WO2018221331A1 - Composition, coating agent, adhesive, and laminate - Google Patents

Composition, coating agent, adhesive, and laminate Download PDF

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Publication number
WO2018221331A1
WO2018221331A1 PCT/JP2018/019746 JP2018019746W WO2018221331A1 WO 2018221331 A1 WO2018221331 A1 WO 2018221331A1 JP 2018019746 W JP2018019746 W JP 2018019746W WO 2018221331 A1 WO2018221331 A1 WO 2018221331A1
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Prior art keywords
polymer
coating agent
weight
olefin polymer
olefin
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PCT/JP2018/019746
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French (fr)
Japanese (ja)
Inventor
義人 廣田
伊東　祐一
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三井化学株式会社
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Application filed by 三井化学株式会社 filed Critical 三井化学株式会社
Priority to JP2019522149A priority Critical patent/JP7142008B2/en
Priority to CN201880028191.9A priority patent/CN110573584A/en
Publication of WO2018221331A1 publication Critical patent/WO2018221331A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions 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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/10—Homopolymers or copolymers of propene
    • C09D123/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions 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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
    • C09D123/28—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • 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
    • C09J123/02—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 not modified by chemical after-treatment
    • C09J123/10—Homopolymers or copolymers of propene
    • C09J123/14—Copolymers of propene
    • 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
    • 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
    • C09J123/28—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 by reaction with halogens or compounds containing halogen
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a composition, a coating agent, an adhesive, and a laminate, and more specifically, a coating agent useful as a paint, primer, adhesive, and pressure-sensitive adhesive, a decorative film, a molded article, a packaging material, and a battery case packaging.
  • the present invention relates to materials and batteries.
  • Polyolefin resins such as polypropylene and polyethylene are widely used because they are inexpensive and have many excellent properties such as moldability, chemical resistance, water resistance, electrical properties, and safety.
  • polyolefin resin is a hydrophobic material with low polarity, it is difficult to adhere polar resins such as acrylic resin, polyester resin, polycarbonate resin, and ABS resin. Therefore, at present, it is difficult to laminate the polar resin on the surface of the polyolefin-based resin or to decorate it with ink, paint, or the like.
  • a method in which a film having a design layer (decorative film) is bonded to a molded body having various shapes for decoration.
  • a highly polar resin such as a urethane resin or an acrylic resin is used as the base material for the design layer. Therefore, when a decorative film is bonded to a molded article of polyolefin resin such as polypropylene, an adhesive layer that adheres a polyolefin resin and a highly polar design layer such as urethane resin or acrylic resin is provided. Desired.
  • Patent Documents 2 to 5 describe layers obtained from an adhesive containing a modified olefin resin and an epoxy compound or an oxazoline compound.
  • Patent Document 1 Although the coating agent described in Patent Document 1 has good adhesion, further improvement has been demanded. Specifically, improvement of workability (dry lamination, etc.) at low temperatures (reduction of laminating temperature), improvement of top coatability as a primer (coating without repellency and good adhesion), and high adhesion (Use as a pressure-sensitive adhesive without heating like a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet for display).
  • the adhesive layer obtained from the adhesives described in Patent Documents 2 to 5 does not have sufficient adhesive strength with a substrate or an adherend, such as an aluminum foil or a polypropylene film, and the adhesive layer can be obtained at a low temperature.
  • a substrate or an adherend such as an aluminum foil or a polypropylene film
  • the adhesive layer can be obtained at a low temperature.
  • the adhesive strength of the resulting adhesive layer was not sufficient.
  • the present invention has excellent adhesion to a polyolefin resin substrate that has not been subjected to preliminary surface treatment such as corona treatment, and at the same time, to a highly polar substrate such as an acrylic resin. Even with a coating film having good adhesiveness, a coating agent having excellent low-temperature workability, top coatability and adhesive strength, a decorative film having at least one layer comprising the coating agent, and the decorative film One of the purposes is to provide a decorated molded body.
  • the present invention forms an adhesive layer excellent in adhesive strength with a substrate such as an aluminum foil and an adherend such as a thermoplastic resin film, particularly an adhesive layer excellent in adhesive strength even under low temperature curing conditions.
  • a coating agent that can be used, and a laminate including the adhesive layer.
  • a coating agent comprising a specific low crystalline olefin polymer and a semi-solid hydrocarbon having a specific kinematic viscosity.
  • the headline and the present invention were completed.
  • the coating agent of the present invention has a heat of fusion measured in accordance with JIS K 7122 in the range of 0 to 50 J / g, and a weight average molecular weight (Mw) measured by GPC method of 1 ⁇ 10 4 to 1000 ⁇ 10 4 .
  • the coating agent of the present invention has excellent adhesion to a polyolefin resin substrate, as well as good adhesion to a highly polar substrate such as an acrylic resin, a polyester resin, a polycarbonate resin, and an ABS resin. In addition to providing a coating film having properties, it is excellent in low-temperature workability, top coatability and adhesive strength.
  • the decorative film of the present invention has excellent adhesion to a polyolefin resin substrate, as well as a highly polar substrate such as an acrylic resin, a polyester resin, a polycarbonate resin, and an ABS resin. Adhesion.
  • the adhesion between the decorative film and the substrate is high.
  • an adhesive layer excellent in adhesive strength and chemical resistance can be obtained, and in particular, an aluminum foil layer and a film layer made of a thermoplastic resin such as polypropylene. Can be bonded with high strength.
  • an adhesive layer having excellent adhesive strength can be easily formed even under low-temperature curing conditions, and a laminate having excellent durability and sufficiently suppressed decrease in adhesive strength.
  • the packaging material, the battery case packaging material, and the like can be easily formed by, for example, a dry lamination method.
  • FIG. 1 is a schematic cross-sectional view of one embodiment of the battery of the present invention.
  • the coating agent of the present invention has a heat of fusion measured in accordance with JIS K 7122 in the range of 0 to 50 J / g, and a weight average molecular weight (Mw) measured by GPC method of 1 ⁇ 10 4 to 1000 ⁇ 10 4 .
  • An olefin polymer (A) and a semisolid hydrocarbon (B) having a kinematic viscosity at 200 ° C. of 1,000 to 100,000 mm 2 / s are contained.
  • the coating agent of the present invention further has a tackifier having an acid value determined according to JIS K 0070 of 10 or more and a weight average molecular weight (Mw) measured by GPC method of 1 ⁇ 10 3 to 3 ⁇ 10 3.
  • C) and / or a curing agent (D) may be contained, and when the curing agent (D) is contained, a catalyst (E) having a pKa of 11 or more may be further contained.
  • the olefin polymer (A) used in the present invention has a heat of fusion measured in accordance with JIS K 7122 in the range of 0 to 50 J / g and a weight average molecular weight (Mw) measured by GPC method of 1 ⁇ 10 4 to 1000 ⁇ 10 4 . That is, in the coating agent of the present invention, as the olefin polymer (A), a polymer having a certain low crystallinity is used.
  • the olefin polymer (A) is referred to as “low crystalline olefin resin (A)” or “low crystalline olefin” for distinction from “semi-solid hydrocarbon (B)” described later. Sometimes referred to as “resin”.
  • the heat of fusion can be determined by differential scanning calorimetry (DSC measurement) according to JIS K 7122, and is specifically calculated from the peak area of the thermogram obtained in the temperature rising process of 10 ° C./min. .
  • DSC measurement differential scanning calorimetry
  • the temperature is raised to the melting point + 20 ° C. or more at 10 ° C./min before the measurement, held at that temperature for 3 minutes, and then 10 ° C./min. Measure the heat of fusion after cooling down to below room temperature.
  • the heat of fusion is from 0 J / g to 50 J / g, the lower limit is preferably 3 J / g, more preferably 5 J / g, and the upper limit is preferably 40 J / g or less, more preferably 30 J / g or less. is there. If it is 50 J / g or less, it is preferable because stability in a state in which the coating agent of the present invention is dissolved in a solvent, that is, in a varnish state is good, and solidification and precipitation hardly occur. On the other hand, from the viewpoint of the strength and tack resistance of the coating film, it is preferable that the lower limit of the heat of fusion is higher.
  • the weight average molecular weight measured by GPC method of the olefin polymer (A) used in the present invention is 1 ⁇ 10 4 or more and 1000 ⁇ 10 4 or less, more preferably 2 ⁇ 10 4 or more and 100 ⁇ 10 4 or less in terms of polystyrene, More preferably, it is 3 ⁇ 10 4 or more and 50 ⁇ 10 4 or less.
  • a weight average molecular weight of 1 ⁇ 10 4 or more is preferable because the strength of the coating film can be sufficiently increased and the adhesion strength is good.
  • the weight average molecular weight is 1000 ⁇ 10 4 or less, the stability in the varnish state is good, and solidification and precipitation hardly occur.
  • the weight average molecular weight of the olefin polymer (A) is a small value (for example, 50 ⁇ 10 4 or less), the adhesion performance tends to be particularly excellent.
  • the olefin polymer (A) used in the present invention is not particularly limited as long as it satisfies the above requirements for heat of fusion and weight average molecular weight.
  • a homopolymer of ⁇ -olefin or two or more ⁇ -olefins can be used.
  • examples include olefin copolymers.
  • the ⁇ -olefin include ⁇ -olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, octene, 4-methyl-1-pentene and the like. That is, examples of the olefin polymer (A) include polymers containing structural units derived from ⁇ -olefins having 2 to 20 carbon atoms.
  • the olefin polymer (A) is an unsaturated monomer other than an ⁇ -olefin (hereinafter referred to as “others”) in the range of 10 mol% or less, assuming that the structural unit derived from the ⁇ -olefin is 100 mol%.
  • the structural unit may be derived from an unsaturated monomer ")".
  • other unsaturated monomers include conjugated polyenes such as butadiene and isoprene, 1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and 5-vinyl.
  • Non-conjugated polyenes such as -2-norbornene, 5-methylene-2-norbornene, and 2,5-norbonadiene are exemplified.
  • the olefin polymer (A) is a copolymer containing two or more kinds of structural units derived from ⁇ -olefin, it may be a random copolymer or a block copolymer.
  • the olefin polymer (A) is prepared by adding, for example, a polymer or copolymer containing a structural unit derived from the ⁇ -olefin to a hydroxyl group, a carboxylic anhydride, —COOX (X: H, M) (H is hydrogen, M May be a modified olefin polymer obtained by graft reaction of an unsaturated monomer containing an alkali metal, an alkaline earth metal, an amine or the like, or may be derived from the ⁇ -olefin.
  • the halogenated olefin polymer obtained by further halogenating the polymer or copolymer containing a structural unit may be sufficient.
  • olefin polymers (A) include one or more selected from the group consisting of the following (A1) to (A3): (A1) a polymer containing a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms (hereinafter referred to as “polymer (A1)”); (A2) A polymer containing a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms, part or all of which is graft-modified with a polar group-containing monomer (hereinafter referred to as “ Referred to as “modified olefin polymer (A2)”); (A3) A polymer containing a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms, a part or all of which is halogenated and modified (hereinafter referred to as “halogenated olefin heavy polymer”). Combined (A3) ").
  • polymers (A1) examples include polymers containing a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms. That is, in the present invention, a polymer containing a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is used as it is as a polymer (A1) without undergoing modification treatment such as graft modification and halogenation modification. You may use for a unification (A). In that sense, the polymer (A1) can also be referred to as an unmodified polymer (A1), and is distinguished from the “modified olefin polymer (A2)” and “halogenated olefin polymer (A3)” described later. Is done.
  • the polymer (A1) has 50 to 50 structural units derived from propylene when the total of structural units derived from ⁇ -olefin having 2 to 20 carbon atoms is 100 mol%.
  • preferable examples of “ ⁇ -olefin having 2 to 20 carbon atoms excluding propylene” include 1-butene and octene.
  • the structural unit derived from propylene is preferably 55 to 90 mol%, more preferably 60 to 85 mol%, Preferably, it is 60 to 80 mol%, and the constituent unit derived from an ⁇ -olefin having 2 to 20 carbon atoms excluding propylene is preferably 45 to 10 mol%, more preferably 40 to 15 mol%, still more preferably 40 to 20 mol%.
  • a propylene-based polymer containing mol% is more preferable.
  • such a polymer (A1) may be used singly or in combination of two or more.
  • the production method is not limited, and a conventionally known method is known. For example, it can be produced according to the methods described in Japanese Patent No. 3939464 and International Publication No. 2004/87775.
  • propylene / 1-butene copolymer suitably used as the polymer (A1) in the present invention as an example
  • such propylene / 1-butene copolymer is, for example, rac-dimethylsilylene- From a suitable metallocene compound such as bis ⁇ 1- (2-methyl-4-phenylindenyl) ⁇ zirconium dichloride, an organoaluminum oxy compound such as aluminoxane, and an organoaluminum compound such as tributylaluminum used as necessary. It can be obtained by copolymerizing propylene and 1-butene in the presence of a metallocene catalyst.
  • the modified olefin polymer (A2) is a polymer containing a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms, part or all of which is graft-modified with a polar group-containing monomer. And a modified olefin polymer.
  • the polymer contains 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight of a structural unit derived from a polar group-containing monomer with respect to 100 parts by weight of the modified olefin polymer. .
  • a polymer (A1a) containing a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is once graft-modified with a polar group-containing monomer, and the resulting graft-modified olefin-based polymer is obtained.
  • the polymer (A2m) itself can be used as the modified olefin polymer (A2) in the olefin polymer (A).
  • examples of the polymer (A1a) include the same as the polymer (A1).
  • the modified olefin polymer (A2) is obtained by mixing the graft modified product of the polymer (A1a) as described above, that is, the graft modified olefin polymer (A2m) and the unmodified polymer (A1a).
  • it may be used in the form of a modified olefin polymer composition.
  • the polymer (A1a) used for graft modification for obtaining the graft-modified olefin polymer (A2m) and the polymer (A1a) used unmodified may be the same or different.
  • This case is an example of a polymer containing a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms, a part of which is graft-modified with a polar group-containing monomer.
  • the weight average molecular weight of the polymer (A1a) that can be used above is not particularly limited as long as the corresponding modified olefin polymer (A2) as a whole satisfies the weight average molecular weight, but is usually 1 ⁇ 10 4 to 1000 ⁇ .
  • the range is 10 4 , preferably 2 ⁇ 10 4 or more and 100 ⁇ 10 4 or less, more preferably 3 ⁇ 10 4 or more and 50 ⁇ 10 4 or less.
  • the heat of fusion measured according to JIS K 7122 is not particularly limited as long as the modified olefin polymer (A2) satisfies the weight average molecular weight, but the heat of fusion is 0 J / g or more and 50 J / g or less,
  • the lower limit is preferably 3 J / g, more preferably 5 J / g, and the upper limit is preferably 40 J / g or less, more preferably 30 J / g or less.
  • the polarity is 100 parts by weight with respect to a total of 100 parts by weight of the graft-modified olefin polymer (A2m) and the optionally used unmodified polymer (A1a). It is preferable to contain 0.1 to 15 parts by weight of a structural unit derived from a group-containing monomer.
  • a polar group-containing monomer is graft copolymerized with the polymer (A1a).
  • polar group-containing monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, unsaturated carboxylic acids and their anhydrides and derivatives, and vinyl ester compounds. Vinyl chloride and the like, and unsaturated carboxylic acids and anhydrides thereof are preferred.
  • hydroxyl group-containing ethylenically unsaturated compound examples include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate.
  • amino group-containing ethylenically unsaturated compound examples include vinyl monomers having at least one amino group or substituted amino group represented by the following formula.
  • R 1 is a hydrogen atom, a methyl group or an ethyl group
  • R 2 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, or an 8 to 12 carbon atom, preferably 6 carbon atoms. -9 cycloalkyl groups.
  • said alkyl group and cycloalkyl group may have a substituent further.
  • Examples of such an amino group-containing ethylenically unsaturated compound include aminomethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, and phenyl methacrylate.
  • Alkyl ester derivatives of acrylic acid or methacrylic acid such as aminomethyl and cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, acrylamide, methacrylamide, N-methylacrylamide, N And imides such as acrylamide derivatives such as N, N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide.
  • epoxy group-containing ethylenically unsaturated compound a monomer having at least one unsaturated bond group and epoxy group polymerizable in one molecule is used.
  • Examples of such an epoxy group-containing ethylenically unsaturated compound include glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate, or maleic acid, fumaric acid, crotonic acid, tetrahydrophthalic acid, itaconic acid, and citraconic acid.
  • unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept
  • unsaturated carboxylic acids such as -2-ene-5,6-dicarboxylic acid or derivatives thereof (for example, acid anhydrides, acid halides, amides, imides, esters, etc.).
  • Examples of the unsaturated carboxylic acid derivative include, for example, maleyl chloride, maleenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6 Dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5 Dimethyl 6-dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate.
  • vinyl ester compound examples include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl persate, vinyl laurate, vinyl stearate, vinyl benzoate, and salicylic acid.
  • vinyl and vinyl cyclohexanecarboxylate examples include vinyl and vinyl cyclohexanecarboxylate.
  • polar group-containing monomers can be used alone or in combination.
  • the polar group-containing monomer is added to the graft-modified olefin polymer (A2m) by 100 parts by weight.
  • Graft copolymerization is preferably carried out so as to be 1 to 15 parts by weight, preferably 0.5 to 10 parts by weight.
  • the amount of the functional group introduced into the modified olefin polymer (A2) can be used as an amount of the standard.
  • the following are mentioned as a measuring method of an acid value.
  • titration is performed using a 0.1 mol / L potassium hydroxide 2-propanol solution (manufactured by Wako Pure Chemical Industries, Ltd.), and the acid value is determined from the titration amount.
  • EP1 is a titration amount (mL)
  • BL1 is a blank value (mL)
  • FA1 is a factor of a titrant (1.00)
  • C1 is a concentration conversion value (5.611 mg / mL: 0.00).
  • SIZE represents the sample collection amount (g).
  • the acid value of the modified olefin polymer (A2) is preferably 0.1 to 100 mgKOH / g, more preferably 0.5 to 60 mgKOH / g, and 0.5 to 30 mgKOH / g. Is more preferable.
  • the modified olefin polymer composition obtained by mixing the graft-modified olefin polymer (A2m) and the unmodified polymer (A1a) is used as the modified olefin polymer (A2)
  • the modification The olefin polymer composition as a whole preferably has an acid value as described above.
  • the graft amount is determined based on the absorption of the carbonyl group of maleic anhydride detected in the vicinity of 1790 cm ⁇ 1 using an infrared spectrophotometer. You can also.
  • graft copolymerizing the polymer (A1a) with at least one polar group-containing monomer selected from the polar group-containing monomers various methods can be exemplified. For example, a method in which a polymer (A1a) is dissolved in an organic solvent, the above polar group-containing monomer and a radical polymerization initiator are added and heated and stirred to cause graft copolymerization reaction, and the polymer (A1a) is heated and melted And adding the polar group-containing monomer and the radical polymerization initiator to the resulting melt, stirring and graft copolymerizing, the polymer (A1a), the polar group-containing monomer and the radical polymerization.
  • the polymer (A1a) is mixed with the polar group-containing monomer and the radical polymerization initiator in an organic solvent.
  • the reaction temperature is preferably 50 ° C. or higher, particularly 80 to 200 ° C., and the reaction time is about 1 minute to 10 hours.
  • the reaction method may be either a batch method or a continuous method, but a batch method is preferable in order to perform graft copolymerization uniformly.
  • the radical polymerization initiator to be used is not particularly limited as long as it promotes the reaction between the polymer (A1a) and the polar group-containing monomer, and organic peroxides and organic peresters are particularly preferable.
  • benzoyl peroxide dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3, 1,4-bis (tert -Butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert -Butyl peroxide) hexane, tert-butyl benzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-buty
  • dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert Dialkyl peroxides such as -butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.
  • the radical polymerization initiator is preferably used in an amount of about 0.001 to 10 parts by weight with respect to 100 parts by weight of the polymer (A1a).
  • modified olefin polymer composition obtained by mixing the graft-modified olefin polymer (A2m) and the unmodified polymer (A1a) is used as the modified olefin polymer (A2)
  • the grafted polar group-containing monomer is used in an amount of 0.1 to 15 parts by weight, preferably 0.8%, based on 100 parts by weight of the total of the graft-modified olefin polymer (A2m) and the unmodified polymer (A1a). It is preferable to prepare so as to be 5 to 10 parts by weight.
  • the graft reaction can be carried out in an organic solvent or without solvent.
  • the graft-modified olefin polymer (A2m) itself is used as the modified olefin polymer (A2).
  • a composition in which the modified olefin polymer (A2) is dissolved in an organic solvent is used as an adhesive or the like, when reacted in an organic solvent, it is used as it is, or further of the same or other types. It is also possible to prepare a coating agent or the like by adding an organic solvent. When the grafting reaction is carried out without using an organic solvent, an organic solvent is added again to dissolve the graft product to obtain the coating agent of the present invention.
  • the graft modified olefin polymer (A2m), which is a graft modified product of the polymer (A1a), and the unmodified polymer (A1a) are mixed and used as the modified olefin polymer (A2). They may be mixed in advance and used for preparing the coating agent, or may be mixed in a solvent when preparing the coating agent.
  • the organic solvent for preparing the coating agent of the present invention during the reaction or after the reaction is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, hexane, heptane, Aliphatic hydrocarbons such as octane and decane, cycloaliphatic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane, decahydronaphthalene, methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol, etc.
  • aromatic hydrocarbons such as benzene, toluene and xylene, hexane, heptane
  • Aliphatic hydrocarbons such as octane and decane
  • cycloaliphatic hydrocarbons such as cyclohe
  • the graft-modified olefin polymer (A2m) constituting the modified olefin polymer (A2) is obtained.
  • one kind of such graft-modified olefin polymer (A2m) is obtained. They may be used alone or in combination of two or more.
  • the modified olefin polymer (A2) is composed of two or more kinds of graft-modified olefin polymers (A2m), preferably the total of the two or more kinds of graft-modified olefin polymers (A2m) and any
  • the grafted polar group-containing monomer is 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight in total with the unmodified polymer (A1a) used in 1. It is preferable to prepare as follows.
  • the modified olefin polymer (A2) has propylene-derived structural units when the total of structural units derived from ⁇ -olefins having 2 to 20 carbon atoms is 100 mol%.
  • preferable examples of “ ⁇ -olefin having 2 to 20 carbon atoms excluding propylene” include 1-butene and octene.
  • the content of the structural units derived from propylene is preferably 55 to 90 mol%, More preferably, it is 60 to 85 mol%, and further preferably 60 to 80 mol%, and the content of the structural unit derived from ⁇ -olefin having 2 to 20 carbon atoms excluding propylene is preferably 45 to 10 mol%, more preferably Is 40 to 15 mol%, more preferably 40 to 20 mol%.
  • (A2) a polymer containing a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms according to the present invention, wherein a part or all of the polymer is graft-modified with a polar group-containing monomer.
  • the polymer includes a modified olefin polymer (A2 ′) containing 0.1 to 15 parts by weight of a structural unit derived from a polar group-containing monomer with respect to 100 parts by weight of the modified olefin polymer;
  • a modified olefin polymer which is a polymer containing 50 to 0 mol% of a structural unit derived from ⁇ -olefin, and a modified olefin which satisfies both the requirements for the graft amount and the types and amounts of the structural units.
  • Any of the fin-based polymers (A2 ′′) is included.
  • Halogenated olefin polymer (A3) As the halogenated olefin polymer (A3), a halogenated olefin polymer obtained by halogenating and modifying a part or all of the polymer containing a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is used. Can be mentioned.
  • a polymer (A1b) containing a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is once halogenated and the resulting halogenated modified olefin polymer (A3m) is obtained.
  • the olefin polymer (A) can be used as the halogenated olefin polymer (A3).
  • examples of the polymer (A1b) include the same as the polymer (A1).
  • the polymer (A3) is preferably a halogenated modified olefin polymer comprising a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms, part or all of which is halogenated.
  • the polymer (A3) has 50 to 100 mol% of propylene-derived structural units when the total of the structural units derived from ⁇ -olefin having 2 to 20 carbon atoms is 100 mol%, and the number of carbons excluding propylene A propylene polymer containing 2 to 20 ⁇ -olefin-derived structural units in an amount of 50 to 0 mol% is preferred.
  • preferable examples of “ ⁇ -olefin having 2 to 20 carbon atoms excluding propylene” include 1-butene and octene.
  • the (A3) polymer containing a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms according to the present invention, which is partially or entirely halogenated, is a halogenated modified olefin polymer.
  • the structural units derived from ⁇ -olefins of 2 to 20 is 100 mol%
  • the structural units derived from propylene are 50 to 100 mol%, and derived from ⁇ -olefins having 2 to 20 carbon atoms excluding propylene.
  • a modified olefin polymer which is a polymer containing 50 to 0 mol% of a structural unit, and both the requirements for the halogenated modification amount and the types and amounts of the structural unit are satisfied. Any halogenated modified olefin polymer (A3 ′′) is included.
  • the halogenated olefin polymer (A3) includes a halogenated modified product of the polymer (A1b) as described above, that is, a halogenated modified olefin polymer (A3m) and an unmodified polymer (A1b). And may be used in the form of a halogenated modified olefin polymer composition.
  • the polymer (A1b) used for halogenation modification to obtain the halogenated modified olefin polymer (A3m) and the polymer (A1b) used unmodified may be the same or different.
  • This case is an example in which a part of a polymer containing a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is halogenated and modified with a polar group-containing monomer.
  • the weight average molecular weight of the polymer (A1b) that can be used in the above is not particularly limited as long as the halogenated olefin polymer (A3) as a whole satisfies the weight average molecular weight, but is usually 1 ⁇ 10 4 to 1000 ⁇ 10 6.
  • the range is 4 , preferably 2 ⁇ 10 4 or more and 100 ⁇ 10 4 or less, more preferably 3 ⁇ 10 4 or more and 50 ⁇ 10 4 or less.
  • the heat of fusion measured according to JIS K 7122 is not particularly limited as long as the halogenated olefin polymer (A3) satisfies the weight average molecular weight. Since the heat of fusion tends to decrease due to halogenation, the polymer (A1b) to be used can be selected accordingly.
  • the halogenated olefin polymer (A3) contains 2 halogens per 100 parts by weight in total of the halogenated modified olefin polymer (A3m) and the optionally used unmodified polymer (A1b). It is preferable to contain ⁇ 40 parts by weight.
  • a chlorinated polyolefin can be suitably used as the halogenated modified olefin polymer (A3m) constituting the halogenated olefin polymer (A3).
  • the chlorinated polyolefin used as the halogenated modified olefin polymer (A3m) in the present invention can be obtained by chlorinating polyolefin by a known method.
  • the chlorinated polyolefin used as the halogenated modified olefin polymer (A3m) was further modified with a polar group-containing monomer such as an unsaturated carboxylic acid and its anhydride (for example, maleic anhydride). It may be a thing.
  • HARDREN CY-9122P HARDREN CY-9124P
  • HARDREN HM-21P HARDREN M-28P
  • HARDREN F-2P HARDREN F-6P
  • HARDREN F-6P both manufactured by Toyobo Co., Ltd., trade name
  • the chlorine content of the chlorinated polyolefin is based on the total of the chlorinated modified olefin polymer used as the halogenated modified olefin polymer (A3m) and the unmodified polymer (A1b) optionally used. It is preferably 10% by weight or more and 40% by weight or less, and more preferably 20% by weight or more and 30% by weight or less. It is preferable that it is not more than the upper limit value because deterioration due to exposure to heat, sunlight, ultraviolet rays, rain, etc. can be suppressed, and if it is not less than the lower limit value, sufficient adhesion can be obtained.
  • such a halogenated modified olefin polymer (A3m) may be used singly or in combination of two or more.
  • Such a halogenated modified olefin polymer (A3m) is prepared by, for example, dissolving a polyolefin in a chlorinated solvent until the chlorine content reaches 16 to 35% by weight in the presence or absence of a radical catalyst. Can be obtained by blowing chlorine gas.
  • examples of the chlorinated solvent used as a solvent for the chlorination reaction include tetrachloroethylene, tetrachloroethane, carbon tetrachloride, and chloroform.
  • the temperature at which the above dissolution and chlorination reaction are carried out is preferably at least the temperature at which the polyolefin dissolves in the chlorinated solvent.
  • the halogenated modification is performed in an organic solvent.
  • the organic solvent can be used as it is, or can be used by further adding the same or other organic solvent.
  • the organic solvent that can be used in this case the same solvents as those used for the modified olefin polymer (A2) can be used. Can be mentioned.
  • the olefin polymer (A) two or more of the polymer (A1), the modified olefin polymer (A2), and the halogenated olefin polymer (A3) are used. Further, they may be used in combination.
  • the olefin polymer (A) used in the present invention is the modified olefin polymer of the polymer (A1), the modified olefin polymer (A2), and the halogenated olefin polymer (A3). It is preferably selected from (A2) and the halogenated olefin polymer (A3), and more preferably selected from the modified olefin polymer (A2).
  • the modified olefin polymer (A2) may contain the unreacted polymer (A1a) that has not been graft-modified as required.
  • the olefin polymer (A) used in the present invention preferably has a kinematic viscosity measured at 40 ° C. exceeding 500,000 mm 2 / s.
  • the kinematic viscosity exceeding 500,000 mm 2 / s is a concept including the case where the fluidity is low and the kinematic viscosity cannot be measured.
  • the coating agent of the present invention contains a semi-solid hydrocarbon (B) having a kinematic viscosity at 200 ° C. of 1,000 to 100,000 mm 2 / s.
  • a semi-solid hydrocarbon (B) having a kinematic viscosity at 200 ° C. of 1,000 to 100,000 mm 2 / s.
  • the adhesion to a base material to be decorated is improved, and more types of base materials can be decorated. Is obtained.
  • the semi-solid hydrocarbon (B) has a low crystallinity compared to the case where the hydrocarbon synthetic oil having a kinematic viscosity at 40 ° C. of 30 to 500,000 mm 2 / s used in Patent Document 1 is used.
  • the olefin polymer (A) is further inhibited from crystallization, tackiness immediately after coating and drying is improved, and excellent low-temperature workability, top coatability and adhesiveness can be obtained.
  • the molecular weight is increased, the strength of the coating film is increased, and the adhesive strength is further improved.
