularly limited, and examples thereof include a method of heating the multilayer laminate sheet with hot air, a method of heating with infrared rays, a method of heating with a salt bath, and a method of heating with an oil bath. However, these may be used in combination. Further, the multilayer laminate sheet may be appropriately stretched while foaming or after foaming. In the above description, an example in which the first and third layers are resin films (non-foamed bodies) has been described, but when the first and third layers are foamed, A foaming agent such as a pyrolyzable foaming agent may be added as an additive to the resin composition for forming the first and third layers, and foamed in step (II).
  • a foaming agent such as a pyrolyzable foaming agent may be added as an additive to the resin composition for forming the first and third layers, and foamed in step (II).
  • the method for producing the multilayer foam sheet of the present invention can also be produced by another method. Specifically, a foam forming the second layer is manufactured in advance, and a resin film or a foam (first and third layers) is superposed on both surfaces of the foam (second layer). , And a method of bonding (also referred to as “second manufacturing method”).
  • a resin for forming the second layer, a pyrolytic foaming agent, and an additive to be blended as necessary are melt-kneaded to obtain a second layer. It is advisable to obtain a foamable resin composition for forming a layer and form the foamable resin composition into a sheet shape (foamable resin composition sheet).
  • the method of melting and kneading the foamable resin composition to form a sheet is not particularly limited, but it is preferable to use an extruder.
  • the obtained foamable resin composition sheet is preferably further cross-linked before foaming described later.
  • a cross-linking method there is also a method of pre-blending an organic peroxide and heating the foamable resin composition sheet to cross-link it, but the cross-linking is performed by irradiating the foamable resin composition sheet with ionizing radiation. Is preferred.
  • the type of ionizing radiation and the irradiation amount are as described in the above-mentioned first manufacturing method.
  • the foamable resin composition sheet may be foamed.
  • the layer made of the foamable resin composition may be treated so that the foaming agent foams.
  • the foaming agent is a pyrolytic foaming agent
  • the multilayer laminate sheet is heated to foam.
  • the heating temperature and the heating method are as described in the first manufacturing method described above. Further, the foamable resin composition sheet may be appropriately stretched while foaming or after foaming.
  • a resin film for forming the first layer and the third layer, or a foam, which is separately prepared, is placed on the foam for forming the second layer, and the foam is adhered to the multilayer foam sheet.
  • it may be heated and pressed by a press machine or the like to perform thermocompression bonding.
  • an adhesive, an adhesive, or the like is applied to the adhesive surface between the second layer and the first layer and the adhesive surface between the second layer and the third layer, or a double-sided adhesive tape is attached. You may put on and stick together with an adhesive, an adhesive, a double-sided adhesive tape, etc.
  • the multilayer foam sheet of the present invention is not particularly limited, but is preferably used, for example, inside an electronic device. For example, it is placed between two members and used as a shock absorber, a sealant, or the like. it can. Further, the multilayer foam sheet can be formed into a frame shape and used in a portable electronic device. Examples of the mobile electronic device include a mobile phone, a camera, a game device, an electronic notebook, and a personal computer. Further, the multilayer foam sheet of the present invention may be used as an adhesive tape described later and used inside an electronic device.
  • the multilayer foam sheet of the present invention may be wound into a roll such as a paper core.
  • a core having a radius of about 3 to 6 inches (76.2 to 152.4 mm) may be used as the core.
  • the multilayer foam sheet When wound on the core, the multilayer foam sheet may be wound so that the layer having a bending stress of not more than a predetermined value is on the core side (inside) as described above. Therefore, it suffices if the third layer is wound so as to be on the winding core side.
  • the layer may be wound so that the layer is on the winding core side (inside).
  • the multilayer foam sheet of the present invention may be used for an adhesive tape having the multilayer foam sheet as a base material.
  • the adhesive tape comprises, for example, a multilayer foam sheet and an adhesive material provided on at least one surface of the multilayer foam sheet.
  • the adhesive tape can be adhered to another member via the adhesive material.
  • the adhesive tape may be a multi-layer foam sheet provided with an adhesive material on both sides, or may be provided with an adhesive material on one side.
  • the pressure-sensitive adhesive may be at least one having a pressure-sensitive adhesive layer, and may be provided on the surface of the multilayer foam sheet (that is, the surfaces 11A and 13A of the first or third layers 11 and 13; see FIGS. 1 and 2). It may be a laminated pressure-sensitive adhesive layer alone or a double-sided pressure-sensitive adhesive sheet attached to the surface of the multilayer foam sheet, but it is preferably a pressure-sensitive adhesive layer alone.
  • the double-sided pressure-sensitive adhesive sheet includes a base material and a pressure-sensitive adhesive layer provided on both surfaces of the base material. The double-sided pressure-sensitive adhesive sheet is used to bond one pressure-sensitive adhesive layer to the multilayer foam sheet and the other pressure-sensitive adhesive layer to another member.
