WO2022230938A1 - 多層シート及びその製造方法 - Google Patents

多層シート及びその製造方法 Download PDF

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Publication number
WO2022230938A1
WO2022230938A1 PCT/JP2022/019093 JP2022019093W WO2022230938A1 WO 2022230938 A1 WO2022230938 A1 WO 2022230938A1 JP 2022019093 W JP2022019093 W JP 2022019093W WO 2022230938 A1 WO2022230938 A1 WO 2022230938A1
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Prior art keywords
layer
mass
acid
multilayer sheet
amino group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2022/019093
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English (en)
French (fr)
Japanese (ja)
Inventor
誠 今堀
健太郎 宮村
圭悟 岩槻
隆 津田
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Toagosei Co Ltd
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Toagosei Co Ltd
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Publication date
Application filed by Toagosei Co Ltd filed Critical Toagosei Co Ltd
Priority to CA3216968A priority Critical patent/CA3216968A1/en
Priority to US18/557,484 priority patent/US20240218210A1/en
Priority to CN202280029172.4A priority patent/CN117178041A/zh
Priority to KR1020237038071A priority patent/KR20240004459A/ko
Priority to JP2023517597A priority patent/JPWO2022230938A1/ja
Priority to EP22795851.9A priority patent/EP4332188A4/en
Publication of WO2022230938A1 publication Critical patent/WO2022230938A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • 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
    • B32B27/08—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 synthetic resin
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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    • 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
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    • 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
    • B32B7/027—Thermal properties
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    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness
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    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2423/00—Presence of polyolefin
    • 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
    • C09J2425/00—Presence of styrenic polymer
    • C09J2425/006—Presence of styrenic polymer in the substrate
    • 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
    • C09J2451/00—Presence of graft polymer
    • C—CHEMISTRY; METALLURGY
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2471/00—Presence of polyether
    • C09J2471/006—Presence of polyether in the substrate

Definitions

  • the present invention relates to a multi-layer sheet excellent in adhesiveness and heat resistance, which can be used for bonding and sealing various parts and which itself can be used as a sheet-shaped member, and a method for producing the same.
  • hot-melt adhesive compositions have been used as adhesive films or sheets (hereinafter collectively referred to as "adhesive members") for lithium-ion batteries, fuel cells, etc. incorporated in notebook computers, smartphones, tablets, automobiles, etc. chemical cells, as well as physical cells such as solar cells and capacitors.
  • Acid-modified olefinic thermoplastic resins hereinafter referred to as " It is known that a relatively good adhesive force can be obtained by using a hot-melt adhesive composition whose main component is "acid-modified polyolefin".
  • hot-melt adhesive compositions are required to have durability to battery constituent materials in addition to adhesive strength.
  • lithium ion batteries lithium hexafluorophosphate used as an electrolyte may react with moisture to generate hydrofluoric acid. may occur, and acid resistance is required.
  • lithium-ion batteries require durability against ethylene carbonate or diethyl carbonate used as a solvent for the electrolyte
  • nickel-hydrogen batteries require durability against strong alkaline aqueous solutions.
  • a cooling liquid containing ethylene glycol, propylene glycol, or the like is circulated inside the cell for the purpose of cooling the cell that has generated heat due to power generation, so durability against ethylene glycol or the like is also required.
  • Patent Document 1 discloses a resin composition composed of 50 to 99% by mass of a low-viscosity propylene-based base polymer satisfying specific properties and 1 to 50% by mass of an acid-modified propylene-based elastomer satisfying specific properties, as well as the resin composition.
  • a hot melt adhesive is disclosed comprising: It has excellent adhesion to polyolefin-based substrates and at the same time has excellent adhesion to metal substrates.
  • Patent Document 2 describes acid-modified polypropylene as an adhesive between metal and nylon resin.
  • an adhesive member with even higher performance and functionality By laminating an acid-modified polyolefin-based adhesive film or sheet on a base material layer to form a multilayer sheet, it is also possible to obtain an adhesive member with even higher performance and functionality.
  • An engineering plastic having excellent rigidity and heat resistance is used for the base layer of this multilayer sheet.
  • strength, rigidity, gas barrier properties, chemical resistance, acid/alkali resistance, heat resistance, etc. are improved, and the above-mentioned lithium ion batteries, fuel cells, etc. It can be suitably used for applications that require durability.
  • the multilayer sheet as an adhesive member for lithium ion batteries and fuel cells, it is possible to reduce the number of constituent members and parts, thereby reducing costs and improving productivity.
  • Patent Document 3 discloses a laminated sheet for sealing electronic devices in which a first sheet and a second sheet are laminated, wherein the first sheet contains an acid-modified polyolefin thermoplastic resin, The second sheet has a higher melting point than the first sheet, and the second sheet has a peel strength of 0.5 to 10.0 [N/15 mm] at 25° C. with respect to the first sheet. Laminated sheets for sealing electronic devices are described. Patent Document 3 describes polyethylene naphthalate as a specific example of the second sheet.
  • a multilayer sheet obtained by laminating an adhesive layer containing an acid-modified polyolefin and a substrate layer containing an engineering plastic such as a heat-resistant polyolefin such as polyethylene naphthalate or cycloolefin polymer, polyphenylene ether, aromatic polyamide resin, etc. Used as an adhesive member.
