WO2022255370A1 - 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
WO2022255370A1
WO2022255370A1 PCT/JP2022/022152 JP2022022152W WO2022255370A1 WO 2022255370 A1 WO2022255370 A1 WO 2022255370A1 JP 2022022152 W JP2022022152 W JP 2022022152W WO 2022255370 A1 WO2022255370 A1 WO 2022255370A1
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Prior art keywords
acid
mass
layer
modified polyolefin
multilayer sheet
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English (en)
French (fr)
Japanese (ja)
Inventor
健太郎 宮村
誠 今堀
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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    • 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
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition

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 acid-modified polyolefin and a substrate layer containing heat-resistant polyolefin such as polyethylene naphthalate and cycloolefin polymer and engineering plastic such as polyphenylene ether is used as an adhesive member.
  • polyester resins such as polyethylene naphthalate hydrolyze when used for a long period of time, and there is 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 are also prone to problems such as cracking during long-term use due to their low toughness.
  • 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 an adhesive multilayer sheet having an adhesive layer containing an acid-modified polyolefin and a substrate layer, the adhesive multilayer sheet having high peel strength to an adherend. It is in.
  • the present inventors have made intensive studies to solve the above problems in developing a multilayer sheet containing an adhesive layer containing an acid-modified polyolefin and a substrate layer containing various engineering resins. Specifically, the present invention was completed by examining various resin compositions of the base material layer that strongly adheres to the acid-modified polyolefin by thermocompression and is excellent in heat resistance, rigidity, and durability.
  • polyamide (a1) is an amorphous polyamide having a glass transition point of 120°C or higher.
  • Polyamide (a1) is a monomer selected from the group consisting of monomer units derived from alicyclic diamines and dicarboxylic acids, monomer units derived from ⁇ -aminocarboxylic acids, and combinations thereof.
  • a substrate layer (A) containing 50 to 100% by mass of polyamide (a1) and 0 to 50% by mass of acid-modified polyolefin (a2), and an adhesive layer (B) containing 160% by weight of acid-modified polyolefin (b1) A method for producing a multilayer sheet, comprising the step of contacting in a molten state at a temperature of °C or above.
  • an adhesive multilayer sheet having an adhesive layer containing an acid-modified polyolefin and a substrate layer, and having high peel strength to an adherend.
  • the multilayer sheet of the present invention includes a substrate layer (A) containing polyamide (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 be a layer comprising polyolefins such as acid-modified polyolefins.
  • the base layer (A) contains polyamide (a1).
  • the polyamide (a1) may be the main component accounting for 50 to 100% by mass of the base layer (A).
  • the mass ratio of the polyamide (a1) in the substrate layer (A) is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. By setting the mass ratio of the polyamide (a1) within such a range, the heat resistance of the multilayer sheet can be improved.
  • the upper limit of the mass ratio of the polyamide (a1) in the substrate layer (A) is not particularly limited, but in one embodiment of the present invention it is preferably 98% by mass or less, more preferably 95% by mass or less. be. When the mass ratio of the polyamide (a1) is within such a range, the moldability of the multilayer sheet can be improved.
  • polyamide (a1) which is the main component of the base layer (A)
  • examples of the polyamide (a1) include polyamides obtained by condensing a diamine and a dicarboxylic acid, polyamides obtained by ring-opening polymerization of lactams or condensation of ⁇ -aminocarboxylic acids, and the like. be done.
  • the monomer units contained in the polyamide (a1) include monomer units derived from diamines, monomer units derived from dicarboxylic acids, monomer units derived from diamines and dicarboxylic acids, ⁇ -aminocarboxylic It can also be represented by the raw material of each monomer unit, such as a monomer unit derived from an acid.