  • the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited, and for example, an acrylic pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, or the like can be used. Further, a release sheet such as release paper may be further attached on the adhesive material.
  • the thickness of the adhesive material is preferably 5 to 200 ⁇ m, more preferably 7 to 150 ⁇ m, and further preferably 10 to 100 ⁇ m.
  • the pressure-sensitive adhesive tape of the present invention may be wound around a winding core to form a roll.
  • the radius of the winding core is as described above.
  • the multilayer foam sheet is bent in a radius of curvature generally according to the size of the winding core because the thickness of the adhesive material is thin as described above even when wound in a state of an adhesive tape.
  • Measurement method The methods for measuring and evaluating each physical property are as follows.
  • ⁇ Tensile Elastic Modulus of First Layer and Third Layer> The tensile elastic moduli of the first layer and the third layer were measured using a tensile tester (Yamato Scientific Co., Ltd., Tensilon RTF series). The measurement conditions were based on JIS K6767.
  • ⁇ Tensile Strength of First Layer and Third Layer The first layer and the third layer were cut into dumbbell-shaped No. 1 type specified in JIS K6251 4.1. Using this as a sample, the tensile strength was measured by a tensile tester (product name: Tensilon RTF235, manufactured by A&D Company) at a measurement temperature of 23° C. according to JISK6767. ⁇ 25% compressive strength> The 25% compressive strength of the multilayer foam sheet was measured according to JIS K6767.
  • ⁇ Apparent density and expansion ratio> The apparent density of the foam was measured according to JIS K7222, and the reciprocal thereof was taken as the expansion ratio.
  • Example 1 Linear low density polyethylene resin obtained by metallocene catalysis as the polyolefin resin for the second layer (Nippon Polyethylene Co., Ltd., trade name “Kernel KF283", density: 0.921g / cm 3) (metallocene LLDPE), Azodicarbonamide was prepared as a thermal decomposition type foaming agent. Further, zinc oxide (trade name “OW-212F” manufactured by Sakai Chemical Industry Co., Ltd.) is used as a decomposition temperature adjusting agent, and 2,6-di-t-butyl-p-cresol, which is a phenolic antioxidant as an antioxidant. Prepared.
  • a foamable resin composition 100 parts by mass of a polyethylene resin, 8.0 parts by mass of a thermal decomposition type foaming agent, 1 part by mass of a decomposition temperature adjusting agent, and 0.5 parts by mass of an antioxidant are respectively supplied to a second extruder and melt-kneaded at 130°C. Then, a foamable resin composition was produced.
  • a linear low-density polyethylene resin (Tama Poly Co., Ltd., trade name "SK615P") was prepared as the polyethylene resin for the first layer and the third layer.
  • the polyethylene resin was supplied to the first extruder and the third extruder, respectively, and melt-kneaded at 130°C.
  • an unfoamed multilayer laminate sheet comprising a layer (second layer) made of a foamable resin composition and resin films (first layer and third layer) laminated on both surfaces of the layer Got Next, the multilayer laminate sheet was irradiated with an electron beam having an accelerating voltage of 500 kV at 2.5 Mrad to crosslink, and then continuously fed into a foaming furnace kept at 250° C. by hot air and an infrared heater to be heated. By foaming, a multilayer foam sheet having a first layer (resin film), a second layer (foam body), and a third layer (resin film) in this order was obtained.
  • Examples 2-14, Comparative Examples 1-2 The types of resin used for the first to third layers, the thickness of the second layer, and the thicknesses of the first and third layers were changed as shown in Table 1. Moreover, the expansion ratio of the second layer was changed as shown in Table 1 by changing the blending amount of the foaming agent. Further, the bubble ratio of the third layer was changed as shown in Table 1 by blending a foaming agent. A multilayer foam sheet was produced in the same manner as in Example 1 except for the above. The details of each resin are as follows.
  • SEBS SEBS, manufactured by JSR Corporation, product name "DYNARON 8600P”
  • SF625P Linear low-density polyethylene, manufactured by TamaPoly Co., Ltd., trade name "SF625P”
  • SB-7 Ethylene-vinyl acetate copolymer, manufactured by TamaPoly Co., Ltd., trade name "SB-7" HD: High-density polyethylene, Tama Poly Co., Ltd., trade name "HD"
  • Table 1 shows the characteristics of the multilayer foam sheets obtained in the examples and comparative examples, and the evaluation results of creases.
  • Multilayer Foam Sheet 11 First Resin Layer 12 Second Resin Layer 13 Third Resin Layer 14, 15 Adhesive Layer C, C2 Neutral Point S, S2 Distance

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KR20250007510A (ko) 2022-04-18 2025-01-14 세키스이가가쿠 고교가부시키가이샤 수지 발포 시트 및 점착 테이프
JP7723474B2 (ja) 2020-10-14 2025-08-14 積水化学工業株式会社 多層発泡体シート及び粘着テープ
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