  • a heat-resistant polyolefin such as polyethylene naphthalate or cycloolefin polymer, polyphenylene ether, aromatic polyamide resin, etc.
  • polyethylene naphthalate and aromatic polyamide resins hydrolyze when used for a long period of time, and have a problem of durability in an environment where they come into contact with moisture.
  • the cycloolefin polymer has a problem that the pressure bonding temperature is restricted because the softening point is not sufficiently high.
  • cycloolefin polymers have low toughness, problems such as cracking tend to occur during long-term use.
  • Polyphenylene ether does not have many problems with deterioration during long-term use, which is seen in other engineering plastics. However, polyphenylene ether has a problem that it does not adhere to the acid-modified polyolefin used for the adhesive layer, and is easily delaminated.
  • the problem to be solved by the present invention is to provide a multilayer sheet comprising an adhesive layer containing an acid-modified polyolefin and a substrate layer containing a polyphenylene ether, wherein the adhesive layer and the substrate layer have high peel strength. .
  • the present inventors have made intensive studies to solve the above problems in developing a multilayer sheet containing an adhesive layer containing acid-modified polyolefin and a substrate layer containing polyphenylene ether. Specifically, the present invention was completed by examining various multilayer sheets in which a functional group was introduced into a substrate layer containing polyphenylene ether.
  • the amino group-containing polymer (a3) of the substrate layer (A) contains a polystyrene chain having an amino group at its terminal.
  • the amino group-containing polymer (a3) of the substrate layer (A) is a styrene-diene-styrene block copolymer.
  • a base layer (A) containing 40 to 99.9% by mass of polyphenylene ether (a1), 0 to 59.9% by mass of polystyrene (a2), and an amino group-containing polymer (a3), and an acid-modified polyolefin A method for producing a multilayer sheet, comprising the step of contacting an adhesive layer (B) containing an adhesive layer (B) in a molten state at 160° C. or higher.
  • a multilayer sheet that includes an adhesive layer containing acid-modified polyolefin and a substrate layer containing polyphenylene ether, and that has high peel strength between the adhesive layer and the substrate layer.
  • the multilayer sheet of the present invention includes a substrate layer (A) containing polyphenylene ether (a1) and an adhesive layer (B) containing acid-modified polyolefin.
  • the substrate layer (A) is an intermediate layer or surface layer
  • the adhesive layer (B) is a surface layer.
  • the surface layer is a layer arranged on either the upper surface or the lower surface
  • the intermediate layer is a layer other than the surface layer.
  • the adhesive layer (B) is provided only on one surface layer, the intermediate layer may not be present, and both the substrate layer (A) and the adhesive layer (B) may be surface layers. .
  • Typical layer structures include a two-layer sheet of base layer (A)/adhesive layer (B) and a three-layer sheet of adhesive layer (B)/base layer (A)/adhesive layer (B). is mentioned. If the interface strength between the substrate layer (A) and the adhesive layer (B) is insufficient, a tie layer (C) may be provided between both layers.
  • the tie layer (C) is a layer that firmly bonds the substrate layer (A) and the adhesive layer (B).
  • a typical layer structure when the tie layer (C) is provided includes a three-layer sheet of base layer (A) / tie layer (C) / adhesive layer (B) and adhesive layer (B) / tie A five-layer sheet of layer (C)/base layer (A)/tie layer (C)/adhesive layer (B) can be mentioned.
  • the substrate layer (A) and the adhesive layer (B) are in direct contact with each other without the tie layer (C) interposed therebetween.
  • the tie layer (C) may contain functional groups capable of bonding with amino groups such as carboxylic acids and carboxylic anhydrides.
  • tie layer (C) may be a layer comprising an acid-modified polyolefin.
  • the base layer (A) contains polyphenylene ether (a1).
  • the polyphenylene ether (a1) may be the main component accounting for 40 to 99.9% by mass of the base layer (A).
  • the mass ratio of the polyphenylene ether (a1) in the substrate layer (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more. By setting the mass ratio of the polyphenylene ether (a1) within such a range, the heat resistance of the multilayer sheet can be improved.
  • the mass ratio of the polyphenylene ether (a1) in the substrate layer (A) is preferably 98% by mass or less, more preferably 95% by mass or less. By having the mass ratio of the polyphenylene ether (a1) within such a range, the moldability of the multilayer sheet can be improved.
  • the base layer (A) may further contain polystyrene (a2).
  • Polystyrene (a2) is different from amino group-containing polymer (a3) and does not contain amino groups.
  • Polystyrene (a2) may be an auxiliary component occupying 0 to 55.9% by mass of the substrate layer (A).
  • Polystyrene (a2) is an optional component, and the substrate layer (A) may not contain polystyrene (a2).
  • the mass ratio of polystyrene (a2) in the substrate layer (A) is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less. When the mass ratio of polystyrene (a2) is within such a range, the heat resistance of the multilayer sheet can be improved.
  • polystyrene (a2) include general-purpose polystyrene (GPPS), which is a polymer of styrene only, and high-impact polystyrene (HIPS), which is GPPS added with rubber to give impact resistance, but styrene and acrylonitrile or Copolymers with (meth)acrylic acid esters can also be used.