  • diamines used as raw materials for polyamide
  • diamine components include 1,6-hexamethylenediamine, 2-methyl-1,5-diaminopentane, 2,2,4-trimethylhexamethylenediamine, linear or branched aliphatic diamines such as 2,4,4-trimethylhexamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,12-decamethylenediamine; '-diaminodicyclohexylmethane (PACM), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (MACM), 4,4'-diaminodicyclohexylpropane, 1,4-diaminocyclohexane, 1,4-bis ( alicyclic diamines such as aminomethyl)-cyclohexane, 2,6-bis(aminomethyl)-norbornane,
  • dicarboxylic acids used as raw materials for polyamide
  • dicarboxylic acid components include adipic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, azelaic acid, and sebacic acid.
  • 1,12-dodecanedioic acid and other linear or branched aliphatic dicarboxylic acids having 6 to 22 carbon atoms 1,12-dodecanedioic acid and other linear or branched aliphatic dicarboxylic acids having 6 to 22 carbon atoms, cyclohexane-1,4-dicarboxylic acid, 4,4′-dicarboxyldicyclohexylmethane, 3,3 Alicyclic dicarboxylic acids such as '-dimethyl-4,4'-dicarboxyldicyclohexylmethane, 4,4'-dicarboxyldicyclohexylpropane, 1,4-bis(carboxymethyl)cyclohexane, 4,4'-diphenylmethanedicarboxylic acid , isophthalic acid, tributyl isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthal
  • lactams used as raw materials for polyamides include ⁇ -caprolactam and ⁇ -laurinlactam.
  • ⁇ -aminocarboxylic acids used as raw materials for polyamide include ⁇ -aminoheptanoic acid and ⁇ -aminononanoic acid. These lactams and ⁇ -aminocarboxylic acids may be used singly or in combination of two or more.
  • polyamides examples include polycaprolactam (PA6), poly- ⁇ -aminoheptanoic acid (PA7), poly- ⁇ -aminononanoic acid (PA9), polyundecaneamide (PA11), polylaurinlactam (PA12), poly Ethylenediamineadipamide (PA26), polytetramethyleneadipamide (PA46), polyhexamethylenediadipamide (PA66), polyhexamethylenesebacamide (PA610), polyhexamethylenedecamide (PA612), poly Octamethylene adipamide (PA86), polydecamethylene adipamide (PA106), polydecamethylene sebacamide (PA1010), polydecamethylene dodecamide (PA1212), metaxylenediamine-6 nylon (MXD6), polyhexamethylene Methyleneisophthalamide (PA6I), polymetaxylyleneisophthalamide (PAMXDI), homopolymer obtained by condensation of bis-(4-amino-3-methyl-cyclo
  • the polyamide (a1) is preferably an amorphous polyamide having a crystalline melting enthalpy of less than 5 J/g. Further, the glass transition temperature of the polyamide (a1) is preferably 120°C or higher, more preferably 140°C or higher. When the glass transition temperature is equal to or higher than the above value, bending during thermocompression bonding can be prevented, and heat resistance and durability during use can be ensured. Although the upper limit of the glass transition temperature is not particularly limited, the glass transition temperature of the polyamide (a1) may be, for example, 220°C or lower.
  • the melting enthalpy and glass transition temperature of the polyamide (a1) were obtained by heating the sample from 25°C to 300°C at a rate of 10°C/min according to JIS K-7122: 1987 using differential calorimetry (DSC). can be obtained from the DSC curve. When there are multiple glass transition temperatures, the highest one is taken as the glass transition temperature.
  • the polyamide (a1) preferably contains an aliphatic ring.
  • the aliphatic ring contained in the polyamide (a1) is preferably an aliphatic ring having 4 to 10 carbon atoms, more preferably an aliphatic ring having 5 to 8 carbon atoms, and particularly preferably a cyclohexane ring.
  • Monomer units containing an alicyclic ring may be monomer units derived from any raw materials such as diamines, dicarboxylic acids and ⁇ -aminocarboxylic acids.
  • the polyamide (a1) is preferably an amorphous polyamide obtained using an alicyclic diamine. That is, the polyamide (a1) is preferably an amorphous polyamide containing monomer units derived from an alicyclic diamine and a dicarboxylic acid.