  • the semi-solid hydrocarbon (B) is not particularly limited as long as the kinematic viscosity is satisfied, but an olefin polymer having 2 to 20 carbon atoms is preferably exemplified. Among them, a polymer obtained by homopolymerizing an olefin having 2 to 20 carbon atoms or a polymer obtained by copolymerizing any mixture of two or more of these olefins is preferably used.
  • Preferred examples of the olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, isobutene, 1-octene, 1-decene, and 1-dodecene.
  • Specific examples of the semisolid hydrocarbon (B) include ethylene-propylene copolymer, isobutene-1-butene copolymer, polyisobutene and the like.
  • semi-solid polyisobutene as the semi-solid hydrocarbon (B).
  • semi-solid hydrocarbon (B) examples thereof include Tetrax and Highmall manufactured by JX Nippon Oil & Energy Corporation, and polyisobutylene manufactured by Sakai Kogyo Co., Ltd.
  • Semi-solid hydrocarbons (B) used in the present invention has a 200 ° C.
  • kinematic viscosity is less 1,000mm 2 / s or more 100,000 mm 2 / s, preferably 1,100mm 2 / s or more 80,000 2 / s, and still more preferably not more than 1,200mm 2 / s or more 60,000 2 / s.
  • the lower limit of the kinematic viscosity in the semi-solid hydrocarbon (B) is a large value, the adhesiveness during construction tends to be superior.
  • the content of the semisolid hydrocarbon (B) in the coating agent of the present invention is preferably 1 to 90 parts by weight with respect to a total of 100 parts by weight of the olefin polymer (A) and the semisolid hydrocarbon (B). More preferably, it is 10 to 85 parts by weight. That is, the content of the olefin polymer (A) is preferably 10 to 99 parts by weight, more preferably 15 to 90 parts by weight.
  • the content of the semi-solid hydrocarbon (B) is within the above range, it is advantageous because it tends to have excellent adhesion and excellent temporal stability.
  • the content of the gaseous hydrocarbon (B) is preferably 10 to 60 parts by weight, and more preferably 20 to 50 parts by weight. That is, the content of the olefin polymer (A) is preferably 40 to 90 parts by weight, and more preferably 50 to 80 parts by weight.
  • a uniform primer layer or topcoat layer can be obtained when top coatability is applied, for example, by spray coating, it is semisolid with respect to a total of 100 parts by weight of the olefin polymer (A) and the semisolid hydrocarbon (B).
  • the content of the gaseous hydrocarbon (B) is preferably 20 to 80 parts by weight, and more preferably 35 to 65 parts by weight. That is, the content of the olefin polymer (A) is preferably 20 to 80 parts by weight, and more preferably 35 to 65 parts by weight.
  • an olefin polymer (A) and a semi-solid hydrocarbon (B) are used to improve the adhesive strength with the adherend.
  • the content of the semi-solid hydrocarbon (B) is preferably 50 to 90 parts by weight, more preferably 70 to 85 parts by weight with respect to 100 parts by weight in total. That is, the content of the olefin polymer (A) is preferably 10 to 50 parts by weight, and more preferably 15 to 30 parts by weight.
  • the semi-solid hydrocarbon (B) used in the present invention can be modified by grafting various vinyl compounds.
  • the vinyl compound include styrenes such as styrene and ⁇ -methylstyrene, acrylic acid esters such as methyl acrylate, butyl acrylate, and octyl acrylate; methacrylic acid esters such as methyl methacrylate and butyl methacrylate.
  • Carboxyl group-containing vinyl compounds such as acrylic acid, methacrylic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and monoethyl maleate; unsaturated dibasic acids such as dimethyl fumarate and dibutyl fumarate Diesters; glycidyl group-containing vinyl compounds such as glycidyl acrylate, acrylate- ⁇ -methylglycidyl acrylate, glycidyl methacrylate, and methacrylate- ⁇ -methylglycidyl; hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hi Hydroxyl-containing vinyl compounds such as loxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate; unsaturated carboxylic acids such as acrylonitrile,
  • the olefin polymer (A) serves to reduce the crystallization rate of the olefin polymer (A). It is thought that the adhesion to the interface may be improved. As a result, it is considered that the olefin polymer (A) originally has the adhesiveness with the olefin resin, polar group-containing resin and metal.
  • the olefin polymer (A) is a modified olefin polymer (A2) and / or a halogenated olefin polymer (A3)
  • the semi-solid hydrocarbon (B) if it is present, adhesion to the substrate Strength increases. The reason for this is not clear, but the presence of the semi-solid hydrocarbon (B) in one part facilitates the movement of molecules having polar groups and halogen atoms in the olefin polymer (A).
  • it contains heteroatoms, or is a metal polar groups and halogen atoms are likely to be unevenly distributed in the portion in contact with the substrate, leading to high adhesive strength. It is also possible to think.
  • semi-solid hydrocarbon (B) may bleed out from the dried coating by using a semi-solid hydrocarbon (B) having a higher kinematic viscosity. It may be suppressed.
  • the effect of adding the semisolid hydrocarbon (B) due to bleed-out is less lost, and the olefin polymer ( It is thought that it is less likely that a layer composed only of the semi-solid hydrocarbon (B) is formed on the surface of A) to lower the adhesive force. It is presumed that the semi-solid hydrocarbon (B) has a high kinematic viscosity and thus has an extraordinar balance of reducing the adverse effects caused by bleed-out.
  • the adhesive strength between the coating film made of the coating agent and the adherend can be stable for a long period of time. Even when the film is not used for bonding immediately after being formed into a film and is used for bonding after a certain period of time, it is estimated that high adhesive strength is expressed.
  • the coating agent of the present invention may contain a tackifier (C) in addition to the olefin polymer (A) and the semisolid hydrocarbon (B).
  • a tackifier C
  • the adhesiveness to the base material to be decorated is improved, and the effect that more types of base material can be decorated is obtained. It is done.
  • the acid value determined according to JIS K 0070 of the tackifier (C) used in the present invention is 10 or more, and preferably 10 to 40.
  • the acid value of the tackifier (C) is in such a range, when the coating agent is used as a coating film, the affinity with the adherend is improved, and it is advantageous in that sufficient adhesion can be obtained.
  • the acid value is actually a value expressed in mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample.
  • the tackifier (C) used in the present invention has a weight average molecular weight (Mw) measured by GPC method of 0.9 ⁇ 10 3 to 3 ⁇ 10 3 , and the lower limit is preferably 1 ⁇ 10 3 Accordingly, in one preferred embodiment of the present invention, the tackifier (C) has a weight average molecular weight of 1 ⁇ 10 3 to 3 ⁇ 10 3 .
  • Mw weight average molecular weight measured by GPC method
  • the lower limit is preferably 1 ⁇ 10 3
  • the tackifier (C) has a weight average molecular weight of 1 ⁇ 10 3 to 3 ⁇ 10 3 .
  • Such a tackifier (C) is not particularly limited as long as it has an acid value and a weight average molecular weight as described above.
  • terpene resins As the types of components that can constitute the tackifier (C), terpene resins; modified terpene resins such as terpene phenol copolymer resins and aromatic modified terpene resins; and rosin resins such as rosin esters and modified rosin resins Among them, rosin esters and derivatives thereof are preferable.
  • examples of rosin ester derivatives include polymerized rosin ester, hydrogenated rosin ester, rosin-modified maleic resin, special rosin ester, and rosin-modified special synthetic resin.
  • tackifier those having the acid value and weight average molecular weight as described above can be employed as the tackifier (C), and specific examples thereof include Halitac 4821, Haritac PCJ, Haritac FK125 (any As well as Pencel (registered trademark) C, Pencel (registered trademark) D-125, and Superester A-125 (all manufactured by Arakawa Chemical Industries, Ltd.).
  • Superester W-125 and Pine Crystal (registered trademark) KE-359 (Arakawa Chemical Industries, Ltd.)
  • Sylvalite RE100L and Sylvalite RE105L both manufactured by Arizona Chemical
  • the content ratio of the tackifier (C) in the coating agent of the present invention is preferably based on 100% by weight of the total of the olefin polymer (A), the semisolid hydrocarbon (B) and the tackifier (C). 5 to 40% by weight.
  • the content of the tackifier (C) is within the above range, there is a tendency that sufficient adhesion can be secured, which is advantageous.
  • the ratio of the olefin polymer (A) is 10%.
  • the proportion of the semi-solid hydrocarbon (B) is 85 to 1% by weight, and the proportion of the tackifier (C) is 40 to 5% by weight.
  • the component is adhesive.
  • the coating agent of the present invention may contain a curing agent (D) as necessary in addition to the olefin polymer (A) and the semisolid hydrocarbon (B).
  • a curing agent (D) when the coating agent of this invention contains a hardening
  • curing agent (D) For example, a polyisocyanate monomer and a polyisocyanate modified body can be mentioned.
  • the polyisocyanate monomer is a monomer compound having a plurality of isocyanate groups in one molecule.
  • examples of such a polyisocyanate monomer include aromatic polyisocyanates and araliphatic polyisocyanates. And aliphatic polyisocyanates.
  • aromatic polyisocyanate examples include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof).
  • 4,4′-diphenyl diisocyanate 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate or mixtures thereof) ( MDI), 4,4′-toluidine diisocyanate (TODI), aromatic diisocyanates such as 4,4′-diphenyl ether diisocyanate, and the like.
  • araliphatic polyisocyanate examples include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra Methyl xylylene diisocyanate or a mixture thereof (TMXDI), and aromatic aliphatic diisocyanates such as ⁇ , ⁇ ′-diisocyanate-1,4-diethylbenzene.
  • XDI xylylene diisocyanate
  • TMXDI tetramethylxylylene diisocyanate
  • TMXDI tetra Methyl xylylene diisocyanate
  • aromatic aliphatic diisocyanates such as ⁇ , ⁇ ′-diisocyanate-1,4-diethylbenzene.
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1 , 5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capate, etc. Group diisocyanate and the like.
  • Aliphatic polyisocyanates include alicyclic polyisocyanates.
  • examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), and 3-isocyanatomethyl-3.
  • polyisocyanate monomers can be used alone or in combination of two or more.
  • examples of the polyisocyanate-modified product include a modified product obtained by reacting the above-described polyisocyanate monomers, and a modified product obtained by reacting the above-described polyisocyanate monomer and another compound.
  • the “other compound” refers to a compound capable of reacting with the above-described polyisocyanate monomer other than the above-described polyisocyanate monomer.
  • a monovalent alcohol hereinafter referred to as “monool”.
  • polyols Polyhydric alcohols
  • compounds having active hydrogen such as amines and water, and carbon dioxide.
  • Examples of monools that can be used in the present invention include butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol, tetradecyl alcohol (myristyl).
  • Alcohol pentadecyl alcohol, hexadecyl alcohol (cetyl alcohol), heptadecyl alcohol, octadecyl alcohol (stearyl alcohol, octadecanol), nonadecyl alcohol, and isomers thereof (2-methyl-1-propanol (iso-)) Butanol), other alkanols (C20-50 alcohol), and alkenyl alcohols such as oleyl alcohol, for example Arca dienol such dienol, for example, aliphatic monool such as polyethylene butylene mono-ol. Examples of monools include alicyclic monools such as cyclohexanol and methylcyclohexanol, and aromatic monomonos such as benzyl alcohol.
  • examples of the polyol that can be used in the present invention include compounds having two or more hydroxyl groups that are generally used in the field of urethane resins. It may have a combined form.
  • a polyol having a monomer form Alkylene glycols such as ethylene glycol and propylene glycol, dihydric alcohols such as cyclohexanediol, cyclohexanedimethanol, and benzenedimethanol; Trihydric alcohols such as glycerin, trimethylol methane, trimethylol ethane, and trimethylol propane; and Examples thereof include alcohols having four or more hydroxyl groups, such as pentaerythritol and dipentaerythritol.
  • a polyol having such a monomer form may be referred to as a “low molecular weight polyol”.
  • examples of the polyol having a polymer form include polymer polyols generally used in the field of urethane resins, such as polyester polyols and polyether polyols.
  • polyisocyanate-modified products include multimers of the above-mentioned polyisocyanate monomers, allophanate-modified products, polyol-modified products, biuret-modified products, urea-modified products, oxadiazinetrione-modified products, carbodiimide-modified products, Examples include modified uretdione and modified uretonimine.
  • examples of the multimer include dimer, trimer, pentamer, and heptamer of polyisocyanate monomer.
  • examples of polyisocyanate monomer trimers include isocyanurate-modified products and iminooxadiazinedione-modified products.
  • examples of the allophanate-modified product include allophanate-modified products produced by the reaction of the polyisocyanate monomer described above and a monol (eg, monools exemplified above such as octadecanol).
  • polyol-modified product examples include a polyol-modified product (alcohol adduct) produced by a reaction between a polyisocyanate monomer and a low molecular weight polyol (for example, a trihydric alcohol).
  • biuret-modified product examples include a biuret-modified product produced by a reaction between the polyisocyanate monomer and water or amines.
  • urea-modified product examples include a urea-modified product produced by the reaction of the above-described polyisocyanate monomer and diamine.
  • modified oxadiazine trione examples include oxadiazine trione produced by the reaction between the polyisocyanate monomer and carbon dioxide.
  • carbodiimide-modified product examples include a carbodiimide-modified product produced by the decarboxylation condensation reaction of the polyisocyanate monomer described above.
  • examples of the polyisocyanate-modified product include polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI) in addition to those described above.
  • aliphatic polyisocyanate and its multimer are particularly preferably used. That is, in a preferred embodiment of the present invention, the curing agent (D) is an aliphatic polyisocyanate or a multimer of aliphatic polyisocyanate.
  • the coating agent of the present invention contains a polyisocyanate monomer or a polyisocyanate-modified product as the curing agent (D)
  • the amount of the curing agent (D) added is the olefin polymer (A) and the semisolid carbonization.
  • the total amount of hydrogen (B) is 100 parts by weight, it is preferably 2 to 30 parts by weight.
  • the coating agent of the present invention preferably contains at least one modified olefin polymer (A2) as the olefin polymer (A).
  • the epoxy compound is a crosslinkable compound having two or more epoxy groups in one molecule.
  • examples of such epoxy compounds include bisphenol A type epoxy resins (different from hydrogenated bisphenol A type epoxy resins), bisphenol type epoxy resins such as bisphenol F type epoxy resins; hydrogenated bisphenol type epoxy resins; novolac type epoxies.
  • the adhesive strength is more excellent, in particular, from the point of obtaining an adhesive layer capable of bonding the aluminum foil layer and a film made of a thermoplastic resin such as polypropylene with higher strength.
  • Bisphenol A liquid epoxy resin, alicyclic epoxy compound, and trimethylolpropane polyglycidyl ether are preferable.
  • the bisphenol A liquid epoxy resin is not particularly limited as long as it is a resin that is liquid at normal temperature (25 ° C.), and a commercially available product may be used.
  • Examples of the commercially available products include EPICLON 840, 840-S, 850, 850-S, EXA-850CRP, 850-LC (manufactured by DIC Corporation), jER828EL, 827 (manufactured by Mitsubishi Chemical Corporation), Epomic R- 140P (manufactured by Mitsui Chemicals, Inc.).
  • the alicyclic epoxy compound is a compound having at least one epoxycycloalkyl group or epoxycycloalkenyl group in the molecule, or at least a group in which at least one epoxy group is bonded to the alicyclic ring by a single bond.
  • Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4 -Epoxycyclohexylmethyl) adipate, vinyl cyclohexylene dioxide, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxy Rate, methylene
  • alicyclic epoxy compound a commercially available product may be used, and examples of the commercially available product include Celoxide 2021P, EHPE3150, EHPE3150CE, and Epolide GT401 (manufactured by Daicel Corporation).
  • 1,2-epoxy-4- (2) of 2,2-bis (hydroxymethyl) -1-butanol can be obtained because an adhesive layer having better adhesive strength can be obtained.
  • 2-oxiranyl) cyclohexane adduct is preferred.
  • trimethylolpropane polyglycidyl ether examples include trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, and mixtures thereof.
  • the oxazoline compound is a crosslinkable compound having two or more oxazoline groups in one molecule.
  • examples of such oxazoline compounds include polymers of oxazoline group-containing monomers and oxazoline group-containing polymers such as copolymers of oxazoline group-containing monomers and other monomers.
  • Examples of the oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline. 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline Is mentioned. These may use 1 type individually and may use 2 or more types.
  • alkyl (meth) acrylate alkyl group having about 1 to 14 carbon atoms
  • acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrenesulfonic acid and salts thereof Unsaturated carboxylic acids such as sodium salt, potassium salt, ammonium salt and tertiary amine salt); unsaturated nitriles such as acrylonitrile and methacrylonitrile;
  • Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether
  • ⁇ -olefins such as ethylene and propylene
  • Halogen-containing ⁇ , ⁇ -unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride
  • Styrene and ⁇ -methyl And ⁇ , ⁇ -unsaturated aromatic monomers such as styrene.
  • the oxazoline compound is preferably an oxazoline compound containing 2-isopropenyl-2-oxazoline from the viewpoint that an adhesive layer having better adhesive strength can be obtained.
  • Examples of commercially available products include “Epocross” series manufactured by Nippon Shokubai Co., Ltd.
  • the epoxy equivalent of the epoxy compound and the oxazoline equivalent of the oxazoline compound are preferably 100 g / eq or more, more preferably from the viewpoint of obtaining an adhesive layer having better adhesive strength, chemical resistance, and electrolytic solution resistance. Is 125 g / eq or more, preferably 1,600 g / eq or less, more preferably 500 g / eq or less.
  • the equivalent can be measured based on JIS K7236.
  • the curing agent (D) is an epoxy group and an oxazoline in the curing agent (D).
  • Group equivalent / Equivalent functional group reactive to the epoxy group or oxazoline group in the polymer (A) is preferably 0.01 or more, more preferably 0.1 or more, and preferably 50 or less, more It is desirable to blend so that it is preferably 30 or less, more preferably 20 or less, and particularly preferably 10 or less.
  • the coating agent of the present invention may contain a catalyst (E) having a pKa of 11 or more.
  • the coating agent of the present invention preferably contains the curing agent (D), and the curing agent (D) is more preferably at least one compound selected from an epoxy compound and an oxazoline compound.
  • the crosslinking reaction can be efficiently promoted even at a low temperature, an adhesive layer excellent in chemical resistance and electrolytic solution resistance can be formed, and excellent in adhesive strength, in particular, an aluminum foil layer and polypropylene, etc. It is possible to obtain an adhesive layer that can be bonded to the thermoplastic resin film layer with high strength.
  • Catalyst (E) may be used alone or in combination of two or more.
  • the catalyst (E) is not particularly limited as long as the pKa is 11 or more, but is preferably a compound that can promote the crosslinking reaction of the curing agent (D).
  • Phosphazene catalysts having strongly basic tertiary amines such as 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,6-diazabicyclo [3.4.0] nonene-5, and phosphazene bases DBU and a phosphazene catalyst are preferable.
  • the pKa is an acid dissociation constant in an aqueous solution at 25 ° C.
  • phosphoric acid has three pKas, that is, pKa 1 , pKa 2, and pKa 3, and pKa in the present invention refers to pKa 1 , that is, the first acid dissociation constant.
  • the blending amount of the catalyst (E) is preferably 1 ppm or more, more preferably 100 ppm or more, and preferably 1 mass% with respect to 100 mass% of the non-volatile content (components other than the solvent) of the coating agent of the present invention. Hereinafter, it is 0.3 mass% or less more preferably.
  • a coating agent having an excellent curing rate can be obtained, and an adhesive layer having excellent chemical resistance, electrolytic solution resistance and adhesive strength can be obtained.
  • the coating agent of the present invention may contain a solvent as required in addition to the olefin polymer (A) and the semisolid hydrocarbon (B).
  • the solvent examples include, but are not limited to, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, and alicyclic carbons such as cyclohexane, cyclohexene and methylcyclohexane.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • aliphatic hydrocarbons such as hexane, heptane, octane and decane
  • alicyclic carbons such as cyclohexane, cyclohexene and methylcyclohexane.
  • Alcohols such as hydrogen, methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol and phenol, ketone solvents such as acetone, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), pentanone, hexanone, isophorone and acetophenone
  • ketone solvents such as methyl cellosolve and ethyl cellosolve
  • esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate and butyl formate
  • trichloroethylene dichloroethyl Emissions
  • halogenated hydrocarbons such as chlorobenzene, Exxsol, mention may be made of petroleum-based solvents such as Isopar.
  • the coating agent of the present invention contains a solvent
  • the olefin polymer (A) and the semisolid state when the total of the olefin polymer (A), the semisolid hydrocarbon (B) and the solvent is 100% by weight.
  • the total amount with the hydrocarbon (B) is usually about 5 to 50% by weight, preferably 8 to 40% by weight.
  • the coating agent of the present invention may contain another olefin resin (F) in addition to the olefin polymer (A) and the semisolid hydrocarbon (B).
  • the “other olefin resin (F)” is not particularly limited as long as it does not correspond to any of the olefin polymer (A) and the semisolid hydrocarbon (B), but polyethylene, polypropylene, poly 1 -Butene, poly-4-methyl-1-pentene homopolymers, random or block copolymers of ⁇ -olefins such as ethylene, propylene, 4-methyl-1-pentene, ethylene / propylene copolymers, ethylene Octene copolymer, propylene / octene copolymer, ethylene / propylene / 1-butene copolymer, ethylene / propylene / terpolymer, cyclic polyolefin, ethylene / vinyl acetate, ethylene / unsaturated
  • transition metal compounds such as titanium oxide (rutile type) and zinc oxide, pigments such as carbon black, thixotropic agents, thickeners, and other tackifiers that do not fall under the above-mentioned tackifier (C). Paints (hereinafter “other tackifiers”), antifoaming agents, surface conditioning agents, anti-settling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, antistatic agents, etc. Additive additives may be added.
  • terpene resin for example, terpene resin; modified terpene resin such as terpene phenol copolymer resin, aromatic modified terpene resin, hydrogenated terpene resin; aliphatic saturated hydrocarbon resin (Arakawa Chemical Industries)
  • rosin resins such as ALCON made by Mitsui Chemicals, FTR series made by Mitsui Chemicals, rosin modified phenolic resins, and rosin esters and modified rosin resins. Things can be adopted.
  • olefin resins (F) transition metal compounds such as titanium oxide (rutile type), zinc oxide, pigments such as carbon black, thixotropic agents, thickeners, the above-mentioned “other tackifiers”, antifoaming
  • additives for paints such as agents, surface conditioners, anti-settling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants and antistatic agents are usually used for the purpose of the coating agent of the present invention. It can add in the range which does not impair.
  • olefin resin (F) when another olefin resin (F) is added, it is preferably more than 0 and 50 parts by weight or less, more preferably 1 to 30 parts by weight, more preferably 100 parts by weight of the olefin polymer (A). Is 1 to 10 parts by weight.
  • the coating agent of the present invention is suitable for use as a primer, paint, hot melt adhesive, dry laminate adhesive, pressure sensitive adhesive sheet, display pressure sensitive adhesive tape, and optically transparent double-sided tape.
  • thermoplastics such as acrylic resin, PET, polycarbonate, ABS, COC, vinyl chloride, polypropylene, surface-treated polyethylene, polystyrene, etc.
  • Resin and metal materials such as aluminum, copper, and SUS can be used as the adherend.
  • thermoplastic resin injection-molded articles, films, or these metal molded articles, and metal foils are coated with the coating agent of the present invention, dried, and another coating agent is further applied on the obtained coating film.
  • Coating / drying or other thermoplastic resin films, molded articles and metal foils, and molded articles can be used by bonding.
  • the method for forming the coating film of the coating agent of the present invention is not particularly limited, and can be performed by a known method.
  • die coating method, flow coating method, spray coating method, bar coating method, gravure coating method, gravure reverse coating method, kiss reverse coating method, micro gravure coating method, roll coating method, blade coating method, rod coating method, roll doctor After applying by the coating method, air knife coating method, comma roll coating method, reverse roll coating method, transfer roll coating method, kiss roll coating method, curtain coating method, dipping coating method, etc., natural drying or heat forced drying, etc.
  • a coating film can be obtained by drying by an appropriate method.
  • the decorative film of the present invention is not particularly limited other than having a layer obtained from the coating agent of the present invention, and can be used in combination with a film having a known design property.
  • a film previously decorated by printing, painting, vapor deposition or the like, or a film decorated by a combination thereof is used as a design layer, and this is used by laminating a layer obtained from the coating agent of the present invention. I can do it.
  • the decorative film of the present invention has at least one layer obtained from the above-described coating agent of the present invention.
  • the decorative film of this invention is obtained from the design layer which consists of a film which has design properties, such as the film previously decorated by printing, coating, vapor deposition, etc., and the coating agent of this invention.
  • Layer In the following description in this specification, this layer may be referred to as a “coating film” in view of its shape. In some cases, the function is referred to as an “adhesive layer” in view of its function.
  • thermoplastic films such as acrylic film, PET film, polycarbonate film, COC film, vinyl chloride film, unstretched polypropylene (hereinafter referred to as “CPP”) film, and The vapor deposition film which vapor-deposited metals, such as aluminum, to the said thermoplastic film is mentioned.
  • the method for producing the decorative film of the present invention is not particularly limited as long as the decorative film has a layer (coating film) obtained from the coating agent of the present invention.
  • a method of dry laminating the coating film of the present invention a method of directly providing a design layer by printing or the like on the coating film of the present invention.
  • Examples include a method in which a clear layer, a paint layer, and a layer made of the coating film of the present invention (that is, a layer obtained from the coating agent of the present invention) are sequentially formed on the film by printing or the like.
  • the decorative film having the coating film of the present invention is, for example, an existing vacuum forming method such as a vacuum forming method or a compressed air vacuum forming method, an insert forming method and an in-mold forming method, and “vacuum forming” described in Japanese Patent No. 3733564.
  • an existing vacuum forming method such as a vacuum forming method or a compressed air vacuum forming method, an insert forming method and an in-mold forming method, and “vacuum forming” described in Japanese Patent No. 3733564.
  • an adherend of the decorative film used in the present invention for example, a polyolefin material such as PP, HIPS, PS, ABS, PC, PC / ABS alloy, PET, acrylic resin, ED steel plate, Mg alloy, Preferred examples include SUS, metal materials such as aluminum alloys, and glass. Further, an adherend in which the resin and the metal material are combined may be used.
  • a polyolefin material such as PP, HIPS, PS, ABS, PC, PC / ABS alloy, PET, acrylic resin, ED steel plate, Mg alloy
  • Preferred examples include SUS, metal materials such as aluminum alloys, and glass.
  • an adherend in which the resin and the metal material are combined may be used.
  • Examples of molded articles obtained by the decoration method include automobile interior and exterior members; various front panels such as AV equipment; surface decorative materials such as buttons and emblems; housings such as mobile phones, housings, display windows, buttons, and the like.
  • Various parts of furniture exterior materials for furniture; interior materials for buildings such as bathrooms, walls, ceilings, floors; exterior walls for siding, etc .; exterior materials for buildings such as fences, roofs, gates, windbreak boards; window frames, doors, handrails, Surface decorative materials for furniture such as sills and duck; optical members such as various displays, lenses, mirrors, goggles and window glass; members for interior and exterior of various vehicles other than automobiles such as trains, aircraft and ships; and bottles and cosmetic containers It can be suitably used for various other applications such as various packaging containers such as small items, packaging materials, prizes, miscellaneous goods such as small items.
  • the laminate in one embodiment of the present invention (hereinafter also referred to as “the present laminate”) is not particularly limited as long as it includes a base material and an adhesive layer composed of a cured product of the present coating agent. Layers may be included.
  • the adhesive layer may be present on one side of the substrate, may be present on both sides, may be present on the entire surface of these surfaces, or may be present in part. May be.
  • the production method of the laminate is not particularly limited, and a conventionally known method can be adopted, but a coating film forming step for forming a coating film from the coating agent on a substrate and the coating film are cured.
  • a method including a curing step is preferred.
  • all the steps can be performed at a low temperature (about 120 ° C. or less, preferably 100 ° C. or less) to obtain a laminate without impairing the properties of the substrate and the adherend. It is preferable from the viewpoint of increasing the degree of freedom in selecting a substrate and an adherend, and even when a laminate is produced at such a low temperature by using this coating agent, the adhesive strength and chemical resistance ( A laminate excellent in (electrolytic solution resistance) can be obtained.
  • the present coating agent is applied on a substrate, and if necessary, the coating agent is dried to form a coating film, and the substrate is immersed in the coating agent, A method of forming a coating film on a substrate by taking out the material and drying the coating agent as necessary is preferable.
  • the coating method is not particularly limited, and a conventionally known method such as a die coating method, a flow coating method, a spray coating method, a bar coating method, a gravure coating method, a gravure reverse coating method, a kiss reverse coating method, or a micro gravure.
  • a coating method such as can be employed.
  • the substrate is not particularly limited and is not particularly limited as long as it is a substrate on which the adhesive layer is to be formed.
  • polyolefin such as polyethylene and polypropylene, ABS resin, polycarbonate (PC), polyester resin such as PET, and the like.
  • Resin base material made of polyamide resin such as polyphenylene sulfide (PPS) and nylon, or resin such as acrylic resin; barrier film such as transparent deposited PET; ED steel sheet, Mg alloy, SUS (stainless steel), aluminum, aluminum alloy Or the inorganic base material which consists of inorganic materials, such as glass;
  • PPS polyphenylene sulfide
  • barrier film such as transparent deposited PET
  • ED steel sheet Mg alloy, SUS (stainless steel), aluminum, aluminum alloy
  • the inorganic base material which consists of inorganic materials, such as glass
  • the base material in which the said resin and the inorganic material were compounded Among these, a metal foil, a polyolefin substrate, and a decorative film are preferable, and an aluminum foil and a polyolefin substrate are more preferable.
  • the surface of the substrate that is in contact with the adhesive layer may be subjected to a conventionally known surface treatment such as a corona treatment in order to improve the adhesive strength.
  • the decorative film examples include a film having a known design property, specifically, a film in which the resin base material or metal foil is previously decorated by printing, painting, vapor deposition, or the like, and has a design property.
  • the laminated body of a film, the said resin-made base materials, metal foil, etc. are mentioned.
  • examples of the film having design properties include films obtained by imparting design properties to thermoplastic films such as acrylic films, PET films, PC films, COC (cyclic olefin copolymer) films, vinyl chloride films, and ABS films.
  • thermoplastic films such as acrylic films, PET films, PC films, COC (cyclic olefin copolymer) films, vinyl chloride films, and ABS films.