  • GPPS general-purpose polystyrene
  • HIPS high-impact polystyrene
  • the copolymer used as polystyrene (a2) contains monomer units derived from styrene as a main component (for example, 50% by mass or more of the total monomer units).
  • the mass ratio of monomer units derived from comonomers other than styrene in the polystyrene (a2) is preferably 20% by mass or less, more preferably 10% by mass or less.
  • the mass ratio of the monomer units derived from the comonomer is 20% by mass or less, the compatibility with the polyphenylene ether (a1) is improved and phase separation can be prevented.
  • the total amount of polyphenylene ether (a1) and polystyrene (a2) in the substrate layer (A) is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.
  • the total amount of polyphenylene ether (a1) and polystyrene (a2) in the substrate layer (A) is preferably 99.9% by mass or less, more preferably 98% by mass or less, and even more preferably 95% by mass or less.
  • the base layer (A) further contains an amino group-containing polymer (a3).
  • the mass ratio of the amino group-containing polymer (a3) in the substrate layer (A) is preferably 0.1% by mass or more, more preferably 2% by mass or more, and particularly preferably 5% by mass or more. When the mass ratio of the amino group-containing polymer (a3) is within such a range, the amino group-containing polymer (a3) sufficiently reacts with the acid-modified polyolefin in the adhesive layer (B), thereby You can improve your grip.
  • the mass ratio of the amino group-containing polymer (a3) in the substrate layer (A) is preferably 40% by mass or less, more preferably 30% by mass or less. When the mass ratio of the amino group-containing polymer (a3) is within such a range, the heat resistance of the substrate can be maintained and the moldability of the multilayer sheet can be improved.
  • the amino group-containing polymer (a3) is not particularly limited as long as it has an amino group.
  • the weight average molecular weight of the amino group-containing polymer (a3) is preferably 1000 or more.
  • the weight average molecular weight of the amino group-containing polymer (a3) is preferably 200,000 or less.
  • the weight average molecular weight is 1,000 or more, moldability and thermal stability are improved, and when the weight average molecular weight is 200,000 or less, the adhesive strength with the adhesive layer (B) or the tie layer (C) is improved.
  • the weight average molecular weight is within such a range, both the physical properties of the substrate layer (A) and the adhesiveness to the adhesive layer (B) can be achieved.
  • a weight average molecular weight is a standard polystyrene conversion value obtained using a gel permeation chromatography (GPC).
  • the amino group-containing polymer (a3) is preferably a polymer having an amino group at the end of the molecule, more preferably a polymer containing a polystyrene chain having an amino group at the end, and particularly preferably having an amino group at the end. It is a polymer containing a polystyrene chain with a molecular weight of 1000 or more. In the polymer having amino groups at the molecular ends, the amino groups may be present only at one end or at both ends. A primary amine or secondary amine can be preferably used as the terminal amino group.
  • Methods for synthesizing a polystyrene chain having an amino group at its terminal include a method of blocking the active terminal with a modifier after anionic living polymerization or radical living polymerization, and radical polymerization of styrene in the presence of a chain transfer agent having an amino group. method.
  • the polymer synthesized by the method of introducing an amino group to the active terminal with a modifier after living polymerization is not limited to a styrene homopolymer, and may be a block copolymer containing a styrene chain.
  • the chain to which amino groups are bonded is preferably a styrene chain.
  • Styrene-diene block copolymers having terminal amino groups are preferably used because they are readily available as commercial products.
  • styrene is anionically polymerized with an initiator such as butyllithium in a hydrocarbon solvent, and 1,3-dimethyl-2-imidazolidine is added after the polymerization.
  • a method of adding a modifying agent such as non to cause an addition reaction with the terminal anion and then treating the reaction product with protons can be mentioned.
  • a styrene-diene block copolymer a diene such as butadiene is anionically polymerized in the first step, styrene is charged in the second step and anionically polymerized, and similarly a modifier is added to introduce an amino group.
  • styrene-diene-based block copolymer a block copolymer having a polystyrene block in the terminal chain, typified by a styrene-diene diblock copolymer and a styrene-diene-styrene triblock copolymer, is preferably used.
  • a triblock copolymer is particularly preferably used because it is readily available on the market.
  • polydiene blocks include polybutadiene and its hydrogenated poly(ethylene-butylene), polyisoprene and its hydrogenated poly(ethylene-propylene), and partially hydrogenated polybutadiene poly( butadiene-butylene) and the like.
  • a method of radically polymerizing styrene in the presence of a chain transfer agent having an amino group 2-aminoethynethiol or its hydrochloride is used as a chain transfer agent, and an azo initiator or organic peroxide is used in an organic solvent.
  • a method of radically polymerizing styrene using a substance is exemplified.
  • hydrochloride is used as the chain transfer agent, it is neutralized with an equivalent amount of alkali and converted to amine.
  • the amino group concentration of the substrate layer (A) is preferably 1 ⁇ eq or more, more preferably 5 ⁇ eq or more. When the concentration of the amino group is within this range, the interlayer adhesion to the adhesive layer (B) or tie layer (C) can be improved.
  • the amino group concentration of the substrate layer (A) is preferably 200 ⁇ eq or less, more preferably 100 ⁇ eq or less. When the amino group concentration is within this range, the heat resistance of the substrate layer (A) can be improved, and troubles such as coloring can be prevented.