  • Specific alicyclic diamines include, for example, 4,4'-methylenebis(cyclohexylamine) (PACM), 4,4'-methylenebis(2-methylcyclohexylamine) (MACM), isophoronediamine (IPD), and the like. be done.
  • PAM 4,4'-methylenebis(cyclohexylamine)
  • MCM 4,4'-methylenebis(2-methylcyclohexylamine)
  • IPD isophoronediamine
  • a commercially available product can also be used as the polyamide (a1).
  • Commercially available products include the Trogamid series from Daicel-Evonik, the Grilamid TR series from Emschemie Japan, and the Rilsanclear series from Arkema.
  • the base layer (A) may further contain an acid-modified polyolefin (a2).
  • the acid-modified polyolefin (a2) may be an auxiliary component occupying 0 to 50% by mass of the substrate layer (A).
  • the acid-modified polyolefin (a2) is an optional component, and the substrate layer (A) may not contain the acid-modified polyolefin (a2).
  • the mass ratio of the acid-modified polyolefin (a2) in the substrate layer (A) is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the lower limit of the content of the acid-modified polyolefin (a2) is not particularly limited, in one embodiment of the present invention, the content of the acid-modified polyolefin (a2) in the substrate layer (A) is preferably 5 % by mass or more, more preferably 10% by mass or more.
  • the toughness and impact resistance of the substrate layer (A) can be improved.
  • the water resistance of the base layer (A) can be improved by including the acid-modified polyolefin (a2) in the base layer (A).
  • the total amount of the polyamide (a1) and the acid-modified polyolefin (a2) in the substrate layer (A) is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more, and is 100% by mass. %.
  • the acid-modified polyolefin (a2) which is an optional component of the base material layer (A), can be the same resin as the acid-modified polyolefin (b1) of the adhesive layer (B) described later, and the composition, physical properties, specific examples, etc. Please refer to the description of the adhesive layer (B).
  • the composition, physical properties, specific examples, etc. of the acid-modified polyolefin (b1) described below can be similarly applied to the acid-modified polyolefin (a2).
  • the acid-modified polyolefin (a2) may be a copolymer obtained by radical copolymerization of an acid group-containing monomer such as acrylic acid, methacrylic acid or maleic anhydride with an olefin. These acid group-containing copolymers are commercially available mainly in the ethylene series. The amount of acid compound contained in such an acid group-containing copolymer and physical properties such as melting point and melt flow rate may be the same as those of the acid-modified polyolefin (b1) of the adhesive layer (B).
  • the substrate layer (A) contains (a1) to (a2) for the purpose of improving toughness and molding stability at low temperatures and improving adhesion with the adhesive layer (B) or the tie layer (C).
  • Polymers other than hereinafter referred to as other polymers (A) can be added.
  • polymers (A) include, for example, styrene-butadiene-styrene block copolymers and hydrogenated products thereof, styrene-based block copolymers such as styrene-isoprene-styrene block copolymers and hydrogenated products thereof, and the like. Acid-modified products and epoxy-modified products of these block copolymers can also be used. Miscibility with the polyamide (a1) is improved by modifying the block copolymer with a functional group.
  • unmodified polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymers, and epoxy modified products may be used in small amounts.
  • 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) of the present invention contains an acid-modified polyolefin (b1).
  • Acid-modified polyolefin (b1) is an unmodified polyolefin (hereinafter also simply referred to as "polyolefin”) is an acid selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, and combinations thereof It is graft-modified with a compound.
  • 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 (b1) 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 (b1) 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 (b1) 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 (b1) 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 (b1) is preferably 160°C or lower, more preferably 150°C or lower. When the melting point of the acid-modified polyolefin (b1) is in such a range, good thermocompression bonding properties can be obtained, and adhesion durability 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). It means the temperature at the apex of the peak.
  • DSC differential scanning calorimeter
  • the melt flow rate of the acid-modified polyolefin (b1) 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 (b1) is preferably 50 g/10 min or less, more preferably 30 g/10 min or less.
  • the melt flow rate in the present invention 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 preferably 90% by mass or more, and 100% by mass.