  • a method for imparting designability for example, an existing vacuum forming method such as a vacuum forming method or a compressed air vacuum forming method, an insert forming method, an in-mold forming method, described in Japanese Patent No. 3733564 TOM method using “vacuum forming equipment”. According to these methods, design properties can be imparted to a laminate having a complicated three-dimensional structure.
  • the thickness of the substrate is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less.
  • a method of drying the coating agent provided on the substrate As a method of drying the coating agent provided on the substrate, a method of leaving the substrate with a coating agent at room temperature (about 20 ° C.) under normal pressure, a method of drying the coating agent under reduced pressure, and the coating agent The method of heating is mentioned. This heating may be performed in one step or in two or more steps.
  • the heating conditions are not particularly limited as long as volatile components such as a solvent are volatilized, but for example, 120 ° C. or lower, preferably 100 ° C. or lower, for example 40 ° C. or higher, for example 3 seconds or longer, preferably 1
  • This laminate is usually used with an adhesive layer adhered to a desired adherend. That is, this laminated body may be an adhesive body in which a base material, an adhesive layer, and an adherend are laminated in this order.
  • Examples of the adherend include the same materials as the base material.
  • the coating agent may be applied between the base material and the adherend, and after the drying step as necessary, a curing step may be performed, but before the drying step, Alternatively, a so-called dry laminating method is preferable in which the coating agent or the coating film is brought into contact with the adherend after the coating film forming step, and then the curing step is performed.
  • the curing step includes a method of heating the coating film. This heating may be performed in one step or in two or more steps.
  • suitable conditions are selected, but at a low temperature, for example, 80 ° C. or less, preferably 70 ° C. or less, particularly preferably 60 ° C. or less, and for example, 40 ° C. or more, for example, 1 day or more,
  • a method of curing for a period of preferably 3 days or more, for example 7 days or less (low temperature curing method)
  • a high temperature for example 100 ° C. or more, preferably 120 ° C. or more, for example 200 ° C. or less
  • a method of curing for 1 second or longer, preferably 0.5 seconds or longer, or for 60 seconds or shorter can be used.
  • a low-temperature curing method is preferable from the viewpoint that a laminate can be obtained without impairing the properties of the substrate and adherend, and that the degree of freedom in selecting the substrate and adherend is increased.
  • the substrate and the adherend When the substrate and the adherend are bonded, the substrate and the adherend may be bonded while applying pressure.
  • the pressure is, for example, 0.1 MPa or more, preferably 0.2 MPa or more, and preferably 2 MPa or less.
  • the thickness of the adhesive layer may be appropriately selected according to the desired application and is not particularly limited.
  • the thickness is 0.2 ⁇ m or more, preferably 1 ⁇ m or more, and for example, 100 ⁇ m or less, preferably 20 ⁇ m or less. is there.
  • the laminate includes, for example, automobile interior and exterior members; various front panels such as AV equipment; surface decorative materials such as buttons and emblems; housings for information appliances such as mobile phones and cameras; various parts such as housings, display windows, and buttons. Furniture exterior materials; bathroom interior surfaces, wall surfaces, ceilings, floors and other architectural interior materials; siding exterior walls, fences, roofs, gates, windbreak boards, etc .; window frames, doors, handrails, sills, Interior materials such as surface decoration materials for duck and furniture; optical members such as various displays, lenses, mirrors, goggles and window glass; interior and exterior materials for various vehicles other than automobiles such as trains, aircraft and ships; bottles and cosmetic containers It can be used for various containers such as small items; packaging materials; and other various articles.
  • the packaging material in one embodiment of the present invention includes a laminate in which an inner layer, an adhesive layer, and a base material are laminated in this order.
  • the adhesive layer is a layer made of a cured product of the coating agent.
  • the packaging material Since the packaging material has the adhesive layer, it has excellent adhesive strength between the base material and the inner layer, and is excellent in chemical resistance and electrolytic solution resistance. For this reason, even if this packaging material is used over a long period of time, a decrease in the adhesive strength between the base material and the inner layer can be effectively prevented, and a packaging material having excellent long-term reliability can be obtained.
  • the packaging material is not particularly limited as long as the inner layer, the adhesive layer, and the base material are laminated in this order, and a conventionally known layer may be used on these layers or the surface of the laminate.
  • Such packaging materials include battery case packaging materials with excellent adhesive strength and chemical resistance (electrolytic solution properties), packaging materials for highly alkaline solutions with excellent adhesive strength and alkali resistance, and further adhesive strength and alcohol resistance. It is suitably used for a packaging material for alcohol-containing solutions that excels in the quality.
  • the inner layer corresponds to the adherend described in the column of the laminate, and includes the same layer as the adherend, and is not particularly limited.
  • the packaging material may be a highly alkaline solution packaging material or an alcohol-containing solution.
  • a thermoplastic polyolefin film such as an unstretched polypropylene film or a low-density linear polyethylene is preferably used to impart chemical resistance (electrolytic solution property), heat sealability, etc. to the packaging material. used.
  • Examples of the substrate include the same substrates as those described in the column of the laminate, and are not particularly limited.
  • the thickness of the packaging material may be appropriately selected according to a desired application, and is, for example, 30 ⁇ m or more, and for example, 200 ⁇ m or less.
  • the packaging material may be used in the form of a bag with the inner layer inside so that the inner layer comes into contact with a contained material, for example, a highly alkaline solution or an alcohol-containing solution.
  • examples of the highly alkaline solution include solutions having a pH of, for example, 9 or more, preferably 10 or more.
  • Specific examples include alkaline detergents and hair treatment agents.
  • examples of the alcohol-containing solution include solutions containing methanol, ethanol, propanol, ethylene glycol, and the like.
  • the alcohol concentration in the alcohol-containing solution is, for example, 3% by mass or more, preferably 5% by mass or more, and for example, 95% by mass or less, preferably 80% by mass or less.
  • the battery case packaging material in one embodiment of the present invention includes a laminate in which an inner layer, an inner adhesive layer, a base material, an outer adhesive layer, and an outer layer are laminated in this order.
  • the inner adhesive layer is a layer made of a cured product of the present coating agent.
  • the battery case packaging material has the adhesive layer, it has excellent adhesive strength between the base material and the inner layer, and also has excellent electrolyte resistance. For this reason, even when the battery case packaging material is used for a long period of time, it is possible to effectively prevent a decrease in the adhesive strength between the base material and the inner layer, and to obtain a battery case packaging material having excellent long-term reliability. it can.
  • the battery case packaging material is not particularly limited as long as the inner layer, the inner adhesive layer, the base material, the outer adhesive layer, and the outer layer are laminated in this order. You may use for the surface of.
  • the inner layer corresponds to the adherend described in the column of the laminate, and includes the same layer as the adherend.
  • the battery case packaging material has chemical resistance (electrolytic solution property).
  • a thermoplastic polyolefin film such as an unstretched polypropylene film.
  • the substrate examples include the same substrates as those described in the section of the laminate, and are not particularly limited, but preferably include metal foil, more preferably aluminum foil and SUS foil. Further, the base material surface may be subjected to chemical conversion treatment from the viewpoint of corrosion resistance and the like.
  • the outer adhesive layer may be a layer that allows the outer layer and the base material to adhere to each other, and may be a layer made of a cured product of the present coating agent.
  • An adhesive for dry lamination, a solventless adhesive It may be a layer obtained using a conventionally known adhesive such as.
  • the outer layer is not particularly limited, but in order to impart heat resistance in the heat sealing process during battery production, moldability during processing, pinhole resistance, insulation during distribution, etc., preferably a polyester film, A multilayer film in which stretched or unstretched films such as polyamide film and polypropylene film are laminated in a single layer or two or more layers is used.
  • the thickness of the battery case packaging material is, for example, 60 ⁇ m or more, and for example, 160 ⁇ m or less.
  • a battery according to an embodiment of the present invention includes the battery case packaging material and an electrolyte solution packaged in the battery case packaging material, wherein at least a part of an inner layer of the battery case packaging material is the electrolyte solution.
  • the battery is in contact with the battery.
  • limit especially as this battery For example, a lithium ion secondary battery is mentioned.
  • the battery will be described with reference to FIG. 1 showing an embodiment thereof.
  • the battery 10 includes a battery case packaging material 1 and an electrolyte solution 11 packaged in the battery case packaging material 1.
  • the battery 10 also includes a positive electrode 17, a negative electrode 18, and a separator 19 that are accommodated in the battery case packaging material 1.
  • the battery case packaging material 1 is formed in a bag shape so that the electrolyte solution 11 contacts the inner surface of the inner layer 3 of the battery case packaging material 1.
  • the inner layer 3, the inner adhesive layer 5, the substrate 2, the outer adhesive layer 6 and the outer layer 4 are laminated in this order from the inside.
  • the electrolytic solution 11 is not particularly limited, and examples thereof include electrolytic solutions containing lithium salts such as ethylene carbonate, diethyl carbonate, dimethyl carbonate, and lithium hexafluorophosphate.
  • the positive electrode 17 and the negative electrode 18 are disposed so as to be in contact with the electrolyte solution 11 and spaced from each other with a separator 19 therebetween.
  • the melting point and heat of fusion were determined using a differential scanning calorimeter (TA Instruments; DSC-Q1000). In the process of raising the temperature from 30 ° C. to 180 ° C. at 10 ° C./min, holding at 180 ° C. for 3 minutes, lowering the temperature to 0 ° C. at 10 ° C./min, and again raising the temperature to 150 ° C. at 10 ° C./min. From the thermogram at the time of the second temperature increase, the melting point and heat of fusion were determined according to JIS K7122.
  • Detector Shimadzu Corporation; C-R4A Column: TSKG 6000H-TSKG 4000H-TSKG 3000H-TSKG 2000H (manufactured by Tosoh Corporation) -Mobile phase: Tetrahydrofuran-Temperature: 40 ° C ⁇ Flow rate: 0.8ml / min Mw was calculated using a calibration curve prepared from monodisperse standard polystyrene.
  • Chlorine content (% by mass) ⁇ (AB) ⁇ F ⁇ / S ⁇ 100
  • thermoplastic resin (A-1) has a melting point of 78.3 ° C., a heat of fusion of 29.2 J / g, Mw of 330,000, The propylene content was 67.2 mol%.
  • thermoplastic resin (A-2)> A 2 liter autoclave thoroughly purged with nitrogen was charged with 900 mL of hexane and 80 g of 1-butene, 1 mmol of triisobutylaluminum was added, the temperature was raised to 70 ° C., and propylene was supplied to give a total pressure of 7 kg / cm 2 G Next, 0.30 mmol of methylaluminoxane and 0.001 mmol of rac-dimethylsilylene-bis ⁇ 1- (2-methyl-4-phenylindenyl) ⁇ zirconium dichloride in terms of Zr atoms were added, and propylene was continuously added.
  • thermoplastic resin (A-2) has a melting point of 89.2 ° C., a heat of fusion of 31.5 J / g, Mw of 330,000, The propylene content was 73.5 mol%.
  • thermoplastic resin (A-3) The resulting maleic anhydride-modified propylene / 1-butene copolymer (hereinafter also referred to as “thermoplastic resin (A-3)”) has a melting point of 75.8 ° C., a heat of fusion of 28.6 J / g, and Mw is The graft amount of 110,000 maleic anhydride was 1% by weight with respect to 100% by weight of the modified copolymer.
  • thermoplastic resin (A-4) The resulting maleic anhydride-modified propylene / 1-butene copolymer (hereinafter also referred to as “thermoplastic resin (A-4)”) has a melting point of 85.9 ° C., a heat of fusion of 29.9 J / g, and Mw of The graft amount of 110,000 maleic anhydride was 1% by weight with respect to 100% by weight of the modified copolymer.
  • Table 1 shows the physical properties of the low crystalline olefin resin corresponding to the component (A) used in Examples and Comparative Examples described later.
  • a hexane solution of VO (OC 2 H 5 ) Cl 2 adjusted to 16 mmol / L as a catalyst was continuously added in an amount of 500 mL / h, and hexane was continuously supplied in an amount of 500 mL / h. Supplied.
  • the polymerization solution was continuously extracted so that the polymerization solution in the polymerization vessel was always 1 L.
  • ethylene gas was supplied at a rate of 47 L / h, propylene gas at 47 L / h, and hydrogen gas at 20 L / h using a bubbling tube.
  • the copolymerization reaction was carried out at 35 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel.
  • the obtained polymerization solution was deashed with hydrochloric acid, poured into a large amount of methanol and precipitated, and then dried under reduced pressure at 130 ° C. for 24 hours.
  • the ethylene / propylene copolymer obtained (hereinafter also referred to as “hydrocarbon polymer (B-1)”) had an ethylene content of 55.9 mol%, a weight average molecular weight of 14,000, and a 40 ° C. kinematic viscosity.
  • the kinematic viscosity at 37,500 mm 2 / s and 200 ° C. was 132 mm 2 / s.
  • hydrocarbon polymer (B-5) has a weight average molecular weight of 41,000, 200 ° C. kinematic viscosity of 1,400 mm 2 / s, maleic anhydride The amount of acid grafted was 0.5% by weight based on 100% by weight of the modified copolymer.
  • hydrocarbon polymer (B-6) > Production Example 2- except that the hydrocarbon polymer (B-2) was changed to polyisobutylene “Tetrax 5T” (hereinafter also referred to as “hydrocarbon polymer (B-3)”) manufactured by JX Nippon Oil & Energy.
  • the weight average molecular weight of the obtained hydrocarbon polymer (B-6) was 48,000, the kinematic viscosity at 200 ° C. was 5,800 mm 2 / s, and the graft amount of maleic anhydride was 0.5% by weight based on 100% by weight of the modified copolymer.
  • a modified olefin polymer varnish (1) was prepared by dissolving 80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-2) in 400 g of toluene. 500 g of the resulting modified olefin polymer varnish (1) was mixed with 5 g of a curing agent (D-1) to prepare an adhesive composition for laminating.
  • the laminate adhesive composition was diluted with toluene, and using a bar coater, a 40 ⁇ m thick aluminum foil (Al foil) was prepared so that the basis weight of the obtained coated foil was 3.3 g / m 2.
  • the foil with a coating film was obtained by coating at room temperature on the glossy surface of the surface untreated) and volatilizing the solvent. Thereafter, the coated film surface of the obtained foil with coated film and the corona-treated surface of an unstretched polypropylene film (CPP, single-sided corona-treated product) having a thickness of 60 ⁇ m were bonded on a hot stage at 40 ° C., and at 60 ° C. By curing for 3 days, the coating film was cured and the Al foil and the CPP were adhered to each other, thereby obtaining a laminate (composite film) in which the Al foil, the adhesive layer, and the CPP were laminated in this order.
  • CPP unstretched polypropylene film
  • Example 2 A composite film was obtained in the same manner as in Example 1 except that the curing agent (D-1) was changed to the curing agent (D-2) and 500 ppm of the catalyst (E-1) was further added.
  • Example 3 Except for changing 80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-2) to 70 g of the thermoplastic resin (A-3) and 30 g of the hydrocarbon polymer (B-5). A composite film was obtained in the same manner as in Example 1.
  • Example 4 Except for changing 80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-2) to 50 g of the thermoplastic resin (A-3) and 50 g of the hydrocarbon polymer (B-6). A composite film was obtained in the same manner as in Example 1.
  • Example 5 Except for changing 80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-2) to 50 g of the thermoplastic resin (A-3) and 50 g of the hydrocarbon polymer (B-7). A composite film was obtained in the same manner as in Example 1.
  • Example 6 A composite film was obtained in the same manner as in Example 1 except that the thermoplastic resin (A-3) was changed to the thermoplastic resin (A-4) and the bonding temperature at 40 ° C. was changed to 70 ° C.
  • Example 7 A composite film was obtained in the same manner as in Example 2 except that the thermoplastic resin (A-3) was changed to the thermoplastic resin (A-4) and the bonding temperature at 40 ° C. was changed to 70 ° C.
  • Example 8 A composite film was obtained in the same manner as in Example 1 except that the thermoplastic resin (A-3) was changed to the thermoplastic resin (A-5).
  • a modified olefin polymer varnish (2) is prepared by dissolving 45 g of a thermoplastic resin (A-3), 45 g of a hydrocarbon polymer (B-2) and 10 g of a tackifier (C-1) in 400 g of toluene. did. 40 g of the obtained modified olefin polymer varnish (2) was diluted with 60 g of xylene to prepare a primer composition for spray coating. Next, the primer composition for spray coating was applied to a hard PP plate (thickness 2 mm) by spraying and dried at room temperature for 5 minutes to obtain a 10 ⁇ m primer layer on the hard PP.
  • Example 10 A primer / paint laminate film was obtained in the same manner as in Example 9 except that the thermoplastic resin (A-3) was changed to the thermoplastic resin (A-1).
  • a modified olefin polymer varnish (1) was prepared by dissolving 20 g of the thermoplastic resin (A-3) and 80 g of the hydrocarbon-based polymer (B-2) in 400 g of toluene.
  • an aluminum foil Al foil, surface untreated
  • the solvent was evaporated by drying at 100 ° C. for 1 minute to obtain a coated foil.
  • the coated surface of the obtained coated foil was pressure-bonded to a 2 mm thick glass plate at 23 ° C. and 0.1 MPa for 10 seconds, and a laminate in which glass, an adhesive layer and an Al foil were laminated in this order. (Adhesive film laminate) was obtained.
  • Example 12 A pressure-sensitive adhesive film laminate was obtained in the same manner as in Example 11, except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-3).
  • Example 13 A pressure-sensitive adhesive film laminate was obtained in the same manner as in Example 11 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-4).
  • Example 14 Except for changing 20 g of the thermoplastic resin (A-3) and 80 g of the hydrocarbon polymer (B-2) to 30 g of the thermoplastic resin (A-3) and 70 g of the hydrocarbon polymer (B-4). In the same manner as in Example 11, an adhesive film laminate was obtained.

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Abstract

The present invention addresses the problem of providing the following: a coating agent that exhibits an excellent low-temperature workability, overcoatability, and adhesion and that provides a coating film that has an excellent adhesiveness for polyolefin resin substrates that have not been preliminarily subjected to a surface treatment such as a corona treatment, and at the same time that has a good adhesiveness for highly polar substrates such as acrylic resins; a decorative film having at least one layer comprising this coating agent; and a molded article decorated with this decorative film. The coating agent according to the present invention contains (A) an olefin polymer having a heat of fusion as measured in accordance with JIS K 7122 in the range from 0 to 50 J/g and a weight-average molecular weight (Mw) as measured by GPC of 1 × 104 to 1,000 × 104 and (B) a semisolid hydrocarbon having a kinematic viscosity at 200°C of 1,000 to 100,000 mm2/s.

Description

組成物、コーティング剤、接着剤及び積層体Composition, coating agent, adhesive and laminate
　本発明は組成物、コーティング剤、接着剤及び積層体に関し、より詳細には、塗料、プライマー、接着剤、粘着剤として有用なコーティング剤、加飾フィルム、成形体、包材、電池ケース用包材および電池に関する。 The present invention relates to a composition, a coating agent, an adhesive, and a laminate, and more specifically, a coating agent useful as a paint, primer, adhesive, and pressure-sensitive adhesive, a decorative film, a molded article, a packaging material, and a battery case packaging. The present invention relates to materials and batteries.
　ポリプロピレン、ポリエチレン等のポリオレフィン系樹脂は、安価で成形性、耐薬品性、耐水性、電気特性、安全性など多くの優れた性質を有するため、広く用いられている。しかしながら、ポリオレフィン系樹脂は、極性の低い疎水的な材料であるため、アクリル系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、ＡＢＳ樹脂等の極性樹脂を密着させることは困難である。したがって、ポリオレフィン系樹脂の表面に上記極性樹脂を積層させたり、またインキ、塗料等で加飾を施したりすることは困難なのが現状である。 Polyolefin resins such as polypropylene and polyethylene are widely used because they are inexpensive and have many excellent properties such as moldability, chemical resistance, water resistance, electrical properties, and safety. However, since polyolefin resin is a hydrophobic material with low polarity, it is difficult to adhere polar resins such as acrylic resin, polyester resin, polycarbonate resin, and ABS resin. Therefore, at present, it is difficult to laminate the polar resin on the surface of the polyolefin-based resin or to decorate it with ink, paint, or the like.
　また、種々の形状を有する成形体に、意匠層を有するフィルム（加飾フィルム）を貼合して加飾する方法が知られている。一般的に上記意匠層にはウレタン系樹脂やアクリル系樹脂などの極性の高い樹脂が基材として用いられる。したがって、ポリプロピレン等のポリオレフィン系樹脂の成形体に対して加飾フィルムを貼合する場合には、ポリオレフィン系樹脂とウレタン系樹脂やアクリル系樹脂などの極性の高い意匠層とを密着させる接着層が求められる。 Also, a method is known in which a film having a design layer (decorative film) is bonded to a molded body having various shapes for decoration. Generally, a highly polar resin such as a urethane resin or an acrylic resin is used as the base material for the design layer. Therefore, when a decorative film is bonded to a molded article of polyolefin resin such as polypropylene, an adhesive layer that adheres a polyolefin resin and a highly polar design layer such as urethane resin or acrylic resin is provided. Desired.
　本出願人は、ポリオレフィン系樹脂に対する優れた密着性と同時に、アクリル系樹脂等のような極性の高い基材に対しても良好な密着性を有する塗膜を与えるコーティング剤として、特定のオレフィン重合体と特定の炭化水素系合成油を含有するコーティング剤を提案している（特許文献１）。 As a coating agent that gives a coating film having good adhesion to a highly polar substrate such as an acrylic resin as well as excellent adhesion to a polyolefin resin, the present applicant has specified olefin weight. The coating agent containing coalescence and a specific hydrocarbon synthetic oil is proposed (patent document 1).
　また、リチウムイオン２次電池の包材（電池ケース用包材）として、基材であるアルミニウム箔層と、接着剤層と、被着体であるポリプロピレンなどの熱可塑性樹脂製フィルム層（内層）とがこの順で積層された積層体を用いることが知られている。前記接着剤層として、特許文献２～５には、変性オレフィン樹脂とエポキシ化合物またはオキサゾリン化合物とを含む接着剤から得られる層が記載されている。 Moreover, as a packaging material (battery for battery case) of a lithium ion secondary battery, an aluminum foil layer as a base material, an adhesive layer, and a thermoplastic resin film layer (inner layer) such as polypropylene as an adherend. It is known to use a laminate in which and are laminated in this order. As the adhesive layer, Patent Documents 2 to 5 describe layers obtained from an adhesive containing a modified olefin resin and an epoxy compound or an oxazoline compound.
国際公開第２０１３／１６４９７６号パンフレットInternational Publication No. 2013/164976 Pamphlet 特開２００１－５７１８１号公報JP 2001-57181 A 特開２０１２－２１６３６４号公報JP 2012-216364 A 特許第５６６４８３６号公報Japanese Patent No. 5664836 特許第５７００１６６号公報Japanese Patent No. 5700166
　特許文献１に記載のコーティング剤は、良好な密着性を有するものの、さらなる改良が求められていた。具体的には、低温での施工性（ドライラミネーション等）の向上（ラミネート温度の低減）、プライマーとしての上塗り適性の向上（ハジキなく塗装でき、かつ、密着性が良好）、および、高粘着化（ディスプレイ用粘着テープや粘着シートのように非加熱で感圧接着剤としての使用）などが挙げられる。 Although the coating agent described in Patent Document 1 has good adhesion, further improvement has been demanded. Specifically, improvement of workability (dry lamination, etc.) at low temperatures (reduction of laminating temperature), improvement of top coatability as a primer (coating without repellency and good adhesion), and high adhesion (Use as a pressure-sensitive adhesive without heating like a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet for display).
　また、前記特許文献２～５に記載の接着剤から得られる接着剤層は、基材や被着体、例えば、アルミニウム箔やポリプロピレンフィルムなどとの接着強度が十分ではなく、低温で接着剤層を形成する際、特に低温（例：８０℃以下）養生条件で接着剤を硬化させる際には、得られる接着剤層の接着強度が十分ではなかった。 In addition, the adhesive layer obtained from the adhesives described in Patent Documents 2 to 5 does not have sufficient adhesive strength with a substrate or an adherend, such as an aluminum foil or a polypropylene film, and the adhesive layer can be obtained at a low temperature. When forming the adhesive, particularly when the adhesive is cured under curing conditions at a low temperature (eg, 80 ° C. or lower), the adhesive strength of the resulting adhesive layer was not sufficient.
　本発明は、コロナ処理等の予備的な表面処理がなされていないポリオレフィン系樹脂基材に対しても優れた密着性を有し、同時に、アクリル系樹脂等のような極性の高い基材に対しても良好な密着性を有する塗膜を与えるとともに、低温施工性、上塗り適性および粘着力に優れたコーティング剤、該コーティング剤よりなる層を少なくとも１層有する加飾フィルム、および該加飾フィルムによって加飾された成形体を提供することを目的の一つとする。 The present invention has excellent adhesion to a polyolefin resin substrate that has not been subjected to preliminary surface treatment such as corona treatment, and at the same time, to a highly polar substrate such as an acrylic resin. Even with a coating film having good adhesiveness, a coating agent having excellent low-temperature workability, top coatability and adhesive strength, a decorative film having at least one layer comprising the coating agent, and the decorative film One of the purposes is to provide a decorated molded body.
　また、本発明は、アルミニウム箔等の基材および熱可塑性樹脂製フィルム等の被着体との接着強度に優れる接着剤層、特に低温養生条件下でも接着強度に優れる接着剤層を形成することのできるコーティング剤、および該接着剤層を含む積層体等を提供することも目的の一つとする。 Further, the present invention forms an adhesive layer excellent in adhesive strength with a substrate such as an aluminum foil and an adherend such as a thermoplastic resin film, particularly an adhesive layer excellent in adhesive strength even under low temperature curing conditions. Another object is to provide a coating agent that can be used, and a laminate including the adhesive layer.
　本発明者らは、上記状況に鑑み鋭意検討した結果、特定の低結晶性オレフィン重合体に特定の動粘度を有する半固体状炭化水素を配合してなるコーティング剤により、上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the above situation, the present inventors have found that the above-mentioned problems can be solved by a coating agent comprising a specific low crystalline olefin polymer and a semi-solid hydrocarbon having a specific kinematic viscosity. The headline and the present invention were completed.
　本発明のコーティング剤は、ＪＩＳ　Ｋ　７１２２に従って測定した融解熱量が０～５０Ｊ/ｇの範囲にあり、かつＧＰＣ法により測定した重量平均分子量（Ｍｗ）が１×１０4～１０００×１０4であるオレフィン重合体（Ａ）と、
　２００℃動粘度が１，０００～１００，０００ｍｍ2/ｓの半固体状炭化水素（Ｂ）と
を含有することを特徴とする。 The coating agent of the present invention has a heat of fusion measured in accordance with JIS K 7122 in the range of 0 to 50 J / g, and a weight average molecular weight (Mw) measured by GPC method of 1 × 10 4 to 1000 × 10 4 . An olefin polymer (A);
It contains a semisolid hydrocarbon (B) having a kinematic viscosity at 200 ° C. of 1,000 to 100,000 mm 2 / s.
　本発明のコーティング剤は、ポリオレフィン系樹脂基材に対する優れた密着性と同時に、アクリル系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、ＡＢＳ樹脂等のような極性の高い基材に対しても良好な密着性を有する塗膜を与えるとともに、低温施工性、上塗り適性および粘着力に優れている。 The coating agent of the present invention has excellent adhesion to a polyolefin resin substrate, as well as good adhesion to a highly polar substrate such as an acrylic resin, a polyester resin, a polycarbonate resin, and an ABS resin. In addition to providing a coating film having properties, it is excellent in low-temperature workability, top coatability and adhesive strength.
　本発明の加飾フィルムは、ポリオレフィン系樹脂基材に対する優れた密着性と同時に、アクリル系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、ＡＢＳ樹脂等のような極性の高い基材に対しても良好な密着性を有する。 The decorative film of the present invention has excellent adhesion to a polyolefin resin substrate, as well as a highly polar substrate such as an acrylic resin, a polyester resin, a polycarbonate resin, and an ABS resin. Adhesion.
　本発明の成形体は、上記加飾フィルムによって加飾されているため、加飾フィルムと基材との密着性が高い。 Since the molded product of the present invention is decorated with the decorative film, the adhesion between the decorative film and the substrate is high.
　また、本発明の一実施形態によれば、接着強度および耐薬品性（耐電解液性）に優れる接着剤層を得ることができ、特に、アルミニウム箔層とポリプロピレンなどの熱可塑性樹脂製フィルム層とを高い強度で接着することができる。 Moreover, according to one embodiment of the present invention, an adhesive layer excellent in adhesive strength and chemical resistance (electrolytic solution resistance) can be obtained, and in particular, an aluminum foil layer and a film layer made of a thermoplastic resin such as polypropylene. Can be bonded with high strength.
　さらに、本発明の一実施形態によれば、接着強度に優れる接着剤層を低温養生条件下でも容易に形成することができ、耐久性に優れ、接着強度の低下が十分に抑制された積層体、包材および電池ケース用包材等を容易に、例えば、ドライラミネート法で形成することができる。 Furthermore, according to an embodiment of the present invention, an adhesive layer having excellent adhesive strength can be easily formed even under low-temperature curing conditions, and a laminate having excellent durability and sufficiently suppressed decrease in adhesive strength. The packaging material, the battery case packaging material, and the like can be easily formed by, for example, a dry lamination method.
図１は、本発明の電池の一実施形態の概略断面図である。FIG. 1 is a schematic cross-sectional view of one embodiment of the battery of the present invention.
　以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
　［コーティング剤〕
　本発明のコーティング剤は、ＪＩＳ　Ｋ　７１２２に従って測定した融解熱量が０～５０Ｊ/ｇの範囲にあり、かつＧＰＣ法により測定した重量平均分子量（Ｍｗ）が１×１０4～１０００×１０4であるオレフィン重合体（Ａ）と、２００℃動粘度が１，０００～１００，０００ｍｍ2/ｓの半固体状炭化水素（Ｂ）とを含有する。 [Coating agent〕
The coating agent of the present invention has a heat of fusion measured in accordance with JIS K 7122 in the range of 0 to 50 J / g, and a weight average molecular weight (Mw) measured by GPC method of 1 × 10 4 to 1000 × 10 4 . An olefin polymer (A) and a semisolid hydrocarbon (B) having a kinematic viscosity at 200 ° C. of 1,000 to 100,000 mm 2 / s are contained.