  • the substrate layer (A) contains (a1) to (a3 ) (hereinafter referred to as other polymer (A)) can be added.
  • polymers (A) include, for example, styrene-butadiene-styrene block copolymers and hydrogenated products thereof, styrene block copolymers such as styrene-isoprene-styrene block copolymers and hydrogenated products thereof, and polyolefins. and a graft copolymer obtained by grafting a styrene homopolymer or copolymer to the above. These copolymers contain styrene units as subcomponents (for example, 40% by mass or less of the total monomer units). Having a polystyrene chain enables the other polymer (A) to have high miscibility with the polyphenylene ether (a1).
  • unmodified polyolefins such as polyethylene, polypropylene, and ethylene-propylene copolymer may be used.
  • polyolefin in the substrate layer (A), it is expected that the adhesive strength with the adhesive layer (B) or the tie layer (C) containing the same polyolefin resin will be improved. Since these polyolefins are completely incompatible with the polyphenylene ether (a1), it is preferable to use the aforementioned copolymer containing styrene units as a compatibilizer.
  • the content of the other polymer (A) in the substrate layer (A) is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more. % by mass or more. When the amount added falls within this range, the improvement effect of the other polymer (A) is enhanced.
  • the content of the other polymer (A) in the substrate layer (A) is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass. % by mass or less.
  • the multilayer sheet can have high heat resistance and high adhesive strength at high temperatures.
  • the softening point of the substrate layer (A) is preferably 175°C or higher, more preferably 180°C or higher, and particularly preferably 185°C or higher. When the softening point is within this range, the heat resistance of the multilayer sheet is improved.
  • the storage elastic modulus of the base material layer (A) at 160°C is preferably 500 MPa or more. More preferably, the storage elastic modulus of the substrate layer (A) at 170° C. is 500 MPa or more.
  • the storage elastic modulus in the temperature range is 500 MPa or more, the multilayer sheet can be prevented from being deformed or damaged by thermocompression bonding during adhesion.
  • the softening point and storage modulus in the present invention are values obtained using a tensile viscoelasticity apparatus (DMS6100 manufactured by Hitachi High-Tech Sunence). Specifically, the temperature is raised from room temperature to 250° C. at a frequency of 1 Hz and a heating rate of 2° C./min, and changes in storage elastic modulus, loss elastic modulus, and tan ⁇ with temperature are recorded.
  • the softening point as used in the present invention means the temperature at which the value of tan ⁇ shows the maximum value.
  • the melt flow rate of the base layer (A) is preferably 1 g/10 min or more, more preferably 2 g/10 min or more.
  • the melt flow rate of the substrate layer (A) is preferably 50 g/10 min or less, more preferably 30 g/10 min or less. If the melt flow rate of the base material layer (A) is below the lower limit, the melt viscosity will be high and sheet molding will be difficult.
  • melt flow rate is a value measured according to JIS K7210:2014.
  • the melt flow rate of the substrate layer (A) was measured at a resin temperature of 300° C. and a load of 2.16 kg.
  • the base material layer (A) contains an antioxidant, an ultraviolet absorber, a filler, a reinforcing fiber, a release agent, a processing aid, a flame retardant, a plasticizer, a nucleating agent, an antistatic agent, a pigment, a dye, and foaming. agents, and combinations thereof.
  • the adhesive layer (B) contains acid-modified polyolefin.
  • Acid-modified polyolefins are unmodified polyolefins (hereinafter also simply referred to as "polyolefins") grafted with an acid compound selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, and combinations thereof. It is denatured.
  • Examples of monomer units constituting polyolefins include ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 4-methyl-1-pentene, and dienes such as butadiene, isoprene and chloroprene. aromatic vinyl compounds such as styrene, and monomer units derived from monomers selected from the group consisting of combinations thereof.
  • the number of carbon atoms in the monomer is preferably 2-10, more preferably 2-5.
  • polyolefins selected from the group consisting of polymer blends of polyethylene and polypropylene, ethylene-propylene copolymers, and combinations thereof are preferred because they have high adhesion to adherends.
  • Polyethylene is a polymer containing ethylene units as a main component, and may be a homopolymer or a copolymer. In the case of a copolymer, the content of ethylene units in polyethylene is preferably 50% by mass or more, and may be 70% by mass or more.
  • Specific examples of polyethylene include homopolymers such as low-density polyethylene, high-density polyethylene, and linear low-density polyethylene, ethylene-diene monomer copolymers, ethylene-vinyl acetate copolymers, and ethylene-acrylate copolymers. , copolymers such as ethylene-methacrylic acid ester copolymers, and halogen modified products such as chlorinated polyethylene.
  • Polypropylene is a polymer containing propylene units as a main component, and may be a homopolymer or a copolymer. In the case of a copolymer, the content of propylene units in polypropylene is preferably 50% by mass or more, and may be 70% by mass or more. Specific examples of polypropylene include homopolymers such as amorphous polypropylene and crystalline polypropylene, copolymers such as propylene-diene monomer copolymers, and halogen modified products such as chlorinated polypropylene.
  • the ethylene-propylene copolymer is a polymer containing ethylene units and propylene units, and may be composed only of ethylene units and propylene units, or may further contain other monomer units in addition to ethylene units and propylene units. good.