  • the adhesive layer (B) contains a polymer other than the acid-modified polyolefin (b1) ( hereinafter referred to as other 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 preferably 2 N/10 mm or more, 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 within the range of 10-100 ⁇ 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. It is a composition containing as a main component.
  • 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 laminated by heat lamiting, such as multilayer extrusion molding. Sheeting and multilayering may be performed at the same time to form a multilayer. In either case, it is preferred to bring at least one of the adjacent layers into contact in the 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 within these ranges, the reaction between the acid groups or acid anhydride groups contained in the adhesive layer (B) and the amino groups contained in the substrate layer (A) proceeds, increasing the interlayer adhesive strength. can be improved.
  • 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.
  • Base layer (A) The resins described in "Base layer (A) composition" in Table 3 below are melt-kneaded at the blending ratio (% by mass) described in Table 3 to obtain a resin composition for the base layer (A). Obtained.
  • the melt flow rate, softening point, storage modulus, creep amount, thermal change rate, tensile properties, and hot water resistance of the resulting resin composition for the substrate layer (A) are measured as described in (1) to (6) below. Measured on the street. 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.
  • the resin composition for the substrate layer (A) was formed into a sheet having a thickness of about 150 ⁇ m using a desktop press molding machine. This resin sheet was cut into strips of 60 mm ⁇ 10 mm to obtain tensile test pieces. A tensile tester manufactured by Instron (Instron 5566A) was used as the tensile tester, and the distance between jigs was set to 10 mm. evaluated with Breaking strain was calculated using the distance between jigs as the initial length.
  • Hot water test A tensile test piece similar to that described in (5) was immersed in pure water, placed in a pressure container, and stored in a dryer at 125°C. After being immersed for 550 hours and 2700 hours, the test pieces were taken out, air-dried for one day, and subjected to a tensile test in the same manner as described in (5). Hot water resistance was evaluated by the degree of change from the initial values of maximum stress and breaking strain.
  • [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 details of the resin used for the substrate layer (A) in Table 3 are as follows. 1000H: Zylon 1000H manufactured by Asahi Kasei Corporation, polyphenylene ether-polystyrene, glass transition point 184° C. (DSC) TR60: Grilamid TR60 manufactured by Em Chemie, polyamide, glass transition point 190°C TR55LX: Grilamid TR55LX manufactured by Emschemie, polyamide, glass transition point 110°C MA8510: Toughmer MA8510 manufactured by Mitsui Chemicals, Inc., acid-modified polyethylene
  • 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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WO2025009511A1 (ja) * 2023-07-06 2025-01-09 東亞合成株式会社 多層シート

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US6379812B1 (en) * 2000-05-31 2002-04-30 Cryovac, Inc. High modulus, multilayer film
CN103496242A (zh) * 2013-10-17 2014-01-08 江苏昊达有限责任公司 防渗透多层共挤塑料薄膜
WO2014185482A1 (ja) * 2013-05-15 2014-11-20 Kurihara Kazuyuki 悪臭封止袋
JP2018069734A (ja) * 2016-10-21 2018-05-10 日本ポリエチレン株式会社 ポリアミド系共押出易引裂多層フィルム及び包装材
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JPH11198287A (ja) * 1998-01-16 1999-07-27 Dainippon Printing Co Ltd 多層積層ヒ−トシ−ル材、それを使用した積層体および包装用容器
US6379812B1 (en) * 2000-05-31 2002-04-30 Cryovac, Inc. High modulus, multilayer film
WO2014185482A1 (ja) * 2013-05-15 2014-11-20 Kurihara Kazuyuki 悪臭封止袋
CN103496242A (zh) * 2013-10-17 2014-01-08 江苏昊达有限责任公司 防渗透多层共挤塑料薄膜
JP2018069734A (ja) * 2016-10-21 2018-05-10 日本ポリエチレン株式会社 ポリアミド系共押出易引裂多層フィルム及び包装材
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WO2025009511A1 (ja) * 2023-07-06 2025-01-09 東亞合成株式会社 多層シート

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