　本発明のコーティング剤は、さらに、ＪＩＳ　Ｋ　００７０に従って求まる酸価が１０以上であり、かつＧＰＣ法により測定した重量平均分子量（Ｍｗ）が１×１０3～３×１０3である粘着付与剤（Ｃ）および／または硬化剤（Ｄ）を含有してもよく、前記硬化剤（Ｄ）を含有する場合、さらに、ｐＫａが１１以上である触媒（Ｅ）を含有してもよい。 The coating agent of the present invention further has a tackifier having an acid value determined according to JIS K 0070 of 10 or more and a weight average molecular weight (Mw) measured by GPC method of 1 × 10 3 to 3 × 10 3. C) and / or a curing agent (D) may be contained, and when the curing agent (D) is contained, a catalyst (E) having a pKa of 11 or more may be further contained.
　＜オレフィン重合体（Ａ）＞
　本発明で用いられるオレフィン重合体（Ａ）は、ＪＩＳ　Ｋ　７１２２に従って測定した融解熱量が０～５０Ｊ/ｇの範囲にあり、かつＧＰＣ法により測定した重量平均分子量（Ｍｗ）が１×１０4～１０００×１０4である。すなわち、本発明のコーティング剤では、オレフィン重合体（Ａ）として、ある程度結晶性の低いものが用いられる。なお、本明細書においては、後述する「半固体状炭化水素（Ｂ）」との区別のため、オレフィン重合体（Ａ）を、「低結晶性オレフィン樹脂（Ａ）」または「低結晶性オレフィン樹脂」と称する場合がある。 <Olefin polymer (A)>
The olefin polymer (A) used in the present invention has a heat of fusion measured in accordance with JIS K 7122 in the range of 0 to 50 J / g and a weight average molecular weight (Mw) measured by GPC method of 1 × 10 4 to 1000 × 10 4 . That is, in the coating agent of the present invention, as the olefin polymer (A), a polymer having a certain low crystallinity is used. In the present specification, the olefin polymer (A) is referred to as “low crystalline olefin resin (A)” or “low crystalline olefin” for distinction from “semi-solid hydrocarbon (B)” described later. Sometimes referred to as “resin”.
　ここで、融解熱量はＪＩＳ　Ｋ　７１２２に従って、示差走査熱量測定（ＤＳＣ測定）によって求めることができ、具体的には、１０℃／分の昇温過程で得られるサーモグラムのピーク面積から算出される。その測定に際して、本発明においては、測定前の熱履歴をキャンセルする目的で、測定前に１０℃／分で融点＋２０℃以上に昇温し、その温度で３分保持し、次いで１０℃／分で室温以下まで降温後に融解熱量の測定を行う。 Here, the heat of fusion can be determined by differential scanning calorimetry (DSC measurement) according to JIS K 7122, and is specifically calculated from the peak area of the thermogram obtained in the temperature rising process of 10 ° C./min. . At the time of the measurement, in the present invention, for the purpose of canceling the heat history before the measurement, the temperature is raised to the melting point + 20 ° C. or more at 10 ° C./min before the measurement, held at that temperature for 3 minutes, and then 10 ° C./min. Measure the heat of fusion after cooling down to below room temperature.
　前記融解熱量は、０Ｊ／ｇ以上５０Ｊ/ｇ以下であり、下限は好ましくは３Ｊ／ｇ、より好ましくは５Ｊ／ｇであり、上限は好ましくは４０Ｊ／ｇ以下、より好ましくは３０Ｊ／ｇ以下である。５０Ｊ／ｇ以下であれば、本発明のコーティング剤を溶媒に溶解させた状態、すなわちワニス状態での安定性が良好であり、固化、析出が起こりにくいため好ましい。一方、塗膜の強度、耐タック性の点からは、融解熱量の下限がより高い方が好ましい。 The heat of fusion is from 0 J / g to 50 J / g, the lower limit is preferably 3 J / g, more preferably 5 J / g, and the upper limit is preferably 40 J / g or less, more preferably 30 J / g or less. is there. If it is 50 J / g or less, it is preferable because stability in a state in which the coating agent of the present invention is dissolved in a solvent, that is, in a varnish state is good, and solidification and precipitation hardly occur. On the other hand, from the viewpoint of the strength and tack resistance of the coating film, it is preferable that the lower limit of the heat of fusion is higher.
　本発明に用いられるオレフィン重合体（Ａ）のＧＰＣ法により測定した重量平均分子量は、ポリスチレン換算で１×１０4以上１０００×１０4以下、更に好ましくは２×１０4以上１００×１０4以下、より好ましくは３×１０4以上５０×１０4以下である。重量平均分子量が１×１０4以上であると、塗膜の強度を十分高くすることができ、また密着強度が良好であるため好ましい。一方、重量平均分子量が１０００×１０4以下であればワニス状態での安定性が良好であり、固化、析出が起こりにくいため好ましい。とりわけ、オレフィン重合体（Ａ）の重量平均分子量が小さい値であると（例えば５０×１０4以下の場合には）、特に、接着性能が優れる傾向にある。 The weight average molecular weight measured by GPC method of the olefin polymer (A) used in the present invention is 1 × 10 4 or more and 1000 × 10 4 or less, more preferably 2 × 10 4 or more and 100 × 10 4 or less in terms of polystyrene, More preferably, it is 3 × 10 4 or more and 50 × 10 4 or less. A weight average molecular weight of 1 × 10 4 or more is preferable because the strength of the coating film can be sufficiently increased and the adhesion strength is good. On the other hand, if the weight average molecular weight is 1000 × 10 4 or less, the stability in the varnish state is good, and solidification and precipitation hardly occur. In particular, when the weight average molecular weight of the olefin polymer (A) is a small value (for example, 50 × 10 4 or less), the adhesion performance tends to be particularly excellent.
　本発明に用いられるオレフィン重合体（Ａ）は、上記の融解熱量及び重量平均分子量の要件を満たす限り特に限定されるものではないが、例えば、α－オレフィンの単独重合体または２以上のα－オレフィンの共重合体が挙げられる。α－オレフィンとして、炭素数２～２０のα－オレフィンが例示され、例えばエチレン、プロピレン、１－ブテン、オクテン、４－メチル－１－ペンテン等が挙げられる。すなわち、オレフィン重合体（Ａ）として、炭素数２～２０のα－オレフィン由来の構成単位を含む重合体が挙げられる。 The olefin polymer (A) used in the present invention is not particularly limited as long as it satisfies the above requirements for heat of fusion and weight average molecular weight. For example, a homopolymer of α-olefin or two or more α-olefins can be used. Examples include olefin copolymers. Examples of the α-olefin include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, octene, 4-methyl-1-pentene and the like. That is, examples of the olefin polymer (A) include polymers containing structural units derived from α-olefins having 2 to 20 carbon atoms.
　さらに、オレフィン重合体（Ａ）は、前記α－オレフィン由来の構成単位を１００モル％とした場合に、さらに１０モル％以下の範囲で、α－オレフィン以外の不飽和単量体（以下「他の不飽和単量体」）由来の構成単位を有していても良い。ここで、他の不飽和単量体としては例えばブタジエン、イソプレンなどの共役ポリエン類や、１，４－ヘキサジエン、１，７－オクタジエン、ジシクロペンタジエン、５－エチリデン－２－ノルボルネン、５－ビニル－２－ノルボルネン、５－メチレン－２－ノルボルネン、２，５－ノルボナジエンなどの非共役ポリエン類が挙げられる。オレフィン重合体（Ａ）が２種以上のα－オレフィン由来の構成単位を含む共重合体である場合、ランダム共重合体でもブロック共重合体でもよい。 Further, the olefin polymer (A) is an unsaturated monomer other than an α-olefin (hereinafter referred to as “others”) in the range of 10 mol% or less, assuming that the structural unit derived from the α-olefin is 100 mol%. The structural unit may be derived from an unsaturated monomer ")". Examples of other unsaturated monomers include conjugated polyenes such as butadiene and isoprene, 1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and 5-vinyl. Non-conjugated polyenes such as -2-norbornene, 5-methylene-2-norbornene, and 2,5-norbonadiene are exemplified. When the olefin polymer (A) is a copolymer containing two or more kinds of structural units derived from α-olefin, it may be a random copolymer or a block copolymer.
　さらに上記オレフィン重合体（Ａ）は、例えば上記α－オレフィン由来の構成単位を含む重合体または共重合体に、水酸基、無水カルボン酸、－ＣＯＯＸ（Ｘ：Ｈ、Ｍ）（Ｈは水素、Ｍはアルカリ金属、アルカリ土類金属、アミン類由来の陽イオン）等を含有する不飽和単量体をグラフト反応させて得られる変性オレフィン重合体であってもよく、あるいは、上記α－オレフィン由来の構成単位を含む重合体または共重合体をさらにハロゲン化して得られるハロゲン化オレフィン重合体であってもよい。 Further, the olefin polymer (A) is prepared by adding, for example, a polymer or copolymer containing a structural unit derived from the α-olefin to a hydroxyl group, a carboxylic anhydride, —COOX (X: H, M) (H is hydrogen, M May be a modified olefin polymer obtained by graft reaction of an unsaturated monomer containing an alkali metal, an alkaline earth metal, an amine or the like, or may be derived from the α-olefin. The halogenated olefin polymer obtained by further halogenating the polymer or copolymer containing a structural unit may be sufficient.
　このようなオレフィン重合体（Ａ）のうち、本発明で好適に用いられるものとして、以下の（Ａ１）～（Ａ３）からなる群より選ばれる１種以上が挙げられる：
　（Ａ１）炭素数２～２０のα－オレフィン由来の構成単位を含む重合体（以下「重合体（Ａ１）」と称する。）；
　（Ａ２）炭素数２～２０のα－オレフィン由来の構成単位を含む重合体であって、その一部または全部が極性基含有単量体でグラフト変性されてなる変性オレフィン系重合体（以下「変性オレフィン系重合体（Ａ２）」と称する。）；
　（Ａ３）炭素数２～２０のα－オレフィン由来の構成単位を含む重合体であって、その一部または全部がハロゲン化変性されてなるハロゲン化オレフィン系重合体（以下「ハロゲン化オレフィン系重合体（Ａ３）」と称する。）。 Among such olefin polymers (A), those suitably used in the present invention include one or more selected from the group consisting of the following (A1) to (A3):
(A1) a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms (hereinafter referred to as “polymer (A1)”);
(A2) A polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, part or all of which is graft-modified with a polar group-containing monomer (hereinafter referred to as “ Referred to as “modified olefin polymer (A2)”);
(A3) A polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, a part or all of which is halogenated and modified (hereinafter referred to as “halogenated olefin heavy polymer”). Combined (A3) ").
　・重合体（Ａ１）
　重合体（Ａ１）としては、前記した炭素数２～２０のα－オレフィン由来の構成単位を含む重合体が挙げられる。すなわち、本発明においては、炭素数２～２０のα－オレフィン由来の構成単位を含む重合体を、グラフト変性及びハロゲン化変性等の変性処理を行うことなく、そのまま重合体（Ａ１）としてオレフィン重合体（Ａ）に用いてもよい。その意味で、重合体（Ａ１）は、未変性重合体（Ａ１）と呼ぶこともでき、後述する「変性オレフィン系重合体（Ａ２）」および「ハロゲン化オレフィン系重合体（Ａ３）」と区別される。 ・ Polymer (A1)
Examples of the polymer (A1) include polymers containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms. That is, in the present invention, a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms is used as it is as a polymer (A1) without undergoing modification treatment such as graft modification and halogenation modification. You may use for a unification (A). In that sense, the polymer (A1) can also be referred to as an unmodified polymer (A1), and is distinguished from the “modified olefin polymer (A2)” and “halogenated olefin polymer (A3)” described later. Is done.
　ここで、本発明の好適な態様において、重合体（Ａ１）は、炭素数２～２０のα－オレフィン由来の構成単位の合計を１００モル％としたときに、プロピレン由来の構成単位を５０～１００モル％と、プロピレンを除く炭素数２～２０のα－オレフィン由来の構成単位を５０～０モル％とを含有するプロピレン系重合体（Ａ１''）である。ここで、「プロピレンを除く炭素数２～２０のα－オレフィン」の好適な例として、１－ブテン、オクテンなどが挙げられる。ここで炭素数２～２０のα－オレフィン由来の構成単位の合計を１００モル％としたときに、プロピレン由来の構成単位は好ましくは５５～９０モル％、より好ましくは６０～８５モル％、さらに好ましくは６０～８０モル％であり、プロピレンを除く炭素数２～２０のα－オレフィン由来の構成単位は好ましくは４５～１０モル％、より好ましくは４０～１５モル％、さらに好ましくは４０～２０モル％とを含有するプロピレン系重合体がより好ましい。 Here, in a preferred embodiment of the present invention, the polymer (A1) has 50 to 50 structural units derived from propylene when the total of structural units derived from α-olefin having 2 to 20 carbon atoms is 100 mol%. A propylene polymer (A1 ″) containing 100 mol% and 50 to 0 mol% of a structural unit derived from an α-olefin having 2 to 20 carbon atoms excluding propylene. Here, preferable examples of “α-olefin having 2 to 20 carbon atoms excluding propylene” include 1-butene and octene. Here, when the total of the structural units derived from α-olefin having 2 to 20 carbon atoms is 100 mol%, the structural unit derived from propylene is preferably 55 to 90 mol%, more preferably 60 to 85 mol%, Preferably, it is 60 to 80 mol%, and the constituent unit derived from an α-olefin having 2 to 20 carbon atoms excluding propylene is preferably 45 to 10 mol%, more preferably 40 to 15 mol%, still more preferably 40 to 20 mol%. A propylene-based polymer containing mol% is more preferable.
　本発明では、このような重合体（Ａ１）を、１種単独で用いてもよく、あるいは、２種以上を組み合わせて用いてもよい。 In the present invention, such a polymer (A1) may be used singly or in combination of two or more.
　また、本発明で用いられるこのような重合体（Ａ１）は、オレフィン重合体（Ａ）全体として上記融解熱量および上記重量平均分子量（Ｍｗ）を満たす限り、製造方法に限定はなく、従来公知の方法によって得ることができ、例えば、特許３９３９４６４号および国際公開２００４／８７７７５号パンフレットに記載の方法に従って製造することができる。ここで、本発明において重合体（Ａ１）として好適に用いられるプロピレン・１－ブテン共重合体を例にとると、このようなプロピレン・１－ブテン共重合体は、例えば、rac－ジメチルシリレン－ビス｛１－（２－メチル－４－フェニルインデニル）｝ジルコニウムジクロライドなどの適当なメタロセン化合物と、アルミノキサンなどの有機アルミニウムオキシ化合物と、必要に応じて用いられるトリブチルアルミニウムなどの有機アルミニウム化合物とからなるメタロセン系触媒存在下で、プロピレンと１－ブテンを共重合させることにより得ることができる。 Moreover, as long as the polymer (A1) used in the present invention satisfies the heat of fusion and the weight average molecular weight (Mw) of the olefin polymer (A) as a whole, the production method is not limited, and a conventionally known method is known. For example, it can be produced according to the methods described in Japanese Patent No. 3939464 and International Publication No. 2004/87775. Here, taking the propylene / 1-butene copolymer suitably used as the polymer (A1) in the present invention as an example, such propylene / 1-butene copolymer is, for example, rac-dimethylsilylene- From a suitable metallocene compound such as bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, an organoaluminum oxy compound such as aluminoxane, and an organoaluminum compound such as tributylaluminum used as necessary. It can be obtained by copolymerizing propylene and 1-butene in the presence of a metallocene catalyst.
　・変性オレフィン系重合体（Ａ２）
　変性オレフィン系重合体（Ａ２）としては、前記した炭素数２～２０のα－オレフィン由来の構成単位を含む重合体であって、その一部または全部が極性基含有単量体でグラフト変性されてなる変性オレフィン系重合体が挙げられる。そして好ましくは当該変性オレフィン系重合体１００重量部に対して、極性基含有単量体由来の構成単位を０．１～１５重量部、より好ましくは０．５～１０重量部含む重合体である。たとえば、本発明においては、炭素数２～２０のα－オレフィン由来の構成単位を含む重合体（Ａ１ａ）を、一旦極性基含有単量体でグラフト変性し、これによって得られるグラフト変性オレフィン系重合体（Ａ２ｍ）そのものを変性オレフィン系重合体（Ａ２）としてオレフィン重合体（Ａ）に用いることができる。ここで、重合体（Ａ１ａ）としては、上記重合体（Ａ１）と同様のものが挙げられる。 ・ Modified olefin polymer (A2)
The modified olefin polymer (A2) is a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, part or all of which is graft-modified with a polar group-containing monomer. And a modified olefin polymer. Preferably, the polymer contains 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight of a structural unit derived from a polar group-containing monomer with respect to 100 parts by weight of the modified olefin polymer. . For example, in the present invention, a polymer (A1a) containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms is once graft-modified with a polar group-containing monomer, and the resulting graft-modified olefin-based polymer is obtained. The polymer (A2m) itself can be used as the modified olefin polymer (A2) in the olefin polymer (A). Here, examples of the polymer (A1a) include the same as the polymer (A1).
　また、変性オレフィン系重合体（Ａ２）は、上記のような重合体（Ａ１ａ）のグラフト変性物、すなわちグラフト変性オレフィン系重合体（Ａ２ｍ）と、未変性の重合体（Ａ１ａ）とを混合して、変性オレフィン系重合体組成物の形で用いられるものであっても良い。このような場合、グラフト変性オレフィン系重合体（Ａ２ｍ）を得るためのグラフト変性に用いる重合体（Ａ１ａ）と未変性のまま用いる重合体（Ａ１ａ）とは同一でも異なっていてもよい。そしてこの場合が、炭素数２～２０のα－オレフィン由来の構成単位を含む重合体であって、その一部が極性基含有単量体でグラフト変性されてなるものの一例である。 The modified olefin polymer (A2) is obtained by mixing the graft modified product of the polymer (A1a) as described above, that is, the graft modified olefin polymer (A2m) and the unmodified polymer (A1a). In addition, it may be used in the form of a modified olefin polymer composition. In such a case, the polymer (A1a) used for graft modification for obtaining the graft-modified olefin polymer (A2m) and the polymer (A1a) used unmodified may be the same or different. This case is an example of a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, a part of which is graft-modified with a polar group-containing monomer.
　上記で用いることのできる重合体（Ａ１ａ）の重量平均分子量は、対応する変性オレフィン系重合体（Ａ２）全体として前記重量平均分子量を満たせば特に制限はないが、通常１×１０4～１０００×１０4の範囲であり、好ましくは２×１０4以上１００×１０4以下、より好ましくは３×１０4以上５０×１０4以下である。またＪＩＳ Ｋ ７１２２に従って測定される融解熱量は、変性オレフィン系重合体（Ａ２）が前記重量平均分子量を満たせば特に制限はないが、前記融解熱量は、０Ｊ／ｇ以上５０Ｊ/ｇ以下であり、下限は好ましくは３Ｊ／ｇ、より好ましくは５Ｊ／ｇであり、上限は好ましくは４０Ｊ／ｇ以下、より好ましくは３０Ｊ／ｇ以下である。また、本発明で用いられる変性オレフィン系重合体（Ａ２）において、グラフト変性オレフィン系重合体（Ａ２ｍ）と、任意で用いられる未変性の重合体（Ａ１ａ）との合計１００重量部に対し、極性基含有単量体由来の構成単位を０．１～１５重量部含むことが好ましい。 The weight average molecular weight of the polymer (A1a) that can be used above is not particularly limited as long as the corresponding modified olefin polymer (A2) as a whole satisfies the weight average molecular weight, but is usually 1 × 10 4 to 1000 ×. The range is 10 4 , preferably 2 × 10 4 or more and 100 × 10 4 or less, more preferably 3 × 10 4 or more and 50 × 10 4 or less. Further, the heat of fusion measured according to JIS K 7122 is not particularly limited as long as the modified olefin polymer (A2) satisfies the weight average molecular weight, but the heat of fusion is 0 J / g or more and 50 J / g or less, The lower limit is preferably 3 J / g, more preferably 5 J / g, and the upper limit is preferably 40 J / g or less, more preferably 30 J / g or less. Further, in the modified olefin polymer (A2) used in the present invention, the polarity is 100 parts by weight with respect to a total of 100 parts by weight of the graft-modified olefin polymer (A2m) and the optionally used unmodified polymer (A1a). It is preferable to contain 0.1 to 15 parts by weight of a structural unit derived from a group-containing monomer.
　本発明において、変性オレフィン系重合体（Ａ２）を構成するグラフト変性オレフィン系重合体（Ａ２ｍ）を得るために、重合体（Ａ１ａ）に極性基含有単量体をグラフト共重合する。極性基含有単量体としては、水酸基含有エチレン性不飽和化合物、アミノ基含有エチレン性不飽和化合物、エポキシ基含有エチレン性不飽和化合物、不飽和カルボン酸とその無水物およびその誘導体、ビニルエステル化合物、塩化ビニル等を挙げることができるが、不飽和カルボン酸およびその無水物が好ましい。 In the present invention, in order to obtain the graft-modified olefin polymer (A2m) constituting the modified olefin polymer (A2), a polar group-containing monomer is graft copolymerized with the polymer (A1a). Examples of polar group-containing monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, unsaturated carboxylic acids and their anhydrides and derivatives, and vinyl ester compounds. Vinyl chloride and the like, and unsaturated carboxylic acids and anhydrides thereof are preferred.
　水酸基含有エチレン性不飽和化合物としては、たとえば、ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシープロピル（メタ）アクリレート、３－クロロー２－ヒドロキシプロピル（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、ペンタエリスリトールモノ（メタ）アクリレート、トリメチロールプロパンモノ（メタ）アクリレート、テトラメチロールエタンモノ（メタ）アクリレート、ブタンジオールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、２－（６－ヒドロヘキサノイルオキシ）エチルアクリレート等の水酸基含有（メタ）アクリル酸エステルおよび１０－ウンデセン－１－オール、１－オクテン－３－オール、２－メタノールノルボルネン、ヒドロキシスチレン、Ｎ－メチロールアクリルアミド、２－（メタ）アクロイルオキシエチルアシッドフォスフェート、グリセリンモノアリルエーテル、アリルアルコール、アリロキシエタノール、２－ブテン－１，４－ジオール、グリセリンモノアルコール等を挙げることができる。 Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. , 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono ( Hydroxyl group-containing (meth) acrylic acid esters such as (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydrohexanoyloxy) ethyl acrylate, and the like -Undecen-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, N-methylolacrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, ants Examples include roxyethanol, 2-butene-1,4-diol, glycerin monoalcohol and the like.
　アミノ基含有エチレン性不飽和化合物としては、下式で表されるようなアミノ基または置換アミノ基を少なくとも１種類有するビニル系単量体を挙げることができる。 Examples of the amino group-containing ethylenically unsaturated compound include vinyl monomers having at least one amino group or substituted amino group represented by the following formula.
　－ＮＲ1Ｒ2
　式中、Ｒ1は水素原子、メチル基またはエチル基であり、Ｒ2は、水素原子、炭素数１～１２，好ましくは炭素数１～８のアルキル基、炭素数８～１２、好ましくは６～９のシクロアルキル基である。なお、上記のアルキル基、シクロアルキル基は、さらに置換基を有してもよい。 -NR 1 R 2
In the formula, R 1 is a hydrogen atom, a methyl group or an ethyl group, and R 2 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, or an 8 to 12 carbon atom, preferably 6 carbon atoms. -9 cycloalkyl groups. In addition, said alkyl group and cycloalkyl group may have a substituent further.
　このようなアミノ基含有エチレン性不飽和化合物としては、例えば、（メタ）アクリル酸アミノメチル、（メタ）アクリル酸プロピルアミノエチル、メタクリル酸ジメチルアミノエチル、（メタ）アクリル酸アミノプロピル、メタクリル酸フェニルアミノメチル、メタクリル酸シクロヘキシルアミノエチル等のアクリル酸またはメタクリル酸のアルキルエステル系誘導体類、Ｎ－ビニルジエチルアミン、Ｎ－アセチルビニルアミン等のビニルアミン系誘導体類、アクリルアミド、メタクリルアミド、Ｎ－メチルアクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピルアクリルアミド等のアクリルアミド系誘導体等のイミド類を挙げることができる。 Examples of such an amino group-containing ethylenically unsaturated compound include aminomethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, and phenyl methacrylate. Alkyl ester derivatives of acrylic acid or methacrylic acid such as aminomethyl and cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, acrylamide, methacrylamide, N-methylacrylamide, N And imides such as acrylamide derivatives such as N, N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide.
　エポキシ基含有エチレン性不飽和化合物としては、１分子中に重合可能な不飽和結合基及びエポキシ基を少なくとも１個以上有するモノマーが用いられる。 As the epoxy group-containing ethylenically unsaturated compound, a monomer having at least one unsaturated bond group and epoxy group polymerizable in one molecule is used.
　このようなエポキシ基含有エチレン性不飽和化合物としては、たとえば、グリシジルアクリレート、グリシジルメタクリレート等の不飽和カルボン酸のグリシジルエステル、あるいはマレイン酸、フマル酸、クロトン酸、テトラヒドロフタル酸、イタコン酸、シトラコン酸、エンド－シス－ビシクロ［２，２，１］ヘプト－５－エン－２，３－ジカルボン酸（ナジック酸TM）、エンド－シス－ビシクロ［２，２，１］ヘプト－５－エン－２－メチル－２，３－ジカルボン酸（メチルナジック酸TM）等の不飽和ジカルボン酸のモノグリシジルエステル（モノグリシジルエステルの場合のアルキル基の炭素数１～１２）、ｐ－スチレンカルボン酸のアルキルグリシジルエステル、アリルグリシジルエーテル、２－メチルアリルグリシジルエーテル、スチレン－ｐ－グリシジルエーテル、３，４－エポキシ－１－ブテン、３，４－エポキシ－３－メチル－１－ブテン、３，４－エポキシ－１－ペンテン、３，４－エポキシ－３－メチル－１－ペンテン、５，６－エポキシ－１－ヘキセン、ビニルシクロヘキセンモノオキシド等を挙げることができる。 Examples of such an epoxy group-containing ethylenically unsaturated compound include glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate, or maleic acid, fumaric acid, crotonic acid, tetrahydrophthalic acid, itaconic acid, and citraconic acid. Endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ™ ), endo-cis-bicyclo [2,2,1] hept-5-ene-2 -Monoglycidyl esters of unsaturated dicarboxylic acids such as methyl-2,3-dicarboxylic acid (methylnadic acid TM ) (C1-C12 of alkyl group in the case of monoglycidyl esters), alkylglycidyl of p-styrene carboxylic acid Ester, allyl glycidyl ether, 2-methylallyl glycidyl ether Styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl -1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide and the like.
　不飽和カルボン酸類としては、たとえば、アクリル酸、メタクリル酸、マレイン酸、フマル酸、テトラヒドロフタル酸、イタコン酸、シトラコン酸、クロトン酸、イソクロトン酸、ノルボルネンジカルボン酸、ビシクロ［２，２，１］ヘプト－２－エン－５，６－ジカルボン酸等の不飽和カルボン酸またはこれらの誘導体（例えば酸無水物、酸ハライド、アミド、イミド、エステル等）を挙げることができる。 Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept Examples thereof include unsaturated carboxylic acids such as -2-ene-5,6-dicarboxylic acid or derivatives thereof (for example, acid anhydrides, acid halides, amides, imides, esters, etc.).
　不飽和カルボン酸の誘導体としては、例えば、塩化マレニル、マレニルイミド、無水マレイン酸、無水イタコン酸、無水シトラコン酸、テトラヒドロ無水フタル酸、ビシクロ［２，２，１］ヘプト－２－エン－５，６－ジカルボン酸無水物、マレイン酸ジメチル、マレイン酸モノメチル、マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジメチル、シトラコン酸ジエチル、テトラヒドロフタル酸ジメチル、ビシクロ［２，２，１］ヘプト－２－エン－５，６－ジカルボン酸ジメチル、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、グリシジル（メタ）アクリレート、メタクリル酸アミノエチルおよびメタクリル酸アミノプロピル等を挙げることができる。 Examples of the unsaturated carboxylic acid derivative include, for example, maleyl chloride, maleenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6 Dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5 Dimethyl 6-dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate.
　ビニルエステル化合物としては、たとえば、酢酸ビニル、プロピオン酸ビニル、ｎ－酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプロン酸ビニル、パーサティック酸ビニル、ラウリル酸ビニル、ステアリン酸ビニル、安息香酸ビニル、サリチル酸ビニル、シクロヘキサンカルボン酸ビニル等を挙げることができる。 Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl persate, vinyl laurate, vinyl stearate, vinyl benzoate, and salicylic acid. Examples thereof include vinyl and vinyl cyclohexanecarboxylate.
　これらの極性基含有単量体は単独あるいは複数で使用することができる。 These polar group-containing monomers can be used alone or in combination.
　また、グラフト変性オレフィン系重合体（Ａ２ｍ）をそのまま変性オレフィン系重合体（Ａ２）として用いる場合、上記極性基含有単量体はグラフト変性オレフィン系重合体（Ａ２ｍ）１００重量部に対し、０．１～１５重量部、好ましくは０．５～１０重量部となるようにグラフト共重合されるのが好ましい。 When the graft-modified olefin polymer (A2m) is used as it is as the modified olefin polymer (A2), the polar group-containing monomer is added to the graft-modified olefin polymer (A2m) by 100 parts by weight. Graft copolymerization is preferably carried out so as to be 1 to 15 parts by weight, preferably 0.5 to 10 parts by weight.
　これらの極性基含有単量体の含有率は、オレフィン重合体と極性基含有単量体とをラジカル開始剤などの存在下に反応させる際の仕込み比で調整することができ、1Ｈ ＮＭＲ測定などの公知の手段で求めることができる。具体的なＮＭＲ測定条件としては、以下の様な条件を例示できる。 The content of these polar group-containing monomer, it is possible to adjust the olefin polymer and the polar group-containing monomer in the feed ratio of the time of the reaction in the presence of such a radical initiator, 1 H NMR measurements It can obtain | require by well-known means, such as. Specific conditions for NMR measurement include the following conditions.