  • Examples of ethylene-propylene copolymers containing other monomer units include ethylene-propylene-diene monomer copolymers.
  • the total amount of ethylene units and propylene units in the ethylene-propylene copolymer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and 100% by mass. %.
  • Polyolefins include physical blends consisting of multiple components of these resins, reaction blends in which functional groups are reacted between different polymers in a molding machine, graft copolymers and block copolymers consisting of multiple segments, Compositions in which physical blends using these as compatibilizers are microdispersed are also included.
  • the total amount of ethylene units and propylene units in all monomer units contained in the polyolefin is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass. or more, and may be 100% by mass.
  • the mass ratio of ethylene units to propylene units contained in the polyolefin is preferably 10/90 to 40/60, more preferably 15/85 to 35/65.
  • the mass ratio of ethylene units is at least the lower limit of this range, the thermocompression bondability of the acid-modified polyolefin can be improved, and the adhesive strength can be improved.
  • the mass ratio of ethylene units is equal to or less than the upper limit of this range, the adhesive strength at high temperatures can be improved.
  • the "mass ratio of ethylene units and propylene units contained in the polyolefin" means all ethylene units and propylene units contained in polyethylene and polypropylene. means the mass ratio of
  • the mass ratio of ethylene units and propylene units is determined from the absorbance ratio of the characteristic absorption of polyethylene (719 cm ⁇ 1 ) and the characteristic absorption of polypropylene (1167 cm ⁇ 1 ) in the IR spectrum. Specifically, a calibration curve is used to convert the absorbance ratio of ethylene units and propylene units into a mass ratio.
  • a calibration curve can be prepared by blending commercially available polyethylene and polypropylene at various ratios and plotting the blending ratio and the absorbance ratio. Specifically, refer to the examples described later.
  • Polyethylene, polypropylene and ethylene-propylene copolymers may contain monomeric units other than ethylene units and propylene units.
  • monomers forming monomeric units other than ethylene units and propylene units include ⁇ -olefins such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, butadiene, and isoprene. , chloroprene and other diene monomers, vinyl acetate, acrylic acid esters, acrylic acid, methacrylic acid, unsaturated carboxylic acids and their derivatives such as methacrylic acid esters, and aromatic vinyl compounds such as styrene.
  • the content of monomer units other than ethylene units and propylene units in the polyolefin is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • properties such as water resistance, chemical resistance, and durability of polyolefin are enhanced, and polyolefin can be produced at low cost. It becomes possible.
  • polypropylene block polymer is substantially a mixture of polypropylene and propylene-ethylene random copolymer, the first step of obtaining homopolymer of propylene and the step of obtaining propylene-ethylene random copolymer It can be manufactured by a process consisting of a second step.
  • the acid compound used in producing the acid-modified polyolefin is selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, and combinations thereof.
  • An unsaturated carboxylic acid is a compound having an ethylenic double bond and a carboxylic acid group in the same molecule, and includes various unsaturated monocarboxylic acids and unsaturated dicarboxylic acids. These acid compounds may be used alone or in combination of two or more.
  • unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid and isocrotonic acid.
  • unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, nadic acid and endic acid.
  • the unsaturated carboxylic acid anhydride is a compound having an ethylenic double bond and a carboxylic acid anhydride group in the same molecule, and includes acid anhydrides of the above-mentioned unsaturated dicarboxylic acids.
  • acid anhydrides of unsaturated dicarboxylic acids include maleic anhydride, fumaric anhydride, itaconic anhydride, citraconic anhydride, nadic anhydride and endic anhydride.
  • maleic acid and maleic anhydride are preferably used, and maleic anhydride is particularly preferably used, because of their high modifying effect.
  • a known method can be adopted as a graft denaturation method.
  • a radical polymerization initiator such as an organic peroxide or an aliphatic azo compound
  • an acid compound is graft-reacted with a polyolefin in a molten state or in a solution state.
  • the graft reaction temperature is preferably 80 to 160°C when reacting in a solution state, and 150 to 300°C when reacting in a molten state. In both the solution state and the molten state, the reaction rate increases above the lower limit of the above reaction temperature range, and the decrease in the molecular weight of the resin can be suppressed below the upper limit of the above reaction temperature range. You can maintain your strength.
  • the radical polymerization initiator to be used may be selected from commercially available organic peroxides in consideration of the reaction temperature.
  • the amount of the acid compound grafted onto the acid-modified polyolefin is preferably 0.2% by mass or more, more preferably 0.4% by mass or more.
  • the adhesiveness of the adhesive layer (B) can be enhanced.
  • the amount of the acid compound grafted onto the acid-modified polyolefin is preferably 5% by mass or less, more preferably 2% by mass or less. When the amount of the grafted acid compound is within such a range, deterioration of physical properties due to reduction in molecular weight can be suppressed.
  • the amount of the acid compound grafted onto the acid-modified polyolefin is defined by the following formula from the acid value of the acid-modified polyolefin.
  • Graft amount (% by mass) acid value x M x 100/(1000 x 56.1 x V)
  • M and V are defined by the following formulas.
  • the acid value indicates the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of the sample, and is measured according to JIS K 0070:1992.
  • the melting point of the acid-modified polyolefin is preferably 130°C or higher, more preferably 135°C or higher.
  • the heat resistance and adhesive strength at high temperatures of the adhesive layer (B) can be improved.
  • the melting point of the acid-modified polyolefin is preferably 160°C or lower, more preferably 150°C or lower. When the melting point of the acid-modified polyolefin is within such a range, good thermocompression bonding properties can be obtained, and the durability of adhesion at low temperatures can be improved.
  • the melting point refers to an endothermic process that occurs in the process of holding at 180° C. for several minutes, cooling to 0° C., and then raising the temperature to 200° C. by 10° C. per minute using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the melt flow rate of acid-modified polyolefin is preferably 3 g/10 min or more, more preferably 7 g/10 min or more.
  • the melt flow rate of the acid-modified polyolefin is preferably 50 g/10 min or less, more preferably 30 g/10 min or less.
  • melt flow rate is a value measured according to JIS K7210:2014.
  • the melt flow rate of the adhesive layer (B) was measured at a resin temperature of 230° C. and a load of 2.16 kg.
  • the content of the acid-modified polyolefin in the adhesive layer (B) may be 2% by mass or more.
  • acid-modified polyolefin may be used by mixing with unmodified polyolefin, and when acid-modified polyolefin with a high degree of acid modification is used, a small amount of about 2% by mass may be used.
  • the content of the acid-modified polyolefin in the adhesive layer (B) is preferably 30% by mass or more, more preferably 70% by mass or more, particularly 90% by mass or more, even if it is 100% by mass. good.
  • polymer (B) a polymer other than acid-modified polyolefin (hereinafter referred to as polymer (B)) can be added.
  • Other polymers (B) include, for example, styrene-butadiene-styrene block copolymers and hydrogenated products thereof, styrene-isoprene-styrene block copolymers and hydrogenated products thereof, and styrene-isobutylene-styrene block copolymers.
  • styrene-based block copolymers such as hydrogenated products thereof, and styrene-based graft copolymers obtained by grafting styrene homopolymers or copolymers to polyolefins.
  • unmodified polyolefins such as polyethylene, polypropylene and ethylene-propylene copolymers may be added as the other polymer (B).
  • the lower limit of the content of the other polymer (B) in the adhesive layer (B) is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more. % by mass or more. When the amount added falls within this range, the improvement effect of the other polymer (B) is enhanced.
  • the upper limit of the content of the other polymer (B) in the adhesive layer (B) is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably It is 10% by mass or less.
  • the adhesive layer (B) can obtain high heat resistance and high adhesive strength at high temperatures.
  • the content of acid-modified polyolefin can be reduced. In such cases, the content of unmodified polyolefin may be high, and the upper limit of the content of unmodified polyolefin in the adhesive composition may be 98% by weight.
  • the adhesive layer (B) contains antioxidants, ultraviolet absorbers, fillers, reinforcing fibers, release agents, processing aids, flame retardants, plasticizers, nucleating agents, antistatic agents, pigments, dyes, and foaming agents. agents, and combinations thereof.
  • the multilayer sheet of the present invention can be strongly adhered to adherends.
  • the adhesive layer (B) of the multilayer sheet is adhered to an adherend, particularly a SUS304 plate with a thickness of 0.1 mm, to produce a bonded body
  • the multilayer sheet and the adherend, particularly a SUS304 plate with a thickness of 0.1 mm are bonded together.
  • the peel strength at room temperature is 2 N/10 mm or more, preferably 5 N/mm or more.
  • the room temperature is 23° C., and the room temperature peel strength is measured under the conditions described in Examples described later.
  • the base layer (A) preferably has a thickness within the range of 50-300 ⁇ m. Sufficient rigidity is obtained when the thickness of the base material layer (A) is at least this lower limit. When the thickness of the base material layer (A) is equal to or less than this upper limit, the influence on the thickness of an article incorporating a multilayer sheet such as a battery can be reduced.
  • the adhesive layer (B) preferably has a thickness of 10 to 100 ⁇ m. When the thickness of the adhesive layer (B) is at least this lower limit, the occurrence of poor adhesion can be suppressed.
  • the thickness of the adhesive layer (B) is equal to or less than this upper limit, it is possible to prevent the adhesive from oozing out from the multilayer sheet and to prevent defects from occurring in articles incorporating the multilayer sheet, such as batteries.
  • the multilayer sheet and the joined body using the same can exhibit excellent adhesion performance, durability, productivity and economic efficiency.
  • the base material layer (A) and the adhesive layer (B) are generally produced from resin compositions, which are raw materials.
  • the resin composition which is the raw material of the substrate layer (A) and the adhesive layer (B), is a resin composed of the components of the substrate layer (A) or the adhesive layer (B) described above, respectively.
  • is a composition based on The resin composition is prepared by melting and kneading the main component resin and, if necessary, other components with an extruder, Banbury mixer, hot rolls, or the like. It can be produced by a method of cooling and solidifying with the like, and cutting into pellets.
  • the melt-kneading temperature of the resin composition used for the substrate layer (A) is preferably 150 to 320° C., more preferably 180 to 300° C., and the kneading time is usually 0.5 to 20 minutes. It is preferably 1 to 15 minutes.
  • the melt-kneading temperature of the resin composition used for the adhesive layer (B) is preferably 150 to 270° C., more preferably 170 to 250° C., and the kneading time is usually 0.5 to 20 minutes. It is preferably 1 to 15 minutes.