　1Ｈ ＮＭＲ測定の場合、日本電子（株）製ＥＣＸ４００型核磁気共鳴装置を用い、溶媒は重水素化オルトジクロロベンゼンとし、試料濃度２０ｍｇ／０．６ｍＬ、測定温度は１２０℃、観測核は1Ｈ（４００ＭＨｚ）、シーケンスはシングルパルス、パルス幅は５．１２μ秒（４５°パルス）、繰り返し時間は７．０秒、積算回数は５００回以上とする条件である。基準のケミカルシフトは、テトラメチルシランの水素を０ｐｐｍとするが、例えば、重水素化オルトジクロロベンゼンの残存水素由来のピークを７．１０ｐｐｍとしてケミカルシフトの基準値とすることでも同様の結果を得ることが出来る。官能基含有化合物由来の1Ｈなどのピークは、常法によりアサインできる。 In the case of 1 H NMR measurement, an ECX400 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. is used, the solvent is deuterated orthodichlorobenzene, the sample concentration is 20 mg / 0.6 mL, the measurement temperature is 120 ° C., the observation nucleus is 1 H (400 MHz), the sequence is a single pulse, the pulse width is 5.12 μs (45 ° pulse), the repetition time is 7.0 seconds, and the number of integration is 500 times or more. The standard chemical shift is 0 ppm for tetramethylsilane hydrogen. For example, the same result can be obtained by setting the peak derived from residual hydrogen in deuterated orthodichlorobenzene to 7.10 ppm and setting the standard value for chemical shift. I can do it. A peak such as 1 H derived from the functional group-containing compound can be assigned by a conventional method.
　また、上記極性基含有単量体として、上記不飽和カルボン酸およびその無水物など酸性官能基を有する単量体を用いた場合、変性オレフィン系重合体（Ａ２）に導入された官能基の量の目安となる量として、例えば酸価を用いることも可能である。ここで、酸価の測定方法としては、以下のものが挙げられる。 Moreover, when the monomer having an acidic functional group such as the unsaturated carboxylic acid and its anhydride is used as the polar group-containing monomer, the amount of the functional group introduced into the modified olefin polymer (A2) For example, an acid value can be used as an amount of the standard. Here, the following are mentioned as a measuring method of an acid value.
　（酸価の測定）
　基本操作はＪＩＳ Ｋ－２５０１－２００３に準ずる。 (Measurement of acid value)
Basic operation conforms to JIS K-2501-2003.
　変性オレフィン重合体 約１０ｇを正確に測り取り、２００ｍＬトールビーカーに投入する。そこに滴定溶剤として、キシレンとジメチルホルムアミドとを１：１（体積比）で混合してなる混合溶媒を１５０ｍＬ添加する。指示薬として１ｗ／ｖ％のフェノールフタレインエタノール溶液（和光純薬工業社製）を数滴加え、液温を８０℃に加熱して、試料を溶解させる。液温が８０℃で一定になった後、０．１ｍｏｌ／Ｌの水酸化カリウムの２－プロパノール溶液（和光純薬工業社製）を用いて滴定を行い、滴定量から酸価を求める。 Measure approximately 10 g of the modified olefin polymer accurately and put into a 200 mL tall beaker. As a titration solvent, 150 mL of a mixed solvent obtained by mixing xylene and dimethylformamide at 1: 1 (volume ratio) is added. A few drops of 1 w / v% phenolphthalein ethanol solution (Wako Pure Chemical Industries, Ltd.) is added as an indicator, and the liquid temperature is heated to 80 ° C. to dissolve the sample. After the liquid temperature becomes constant at 80 ° C., titration is performed using a 0.1 mol / L potassium hydroxide 2-propanol solution (manufactured by Wako Pure Chemical Industries, Ltd.), and the acid value is determined from the titration amount.
　計算式は
　酸価（ｍｇＫＯＨ／ｇ）＝（ＥＰ１－ＢＬ１）×ＦＡ１×Ｃ１／ＳＩＺＥ
である。 The calculation formula is: Acid value (mgKOH / g) = (EP1-BL1) × FA1 × C1 / SIZE
It is.
　ここで、上記計算式において、ＥＰ１は滴定量（ｍＬ）、ＢＬ１はブランク値（ｍＬ）、ＦＡ１は滴定液のファクター（１．００）、Ｃ１は濃度換算値（５．６１１ｍｇ／ｍＬ：０．１ｍｏ１／Ｌ　ＫＯＨ　１ｍＬの水酸化カリウム相当量）、ＳＩＺＥは試料採取量（ｇ）をそれぞれ表す。 Here, in the above calculation formula, EP1 is a titration amount (mL), BL1 is a blank value (mL), FA1 is a factor of a titrant (1.00), and C1 is a concentration conversion value (5.611 mg / mL: 0.00). 1mo1 / L KOH 1 mL of potassium hydroxide equivalent), SIZE represents the sample collection amount (g).
　この測定を３回繰り返して平均値を酸価とする。 This measurement is repeated three times and the average value is taken as the acid value.
　変性オレフィン系重合体（Ａ２）の酸価は、０．１～１００ｍｇＫＯＨ／ｇであることが望ましく、０．５～６０ｍｇＫＯＨ／ｇであることがより好ましく、０．５～３０ｍｇＫＯＨ／ｇであることがさらに好ましい。ここで、グラフト変性オレフィン系重合体（Ａ２ｍ）と未変性の重合体（Ａ１ａ）とを混合してなる変性オレフィン系重合体組成物が変性オレフィン系重合体（Ａ２）として用いられる場合、当該変性オレフィン系重合体組成物全体として上記のような酸価を有することが好ましい。 The acid value of the modified olefin polymer (A2) is preferably 0.1 to 100 mgKOH / g, more preferably 0.5 to 60 mgKOH / g, and 0.5 to 30 mgKOH / g. Is more preferable. Here, when the modified olefin polymer composition obtained by mixing the graft-modified olefin polymer (A2m) and the unmodified polymer (A1a) is used as the modified olefin polymer (A2), the modification The olefin polymer composition as a whole preferably has an acid value as described above.
　また、上記極性基含有単量体として無水マレイン酸を用いる場合には、赤外分光光度計を用いて1790ｃｍ-1付近に検出される無水マレイン酸のカルボニル基の吸収に基づいてグラフト量を求めることもできる。 When maleic anhydride is used as the polar group-containing monomer, the graft amount is determined based on the absorption of the carbonyl group of maleic anhydride detected in the vicinity of 1790 cm −1 using an infrared spectrophotometer. You can also.
　上記重合体（Ａ１ａ）に、上記極性基含有単量体から選ばれる少なくとも１種の極性基含有単量体をグラフト共重合させる方法として、種々の方法を挙げることができる。たとえば、重合体（Ａ１ａ）を有機溶媒に溶解し、上記極性基含有単量体およびラジカル重合開始剤を添加して加熱、攪拌してグラフト共重合反応させる方法、重合体（Ａ１ａ）を加熱溶融して、得られる溶融物に上記極性基含有単量体およびラジカル重合開始剤を添加し、攪拌してグラフト共重合させる方法、上記重合体（Ａ１ａ）、上記極性基含有単量体およびラジカル重合開始剤を予め混合し、得られる混合物を押出機に供給して加熱混練しながらグラフト共重合反応させる方法、重合体（Ａ１ａ）に、上記極性基含有単量体およびラジカル重合開始剤を有機溶媒に溶解してなる溶液を含浸させた後、エチレン・α－オレフィンランダム共重合体が溶解しない最高の温度まで加熱し、グラフト共重合反応させる方法などを挙げることができる。 As the method of graft copolymerizing the polymer (A1a) with at least one polar group-containing monomer selected from the polar group-containing monomers, various methods can be exemplified. For example, a method in which a polymer (A1a) is dissolved in an organic solvent, the above polar group-containing monomer and a radical polymerization initiator are added and heated and stirred to cause graft copolymerization reaction, and the polymer (A1a) is heated and melted And adding the polar group-containing monomer and the radical polymerization initiator to the resulting melt, stirring and graft copolymerizing, the polymer (A1a), the polar group-containing monomer and the radical polymerization. A method in which an initiator is mixed in advance, and the resulting mixture is supplied to an extruder and subjected to graft copolymerization while heating and kneading. The polymer (A1a) is mixed with the polar group-containing monomer and the radical polymerization initiator in an organic solvent. And a method in which a graft copolymerization reaction is performed by impregnating a solution obtained by dissolving in an aqueous solution and then heating to a maximum temperature at which the ethylene / α-olefin random copolymer does not dissolve. Kill.
　反応温度は、５０℃以上、特に８０～２００℃の範囲が好適であり、反応時間は１分～１０時間程度である。 The reaction temperature is preferably 50 ° C. or higher, particularly 80 to 200 ° C., and the reaction time is about 1 minute to 10 hours.
　反応方式は、回分式、連続式のいずれでも良いが、グラフト共重合を均一に行うためには回分式が好ましい。 The reaction method may be either a batch method or a continuous method, but a batch method is preferable in order to perform graft copolymerization uniformly.
　使用するラジカル重合開始剤は、上記重合体（Ａ１ａ）と上記極性基含有単量体との反応を促進するものであれば何でも良いが、特に有機ペルオキシド、有機ペルエステルが好ましい。 The radical polymerization initiator to be used is not particularly limited as long as it promotes the reaction between the polymer (A1a) and the polar group-containing monomer, and organic peroxides and organic peresters are particularly preferable.
　具体的には、ベンゾイルペルオキシド、ジクロルベンゾイルペルオキシド、ジクミルペルオキシド、ジ－tert－ブチルペルオキシド、２，５－ジメチル－２，５－ジ（ペルオキシベンゾエート）ヘキシン－３、１，４－ビス（tert－ブチルペルオキシイソプロピル）ベンゼン、ラウロイルペルオキシド、tert－ブチルペルアセテート、２，５－ジメチル－２，５－ジ（tert－ブチルペルオキシ）ヘキシン－３、２，５－ジメチル－２，５－ジ（tert－ブチルペルオキシド）ヘキサン、tert－ブチルベンゾエート、tert－ブチルペルフェニルアセテート、tert－ブチルペルイソブチレート、tert－ブチルペル－sec－オクトエート、tert－ブチルペルピバレート、クミルペルピバレートおよびtert－ブチルペルジエチルアセテートがあり、その他アゾ化合物、たとえば、アゾビス－イソブチルニトリル、ジメチルアゾイソブチルニトリルがある。 Specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3, 1,4-bis (tert -Butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert -Butyl peroxide) hexane, tert-butyl benzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl Perdiethyl acetate, other azo compounds, For example, it azobis - isobutyronitrile, there are dimethyl azoisobutyronitrile.
　これらのうちでは、ジクミルペルオキシド、ジ－tert－ブチルペルオキシド、２，５－ジメチル－２，５－ジ（tert－ブチルペルオキシ）ヘキシン－３，２，５－ジメチル－２，５－ジ（tert－ブチルペルオキシ）ヘキサン、１，４－ビス（tert－ブチルペルオキシイソプロピル）ベンゼン等のジアルキルペルオキシドが好ましい。 Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert Dialkyl peroxides such as -butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.
　ラジカル重合開始剤は、上記重合体（Ａ１ａ）１００重量部に対して、０．００１～１０重量部程度の量で使用されることが好ましい。 The radical polymerization initiator is preferably used in an amount of about 0.001 to 10 parts by weight with respect to 100 parts by weight of the polymer (A1a).
　また、上記グラフト変性オレフィン系重合体（Ａ２ｍ）と、未変性の重合体（Ａ１ａ）とを混合してなる変性オレフィン系重合体組成物を変性オレフィン系重合体（Ａ２）として用いる場合には、グラフト変性オレフィン系重合体（Ａ２ｍ）と未変性の重合体（Ａ１ａ）との合計１００重量部に対し、グラフトされた極性基含有単量体が、０．１～１５重量部、好ましくは０．５～１０重量部となるように調製するのが好ましい。 When the modified olefin polymer composition obtained by mixing the graft-modified olefin polymer (A2m) and the unmodified polymer (A1a) is used as the modified olefin polymer (A2), The grafted polar group-containing monomer is used in an amount of 0.1 to 15 parts by weight, preferably 0.8%, based on 100 parts by weight of the total of the graft-modified olefin polymer (A2m) and the unmodified polymer (A1a). It is preferable to prepare so as to be 5 to 10 parts by weight.
　グラフト反応は前記の通り、有機溶剤中、または無溶媒で行うことができるが、本発明においては変性オレフィン系重合体（Ａ２）としてグラフト変性オレフィン系重合体（Ａ２ｍ）そのものをオレフィン重合体（Ａ）として用いる場合、通常、当該変性オレフィン系重合体（Ａ２）を有機溶剤に溶解した組成物を接着剤等として使用するので、有機溶剤中で反応した場合はそのまま、またはさらに同種または他種の有機溶剤を加えてコーティング剤等を調製することも可能である。有機溶剤を用いずにグラフト反応を行った場合には、あらためて有機溶剤を添加してグラフト生成物を溶解し、本発明のコーティング剤等とする。 As described above, the graft reaction can be carried out in an organic solvent or without solvent. In the present invention, the graft-modified olefin polymer (A2m) itself is used as the modified olefin polymer (A2). In general, since a composition in which the modified olefin polymer (A2) is dissolved in an organic solvent is used as an adhesive or the like, when reacted in an organic solvent, it is used as it is, or further of the same or other types. It is also possible to prepare a coating agent or the like by adding an organic solvent. When the grafting reaction is carried out without using an organic solvent, an organic solvent is added again to dissolve the graft product to obtain the coating agent of the present invention.
　また、重合体（Ａ１ａ）のグラフト変性物であるグラフト変性オレフィン系重合体（Ａ２ｍ）と、未変性の重合体（Ａ１ａ）とを混合して変性オレフィン系重合体（Ａ２）として用いる場合には、あらかじめ混合しておいてからコーティング剤の調製に用いても良いし、コーティング剤の調製時に溶媒中で混合してもよい。 When the graft modified olefin polymer (A2m), which is a graft modified product of the polymer (A1a), and the unmodified polymer (A1a) are mixed and used as the modified olefin polymer (A2). They may be mixed in advance and used for preparing the coating agent, or may be mixed in a solvent when preparing the coating agent.
　このように反応時、または反応後に加えて、本発明のコーティング剤を調製するための有機溶媒としては、特に限定されないが、たとえば、ベンゼン、トルエン、キシレン等の芳香族炭化水素、ヘキサン、ヘプタン、オクタン、デカン等の脂肪族炭化水素、シクロヘキサン、シクロヘキセン、メチルシクロヘキサン、エチルシクロヘキサン、デカヒドロナフタリン等の脂環式炭化水素、メタノール、エタノール、イソプロピルアルコール、ブタノール、ペンタノール、ヘキサノール、プロパンジオール、フェノール等のアルコール、アセトン、メチルイソブチルケトン、メチルエチルケトン、ペンタノン、ヘキサノン、イソホロン、アセトフェノン等のケトン系溶媒、メチルセルソルブ、エチルセルソルブ等のセルソルブ類、酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル、ギ酸ブチル等のエステル類、トリクロルエチレン、ジクロルエチレン、クロルベンゼン等のハロゲン化炭化水素等を挙げることができる。この中では、芳香族炭化水素、脂肪族炭化水素、ケトン類が好ましい。これらは１種単独でも２種以上組み合わせてもよい。 The organic solvent for preparing the coating agent of the present invention during the reaction or after the reaction is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, hexane, heptane, Aliphatic hydrocarbons such as octane and decane, cycloaliphatic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane, decahydronaphthalene, methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol, etc. Alcohols, acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, isophorone, ketone solvents such as acetophenone, cell solves such as methyl cellosolve, ethyl cellosolve, methyl acetate, Ethyl, butyl acetate, methyl propionate, and butyl formate, mention may be made of trichlorethylene, dichloroethylene, halogenated hydrocarbons such as chlorobenzene. Of these, aromatic hydrocarbons, aliphatic hydrocarbons, and ketones are preferable. These may be used alone or in combination of two or more.
　以上の方法により、変性オレフィン系重合体（Ａ２）を構成するグラフト変性オレフィン系重合体（Ａ２ｍ）が得られるが、本発明では、このようなグラフト変性オレフィン系重合体（Ａ２ｍ）を、１種単独で用いてもよく、あるいは、２種以上を組み合わせて用いてもよい。 By the above method, the graft-modified olefin polymer (A2m) constituting the modified olefin polymer (A2) is obtained. In the present invention, one kind of such graft-modified olefin polymer (A2m) is obtained. They may be used alone or in combination of two or more.
　変性オレフィン系重合体（Ａ２）が、２種以上のグラフト変性オレフィン系重合体（Ａ２ｍ）から構成される場合、好ましくは当該２種以上のグラフト変性オレフィン系重合体（Ａ２ｍ）の合計と、任意で用いられる未変性の重合体（Ａ１ａ）との合計１００重量部に対し、グラフトされた極性基含有単量体が、０．１～１５重量部、好ましくは０．５～１０重量部となるように調製するのが好ましい。 When the modified olefin polymer (A2) is composed of two or more kinds of graft-modified olefin polymers (A2m), preferably the total of the two or more kinds of graft-modified olefin polymers (A2m) and any The grafted polar group-containing monomer is 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight in total with the unmodified polymer (A1a) used in 1. It is preferable to prepare as follows.
　また、本発明の好適な態様において、変性オレフィン系重合体（Ａ２）は、炭素数２～２０のα－オレフィン由来の構成単位の合計を１００モル％としたときに、プロピレン由来の構成単位を５０～１００モル％と、プロピレンを除く炭素数２～２０のα－オレフィン由来の構成単位を５０～０モル％とを含有する重合体である。ここで、「プロピレンを除く炭素数２～２０のα－オレフィン」の好適な例として、１－ブテン、オクテンなどが挙げられる。ここでより好適な態様としては、炭素数２～２０のα－オレフィン由来の構成単位の合計を１００モル％としたときに、プロピレン由来の構成単位の含有量は好ましくは５５～９０モル％、より好ましくは６０～８５モル％、さらに好ましくは６０～８０モル％であり、プロピレンを除く炭素数２～２０のα－オレフィン由来の構成単位の含有量は好ましくは４５～１０モル％、より好ましくは４０～１５モル％、さらに好ましくは４０～２０モル％である。 In a preferred embodiment of the present invention, the modified olefin polymer (A2) has propylene-derived structural units when the total of structural units derived from α-olefins having 2 to 20 carbon atoms is 100 mol%. A polymer containing 50 to 100 mol% and 50 to 0 mol% of a structural unit derived from an α-olefin having 2 to 20 carbon atoms excluding propylene. Here, preferable examples of “α-olefin having 2 to 20 carbon atoms excluding propylene” include 1-butene and octene. As a more preferred embodiment, when the total of structural units derived from α-olefin having 2 to 20 carbon atoms is 100 mol%, the content of the structural units derived from propylene is preferably 55 to 90 mol%, More preferably, it is 60 to 85 mol%, and further preferably 60 to 80 mol%, and the content of the structural unit derived from α-olefin having 2 to 20 carbon atoms excluding propylene is preferably 45 to 10 mol%, more preferably Is 40 to 15 mol%, more preferably 40 to 20 mol%.
　従って、本発明の（Ａ２）炭素数２～２０のα－オレフィン由来の構成単位を含む重合体であって、その一部または全部が極性基含有単量体でグラフト変性されてなる変性オレフィン系重合体には、当該変性オレフィン系重合体１００重量部に対して、極性基含有単量体由来の構成単位を０．１～１５重量部含む変性オレフィン系重合体（Ａ２'）；当該変性オレフィン系重合体が、炭素数２～２０のα－オレフィン由来の構成単位の合計を１００モル％としたときに、プロピレン由来の構成単位を５０～１００モル％と、プロピレンを除く炭素数２～２０のα－オレフィン由来の構成単位を５０～０モル％とを含有する重合体である変性オレフィン系重合体、及び前記グラフト量の要件と構成単位の種類・量の要件との両方を満たす変性オレフィン系重合体（Ａ２''）のいずれも含まれる。 Accordingly, (A2) a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms according to the present invention, wherein a part or all of the polymer is graft-modified with a polar group-containing monomer. The polymer includes a modified olefin polymer (A2 ′) containing 0.1 to 15 parts by weight of a structural unit derived from a polar group-containing monomer with respect to 100 parts by weight of the modified olefin polymer; When the total amount of the structural units derived from α-olefin having 2 to 20 carbon atoms is 100 mol% in the polymer, the structural unit derived from propylene is 50 to 100 mol%, and the number of carbon atoms excluding propylene is 2 to 20 A modified olefin polymer which is a polymer containing 50 to 0 mol% of a structural unit derived from α-olefin, and a modified olefin which satisfies both the requirements for the graft amount and the types and amounts of the structural units. Any of the fin-based polymers (A2 ″) is included.
　・ハロゲン化オレフィン系重合体（Ａ３）
　ハロゲン化オレフィン系重合体（Ａ３）としては、前記した炭素数２～２０のα－オレフィン由来の構成単位を含む重合体の一部または全部がハロゲン化変性されてなるハロゲン化オレフィン系重合体が挙げられる。たとえば、本発明においては、炭素数２～２０のα－オレフィン由来の構成単位を含む重合体（Ａ１ｂ）を、一旦ハロゲン化変性し、これによって得られるハロゲン化変性オレフィン系重合体（Ａ３ｍ）を、ハロゲン化オレフィン系重合体（Ａ３）としてオレフィン重合体（Ａ）に用いることができる。ここで、重合体（Ａ１ｂ）としては、上記重合体（Ａ１）と同様のものが挙げられる。 ・ Halogenated olefin polymer (A3)
As the halogenated olefin polymer (A3), a halogenated olefin polymer obtained by halogenating and modifying a part or all of the polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms is used. Can be mentioned. For example, in the present invention, a polymer (A1b) containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms is once halogenated and the resulting halogenated modified olefin polymer (A3m) is obtained. The olefin polymer (A) can be used as the halogenated olefin polymer (A3). Here, examples of the polymer (A1b) include the same as the polymer (A1).
　重合体（Ａ３）は、好ましくは炭素数２～２０のα－オレフィン由来の構成単位を含む重合体であって、その一部または全部がハロゲン化変性されてなるハロゲン化変性オレフィン重合体であり、当該ハロゲン化変性オレフィン重合体１００重量部に対してハロゲン含有量が２～４０重量部であるハロゲン化変性オレフィン系重合体である。 The polymer (A3) is preferably a halogenated modified olefin polymer comprising a structural unit derived from an α-olefin having 2 to 20 carbon atoms, part or all of which is halogenated. A halogenated modified olefin polymer having a halogen content of 2 to 40 parts by weight per 100 parts by weight of the halogenated modified olefin polymer.
　また重合体（Ａ３）は、炭素数２～２０のα－オレフィン由来の構成単位の合計を１００モル％としたときに、プロピレン由来の構成単位を５０～１００モル％と、プロピレンを除く炭素数２～２０のα－オレフィン由来の構成単位を５０～０モル％とを含有するプロピレン系重合体であることが好ましい。ここで、「プロピレンを除く炭素数２～２０のα－オレフィン」の好適な例として、１－ブテン、オクテンなどが挙げられる。 In addition, the polymer (A3) has 50 to 100 mol% of propylene-derived structural units when the total of the structural units derived from α-olefin having 2 to 20 carbon atoms is 100 mol%, and the number of carbons excluding propylene A propylene polymer containing 2 to 20 α-olefin-derived structural units in an amount of 50 to 0 mol% is preferred. Here, preferable examples of “α-olefin having 2 to 20 carbon atoms excluding propylene” include 1-butene and octene.
　従って、本発明の（Ａ３）炭素数２～２０のα－オレフィン由来の構成単位を含む重合体であって、その一部または全部がハロゲン化変性されてなるハロゲン化変性オレフィン系重合体には、当該ハロゲン化変性オレフィン系重合体１００重量部に対して、ハロゲン含有量が２～４０重量部であるハロゲン化変性オレフィン系重合体（Ａ３'）；当該ハロゲン化変性オレフィン系重合体が、炭素数２～２０のα－オレフィン由来の構成単位の合計を１００モル％としたときに、プロピレン由来の構成単位を５０～１００モル％と、プロピレンを除く炭素数２～２０のα－オレフィン由来の構成単位を５０～０モル％とを含有する重合体である変性オレフィン系重合体、及び前記ハロゲン化変性量の要件と構成単位の種類・量の要件との両方を満たすハロゲン化変性オレフィン系重合体（Ａ３''）のいずれも含まれる。 Therefore, the (A3) polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms according to the present invention, which is partially or entirely halogenated, is a halogenated modified olefin polymer. The halogenated modified olefin polymer (A3 ′) having a halogen content of 2 to 40 parts by weight with respect to 100 parts by weight of the halogenated modified olefin polymer; the halogenated modified olefin polymer is carbon When the total of the structural units derived from α-olefins of 2 to 20 is 100 mol%, the structural units derived from propylene are 50 to 100 mol%, and derived from α-olefins having 2 to 20 carbon atoms excluding propylene. A modified olefin polymer which is a polymer containing 50 to 0 mol% of a structural unit, and both the requirements for the halogenated modification amount and the types and amounts of the structural unit are satisfied. Any halogenated modified olefin polymer (A3 ″) is included.
　また、ハロゲン化オレフィン系重合体（Ａ３）は、上記のような重合体（Ａ１ｂ）のハロゲン化変性物、すなわちハロゲン化変性オレフィン系重合体（Ａ３ｍ）と、未変性の重合体（Ａ１ｂ）とを混合して、ハロゲン化変性オレフィン系重合体組成物の形で用いられるものであってもよい。このような場合、ハロゲン化変性オレフィン系重合体（Ａ３ｍ）を得るためのハロゲン化変性に用いる重合体（Ａ１ｂ）と未変性のまま用いる重合体（Ａ１ｂ）とは同一でも異なっていても良い。そしてこの場合が、炭素数２～２０のα－オレフィン由来の構成単位を含む重合体の一部が極性基含有単量体でハロゲン化変性されてなるものの一例である。 The halogenated olefin polymer (A3) includes a halogenated modified product of the polymer (A1b) as described above, that is, a halogenated modified olefin polymer (A3m) and an unmodified polymer (A1b). And may be used in the form of a halogenated modified olefin polymer composition. In such a case, the polymer (A1b) used for halogenation modification to obtain the halogenated modified olefin polymer (A3m) and the polymer (A1b) used unmodified may be the same or different. This case is an example in which a part of a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms is halogenated and modified with a polar group-containing monomer.
　上記で用いることのできる重合体（Ａ１ｂ）の重量平均分子量は、ハロゲン化オレフィン系重合体（Ａ３）全体として前記重量平均分子量を満たせば特に制限はないが、通常１×１０4～１０００×１０4の範囲であり、好ましくは２×１０4以上１００×１０4以下、より好ましくは３×１０4以上５０×１０4以下である。またＪＩＳ Ｋ ７１２２に従って測定される融解熱量は、ハロゲン化オレフィン系重合体（Ａ３）が前記重量平均分子量を満たせば特に制限はない。ハロゲン化により融解熱量は下がる傾向にあるので、それに応じて用いる重合体（Ａ１ｂ）を選択しうる。 The weight average molecular weight of the polymer (A1b) that can be used in the above is not particularly limited as long as the halogenated olefin polymer (A3) as a whole satisfies the weight average molecular weight, but is usually 1 × 10 4 to 1000 × 10 6. The range is 4 , preferably 2 × 10 4 or more and 100 × 10 4 or less, more preferably 3 × 10 4 or more and 50 × 10 4 or less. The heat of fusion measured according to JIS K 7122 is not particularly limited as long as the halogenated olefin polymer (A3) satisfies the weight average molecular weight. Since the heat of fusion tends to decrease due to halogenation, the polymer (A1b) to be used can be selected accordingly.
　また、ハロゲン化オレフィン系重合体（Ａ３）は、ハロゲン化変性オレフィン系重合体（Ａ３ｍ）と、任意で用いられる未変性の重合体（Ａ１ｂ）との合計１００重量部に対して、ハロゲンを２～４０重量部含むことが好ましい。 The halogenated olefin polymer (A3) contains 2 halogens per 100 parts by weight in total of the halogenated modified olefin polymer (A3m) and the optionally used unmodified polymer (A1b). It is preferable to contain ˜40 parts by weight.
　本発明では、ハロゲン化オレフィン系重合体（Ａ３）を構成するハロゲン化変性オレフィン系重合体（Ａ３ｍ）として、塩素化ポリオレフィンを好適に用いることができる。 In the present invention, a chlorinated polyolefin can be suitably used as the halogenated modified olefin polymer (A3m) constituting the halogenated olefin polymer (A3).
　本発明でハロゲン化変性オレフィン系重合体（Ａ３ｍ）として用いられる塩素化ポリオレフィンは、公知の方法でポリオレフィンを塩素化することによって得られる。ここで、ハロゲン化変性オレフィン系重合体（Ａ３ｍ）として用いられる塩素化ポリオレフィンは、不飽和カルボン酸およびその無水物（例えば、無水マレイン酸）などの極性基含有単量体によって、さらに変性されたものであってもよい。例えば、ハードレンＣＹ－９１２２Ｐ、ハードレンＣＹ－９１２４Ｐ、ハードレンＨＭ－２１Ｐ、ハードレンＭ－２８Ｐ、ハードレンＦ－２Ｐ及びハードレンＦ－６Ｐ（いずれも東洋紡績（株）製、商品名）等の市販品が好適に用いられる。 The chlorinated polyolefin used as the halogenated modified olefin polymer (A3m) in the present invention can be obtained by chlorinating polyolefin by a known method. Here, the chlorinated polyolefin used as the halogenated modified olefin polymer (A3m) was further modified with a polar group-containing monomer such as an unsaturated carboxylic acid and its anhydride (for example, maleic anhydride). It may be a thing. For example, commercially available products such as HARDREN CY-9122P, HARDREN CY-9124P, HARDREN HM-21P, HARDREN M-28P, HARDREN F-2P, HARDREN F-6P (both manufactured by Toyobo Co., Ltd., trade name) are suitable. Used for.
　塩素化ポリオレフィンの塩素含有率は、ハロゲン化変性オレフィン系重合体（Ａ３ｍ）として用いられる塩素化変性オレフィン系重合体と、任意で用いられる未変性の重合体（Ａ１ｂ）との合計を基準として、１０重量％以上４０重量％以下が好ましく、更に好ましくは２０重量％以上３０重量％以下である。上限値以下であると、熱や太陽光、紫外線、雨等の暴露による劣化を抑えることができ、下限値以上であると、十分な密着性が得られるので好ましい。 The chlorine content of the chlorinated polyolefin is based on the total of the chlorinated modified olefin polymer used as the halogenated modified olefin polymer (A3m) and the unmodified polymer (A1b) optionally used. It is preferably 10% by weight or more and 40% by weight or less, and more preferably 20% by weight or more and 30% by weight or less. It is preferable that it is not more than the upper limit value because deterioration due to exposure to heat, sunlight, ultraviolet rays, rain, etc. can be suppressed, and if it is not less than the lower limit value, sufficient adhesion can be obtained.