  • the resin composition used for the substrate layer (A) and the resin composition used for the adhesive layer (B) thus obtained are subjected to conventionally known methods such as compression molding, injection molding, extrusion molding, By multilayer extrusion molding, profile extrusion molding, or blow molding, multilayer sheets can be formed into various shapes depending on the application.
  • the base material layer (A), the adhesive layer (B) and, if necessary, the tie layer (C) may be prepared in advance as sheets, and may be laminated by heat lamination, such as multi-layer extrusion molding. Sheeting and multilayering may be performed at the same time to form a multilayer. In either case, it is preferable to bring at least one of the adjacent layers into contact in a molten state.
  • the contact temperature is preferably 160° C. or higher, more preferably 190° C. or higher, and particularly preferably 220° C. or higher. When the contact temperature is at least the lower limit, the acid group or acid anhydride group contained in the adhesive layer (B) and the amino group contained in the substrate layer (A) form a bond, which can improve interlayer adhesion.
  • the multilayer sheet of the present invention is preferably formed into a sheet by multilayer extrusion from the viewpoint of productivity and manufacturing cost.
  • a layered molten resin extruded from a T-die is cooled and stretched by rolls or the like to form a sheet.
  • co-extrusion in which multiple resins are extruded at the same time, enables multi-layer molding.
  • Specific methods of co-extrusion include the "feed block method,” in which the resins are merged before the T-die, and the "multi-manifold method,” in which the single layers are spread out in a manifold and then merged at the lip, which is the discharge port of the T-die. There is a law. Any of these methods may be used in the production of the multilayer sheet of the present invention, and other methods may also be used.
  • the multilayer sheet of the present invention can be adhered to adherends made of various materials such as metals, glass, ceramics, and plastics. Thereby, a joined body including the multilayer sheet and the adherend can be produced.
  • adherends made of various materials such as metals, glass, ceramics, and plastics.
  • a joined body including the multilayer sheet and the adherend can be produced.
  • a bonded body including a multilayer sheet can be used as a member/component of a layered battery.
  • the metal used as the adherend may be a generally known metal plate, flat metal plate or metal foil, and iron, copper, aluminum, lead, zinc, titanium, chromium, stainless steel, etc. can be used. Among these, iron, aluminum, titanium, and stainless steel are particularly preferred.
  • thermoplastic or thermosetting resins can be used for the plastic used as the adherend.
  • a composite material in which an inorganic material such as glass or ceramics, a filler such as metal or carbon, or a fiber is combined with a resin may be used.
  • Adhesive layer (B) Maleic anhydride-modified polyolefins A to B containing polypropylene, polyethylene, ethylene-propylene copolymer and maleic anhydride-modified products thereof as main components were prepared.
  • the PE/PP compounding ratio of maleic anhydride-modified polyolefins A to B and the amount of maleic anhydride were confirmed by the procedures described in (1) and (2) below.
  • PE / PP blending ratio Commercially available polyethylene resin (P9210 manufactured by Keiyo Polyethylene Co., Ltd.) and polypropylene resin (Waymax MFX3 manufactured by Japan Polypropylene Co., Ltd.) are melt-kneaded with an extruder at various blending ratios. The resulting resin mixture was molded using a desktop press molding machine to prepare a resin sheet having a thickness of about 2 mm.
  • the number of repetitions was set to 4 or more in consideration of measurement errors.
  • the approximation curve of this plot was used as a calibration curve for determining the PE/PP blending ratio.
  • the maleic anhydride-modified polyolefins A to B were molded into resin sheets with a thickness of 2 mm, and the IR spectrum was similarly measured using the cross section as the measurement surface. Based on the obtained IR spectrum, the prepared calibration curve was used to determine the PE/PP mixing ratio of the maleic anhydride-modified polyolefins A to B. Table 2 shows the results.
  • Melt flow rate (MFR) is measured using a commercially available melt indexer (G-02 manufactured by Toyo Seiki Seisakusho Co., Ltd.) in accordance with JIS K7210: 2014, resin temperature 230 ° C., load 2. Measured at 16 kg. Table 2 shows the results.
  • ABN-E 2-aminoethanethiol hydrochloride, 2,2'-azobis-(2-methylbutyronitrile)
  • the polymerization liquid was diluted with methyl ethyl ketone until it became transparent, and a large amount of methanol was poured therein to precipitate polystyrene, which was then filtered, washed and dried to obtain a powder of amino-terminated polystyrene.
  • the polystyrene equivalent molecular weight determined by gel permeation chromatography was 3,000 in number average molecular weight and 5,100 in weight average molecular weight.
  • the resins (PPE/PS and amino group-containing polymer) described in "Base material layer (A) composition" in Table 3 below are melt-kneaded at the blending ratio (% by mass) described in Table 3, and the base material A resin composition for the layer (A) was obtained.
  • the melt flow rate, softening point, storage modulus, creep amount, and thermal change rate of the obtained resin composition for base layer (A) were measured as described in (1) to (4) below. The results are shown in Table 3 together with the composition.
  • Melt flow rate Melt flow rate (MFR) is measured using a commercially available melt indexer (G-02 manufactured by Toyo Seiki Seisakusho Co., Ltd.) in accordance with JIS K7210: 2014 at 300 ° C. and a load of 2.16 kg. measured by
  • the softening point and storage elastic modulus are values obtained using a tensile viscoelasticity apparatus (DMS6100 manufactured by Hitachi High-Tech Sunence). Specifically, the temperature was raised from room temperature to 250° C. at a frequency of 1 Hz and a heating rate of 2° C./min, and changes in storage elastic modulus, loss elastic modulus, and tan ⁇ with temperature were recorded. The softening point was defined as the temperature at which the value of tan ⁇ showed the maximum value.
  • the resin composition for the base material layer (A) was formed into a sheet having a thickness of 1 mm using a desktop press molding machine. This resin sheet was cut into a size of 10 mm ⁇ 10 mm, and five sheets were stacked to form a sample having a thickness of 5 mm. Using a hot press machine (digital press CYPT-50 manufactured by Sintokogyo Co., Ltd.), heating was performed at a temperature of 170° C. and a pressure of 6 MPa for 12 hours, and the creep amount (%) was calculated from the change in thickness.
  • a hot press machine digital press CYPT-50 manufactured by Sintokogyo Co., Ltd.
  • the resin composition for the substrate layer (A) was molded into a sheet having a thickness of about 100 ⁇ m using a desktop press molding machine. This resin sheet was cut into a size of 200 mm ⁇ 100 mm and used as a sample. The prepared sample was suspended in a dryer at 180° C. for 30 seconds, and the heat change rate was calculated from the dimensional change before and after heating.
  • the thermal rate of change is the average of the absolute value of the long side rate of change and the absolute value of the short side rate of change.
  • [3-layer sheet] In each example, a three-layer sheet was prepared as described below using the resin composition for the base layer (A) and the maleic anhydride-modified polyolefin for the adhesive layer (B) described in Table 3. , evaluated.
  • the resin composition for the base layer (A) was formed into a base layer (A) having a thickness of about 150 ⁇ m using a desktop press molding machine.
  • a maleic anhydride-modified polyolefin for the adhesive layer (B) was made into an adhesive layer (B) having a thickness of about 50 ⁇ m using a desktop press molding machine.
  • the base material layer (A) and the adhesive layer (B) are superimposed in the order of adhesive layer (B)/base material layer (A)/adhesive layer (B), and the same desktop press molding machine is used.
  • a three-layer sheet was obtained by thermocompression bonding for 10 seconds at the compression temperature shown in Table 3.
  • Test pieces A SUS304 plate with a thickness of 0.1 mm was used as an adherend, and both sides of the three-layer sheet were sandwiched between SUS304 plates and thermocompression bonded (160° C., 10 seconds, 0.3 MPa) with a precision press to produce a joined body. .
  • This joined body was cut into strips having a width of 10 mm to obtain test pieces.
  • the adhesive portion of the test piece had a width of 10 mm and a length of 15 mm.
  • the room temperature peel strength, hot water peel strength, and constant load immersion drop time of the obtained test pieces were measured as described in (1) to (3) below.
  • the constant load immersion test is a test method in which a test piece is held in hot water at 95° C. under a constant peeling load, and adhesion durability is evaluated by the time (dropping time) until the SUS304 plate peels off.
  • the test pieces are the same as those used for measuring the peel strength.
  • One of the handle portions of the test piece was connected to a fixed base with a wire, and the other was connected to a weight.
  • a test piece was suspended in hot water at 95° C. together with a weight from a fixed stand placed on the water surface, and a peeling load (1 N) was applied by the weight in water. At this time, the time required for the SUS304 plate as the adherend to be completely separated (falling time) was measured.
  • the results are shown in Table 3 as constant load immersion drop time (hr).
  • the multilayer sheet of the present invention is useful for bonding and sealing metals and other materials, and can be suitably used for applications in which the resulting joined body may come into contact with moisture continuously or intermittently. Since it has a substrate layer (A) with excellent rigidity and heat resistance, it is useful as a constituent member of a battery, and can contribute to a reduction in the number of battery parts and cost, and a significant improvement in productivity.
  • Other applications include, for example, electric wires and cables in which metal conductors or optical fibers are coated with resin moldings, automobile mechanical parts, automobile exterior parts, automobile interior parts, molded substrates for power supply, light reflectors for light source reflection, and solid methanol batteries.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
PCT/JP2022/019093 2021-04-28 2022-04-27 多層シート及びその製造方法 Ceased WO2022230938A1 (ja)

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CA3216968A CA3216968A1 (en) 2021-04-28 2022-04-27 Multilayer sheet and production method thereof
US18/557,484 US20240218210A1 (en) 2021-04-28 2022-04-27 Multilayer sheet and production method thereof
CN202280029172.4A CN117178041A (zh) 2021-04-28 2022-04-27 多层片材及其制造方法
KR1020237038071A KR20240004459A (ko) 2021-04-28 2022-04-27 다층 시트 및 그 제조 방법
JP2023517597A JPWO2022230938A1 (https=) 2021-04-28 2022-04-27
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CN117178041A (zh) 2023-12-05
KR20240004459A (ko) 2024-01-11
CA3216968A1 (en) 2022-11-03
EP4332188A1 (en) 2024-03-06
US20240218210A1 (en) 2024-07-04
JPWO2022230938A1 (https=) 2022-11-03

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