　本発明では、このようなハロゲン化変性オレフィン系重合体（Ａ３ｍ）を、１種単独で用いてもよく、あるいは、２種以上を組み合わせて用いてもよい。 In the present invention, such a halogenated modified olefin polymer (A3m) may be used singly or in combination of two or more.
　このようなハロゲン化変性オレフィン系重合体（Ａ３ｍ）は、例えば、塩素系溶媒中にポリオレフィンを溶解し、ラジカル触媒の存在下または不存在下で、塩素含有率が１６～３５重量％になるまでは塩素ガスを吹き込むことで得ることができる。 Such a halogenated modified olefin polymer (A3m) is prepared by, for example, dissolving a polyolefin in a chlorinated solvent until the chlorine content reaches 16 to 35% by weight in the presence or absence of a radical catalyst. Can be obtained by blowing chlorine gas.
　ここで、塩素化反応の溶媒として用いられる塩素系溶媒としては、例えば、テトラクロロエチレン、テトラクロロエタン、四塩化炭素、クロロホルム等が挙げられる。 Here, examples of the chlorinated solvent used as a solvent for the chlorination reaction include tetrachloroethylene, tetrachloroethane, carbon tetrachloride, and chloroform.
　上記溶解および塩素化反応を行う温度としては、塩素系溶媒中でポリオレフィンが溶解する温度以上が望ましい。 The temperature at which the above dissolution and chlorination reaction are carried out is preferably at least the temperature at which the polyolefin dissolves in the chlorinated solvent.
　なお、本発明において、オレフィン系重合体（Ａ）としてハロゲン化オレフィン系重合体（Ａ３）を用いてコーティング剤を調製する場合にあっても、ハロゲン化変性を有機溶媒中で行った場合には、そのまま用いることができ、あるいは、同種又は他種の有機溶媒をさらに加えて用いることができ、その際用いうる有機溶媒として、変性オレフィン系重合体（Ａ２）について用いられるものと同様の溶媒が挙げられる。 In the present invention, even when the coating agent is prepared using the halogenated olefin polymer (A3) as the olefin polymer (A), the halogenated modification is performed in an organic solvent. The organic solvent can be used as it is, or can be used by further adding the same or other organic solvent. As the organic solvent that can be used in this case, the same solvents as those used for the modified olefin polymer (A2) can be used. Can be mentioned.
　さらに、本発明においては、オレフィン重合体（Ａ）として、上記重合体（Ａ１）、上記変性オレフィン系重合体（Ａ２）、および上記ハロゲン化オレフィン系重合体（Ａ３）のうちの２種以上をさらに組み合わせて用いてもよい。 Further, in the present invention, as the olefin polymer (A), two or more of the polymer (A1), the modified olefin polymer (A2), and the halogenated olefin polymer (A3) are used. Further, they may be used in combination.
　本発明で用いられるオレフィン重合体（Ａ）は、上記重合体（Ａ１）と上記変性オレフィン系重合体（Ａ２）と上記ハロゲン化オレフィン系重合体（Ａ３）とのうち、上記変性オレフィン系重合体（Ａ２）と上記ハロゲン化オレフィン系重合体（Ａ３）から選ばれることが好ましく、上記変性オレフィン系重合体（Ａ２）から選ばれることが更に好ましい。このとき、上記変性オレフィン系重合体（Ａ２）には必要に応じ、グラフト変性されなかった未反応の上記重合体（Ａ１ａ）が含まれていてもいい。 The olefin polymer (A) used in the present invention is the modified olefin polymer of the polymer (A1), the modified olefin polymer (A2), and the halogenated olefin polymer (A3). It is preferably selected from (A2) and the halogenated olefin polymer (A3), and more preferably selected from the modified olefin polymer (A2). At this time, the modified olefin polymer (A2) may contain the unreacted polymer (A1a) that has not been graft-modified as required.
　なお、本発明で用いられるオレフィン重合体（Ａ）は、４０℃で測定した動粘度が５０００００ｍｍ2/ｓを超えることが好ましい。ここで、動粘度が５０００００ｍｍ2/ｓを超える、とは流動性が低く動粘度が測定できないような場合を含む概念である。 The olefin polymer (A) used in the present invention preferably has a kinematic viscosity measured at 40 ° C. exceeding 500,000 mm 2 / s. Here, the kinematic viscosity exceeding 500,000 mm 2 / s is a concept including the case where the fluidity is low and the kinematic viscosity cannot be measured.
　＜半固体状炭化水素（Ｂ）＞
　本発明のコーティング剤は、２００℃動粘度が１，０００～１００，０００ｍｍ2/ｓの半固体状炭化水素（Ｂ）を含有する。これにより、半固体状炭化水素を含有しないコーティング剤と比べて、加飾対象とする基材への密着性が向上するとともに、より多くの種類の基材への加飾が可能となるという効果が得られるのである。また、半固体状炭化水素（Ｂ）は、特許文献１で用いられている４０℃動粘度が３０～５００，０００ｍｍ2/ｓの炭化水素系合成油を用いた場合と比較して、低結晶性オレフィン重合体（Ａ）の結晶化をより阻害することから、塗工乾燥直後のタック性が向上し、優れた低温施工性、上塗り適性および粘着性が得られるという効果も奏する。加えて、分子量がより大きくなったことから、塗膜の強度が上がり、接着強度が更に向上するという効果も奏する。 <Semi-solid hydrocarbon (B)>
The coating agent of the present invention contains a semi-solid hydrocarbon (B) having a kinematic viscosity at 200 ° C. of 1,000 to 100,000 mm 2 / s. As a result, compared to a coating agent that does not contain a semi-solid hydrocarbon, the adhesion to a base material to be decorated is improved, and more types of base materials can be decorated. Is obtained. Further, the semi-solid hydrocarbon (B) has a low crystallinity compared to the case where the hydrocarbon synthetic oil having a kinematic viscosity at 40 ° C. of 30 to 500,000 mm 2 / s used in Patent Document 1 is used. Since the olefin polymer (A) is further inhibited from crystallization, tackiness immediately after coating and drying is improved, and excellent low-temperature workability, top coatability and adhesiveness can be obtained. In addition, since the molecular weight is increased, the strength of the coating film is increased, and the adhesive strength is further improved.
　半固体状炭化水素（Ｂ）としては、上記動粘度を満たす限り特に限定されないものの、炭素数２～２０のオレフィンの重合体が好適に挙げられる。その中でも、炭素数２～２０のオレフィンを単独重合させて得られるポリマー、または、２種以上のこれらのオレフィンの任意の混合物を共重合させて得られるポリマーが好ましく用いられる。上記炭素数２～２０のオレフィンとしては、例えば、エチレン、プロピレン、１－ブテン、イソブテン、１－オクテン、１－デセン、および１－ドデセンなどが好ましく用いられる。半固体状炭化水素（Ｂ）の具体例としては、エチレン-プロピレン共重合体、イソブテン-１－ブテン共重合体、ポリイソブテンなどが挙げられる。 The semi-solid hydrocarbon (B) is not particularly limited as long as the kinematic viscosity is satisfied, but an olefin polymer having 2 to 20 carbon atoms is preferably exemplified. Among them, a polymer obtained by homopolymerizing an olefin having 2 to 20 carbon atoms or a polymer obtained by copolymerizing any mixture of two or more of these olefins is preferably used. Preferred examples of the olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, isobutene, 1-octene, 1-decene, and 1-dodecene. Specific examples of the semisolid hydrocarbon (B) include ethylene-propylene copolymer, isobutene-1-butene copolymer, polyisobutene and the like.
　本発明では、半固体状炭化水素（Ｂ）として、半固体状ポリイソブテンを用いることが好ましい。これらは、市場から容易に入手できる。例えば、ＪＸ日鉱日石エネルギー（株）製のテトラックス、ハイモール、巴工業（株）製のポリイソブチレン等が挙げられる。 In the present invention, it is preferable to use semi-solid polyisobutene as the semi-solid hydrocarbon (B). These are readily available from the market. Examples thereof include Tetrax and Highmall manufactured by JX Nippon Oil & Energy Corporation, and polyisobutylene manufactured by Sakai Kogyo Co., Ltd.
　上述したこれらの半固体状炭化水素（Ｂ）は、１種単独で、あるいは２種以上を組み合わせて用いることができる。 These semi-solid hydrocarbons (B) described above can be used singly or in combination of two or more.
　本発明に用いられる半固体状炭化水素（Ｂ）は２００℃動粘度が１，０００ｍｍ2/ｓ以上１００，０００ｍｍ2/ｓ以下であり、好ましくは１，１００ｍｍ2/ｓ以上８０，０００ｍｍ2/ｓ以下、更に好ましくは１，２００ｍｍ2/ｓ以上６０，０００ｍｍ2/ｓ以下である。半固体状炭化水素（Ｂ）における上記動粘度の下限が大きい値であると、施工時の密着性により優れる傾向にある。 Semi-solid hydrocarbons (B) used in the present invention has a 200 ° C. kinematic viscosity is less 1,000mm 2 / s or more 100,000 mm 2 / s, preferably 1,100mm 2 / s or more 80,000 2 / s, and still more preferably not more than 1,200mm 2 / s or more 60,000 2 / s. When the lower limit of the kinematic viscosity in the semi-solid hydrocarbon (B) is a large value, the adhesiveness during construction tends to be superior.
　本発明のコーティング剤における半固体状炭化水素（Ｂ）の含有量は、オレフィン重合体（Ａ）と半固体状炭化水素（Ｂ）との合計１００重量部に対し、好ましくは１～９０重量部、より好ましくは１０～８５重量部である。すなわち、オレフィン重合体（Ａ）の含有量は、好ましくは１０～９９重量部、より好ましくは１５～９０重量部である。半固体状炭化水素（Ｂ）の含有量が上記範囲内であると、密着性に優れ、且つ、経時安定性にも優れる傾向にあり有利である。 The content of the semisolid hydrocarbon (B) in the coating agent of the present invention is preferably 1 to 90 parts by weight with respect to a total of 100 parts by weight of the olefin polymer (A) and the semisolid hydrocarbon (B). More preferably, it is 10 to 85 parts by weight. That is, the content of the olefin polymer (A) is preferably 10 to 99 parts by weight, more preferably 15 to 90 parts by weight. When the content of the semi-solid hydrocarbon (B) is within the above range, it is advantageous because it tends to have excellent adhesion and excellent temporal stability.
　金属と樹脂とのラミネート、例えばアルミニウム箔とポリプロピレンフィルムとの接着強度を向上するためには、オレフィン重合体（Ａ）と半固体状炭化水素（Ｂ）との合計１００重量部に対し、半固体状炭化水素（Ｂ）の含有量は１０～６０重量部が好ましく、２０～５０重量部であると、より好ましい。すなわちオレフィン重合体（Ａ）の含有量は４０～９０重量部が好ましく、５０～８０重量部がより好ましい。 In order to improve the adhesive strength between a metal and resin laminate, for example, an aluminum foil and a polypropylene film, a semi-solid with respect to a total of 100 parts by weight of the olefin polymer (A) and the semi-solid hydrocarbon (B). The content of the gaseous hydrocarbon (B) is preferably 10 to 60 parts by weight, and more preferably 20 to 50 parts by weight. That is, the content of the olefin polymer (A) is preferably 40 to 90 parts by weight, and more preferably 50 to 80 parts by weight.
　上塗り適性、例えばスプレー塗装した際に均一なプライマー層ないし上塗り層が得られるという観点からは、オレフィン重合体（Ａ）と半固体状炭化水素（Ｂ）との合計１００重量部に対し、半固体状炭化水素（Ｂ）の含有量は２０～８０重量部が好ましく、３５～６５重量部であるとより好ましい。すなわちオレフィン重合体（Ａ）の含有量は２０～８０重量部が好ましく、３５～６５重量部がより好ましい。 From the viewpoint that a uniform primer layer or topcoat layer can be obtained when top coatability is applied, for example, by spray coating, it is semisolid with respect to a total of 100 parts by weight of the olefin polymer (A) and the semisolid hydrocarbon (B). The content of the gaseous hydrocarbon (B) is preferably 20 to 80 parts by weight, and more preferably 35 to 65 parts by weight. That is, the content of the olefin polymer (A) is preferably 20 to 80 parts by weight, and more preferably 35 to 65 parts by weight.
　ディスプレイ用粘着テープや粘着シートのように非加熱で感圧接着剤として用いる場合、被着体との接着強度を向上するためには、オレフィン重合体（Ａ）と半固体状炭化水素（Ｂ）との合計１００重量部に対し、半固体状炭化水素（Ｂ）の含有量は５０～９０重量部が好ましく、７０～８５重量部であると、より好ましい。すなわちオレフィン重合体（Ａ）の含有量は１０～５０重量部が好ましく、１５～３０重量部がより好ましい。 When used as a pressure-sensitive adhesive without heating, such as a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet, an olefin polymer (A) and a semi-solid hydrocarbon (B) are used to improve the adhesive strength with the adherend. The content of the semi-solid hydrocarbon (B) is preferably 50 to 90 parts by weight, more preferably 70 to 85 parts by weight with respect to 100 parts by weight in total. That is, the content of the olefin polymer (A) is preferably 10 to 50 parts by weight, and more preferably 15 to 30 parts by weight.
　また、本発明に用いられる半固体状炭化水素（Ｂ）は、種々ビニル化合物のグラフト等で変性することができる。上記ビニル化合物としてはスチレン、α－メチルスチレン等のスチレン類、アクリル酸メチル、アクリル酸ブチル、アクリル酸オクチル等のアクリル酸エステル類；メタアクリル酸メチル、メタアクリル酸ブチル等のメタアクリル酸エステル類；アクリル酸、メタアクリル酸、ケイヒ酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、マレイン酸モノエチル等のカルボキシル基含有ビニル化合物；フマル酸ジメチル、フマル酸ジブチル等の不飽和二塩基酸のジエステル類；アクリル酸グリシジル、アクリル酸－β－メチルグリシジル、メタアクリル酸グリシジル、およびメタアクリル酸－β－メチルグリシジル等のグリシジル基含有ビニル化合物；ヒドロキシエチルアクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチルアクリレート、ラクトン変性ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピルアクリレート等の水酸基含有ビニル化合物；アクリロニトリル、メタアクリロニトリル、ケイヒ酸等の不飽和カルボン酸類；アクリルアミド、メタアクリルアミド、Ｎ置換アクリルアミド、Ｎ置換メタアクリルアミド、アクリルアミドプロパンスルフォン酸等が挙げられる。上記ビニル化合物は、１種単独で用いてもよく、あるいは、２種以上を組み合わせて用いてもよい。 The semi-solid hydrocarbon (B) used in the present invention can be modified by grafting various vinyl compounds. Examples of the vinyl compound include styrenes such as styrene and α-methylstyrene, acrylic acid esters such as methyl acrylate, butyl acrylate, and octyl acrylate; methacrylic acid esters such as methyl methacrylate and butyl methacrylate. Carboxyl group-containing vinyl compounds such as acrylic acid, methacrylic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and monoethyl maleate; unsaturated dibasic acids such as dimethyl fumarate and dibutyl fumarate Diesters; glycidyl group-containing vinyl compounds such as glycidyl acrylate, acrylate-β-methylglycidyl acrylate, glycidyl methacrylate, and methacrylate-β-methylglycidyl; hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hi Hydroxyl-containing vinyl compounds such as loxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate; unsaturated carboxylic acids such as acrylonitrile, methacrylonitrile, and cinnamic acid Acids: Examples include acrylamide, methacrylamide, N-substituted acrylamide, N-substituted methacrylamide, and acrylamide propane sulfonic acid. The said vinyl compound may be used individually by 1 type, or may be used in combination of 2 or more type.
　オレフィン重合体（Ａ）と半固体状炭化水素（Ｂ）との相溶性が良いものであれば、オレフィン重合体（Ａ）の結晶化速度を低下させる働きをして、その分、被着体界面に対する密着性が良くなるのではないかとも考えられる。その結果、オレフィン重合体（Ａ）が本来有する、オレフィン樹脂や極性基含有樹脂や金属との接着性が発現するようになるのではないかとも考えている。 If the compatibility between the olefin polymer (A) and the semi-solid hydrocarbon (B) is good, the olefin polymer (A) serves to reduce the crystallization rate of the olefin polymer (A). It is thought that the adhesion to the interface may be improved. As a result, it is considered that the olefin polymer (A) originally has the adhesiveness with the olefin resin, polar group-containing resin and metal.
　特にオレフィン重合体（Ａ）が変性オレフィン系重合体（Ａ２）及び／またはハロゲン化オレフィン系重合体（Ａ３）である場合は、半固体状炭化水素（Ｂ）が存在すると、基材との接着強度が高くなる。この理由は定かではないが、一つには半固体状炭化水素（Ｂ）が存在することで、オレフィン重合体（Ａ）のうち極性基やハロゲン原子を有する分子が動き易くなり、例えば基材が、ヘテロ原子などを含有するものである、あるいは金属であるなどの場合であれば、当該基材と接する部分に極性基やハロゲン原子が偏在化しやすくなり、高い接着強度に繋がるのではないかと考えることも可能である。 In particular, when the olefin polymer (A) is a modified olefin polymer (A2) and / or a halogenated olefin polymer (A3), if the semi-solid hydrocarbon (B) is present, adhesion to the substrate Strength increases. The reason for this is not clear, but the presence of the semi-solid hydrocarbon (B) in one part facilitates the movement of molecules having polar groups and halogen atoms in the olefin polymer (A). However, if it contains heteroatoms, or is a metal, polar groups and halogen atoms are likely to be unevenly distributed in the portion in contact with the substrate, leading to high adhesive strength. It is also possible to think.
　また、半固体状炭化水素（Ｂ）の動粘度が高いと接着強度が高い傾向にある。この理由は定かではないが、一つには半固体状炭化水素（Ｂ）として動粘度がより高いものを使うことで、半固体状炭化水素（Ｂ）が乾燥塗膜からブリードアウトすることが抑制されているのではないかと考えられる。この場合、ブリードアウトにより半固体状炭化水素（Ｂ）の添加効果（可塑性を付与し極性基やハロゲン原子を有する分子が動き易くなる）が失われるということがより少なくなり、またオレフィン重合体（Ａ）の表面に半固体状炭化水素（Ｂ）のみより構成される層が形成して接着力を低めるということがより少なくなっているのではないか、と考えられる。このように半固体状炭化水素（Ｂ）の動粘度が高いことで、ブリードアウトによる悪影響をより低減するという絶妙のバランスとなっているのではないかと推定している。 Also, when the kinematic viscosity of the semi-solid hydrocarbon (B) is high, the adhesive strength tends to be high. The reason for this is not clear, but in one case, semi-solid hydrocarbon (B) may bleed out from the dried coating by using a semi-solid hydrocarbon (B) having a higher kinematic viscosity. It may be suppressed. In this case, the effect of adding the semisolid hydrocarbon (B) due to bleed-out (plasticity is imparted and molecules having polar groups and halogen atoms are easy to move) is less lost, and the olefin polymer ( It is thought that it is less likely that a layer composed only of the semi-solid hydrocarbon (B) is formed on the surface of A) to lower the adhesive force. It is presumed that the semi-solid hydrocarbon (B) has a high kinematic viscosity and thus has an exquisite balance of reducing the adverse effects caused by bleed-out.
　さらに、半固体状炭化水素（Ｂ）がブリードアウトしにくいのではないかという考察からは、コーティング剤より成る塗膜と被着体との接着強度が長期間安定でいられる、あるいはコーティング剤を膜にした直後に接着に使用せず、ある程度の時間経過してから接着に使用する場合にも、高い接着強度を発現することが推測される。 Furthermore, from the consideration that the semi-solid hydrocarbon (B) is difficult to bleed out, the adhesive strength between the coating film made of the coating agent and the adherend can be stable for a long period of time. Even when the film is not used for bonding immediately after being formed into a film and is used for bonding after a certain period of time, it is estimated that high adhesive strength is expressed.
　＜粘着付与剤（Ｃ）＞
　本発明のコーティング剤は、上記オレフィン重合体（Ａ）および上記半固体状炭化水素（Ｂ）に加えて、粘着付与剤（Ｃ）を含有してもよい。これにより、粘着付与剤を含有しないコーティング剤と比べて、加飾対象とする基材への密着性が向上するとともに、より多くの種類の基材への加飾が可能となるという効果が得られるのである。 <Tackifier (C)>
The coating agent of the present invention may contain a tackifier (C) in addition to the olefin polymer (A) and the semisolid hydrocarbon (B). As a result, compared to a coating agent that does not contain a tackifier, the adhesiveness to the base material to be decorated is improved, and the effect that more types of base material can be decorated is obtained. It is done.
　ここで、本発明で用いられる粘着付与剤（Ｃ）が有する、ＪＩＳ　Ｋ　００７０に従って求まる酸価は、１０以上であり、好ましくは１０～４０である。粘着付与剤（Ｃ）の酸価がこのような範囲であると、コーティング剤を塗膜としたときに、被着体との親和力が向上し、充分な密着性が得られる点で有利である。なお、この酸価は、実際には、試料１ｇ中に含有する酸などを中和するのに必要とする水酸化カリウムのｍｇ数で表される値である。 Here, the acid value determined according to JIS K 0070 of the tackifier (C) used in the present invention is 10 or more, and preferably 10 to 40. When the acid value of the tackifier (C) is in such a range, when the coating agent is used as a coating film, the affinity with the adherend is improved, and it is advantageous in that sufficient adhesion can be obtained. . The acid value is actually a value expressed in mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample.
　また、本発明で用いられる粘着付与剤（Ｃ）が有する、ＧＰＣ法により測定した重量平均分子量（Ｍｗ）は０．９×１０3～３×１０3であるところ、下限値は、好ましくは１×１０3である。したがって、本発明の好適な態様の一つでは、粘着付与剤（Ｃ）の重量平均分子量は１×１０3～３×１０3である。粘着付与剤（Ｃ）の重量平均分子量がこのような範囲であると、コーティング剤を塗膜としたときに、オレフィン重合体（Ａ）および半固体状炭化水素（Ｂ）との良好な相溶性が担保され、経時安定性が良好且つ充分な密着性が得られる点で有利である。 In addition, the tackifier (C) used in the present invention has a weight average molecular weight (Mw) measured by GPC method of 0.9 × 10 3 to 3 × 10 3 , and the lower limit is preferably 1 × 10 3 Accordingly, in one preferred embodiment of the present invention, the tackifier (C) has a weight average molecular weight of 1 × 10 3 to 3 × 10 3 . When the weight average molecular weight of the tackifier (C) is in such a range, good compatibility with the olefin polymer (A) and the semisolid hydrocarbon (B) when the coating agent is used as a coating film. This is advantageous in that it is ensured, stability over time is good, and sufficient adhesion is obtained.
　このような粘着付与剤（Ｃ）としては、上記のような酸価及び重量平均分子量を有する限り特に限定されない。ただ、粘着付与剤（Ｃ）を構成しうる成分のタイプとして、テルペン樹脂；テルペンフェノール共重合体樹脂、芳香族変性テルペン樹脂などの変性テルペン樹脂；並びに、ロジンエステル、変性ロジン樹脂などのロジン樹脂等が挙げられ、その中でもロジンエステル及びその誘導体が好適に挙げられる。ここで、ロジンエステルの誘導体として、重合ロジンエステル、水素化ロジンエステル、ロジン変性マレイン酸樹脂、特殊ロジンエステル、ロジン変性特殊合成樹脂などが挙げられる。本発明では、これらのうち、上記のような酸価及び重量平均分子量を有するものを粘着付与剤（Ｃ）として採用することができ、その具体例として、ハリタック４８２１，ハリタックＰＣＪ，ハリタックＦＫ１２５（いずれもハリマ化成株式会社製）、ペンセル（登録商標）Ｃ，ペンセル（登録商標）Ｄ－１２５，スーパーエステルＡ－１２５（いずれも荒川化学工業株式会社製）などが挙げられる。また、スーパーエステルＷ－１２５およびパインクリスタル（登録商標）ＫＥ－３５９（荒川化学工業株式会社製）、並びに、Ｓｙｌｖａｌｉｔｅ　ＲＥ１００ＬおよびＳｙｌｖａｌｉｔｅ　ＲＥ１０５Ｌ（いずれもＡｒｉｚｏｎａ　Ｃｈｅｍｉｃａｌ社製）もまた、具体例として挙げることができる。 Such a tackifier (C) is not particularly limited as long as it has an acid value and a weight average molecular weight as described above. However, as the types of components that can constitute the tackifier (C), terpene resins; modified terpene resins such as terpene phenol copolymer resins and aromatic modified terpene resins; and rosin resins such as rosin esters and modified rosin resins Among them, rosin esters and derivatives thereof are preferable. Here, examples of rosin ester derivatives include polymerized rosin ester, hydrogenated rosin ester, rosin-modified maleic resin, special rosin ester, and rosin-modified special synthetic resin. In the present invention, those having the acid value and weight average molecular weight as described above can be employed as the tackifier (C), and specific examples thereof include Halitac 4821, Haritac PCJ, Haritac FK125 (any As well as Pencel (registered trademark) C, Pencel (registered trademark) D-125, and Superester A-125 (all manufactured by Arakawa Chemical Industries, Ltd.). In addition, Superester W-125 and Pine Crystal (registered trademark) KE-359 (Arakawa Chemical Industries, Ltd.), and Sylvalite RE100L and Sylvalite RE105L (both manufactured by Arizona Chemical) may also be mentioned as specific examples. it can.
　本発明のコーティング剤における粘着付与剤（Ｃ）の含有割合は、オレフィン重合体（Ａ）と半固体状炭化水素（Ｂ）と粘着付与剤（Ｃ）との合計１００重量％に対し、好ましくは５～４０重量％である。粘着付与剤（Ｃ）の含有量が上記範囲内であると、充分な密着性が確保できる傾向にあり有利である。 The content ratio of the tackifier (C) in the coating agent of the present invention is preferably based on 100% by weight of the total of the olefin polymer (A), the semisolid hydrocarbon (B) and the tackifier (C). 5 to 40% by weight. When the content of the tackifier (C) is within the above range, there is a tendency that sufficient adhesion can be secured, which is advantageous.
　すなわち、本発明のコーティング剤において、オレフィン重合体（Ａ）と半固体状炭化水素（Ｂ）と粘着付与剤（Ｃ）との合計１００重量％とすると、オレフィン重合体（Ａ）の割合は１０～８８重量％であり、半固体状炭化水素（Ｂ）の割合は８５～１重量％であり、粘着付与剤（Ｃ）の割合は４０～５重量％である。 That is, in the coating agent of the present invention, when the total of the olefin polymer (A), the semisolid hydrocarbon (B), and the tackifier (C) is 100% by weight, the ratio of the olefin polymer (A) is 10%. The proportion of the semi-solid hydrocarbon (B) is 85 to 1% by weight, and the proportion of the tackifier (C) is 40 to 5% by weight.
　なお、本発明では、粘着付与剤（Ｃ）に該当するための要件を満たすと同時に、上記半固体状炭化水素（Ｂ）に該当するための要件をも満たす成分については、その成分を、粘着付与剤（Ｃ）ではなく、半固体状炭化水素（Ｂ）に該当するものとして取り扱う。 In the present invention, for a component that satisfies the requirements for corresponding to the tackifier (C) and also satisfies the requirements for corresponding to the semi-solid hydrocarbon (B), the component is adhesive. Treat as a semi-solid hydrocarbon (B), not an imparting agent (C).
　＜硬化剤（Ｄ）＞
　本発明のコーティング剤は、上記オレフィン重合体（Ａ）および上記半固体状炭化水素（Ｂ）に加えて、必要に応じて硬化剤（Ｄ）を含んでいてもよい。本発明のコーティング剤が硬化剤（Ｄ）を含むことで、塗膜強度が向上し、密着性、耐熱性、耐薬品性により優れるという利点がある。 <Curing agent (D)>
The coating agent of the present invention may contain a curing agent (D) as necessary in addition to the olefin polymer (A) and the semisolid hydrocarbon (B). When the coating agent of this invention contains a hardening | curing agent (D), there exists an advantage that coating-film intensity | strength improves and it is excellent by adhesiveness, heat resistance, and chemical resistance.
　硬化剤（Ｄ）としては、特に限定されないが、たとえば、ポリイソシアネート単量体、ポリイソシアネート変性体を挙げることができる。 Although it does not specifically limit as a hardening | curing agent (D), For example, a polyisocyanate monomer and a polyisocyanate modified body can be mentioned.
　このうち、ポリイソシアネート単量体は、一分子中に複数のイソシアネート基を有する単量体化合物であり、そのようなポリイソシアネート単量体としては、例えば、芳香族ポリイソシアネート、芳香脂肪族ポリイソシアネート、脂肪族ポリイソシアネートなどが挙げられる。 Among these, the polyisocyanate monomer is a monomer compound having a plurality of isocyanate groups in one molecule. Examples of such a polyisocyanate monomer include aromatic polyisocyanates and araliphatic polyisocyanates. And aliphatic polyisocyanates.
　ここで、芳香族ポリイソシアネートとしては、例えば、トリレンジイソシアネート（２，４－または２，６－トリレンジイソシアネートもしくはその混合物）（ＴＤＩ）、フェニレンジイソシアネート（ｍ－、ｐ－フェニレンジイソシアネートもしくはその混合物）、４，４'－ジフェニルジイソシアネート、１，５－ナフタレンジイソシアネート（ＮＤＩ）、ジフェニルメタンジイソシネート（４，４'－、２，４'－または２，２'－ジフェニルメタンジイソシネートもしくはその混合物）（ＭＤＩ）、４，４'－トルイジンジイソシアネート（ＴＯＤＩ）、４，４'－ジフェニルエーテルジイソシアネートなどの芳香族ジイソシアネートなどが挙げられる。 Examples of the aromatic polyisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof). 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate or mixtures thereof) ( MDI), 4,4′-toluidine diisocyanate (TODI), aromatic diisocyanates such as 4,4′-diphenyl ether diisocyanate, and the like.
　芳香脂肪族ポリイソシアネートとしては、例えば、キシリレンジイソシアネート（１，３－または１，４－キシリレンジイソシアネートもしくはその混合物）（ＸＤＩ）、テトラメチルキシリレンジイソシアネート（１，３－または１，４－テトラメチルキシリレンジイソシアネートもしくはその混合物）（ＴＭＸＤＩ）、ω，ω'－ジイソシアネート－１，４－ジエチルベンゼンなどの芳香脂肪族ジイソシアネートなどが挙げられる。 Examples of the araliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra Methyl xylylene diisocyanate or a mixture thereof (TMXDI), and aromatic aliphatic diisocyanates such as ω, ω′-diisocyanate-1,4-diethylbenzene.
　脂肪族ポリイソシアネートとしては、例えば、トリメチレンジイソシアネート、１，２－プロピレンジイソシアネート、ブチレンジイソシアネート（テトラメチレンジイソシアネート、１，２－ブチレンジイソシアネート、２，３－ブチレンジイソシアネート、１，３－ブチレンジイソシアネート）、１，５－ペンタメチレンジイソシアネート（ＰＤＩ）、１，６－ヘキサメチレンジイソシアネート（ＨＤＩ）、２，４，４－または２，２，４－トリメチルヘキサメチレンジイソシアネート、２，６－ジイソシアネートメチルカプエートなどの脂肪族ジイソシアネートなどが挙げられる。 Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1 , 5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capate, etc. Group diisocyanate and the like.
　また、脂肪族ポリイソシアネートには、脂環族ポリイソシアネートが含まれる。脂環族ポリイソシアネートとしては、例えば、１，３－シクロペンタンジイソシアネート、１，３－シクロペンテンジイソシアネート、シクロヘキサンジイソシアネート（１，４－シクロヘキサンジイソシアネート、１，３－シクロヘキサンジイソシアネート）、３－イソシアナトメチル－３，５，５－トリメチルシクロヘキシルイソシアネート（イソホロジイソシアネート）（ＩＰＤＩ）、メチレンビス（シクロヘキシルイソシアネート）（４，４'－、２，４'－もしくは２，２'－メチレンビス（シクロヘキシルイソシアネート）、これらのＴｒａｎｓ，Ｔｒａｎｓ－体、Ｔｒａｎｓ，Ｃｉｓ－体もしくはＣｉｓ，Ｃｉｓ－体、あるいは、これらの混合物）（Ｈ12ＭＤＩ）、メチルシクロヘキサンジイソシアネート（メチル－２，４－シクロヘキサンジイソシアネート、メチル－２，６－シクロヘキサンジイソシアネート）、ノルボルナンジイソシアネート（各種異性体もしくはその混合物）（ＮＢＤＩ）、ビス（イソシアナトメチル）シクロヘキサン（１，３－もしくは１，４－ビス（イソシアナトメチル）シクロヘキサン、またはこれらの混合物）（Ｈ6ＸＤＩ）などの脂環族ジイソシアネートが挙げられる。 Aliphatic polyisocyanates include alicyclic polyisocyanates. Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexylisocyanate (isophorodiisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis (cyclohexylisocyanate), these Trans, Trans-form, Trans, Cis-form or Cis, Cis-form, or a mixture thereof (H 12 MDI), methylcyclohexane diisocyanate (methyl-2,4-cycl) Rhohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) And cycloaliphatic diisocyanates such as cyclohexane, or mixtures thereof) (H 6 XDI).
　これらポリイソシアネート単量体は、単独使用または２種類以上併用することができる。 These polyisocyanate monomers can be used alone or in combination of two or more.
　一方、ポリイソシアネート変性体としては、上記したポリイソシアネート単量体同士が反応してなる変性体、および、上記したポリイソシアネート単量体と他の化合物とが反応してなる変性体が挙げられ、通常、平均官能基数が２を超過するものを用いることができる。ここで、「他の化合物」とは、上記したポリイソシアネート単量体以外の、上記したポリイソシアネート単量体と反応可能な化合物をいい、その例として、１価のアルコール（以下「モノオール」）、多価のアルコール（以下「ポリオール」）、アミンおよび水など活性水素を有する化合物、並びに、二酸化炭素が挙げられる。 On the other hand, examples of the polyisocyanate-modified product include a modified product obtained by reacting the above-described polyisocyanate monomers, and a modified product obtained by reacting the above-described polyisocyanate monomer and another compound. Usually, those having an average functional group number exceeding 2 can be used. Here, the “other compound” refers to a compound capable of reacting with the above-described polyisocyanate monomer other than the above-described polyisocyanate monomer. As an example, a monovalent alcohol (hereinafter referred to as “monool”). ), Polyhydric alcohols (hereinafter “polyols”), compounds having active hydrogen such as amines and water, and carbon dioxide.
　ここで、本発明で用いうるモノオールとしては、例えば、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、ノナノール、デカノール、ウンデシルアルコール、ドデシルアルコール（ラウリルアルコール）、トリデシルアルコール、テトラデシルアルール（ミリスチルアルコール）、ペンタデシルアルコール、ヘキサデシルアルコール（セチルアルコール）、ヘプタデシルアルコール、オクタデシルアルコール（ステアリルアルコール、オクタデカノール）、ノナデシルアルコール、およびそれらの異性体（２－メチル－１－プロパノール（ｉｓｏ－ブタノール）を含む）、さらには、その他のアルカノール（Ｃ２０～５０アルコール）や、例えば、オレイルアルコールなどのアルケニルアルコール、例えば、オクタジエノールなどのアルカジエノール、例えば、ポリエチレンブチレンモノオールなどの脂肪族モノオールが挙げられる。また、モノオールとして、例えば、シクロヘキサノール、メチルシクロヘキサノールなどの脂環族モノオール、例えば、ベンジルアルコールなどの芳香脂肪族モノオールなども挙げられる。 Examples of monools that can be used in the present invention include butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol, tetradecyl alcohol (myristyl). Alcohol), pentadecyl alcohol, hexadecyl alcohol (cetyl alcohol), heptadecyl alcohol, octadecyl alcohol (stearyl alcohol, octadecanol), nonadecyl alcohol, and isomers thereof (2-methyl-1-propanol (iso-)) Butanol), other alkanols (C20-50 alcohol), and alkenyl alcohols such as oleyl alcohol, for example Arca dienol such dienol, for example, aliphatic monool such as polyethylene butylene mono-ol. Examples of monools include alicyclic monools such as cyclohexanol and methylcyclohexanol, and aromatic monomonos such as benzyl alcohol.
　また、本発明で用いうるポリオールとしては、ウレタン樹脂の分野で一般的に用いられている水酸基を２つ以上有する化合物が挙げられ、単量体の形態を有していてもよく、あるいは、重合体の形態を有していてもよい。 In addition, examples of the polyol that can be used in the present invention include compounds having two or more hydroxyl groups that are generally used in the field of urethane resins. It may have a combined form.
　このうち、単量体の形態を有するポリオールの例として、
　エチレングリコール、プロピレングリコールなどのアルキレングリコール、シクロヘキサンジオール、シクロヘキサンジメタノール、および、ベンゼンジメタノールなどの２価アルコール；
　グリセリン、トリメチロールメタン、トリメチロールエタン、および、トリメチロールプロパンなどの３価アルコール；並びに、
　ペンタエリスリトール、ジペンタエリスリトールなど、４つ以上の水酸基を有するアルコール
が挙げられる。なお、本明細書において、このような単量体の形態を有するポリオールは、「低分子量ポリオール」とも呼ばれることがある。 Among these, as an example of a polyol having a monomer form,
Alkylene glycols such as ethylene glycol and propylene glycol, dihydric alcohols such as cyclohexanediol, cyclohexanedimethanol, and benzenedimethanol;
Trihydric alcohols such as glycerin, trimethylol methane, trimethylol ethane, and trimethylol propane; and
Examples thereof include alcohols having four or more hydroxyl groups, such as pentaerythritol and dipentaerythritol. In the present specification, a polyol having such a monomer form may be referred to as a “low molecular weight polyol”.
　一方、重合体の形態を有するポリオールとして、ポリエステルポリオール、ポリエーテルポリオールなど、ウレタン樹脂の分野で一般的に用いられているポリマーポリオールが挙げられる。 On the other hand, examples of the polyol having a polymer form include polymer polyols generally used in the field of urethane resins, such as polyester polyols and polyether polyols.
　このようなポリイソシアネート変性体の具体例として、上記したポリイソシアネート単量体の多量体、アロファネート変性体、ポリオール変性体、ビウレット変性体、ウレア変性体、オキサジアジントリオン変性体、カルボジイミド変性体、ウレトジオン変性体およびウレトンイミン変性体などが挙げられる。 Specific examples of such polyisocyanate-modified products include multimers of the above-mentioned polyisocyanate monomers, allophanate-modified products, polyol-modified products, biuret-modified products, urea-modified products, oxadiazinetrione-modified products, carbodiimide-modified products, Examples include modified uretdione and modified uretonimine.
　ここで、上記多量体の例として、ポリイソシアネート単量体の２量体、３量体、５量体、７量体などが挙げられる。このうち、ポリイソシアネート単量体の３量体の例として、イソシアヌレート変性体、イミノオキサジアジンジオン変性体が挙げられる。 Here, examples of the multimer include dimer, trimer, pentamer, and heptamer of polyisocyanate monomer. Among these, examples of polyisocyanate monomer trimers include isocyanurate-modified products and iminooxadiazinedione-modified products.
　また、上記アロファネート変性体の例として、上記したポリイソシアネート単量体と、モノオール（例えば、オクタデカノールなど上記に例示したモノオール）との反応より生成するアロファネート変性体などが挙げられる。 In addition, examples of the allophanate-modified product include allophanate-modified products produced by the reaction of the polyisocyanate monomer described above and a monol (eg, monools exemplified above such as octadecanol).
　上記ポリオール変性体として、例えば、ポリイソシアネート単量体と低分子量ポリオール（例えば、３価アルコールなど）との反応より生成するポリオール変性体（アルコール付加体）などが挙げられる。 Examples of the polyol-modified product include a polyol-modified product (alcohol adduct) produced by a reaction between a polyisocyanate monomer and a low molecular weight polyol (for example, a trihydric alcohol).
　上記ビウレット変性体として、例えば、上記したポリイソシアネート単量体と、水やアミン類との反応により生成するビウレット変性体などが挙げられる。 Examples of the biuret-modified product include a biuret-modified product produced by a reaction between the polyisocyanate monomer and water or amines.
　上記ウレア変性体として、例えば、上記したポリイソシアネート単量体とジアミンとの反応により生成するウレア変性体などが挙げられる。 Examples of the urea-modified product include a urea-modified product produced by the reaction of the above-described polyisocyanate monomer and diamine.
　上記オキサジアジントリオン変性体として、例えば、上記したポリイソシアネート単量体と炭酸ガスとの反応により生成するオキサジアジントリオンなどが挙げられる。 Examples of the modified oxadiazine trione include oxadiazine trione produced by the reaction between the polyisocyanate monomer and carbon dioxide.
　上記カルボジイミド変性体として、上記したポリイソシアネート単量体の脱炭酸縮合反応により生成するカルボジイミド変性体などが挙げられる。 Examples of the carbodiimide-modified product include a carbodiimide-modified product produced by the decarboxylation condensation reaction of the polyisocyanate monomer described above.
　さらに、ポリイソシアネート変性体として、上記したもののほか、ポリメチレンポリフェニルポリイソシアネート（クルードＭＤＩ、ポリメリックＭＤＩ）なども挙げられる。 Furthermore, examples of the polyisocyanate-modified product include polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI) in addition to those described above.
　本発明においては、上述したポリイソシアネート単量体およびポリイソシアネート変性体の中でも、特に脂肪族ポリイソシアネートおよびその多量体が好適に使用される。すなわち、本発明の好適な態様では、硬化剤（Ｄ）は、脂肪族ポリイソシアネートまたは脂肪族ポリイソシアネートの多量体である。 In the present invention, among the above-described polyisocyanate monomer and polyisocyanate-modified product, aliphatic polyisocyanate and its multimer are particularly preferably used. That is, in a preferred embodiment of the present invention, the curing agent (D) is an aliphatic polyisocyanate or a multimer of aliphatic polyisocyanate.
　これらは１種単独で用いてもよく、あるいは、２種以上の組み合わせとして用いてもよい。 These may be used alone or in combination of two or more.
　本発明のコーティング剤が、硬化剤（Ｄ）としてポリイソシアネート単量体またはポリイソシアネート変性体を含む場合における、当該硬化剤（Ｄ）の添加量は、オレフィン重合体（Ａ）と半固体状炭化水素（Ｂ）との合計を１００重量部としたときに、２～３０重量部であることが好ましい。 When the coating agent of the present invention contains a polyisocyanate monomer or a polyisocyanate-modified product as the curing agent (D), the amount of the curing agent (D) added is the olefin polymer (A) and the semisolid carbonization. When the total amount of hydrogen (B) is 100 parts by weight, it is preferably 2 to 30 parts by weight.
　上記硬化物（Ｄ）としては、エポキシ化合物およびオキサゾリン化合物から選ばれる少なくとも１種の化合物を用いることもできる。この場合、本発明のコーティング剤は、前記オレフィン重合体（Ａ）として、前記変性オレフィン系重合体（Ａ２）を少なくとも１種含むことが好ましい。これにより、硬化時の体積変化が小さく、低温で硬化可能なコーティング剤を得ることができ、特に、接着強度に優れた接着剤層を得ることができる。 As the cured product (D), at least one compound selected from an epoxy compound and an oxazoline compound can also be used. In this case, the coating agent of the present invention preferably contains at least one modified olefin polymer (A2) as the olefin polymer (A). Thereby, the volume change at the time of hardening is small, and the coating agent which can be hardened at low temperature can be obtained, and especially the adhesive bond layer excellent in adhesive strength can be obtained.
　前記エポキシ化合物は、１分子中に２個以上のエポキシ基を有する架橋可能な化合物である。このようなエポキシ化合物としては、例えば、ビスフェノールＡ型エポキシ樹脂（水添ビスフェノールＡ型エポキシ樹脂とは異なる）、ビスフェノールＦ型エポキシ樹脂などのビスフェノール型エポキシ樹脂；水添ビスフェノール型エポキシ樹脂；ノボラック型エポキシ樹脂；ビフェニル型エポキシ樹脂；スチルベン型エポキシ樹脂；ハイドロキノン型エポキシ樹脂；ナフタレン骨格型エポキシ樹脂；テトラフェニロールエタン型エポキシ樹脂；トリスヒドロキシフェニルメタン型エポキシ樹脂；ジシクロペンタジエンフェノール型エポキシ樹脂；３'，４'－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物などの脂環式エポキシ樹脂；ヘキサヒドロ無水フタル酸のジグリシジルエステルなどの多塩基酸のポリグリシジルエステル；ソルビトールポリグリシジルエーテル、ソルビタンポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ジグリセロールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ヘキサンジオールジグリシジルエーテル、水添ビスフェノールＡジグリシジルエーテルおよびシクロヘキサンジメタノールジグリシジルエーテルなどのグリシジルエーテル；ポリブタジエンまたはポリイソプレン等のジエンポリマー型エポキシ樹脂；テトラグリシジルジアミノジフェニルメタン、テトラグリシジルビスアミノメチルシクロヘキサン、ジグリシジルアニリン、テトラグリシジルメタキシリレンジアミンなどのグリシジルアミン型エポキシ樹脂；トリアジンまたはヒダントインなどの複素環含有エポキシ樹脂；が挙げられる。 The epoxy compound is a crosslinkable compound having two or more epoxy groups in one molecule. Examples of such epoxy compounds include bisphenol A type epoxy resins (different from hydrogenated bisphenol A type epoxy resins), bisphenol type epoxy resins such as bisphenol F type epoxy resins; hydrogenated bisphenol type epoxy resins; novolac type epoxies. Resin; Biphenyl type epoxy resin; Stilbene type epoxy resin; Hydroquinone type epoxy resin; Naphthalene skeleton type epoxy resin; Tetraphenylol ethane type epoxy resin; Trishydroxyphenylmethane type epoxy resin; Dicyclopentadiene phenol type epoxy resin; 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4- (2-oxira of 2,2-bis (hydroxymethyl) -1-butanol E) cycloaliphatic epoxy resin such as cyclohexane adduct; polyglycidyl ester of polybasic acid such as diglycidyl ester of hexahydrophthalic anhydride; sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane Glycidyl ethers such as polyglycidyl ether, polypropylene glycol diglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether and cyclohexanedimethanol diglycidyl ether; polybutadiene or polyisoprene Diene polymer type epoxy resin such as tetraglycidyldiaminodi And glycidylamine type epoxy resins such as phenylmethane, tetraglycidylbisaminomethylcyclohexane, diglycidylaniline, and tetraglycidylmetaxylylenediamine; and heterocyclic-containing epoxy resins such as triazine and hydantoin.
　前記エポキシ化合物の中でも、より接着強度に優れる、特に、アルミニウム箔層とポリプロピレンなどの熱可塑性樹脂製フィルム層とをより高い強度で接着することができる接着剤層を得ることができる等の点から、ビスフェノールＡ型液状エポキシ樹脂、脂環式エポキシ化合物、トリメチロールプロパンポリグリシジルエーテルが好ましい。 Among the epoxy compounds, the adhesive strength is more excellent, in particular, from the point of obtaining an adhesive layer capable of bonding the aluminum foil layer and a film made of a thermoplastic resin such as polypropylene with higher strength. Bisphenol A liquid epoxy resin, alicyclic epoxy compound, and trimethylolpropane polyglycidyl ether are preferable.
　前記ビスフェノールＡ型液状エポキシ樹脂としては、常温（２５℃）で液状である樹脂であれば特に制限されず、市販品を用いてもよい。 The bisphenol A liquid epoxy resin is not particularly limited as long as it is a resin that is liquid at normal temperature (25 ° C.), and a commercially available product may be used.
　該市販品としては、例えば、ＥＰＩＣＬＯＮ８４０、８４０－Ｓ、８５０、８５０－Ｓ、ＥＸＡ－８５０ＣＲＰ、８５０－ＬＣ（ＤＩＣ（株）製）、ｊＥＲ８２８ＥＬ、８２７（三菱化学（株）製）、エポミックＲ－１４０Ｐ（三井化学（株）製）が挙げられる。 Examples of the commercially available products include EPICLON 840, 840-S, 850, 850-S, EXA-850CRP, 850-LC (manufactured by DIC Corporation), jER828EL, 827 (manufactured by Mitsubishi Chemical Corporation), Epomic R- 140P (manufactured by Mitsui Chemicals, Inc.).
　前記脂環式エポキシ化合物は、エポキシシクロアルキル基またはエポキシシクロアルケニル基を分子内に少なくとも１個有する化合物、または、少なくとも１個のエポキシ基が脂環に単結合で結合した基を分子内に少なくとも１個有する化合物のことをいう。 The alicyclic epoxy compound is a compound having at least one epoxycycloalkyl group or epoxycycloalkenyl group in the molecule, or at least a group in which at least one epoxy group is bonded to the alicyclic ring by a single bond. A compound having one.
　前記脂環式エポキシ化合物としては、例えば、３，４－エポキシシクロヘキセニルメチル－３'，４'－エポキシシクロヘキセンカルボキシレート、３'，４'－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシシクロヘキシルオクチル－３，４－エポキシシクロヘキサンカルボキシレート、２－（３，４－エポキシシクロヘキシル－５，５－スピロ－３，４－エポキシ）シクロヘキサン－ｍ－ジオキサン、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、ビニルシクロヘキセンジオキサイド、ビス（３，４－エポキシ－６－メチルシクロヘキシルメチル）アジペート、３，４－エポキシ－６－メチルシクロヘキシル－３，４－エポキシ－６－メチルシクロヘキサンカルボキシレート、メチレンビス（３，４－エポキシシクロヘキサン）、ジシクロペンタジエンジエポキサイド、エチレングリコールジ（３，４－エポキシシクロヘキシルメチル）エーテル、エチレンビス（３，４－エポキシシクロヘキサンカルボキシレート）、１，２，８，９－ジエポキシリモネン、２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物、特開２００８－２１４５５５号公報に記載の化合物が挙げられる。 Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4 -Epoxycyclohexylmethyl) adipate, vinyl cyclohexylene dioxide, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxy Rate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), 1,2,8 , 9-diepoxylimonene, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, and compounds described in JP-A-2008-214555 Can be mentioned.
　前記脂環式エポキシ化合物としては、市販品を用いてもよく、該市販品としては、例えば、セロキサイド２０２１Ｐ、ＥＨＰＥ３１５０、ＥＨＰＥ３１５０ＣＥ、エポリードＧＴ４０１（以上、（株）ダイセル製）が挙げられる。 As the alicyclic epoxy compound, a commercially available product may be used, and examples of the commercially available product include Celoxide 2021P, EHPE3150, EHPE3150CE, and Epolide GT401 (manufactured by Daicel Corporation).
　前記脂環式エポキシ化合物としては、より接着強度に優れる接着剤層を得ることができる等の点から、２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物が好ましい。 As the alicyclic epoxy compound, 1,2-epoxy-4- (2) of 2,2-bis (hydroxymethyl) -1-butanol can be obtained because an adhesive layer having better adhesive strength can be obtained. 2-oxiranyl) cyclohexane adduct is preferred.
　前記トリメチロールプロパンポリグリシジルエーテルとしては、例えば、トリメチロールプロパンジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、これらの混合物が挙げられる。 Examples of the trimethylolpropane polyglycidyl ether include trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, and mixtures thereof.
　前記トリメチロールプロパンポリグリシジルエーテルとしては、市販品を用いてもよく、該市販品としては、例えば、ＥＸ－３２１Ｌ（ナガセケムテックス（株）製）等が挙げられる。 Commercially available products may be used as the trimethylolpropane polyglycidyl ether. Examples of the commercially available products include EX-321L (manufactured by Nagase ChemteX Corporation).
　前記オキサゾリン化合物は、１分子中に２個以上のオキサゾリン基を有する架橋可能な化合物である。このようなオキサゾリン化合物としては、例えば、オキサゾリン基含有モノマーの重合体、オキサゾリン基含有モノマーと他のモノマーとの共重合体などのオキサゾリン基含有ポリマーが挙げられる。 The oxazoline compound is a crosslinkable compound having two or more oxazoline groups in one molecule. Examples of such oxazoline compounds include polymers of oxazoline group-containing monomers and oxazoline group-containing polymers such as copolymers of oxazoline group-containing monomers and other monomers.
　前記オキサゾリン基含有モノマーとしては、例えば、２－ビニル－２－オキサゾリン、２－ビニル－４－メチル－２－オキサゾリン、２－ビニル－５－メチル－２－オキサゾリン、２－イソプロペニル－２－オキサゾリン、２－イソプロペニル－４－メチル－２－オキサゾリン、２－イソプロペニル－５－エチル－２－オキサゾリン、２－イソプロペニル－２－オキサゾリン、２－イソプロペニル－４，４－ジメチル－２－オキサゾリンが挙げられる。これらは１種単独を使用してもよく、２種以上を使用してもよい。 Examples of the oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline. 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline Is mentioned. These may use 1 type individually and may use 2 or more types.
　前記他のモノマーとしては、例えば、アルキル（メタ）アクリレート（アルキル基の炭素数１～１４程度）；アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸、クロトン酸、スチレンスルホン酸およびその塩（ナトリウム塩、カリウム塩、アンモニウム塩、第三級アミン塩等）などの不飽和カルボン酸類；アクリロニトリル、メタクリロニトリルなどの不飽和ニトリル類；（メタ）アクリルアミド、Ｎ－アルキル（メタ）アクリルアミド、Ｎ，Ｎ－ジアルキル（メタ）アクリルアミド、（アルキル基：メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、２－エチルヘキシル基、シクロヘキシル基等）などの不飽和アミド類；酢酸ビニル、プロピオン酸ビニルなどのビニルエステル類；メチルビニルエーテル、エチルビニルエーテルなどのビニルエーテル類；エチレン、プロピレンなどのα－オレフィン類；塩化ビニル、塩化ビニリデン、フッ化ビニルなどの含ハロゲンα，β－不飽和モノマー類；スチレン、α－メチルスチレンなどのα，β－不飽和芳香族モノマーが挙げられる。これらは１種単独を使用してもよく、２種以上を使用してもよい。 Examples of the other monomer include alkyl (meth) acrylate (alkyl group having about 1 to 14 carbon atoms); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrenesulfonic acid and salts thereof (Unsaturated carboxylic acids such as sodium salt, potassium salt, ammonium salt and tertiary amine salt); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth) acrylamide, N-alkyl (meth) acrylamide, N , N-dialkyl (meth) acrylamide, (alkyl group: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.) Unsaturated amides; vinyl acetate, vinyl propionate, etc. Steal; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; Halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride; Styrene and α-methyl And α, β-unsaturated aromatic monomers such as styrene. These may use 1 type individually and may use 2 or more types.
　前記オキサゾリン化合物としては、より接着強度に優れる接着剤層を得ることができる等の点から、２－イソプロペニル－２－オキサゾリンを含有するオキサゾリン化合物が好ましい。市販品としては、例えば、日本触媒（株）製「エポクロス」シリーズが挙げられる。 The oxazoline compound is preferably an oxazoline compound containing 2-isopropenyl-2-oxazoline from the viewpoint that an adhesive layer having better adhesive strength can be obtained. Examples of commercially available products include “Epocross” series manufactured by Nippon Shokubai Co., Ltd.
　前記エポキシ化合物のエポキシ当量およびオキサゾリン化合物のオキサゾリン当量は、より接着強度および耐薬品性、耐電解液性に優れる接着剤層を得ることができる等の点から、好ましくは１００ｇ／ｅｑ以上、より好ましくは１２５ｇ／ｅｑ以上であり、また、好ましくは１，６００ｇ／ｅｑ以下、より好ましくは５００ｇ／ｅｑ以下である。 The epoxy equivalent of the epoxy compound and the oxazoline equivalent of the oxazoline compound are preferably 100 g / eq or more, more preferably from the viewpoint of obtaining an adhesive layer having better adhesive strength, chemical resistance, and electrolytic solution resistance. Is 125 g / eq or more, preferably 1,600 g / eq or less, more preferably 500 g / eq or less.
　前記当量は、ＪＩＳ　Ｋ７２３６に基づいて測定することができる。 The equivalent can be measured based on JIS K7236.
　本発明のコーティング剤が、硬化剤（Ｄ）として、エポキシ化合物およびオキサゾリン化合物から選ばれる少なくとも１種の化合物を含む場合、当該硬化剤（Ｄ）は、硬化剤（Ｄ）中のエポキシ基およびオキサゾリン基当量／重合体（Ａ）中のエポキシ基またはオキサゾリン基に対し反応性の官能基の当量が、好ましくは０．０１以上、より好ましくは０．１以上となり、また、好ましくは５０以下、より好ましくは３０以下、さらに好ましくは２０以下、特に好ましくは１０以下となるように配合することが望ましい。硬化剤（Ｄ）の配合量が前記範囲にあると、より接着強度および耐薬品性、耐電解液性に優れる接着剤層を得ることができる。 When the coating agent of the present invention contains at least one compound selected from an epoxy compound and an oxazoline compound as the curing agent (D), the curing agent (D) is an epoxy group and an oxazoline in the curing agent (D). Group equivalent / Equivalent functional group reactive to the epoxy group or oxazoline group in the polymer (A) is preferably 0.01 or more, more preferably 0.1 or more, and preferably 50 or less, more It is desirable to blend so that it is preferably 30 or less, more preferably 20 or less, and particularly preferably 10 or less. When the blending amount of the curing agent (D) is in the above range, an adhesive layer that is more excellent in adhesive strength, chemical resistance, and electrolytic solution resistance can be obtained.
　＜触媒（Ｅ）＞
　本発明のコーティング剤は、ｐＫａが１１以上である触媒（Ｅ）を含有してもよい。この場合、本発明のコーティング剤は前記硬化剤（Ｄ）を含有することが好ましく、さらに前記硬化剤（Ｄ）はエポキシ化合物およびオキサゾリン化合物から選ばれる少なくとも１種の化合物であることがより好ましい。 <Catalyst (E)>
The coating agent of the present invention may contain a catalyst (E) having a pKa of 11 or more. In this case, the coating agent of the present invention preferably contains the curing agent (D), and the curing agent (D) is more preferably at least one compound selected from an epoxy compound and an oxazoline compound.
　前記触媒（Ｅ）を用いることで、低温でも効率よく架橋反応を促進でき、耐薬品性、耐電解液性に優れる接着剤層を形成でき、接着強度に優れる、特に、アルミニウム箔層とポリプロピレンなどの熱可塑性樹脂製フィルム層とを高い強度で接着することができる接着剤層を得ることができる。 By using the catalyst (E), the crosslinking reaction can be efficiently promoted even at a low temperature, an adhesive layer excellent in chemical resistance and electrolytic solution resistance can be formed, and excellent in adhesive strength, in particular, an aluminum foil layer and polypropylene, etc. It is possible to obtain an adhesive layer that can be bonded to the thermoplastic resin film layer with high strength.
　触媒（Ｅ）は、１種単独で使用してもよく、２種以上を使用してもよい。 Catalyst (E) may be used alone or in combination of two or more.
　前記触媒（Ｅ）としては、ｐＫａが１１以上の化合物であれば特に制限されないが、前記硬化剤（Ｄ）の架橋反応を促進できる化合物であることが好ましく、このような化合物としては、例えば、１，８－ジアザビシクロ［５．４．０］ウンデセン－７（ＤＢＵ）、１，６－ジアザビシクロ［３．４．０］ノネン－５等の強塩基性第三級アミン、ホスファゼン塩基を有するホスファゼン触媒が挙げられ、ＤＢＵ、ホスファゼン触媒が好ましい。 The catalyst (E) is not particularly limited as long as the pKa is 11 or more, but is preferably a compound that can promote the crosslinking reaction of the curing agent (D). Phosphazene catalysts having strongly basic tertiary amines such as 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,6-diazabicyclo [3.4.0] nonene-5, and phosphazene bases DBU and a phosphazene catalyst are preferable.
　なお、前記ｐＫａは、２５℃、水溶液中における酸解離定数のことである。また、例えば、リン酸には、３つのｐＫａ、つまり、ｐＫａ1、ｐＫａ2およびｐＫａ3があるが、本発明におけるｐＫａは、ｐＫａ1、つまり、第一酸解離定数のことをいう。 The pKa is an acid dissociation constant in an aqueous solution at 25 ° C. In addition, for example, phosphoric acid has three pKas, that is, pKa 1 , pKa 2, and pKa 3, and pKa in the present invention refers to pKa 1 , that is, the first acid dissociation constant.
　前記触媒（Ｅ）の配合量は、本発明のコーティング剤の不揮発分（溶媒以外の成分）１００質量％に対し、好ましくは１ｐｐｍ以上、より好ましくは１００ｐｐｍ以上であり、また、好ましくは１質量％以下、より好ましくは０．３質量％以下である。触媒（Ｅ）の配合量が前記範囲にあると、硬化速度に優れるコーティング剤が得られ、また、耐薬品性、耐電解液性および接着強度に優れる接着剤層を得ることができる。 The blending amount of the catalyst (E) is preferably 1 ppm or more, more preferably 100 ppm or more, and preferably 1 mass% with respect to 100 mass% of the non-volatile content (components other than the solvent) of the coating agent of the present invention. Hereinafter, it is 0.3 mass% or less more preferably. When the blending amount of the catalyst (E) is in the above range, a coating agent having an excellent curing rate can be obtained, and an adhesive layer having excellent chemical resistance, electrolytic solution resistance and adhesive strength can be obtained.
　＜溶媒＞
　本発明のコーティング剤は、上記オレフィン重合体（Ａ）および上記半固体状炭化水素（Ｂ）などに加えて、必要に応じて溶媒を含んでいてもよい。 <Solvent>
The coating agent of the present invention may contain a solvent as required in addition to the olefin polymer (A) and the semisolid hydrocarbon (B).
　該溶媒としては、特に限定されないが、たとえば、ベンゼン、トルエン、キシレン等の芳香族炭化水素、ヘキサン、ヘプタン、オクタン、デカン等の脂肪族炭化水素、シクロヘキサン、シクロヘキセン、メチルシクロヘキサン等の脂環式炭化水素、メタノール、エタノール、イソプロピルアルコール、ブタノール、ペンタノール、ヘキサノール、プロパンジオール、フェノール等のアルコール、アセトン、メチルイソブチルケトン（ＭＩＢＫ）、メチルエチルケトン（ＭＥＫ）、ペンタノン、ヘキサノン、イソホロン、アセトフェノン等のケトン系溶媒、メチルセルソルブ、エチルセルソルブ等のセルソルブ類、酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル、ギ酸ブチル等のエステル類、トリクロルエチレン、ジクロルエチレン、クロルベンゼン等のハロゲン化炭化水素、エクソール、アイソパー等の石油系溶剤等を挙げることができる。その中でも、トルエン、メチルシクロヘキサン/ＭＩＢＫ混合溶剤、メチルシクロヘキサン/ＭＥＫ混合溶剤、メチルシクロヘキサン/酢酸エチル混合溶剤、シクロヘキサン/ＭＥＫ混合溶剤、シクロヘキサン/酢酸エチル混合溶剤、エクソール/シクロヘキサノン混合溶剤、ミネラルスピリット／シクロヘキサノン混合溶剤が好適に使用される。また、水などに分散せしめたものを使用してもよい。 Examples of the solvent include, but are not limited to, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, and alicyclic carbons such as cyclohexane, cyclohexene and methylcyclohexane. Alcohols such as hydrogen, methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol and phenol, ketone solvents such as acetone, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), pentanone, hexanone, isophorone and acetophenone Cellsolves such as methyl cellosolve and ethyl cellosolve, esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate and butyl formate, trichloroethylene, dichloroethyl Emissions, halogenated hydrocarbons such as chlorobenzene, Exxsol, mention may be made of petroleum-based solvents such as Isopar. Among them, toluene, methylcyclohexane / MIBK mixed solvent, methylcyclohexane / MEK mixed solvent, methylcyclohexane / ethyl acetate mixed solvent, cyclohexane / MEK mixed solvent, cyclohexane / ethyl acetate mixed solvent, Exol / cyclohexanone mixed solvent, mineral spirit / cyclohexanone A mixed solvent is preferably used. Moreover, you may use what was disperse | distributed to water etc.
　これらは１種単独で用いてもよく、あるいは、２種以上の組み合わせとして用いてもよい。 These may be used alone or in combination of two or more.
　本発明のコーティング剤が溶媒を含む場合において、オレフィン重合体（Ａ）と半固体状炭化水素（Ｂ）と溶媒との合計を１００重量％とした場合におけるオレフィン重合体（Ａ）と半固体状炭化水素（Ｂ）との合計量は、通常、５～５０重量％程度、好ましくは８～４０重量％の割合である。 When the coating agent of the present invention contains a solvent, the olefin polymer (A) and the semisolid state when the total of the olefin polymer (A), the semisolid hydrocarbon (B) and the solvent is 100% by weight. The total amount with the hydrocarbon (B) is usually about 5 to 50% by weight, preferably 8 to 40% by weight.
　＜その他の構成成分＞
　本発明のコーティング剤は、上記オレフィン重合体（Ａ）と、上記半固体状炭化水素（Ｂ）の他に、他のオレフィン系樹脂（Ｆ）を含んでもよい。この「他のオレフィン系樹脂（Ｆ）」としては、上記オレフィン重合体（Ａ）および上記半固体状炭化水素（Ｂ）の何れにも該当しない限り特に制限はないものの、ポリエチレン、ポリプロピレン、ポリ１－ブテン、ポリ４－メチル－１－ペンテンの単独重合体、エチレン、プロピレン、４－メチル－１－ペンテン等のα－オレフィン同士のランダムあるいはブロック共重合体、エチレン・プロピレン共重合体、エチレン・オクテン共重合体、プロピレン・オクテン共重合体、エチレン・プロピレン・１－ブテン共重合体、エチレン・プロピレン・ターポリマー、環状ポリオレフィン、エチレン・酢酸ビニル、エチレン・不飽和カルボン酸の共重合体、エチレン・ビニルアルコール、アイオノマー樹脂等が挙げられる。 <Other components>
The coating agent of the present invention may contain another olefin resin (F) in addition to the olefin polymer (A) and the semisolid hydrocarbon (B). The “other olefin resin (F)” is not particularly limited as long as it does not correspond to any of the olefin polymer (A) and the semisolid hydrocarbon (B), but polyethylene, polypropylene, poly 1 -Butene, poly-4-methyl-1-pentene homopolymers, random or block copolymers of α-olefins such as ethylene, propylene, 4-methyl-1-pentene, ethylene / propylene copolymers, ethylene Octene copolymer, propylene / octene copolymer, ethylene / propylene / 1-butene copolymer, ethylene / propylene / terpolymer, cyclic polyolefin, ethylene / vinyl acetate, ethylene / unsaturated carboxylic acid copolymer, ethylene -Vinyl alcohol, ionomer resin, etc. are mentioned.
　また、必要に応じて、酸化チタン（ルチル型）、酸化亜鉛などの遷移金属化合物、カーボンブラック等の顔料、揺変剤、増粘剤、上記粘着付与剤（Ｃ）に該当しないその他の粘着付与剤（以下、「その他の粘着付与剤」）、消泡剤、表面調整剤、沈降防止剤、酸化防止剤、耐候剤、熱安定剤、光安定剤、顔料分散剤、帯電防止剤などの塗料用添加剤を添加しても良い。ここで、「その他の粘着付与剤」として、例えば、テルペン樹脂；テルペンフェノール共重合体樹脂、芳香族変性テルペン樹脂、水添テルペン樹脂などの変性テルペン樹脂；脂肪族飽和炭化水素樹脂（荒川化学工業社製 アルコン）、高級炭化水素樹脂（三井化学社製 ＦＴＲシリーズ）、ロジン変性フェノール樹脂、並びに、ロジンエステル、変性ロジン樹脂などのロジン樹脂等のうち、上記粘着付与剤（Ｃ）には該当しないものを採用しうる。 If necessary, transition metal compounds such as titanium oxide (rutile type) and zinc oxide, pigments such as carbon black, thixotropic agents, thickeners, and other tackifiers that do not fall under the above-mentioned tackifier (C). Paints (hereinafter “other tackifiers”), antifoaming agents, surface conditioning agents, anti-settling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, antistatic agents, etc. Additive additives may be added. Here, as the “other tackifier”, for example, terpene resin; modified terpene resin such as terpene phenol copolymer resin, aromatic modified terpene resin, hydrogenated terpene resin; aliphatic saturated hydrocarbon resin (Arakawa Chemical Industries) Among the above-mentioned tackifiers (C), among other types of rosin resins such as ALCON made by Mitsui Chemicals, FTR series made by Mitsui Chemicals, rosin modified phenolic resins, and rosin esters and modified rosin resins. Things can be adopted.
　これら他のオレフィン系樹脂（Ｆ）、酸化チタン（ルチル型）、酸化亜鉛などの遷移金属化合物、カーボンブラック等の顔料、揺変剤、増粘剤、上記「その他の粘着付与剤」、消泡剤、表面調整剤、沈降防止剤、酸化防止剤、耐候剤、熱安定剤、光安定剤、顔料分散剤、帯電防止剤などの塗料用添加剤は、通常、本発明のコーティング剤の目的を損なわない範囲で添加することができる。 These other olefin resins (F), transition metal compounds such as titanium oxide (rutile type), zinc oxide, pigments such as carbon black, thixotropic agents, thickeners, the above-mentioned “other tackifiers”, antifoaming Additives for paints such as agents, surface conditioners, anti-settling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants and antistatic agents are usually used for the purpose of the coating agent of the present invention. It can add in the range which does not impair.
　例えば、他のオレフィン系樹脂（Ｆ）を添加する場合、上記オレフィン重合体（Ａ）１００重量部に対し、好ましくは０を超えて５０重量部以下、より好ましくは１～３０重量部、より好ましくは１～１０重量部である。 For example, when another olefin resin (F) is added, it is preferably more than 0 and 50 parts by weight or less, more preferably 1 to 30 parts by weight, more preferably 100 parts by weight of the olefin polymer (A). Is 1 to 10 parts by weight.
　また、他のオレフィン系樹脂（Ｆ）を含まないことも一つの実施態様である。 Moreover, it is also one embodiment that other olefin resin (F) is not included.
　［用途］
　本発明のコーティング剤はプライマーや塗料、ホットメルト接着剤、ドライラミネート用接着剤、粘着シート、ディスプレイ用粘着テープ、光学透明両面テープとして用いるのに好適である。本発明のコーティング剤をプライマーや塗料、ホットメルト接着剤、ドライラミネート用接着剤として使用する場合、アクリル樹脂、ＰＥＴ、ポリカーボネート、ABS、ＣＯＣ、塩化ビニル、ポリプロピレン、表面処理ポリエチレン、ポリスチレン等の熱可塑性樹脂、及びアルミニウムや銅、SUSなどの金属材料を被着体として使用することが出来る。具体的にはこれら熱可塑性樹脂の射出成形体、フィルム、もしくはこれら金属の成形体、金属箔に本発明のコーティング剤を塗工、乾燥し、得られた塗膜上に更に他のコーティング剤を塗工・乾燥もしくは他の熱可塑性樹脂フィルム、成形体および金属箔、成形体を貼合して使用することが出来る。 [Usage]
The coating agent of the present invention is suitable for use as a primer, paint, hot melt adhesive, dry laminate adhesive, pressure sensitive adhesive sheet, display pressure sensitive adhesive tape, and optically transparent double-sided tape. When the coating agent of the present invention is used as a primer, paint, hot melt adhesive, or dry laminate adhesive, thermoplastics such as acrylic resin, PET, polycarbonate, ABS, COC, vinyl chloride, polypropylene, surface-treated polyethylene, polystyrene, etc. Resin and metal materials such as aluminum, copper, and SUS can be used as the adherend. Specifically, these thermoplastic resin injection-molded articles, films, or these metal molded articles, and metal foils are coated with the coating agent of the present invention, dried, and another coating agent is further applied on the obtained coating film. Coating / drying or other thermoplastic resin films, molded articles and metal foils, and molded articles can be used by bonding.
　本発明のコーティング剤の塗膜を形成する方法としては特に制限がなく、公知の方法で行うことが出来る。例えば、ダイコート法、フローコート法、スプレーコート法、バーコート法、グラビアコート法、グラビアリバースコート法、キスリバースコート法、マイクログラビアコート法、ロールコート法、ブレードコート法、ロッドコート法、ロールドクターコート法、エアナイフコート法、コンマロールコート法、リバースロールコート法、トランスファーロールコート法、キスロールコート法、カーテンコート法及びディッピングコート法等の方法で塗布した後、自然乾燥あるいは加熱強制乾燥等、適宜の方法によって乾燥させることで塗膜を得ることが出来る。 The method for forming the coating film of the coating agent of the present invention is not particularly limited, and can be performed by a known method. For example, die coating method, flow coating method, spray coating method, bar coating method, gravure coating method, gravure reverse coating method, kiss reverse coating method, micro gravure coating method, roll coating method, blade coating method, rod coating method, roll doctor After applying by the coating method, air knife coating method, comma roll coating method, reverse roll coating method, transfer roll coating method, kiss roll coating method, curtain coating method, dipping coating method, etc., natural drying or heat forced drying, etc. A coating film can be obtained by drying by an appropriate method.
　本発明の加飾フィルムは、本発明のコーティング剤から得られる層を有する以外に特に制限は無く、公知の意匠性を有するフィルムと組み合わせて用いる事ができる。例えば、予め印刷・塗装・蒸着等で加飾されたフィルム、もしくはこれらの組み合わせによって加飾されたフィルムを意匠層とし、これと、本発明のコーティング剤から得られる層とを積層させて用いることが出来る。 The decorative film of the present invention is not particularly limited other than having a layer obtained from the coating agent of the present invention, and can be used in combination with a film having a known design property. For example, a film previously decorated by printing, painting, vapor deposition or the like, or a film decorated by a combination thereof is used as a design layer, and this is used by laminating a layer obtained from the coating agent of the present invention. I can do it.
　言い換えると、本発明の加飾フィルムは、上述の本発明のコーティング剤から得られる層、を少なくとも１層有している。そして、その典型的な態様において、本発明の加飾フィルムは、予め印刷・塗装・蒸着等で加飾されたフィルムなどの意匠性を有するフィルムからなる意匠層と、本発明のコーティング剤から得られる層とを有している。なお、本明細書における以下の記載では、この層を、その形状に着目して「塗膜」と呼ぶ場合がある。またその機能に着目して「接着層」と呼ぶ場合がある。 In other words, the decorative film of the present invention has at least one layer obtained from the above-described coating agent of the present invention. And in the typical aspect, the decorative film of this invention is obtained from the design layer which consists of a film which has design properties, such as the film previously decorated by printing, coating, vapor deposition, etc., and the coating agent of this invention. Layer. In the following description in this specification, this layer may be referred to as a “coating film” in view of its shape. In some cases, the function is referred to as an “adhesive layer” in view of its function.
　ここで、該意匠層を有するフィルムの材質としては、アクリルフィルム、ＰＥＴフィルム、ポリカーボネートフィルム、ＣＯＣフィルム、塩化ビニルフィルム、無延伸ポリプロピレン（Cast Polypropylene；以下「ＣＰＰ」）フィルム等の熱可塑性フィルム、並びに、上記熱可塑性フィルムにアルミニウム等金属を蒸着させた蒸着フィルムが挙げられる。 Here, as a material of the film having the design layer, thermoplastic films such as acrylic film, PET film, polycarbonate film, COC film, vinyl chloride film, unstretched polypropylene (hereinafter referred to as “CPP”) film, and The vapor deposition film which vapor-deposited metals, such as aluminum, to the said thermoplastic film is mentioned.
　本発明の加飾フィルムの製造方法としては、加飾フィルムに本発明のコーティング剤から得られる層（塗膜）が具備されていればよく、特に制限は無い。具体的には、意匠層を有する加飾フィルムの被着体と相対峙する面に、本発明の塗膜をドライラミネートする方法、本発明の塗膜に印刷等で直接意匠層を設ける方法、上記フィルムにクリア層、塗料層、本発明の塗膜からなる層（すなわち、本発明のコーティング剤から得られる層）を順次印刷等で形成していく方法等が挙げられる。 The method for producing the decorative film of the present invention is not particularly limited as long as the decorative film has a layer (coating film) obtained from the coating agent of the present invention. Specifically, on the surface facing the adherend of the decorative film having a design layer, a method of dry laminating the coating film of the present invention, a method of directly providing a design layer by printing or the like on the coating film of the present invention, Examples include a method in which a clear layer, a paint layer, and a layer made of the coating film of the present invention (that is, a layer obtained from the coating agent of the present invention) are sequentially formed on the film by printing or the like.
　本発明の塗膜を有する加飾フィルムは、例えば、真空成形法、圧空真空成形法等の既存の真空成形方法、インサート成形法及びインモールド成形法、また、特許第３７３３５６４に記載の「真空成形装置」によるＴＯＭ工法等を利用することで、複雑な三次元構造を有する成形体に加飾を施すことができる。 The decorative film having the coating film of the present invention is, for example, an existing vacuum forming method such as a vacuum forming method or a compressed air vacuum forming method, an insert forming method and an in-mold forming method, and “vacuum forming” described in Japanese Patent No. 3733564. By using the TOM method using the “apparatus”, a molded body having a complicated three-dimensional structure can be decorated.
　本発明で用いられる、該加飾フィルムの被着体としては、例えば、ＰＰ等のポリオレフィン材料、ＨＩＰＳ、ＰＳ、ＡＢＳ、ＰＣ、ＰＣ・ＡＢＳアロイ、ＰＥＴ、アクリル樹脂や、ＥＤ鋼板、Ｍｇ合金、ＳＵＳ、アルミニウム合金などの金属材料、ガラスが好適に挙げられる。また、上記樹脂と上記金属材料などが複合化された被着体であっても構わない。 As an adherend of the decorative film used in the present invention, for example, a polyolefin material such as PP, HIPS, PS, ABS, PC, PC / ABS alloy, PET, acrylic resin, ED steel plate, Mg alloy, Preferred examples include SUS, metal materials such as aluminum alloys, and glass. Further, an adherend in which the resin and the metal material are combined may be used.
　該加飾方法によって得られる成形体としては、例えば、自動車内外装用部材；ＡＶ機器等の各種フロントパネル；ボタン、エンブレム等の表面化粧材；携帯電話等の筐体、ハウジング、表示窓、ボタン等の各種部品；家具用外装材；浴室、壁面、天井、床等の建築用内装材；サイディング等の外壁、塀、屋根、門扉、破風板等の建築用外装材；窓枠、扉、手すり、敷居、鴨居等の家具類の表面化粧材；各種ディスプレイ、レンズ、ミラー、ゴーグル、窓ガラス等の光学部材；電車、航空機、船舶等の自動車以外の各種乗り物の内外装用部材；及び瓶、化粧品容器、小物入れ等の各種包装容器、包装材料、景品、小物等の雑貨等のその他各種用途に好適に使用することができる。 Examples of molded articles obtained by the decoration method include automobile interior and exterior members; various front panels such as AV equipment; surface decorative materials such as buttons and emblems; housings such as mobile phones, housings, display windows, buttons, and the like. Various parts of furniture; exterior materials for furniture; interior materials for buildings such as bathrooms, walls, ceilings, floors; exterior walls for siding, etc .; exterior materials for buildings such as fences, roofs, gates, windbreak boards; window frames, doors, handrails, Surface decorative materials for furniture such as sills and duck; optical members such as various displays, lenses, mirrors, goggles and window glass; members for interior and exterior of various vehicles other than automobiles such as trains, aircraft and ships; and bottles and cosmetic containers It can be suitably used for various other applications such as various packaging containers such as small items, packaging materials, prizes, miscellaneous goods such as small items.
　＜積層体＞
　本発明の一実施形態における積層体（以下「本積層体」ともいう。）は、基材と、前記本コーティング剤の硬化物からなる接着剤層とを含めば特に制限されず、これら以外の層を含んでもよい。 <Laminated body>
The laminate in one embodiment of the present invention (hereinafter also referred to as “the present laminate”) is not particularly limited as long as it includes a base material and an adhesive layer composed of a cured product of the present coating agent. Layers may be included.
　本積層体において、接着剤層は、基材の片面に存在していてもよく、両面に存在していてもよく、これらの面の全面に存在していてもよく、一部に存在していてもよい。 In this laminate, the adhesive layer may be present on one side of the substrate, may be present on both sides, may be present on the entire surface of these surfaces, or may be present in part. May be.
　本積層体の製造方法としては、特に制限されず、従来公知の方法を採用することができるが、基材上に本コーティング剤から塗膜を形成する塗膜形成工程および該塗膜を硬化させる養生工程を含む方法が好ましい。 The production method of the laminate is not particularly limited, and a conventionally known method can be adopted, but a coating film forming step for forming a coating film from the coating agent on a substrate and the coating film are cured. A method including a curing step is preferred.
　本積層体の製造方法は、その全ての工程を低温（約１２０℃以下、好ましくは１００℃以下）で行うことが、基材や被着体が有する特性を損なうことなく積層体を得ることができ、基材や被着体の選択自由度が増す等の点から好ましく、また、本コーティング剤を用いることで、このような低温で積層体を製造しても、接着強度および耐薬品性（耐電解液性）に優れる積層体を得ることができる。 In the production method of the laminate, all the steps can be performed at a low temperature (about 120 ° C. or less, preferably 100 ° C. or less) to obtain a laminate without impairing the properties of the substrate and the adherend. It is preferable from the viewpoint of increasing the degree of freedom in selecting a substrate and an adherend, and even when a laminate is produced at such a low temperature by using this coating agent, the adhesive strength and chemical resistance ( A laminate excellent in (electrolytic solution resistance) can be obtained.
　前記塗膜形成工程としては、基材上に本コーティング剤を塗布して、必要により該コーティング剤を乾燥させることで塗膜を形成する方法、および、本コーティング剤に基材を浸漬し、基材を取り出し、必要により該コーティング剤を乾燥させることで基材上に塗膜を形成する方法が好ましい。 As the coating film forming step, the present coating agent is applied on a substrate, and if necessary, the coating agent is dried to form a coating film, and the substrate is immersed in the coating agent, A method of forming a coating film on a substrate by taking out the material and drying the coating agent as necessary is preferable.
　前記塗布の方法としては、特に制限されず、従来公知の方法、例えば、ダイコート法、フローコート法、スプレーコート法、バーコート法、グラビアコート法、グラビアリバースコート法、キスリバースコート法、マイクログラビアコート法、ロールコート法、ブレードコート法、ロッドコート法、ロールドクターコート法、エアナイフコート法、コンマロールコート法、リバースロールコート法、トランスファーロールコート法、キスロールコート法、カーテンコート法、印刷法などの塗布方法を採用することができる。 The coating method is not particularly limited, and a conventionally known method such as a die coating method, a flow coating method, a spray coating method, a bar coating method, a gravure coating method, a gravure reverse coating method, a kiss reverse coating method, or a micro gravure. Coating method, roll coating method, blade coating method, rod coating method, roll doctor coating method, air knife coating method, comma roll coating method, reverse roll coating method, transfer roll coating method, kiss roll coating method, curtain coating method, printing method A coating method such as can be employed.
　前記基材としては、特に制限されず、前記接着剤層を形成したい基材であれば特に制限されないが、例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン、ＡＢＳ樹脂、ポリカーボネート（ＰＣ）、ＰＥＴなどのポリエステル樹脂、ポリフェニレンサルファイド（ＰＰＳ）、ナイロンなどのポリアミド樹脂、または、アクリル樹脂などの樹脂からなる樹脂製基材；透明蒸着ＰＥＴなどのバリアフィルム；ＥＤ鋼板、Ｍｇ合金、ＳＵＳ（ステンレス）、アルミニウム、アルミニウム合金またはガラスなどの無機材料からなる無機基材；前記樹脂と無機材料が複合化された基材；加飾フィルム；が挙げられる。これらの中でも、金属箔、ポリオレフィン製基材および加飾フィルムが好ましく、アルミニウム箔およびポリオレフィン製基材がより好ましい。 The substrate is not particularly limited and is not particularly limited as long as it is a substrate on which the adhesive layer is to be formed. For example, polyolefin such as polyethylene and polypropylene, ABS resin, polycarbonate (PC), polyester resin such as PET, and the like. Resin base material made of polyamide resin such as polyphenylene sulfide (PPS) and nylon, or resin such as acrylic resin; barrier film such as transparent deposited PET; ED steel sheet, Mg alloy, SUS (stainless steel), aluminum, aluminum alloy Or the inorganic base material which consists of inorganic materials, such as glass; The base material in which the said resin and the inorganic material were compounded; Among these, a metal foil, a polyolefin substrate, and a decorative film are preferable, and an aluminum foil and a polyolefin substrate are more preferable.
　なお、前記基材の接着剤層と接する面には、接着強度向上のため、コロナ処理などの従来公知の表面処理を施してもよい。 It should be noted that the surface of the substrate that is in contact with the adhesive layer may be subjected to a conventionally known surface treatment such as a corona treatment in order to improve the adhesive strength.
　前記加飾フィルムとしては、公知の意匠性を有するフィルムが挙げられ、具体的には、予め印刷・塗装・蒸着などで前記樹脂製基材や金属箔が加飾されたフィルム、意匠性を有するフィルムと前記樹脂製基材や金属箔との積層体等が挙げられる。 Examples of the decorative film include a film having a known design property, specifically, a film in which the resin base material or metal foil is previously decorated by printing, painting, vapor deposition, or the like, and has a design property. The laminated body of a film, the said resin-made base materials, metal foil, etc. are mentioned.
　ここで、意匠性を有するフィルムとしては、アクリルフィルム、ＰＥＴフィルム、ＰＣフィルム、ＣＯＣ（環状オレフィンコポリマー）フィルム、塩化ビニルフィルム、ＡＢＳフィルムなどの熱可塑性フィルムに意匠性を付与したフィルムが挙げられる。 Here, examples of the film having design properties include films obtained by imparting design properties to thermoplastic films such as acrylic films, PET films, PC films, COC (cyclic olefin copolymer) films, vinyl chloride films, and ABS films.
　なお、前記接着剤層または前記塗膜に、従来公知の方法で意匠性を付与してもよい。 In addition, you may provide the designability by the conventionally well-known method to the said adhesive bond layer or the said coating film.
　意匠性を付与する方法（加飾を施す方法）としては、例えば、真空成形法、圧空真空成形法などの既存の真空成形方法、インサート成形法、インモールド成形法、特許第３７３３５６４号公報に記載の「真空成形装置」によるＴＯＭ工法などが挙げられる。これらの方法によれば、複雑な三次元構造を有する積層体にも意匠性を付与することができる。 As a method for imparting designability (a method for decorating), for example, an existing vacuum forming method such as a vacuum forming method or a compressed air vacuum forming method, an insert forming method, an in-mold forming method, described in Japanese Patent No. 3733564 TOM method using “vacuum forming equipment”. According to these methods, design properties can be imparted to a laminate having a complicated three-dimensional structure.
　前記基材の厚みは、好ましくは１μｍ以上、より好ましくは５μｍ以上であり、また、好ましくは５００μｍ以下、より好ましくは１００μｍ以下である。 The thickness of the substrate is preferably 1 μm or more, more preferably 5 μm or more, and preferably 500 μm or less, more preferably 100 μm or less.
　前記基材上に設けたコーティング剤を乾燥させる方法としては、コーティング剤付基材を常温（約２０℃）、常圧下で放置する方法、減圧下で前記コーティング剤を乾燥させる方法、前記コーティング剤を加熱する方法が挙げられる。この加熱は、一段階で行っても、二段階以上で行ってもよい。 As a method of drying the coating agent provided on the substrate, a method of leaving the substrate with a coating agent at room temperature (about 20 ° C.) under normal pressure, a method of drying the coating agent under reduced pressure, and the coating agent The method of heating is mentioned. This heating may be performed in one step or in two or more steps.
　該加熱の条件としては、溶媒等の揮発成分が揮発する条件である限り特に制限されないが、例えば１２０℃以下、好ましくは１００℃以下で、例えば４０℃以上で、例えば３秒間以上、好ましくは１分間以上の時間、また、例えば１時間以下の時間加熱する条件が挙げられる。 The heating conditions are not particularly limited as long as volatile components such as a solvent are volatilized, but for example, 120 ° C. or lower, preferably 100 ° C. or lower, for example 40 ° C. or higher, for example 3 seconds or longer, preferably 1 A condition of heating for a time of minutes or more, for example, a time of 1 hour or less, is mentioned.
　本積層体は、通常、接着剤層を所望の被着体に接着させて使用する。つまり、本積層体は、基材、接着剤層および被着体がこの順で積層された接着体であってもよい。 This laminate is usually used with an adhesive layer adhered to a desired adherend. That is, this laminated body may be an adhesive body in which a base material, an adhesive layer, and an adherend are laminated in this order.
　該被着体としては、前記基材と同様のものが挙げられる。 Examples of the adherend include the same materials as the base material.
　前記接着体の製造方法としては、基材と被着体との間に本コーティング剤を塗布し、必要により前記乾燥工程を経た後、養生工程を行ってもよいが、前記乾燥工程の前、または、前記塗膜形成工程の後に、コーティング剤または塗膜と被着体とを接触させ、次いで、前記養生工程を行う、いわゆるドライラミネート法が望ましい。 As a method for producing the adhesive body, the coating agent may be applied between the base material and the adherend, and after the drying step as necessary, a curing step may be performed, but before the drying step, Alternatively, a so-called dry laminating method is preferable in which the coating agent or the coating film is brought into contact with the adherend after the coating film forming step, and then the curing step is performed.
　前記養生工程としては、前記塗膜を加熱する方法が挙げられる。この加熱は、一段階で行っても、二段階以上で行ってもよい。 The curing step includes a method of heating the coating film. This heating may be performed in one step or in two or more steps.
　該加熱の条件としては、適宜の条件が選択されるが、低温、例えば８０℃以下、好ましくは７０℃以下、特に好ましくは６０℃以下で、また、例えば４０℃以上で、例えば１日間以上、好ましくは３日間以上の時間、また、例えば７日間以下の時間養生する方法（低温養生法）、高温、例えば１００℃以上、好ましくは１２０℃以上で、また、例えば２００℃以下で、例えば０．１秒間以上、好ましくは０．５秒間以上の時間、また、例えば６０秒間以下の時間養生する方法（高温養生法）が挙げられる。これらの中でも、基材や被着体が有する特性を損なうことなく積層体を得ることができ、また、基材や被着体の選択自由度が増す等の点から、低温養生法が好ましい。 As the heating conditions, suitable conditions are selected, but at a low temperature, for example, 80 ° C. or less, preferably 70 ° C. or less, particularly preferably 60 ° C. or less, and for example, 40 ° C. or more, for example, 1 day or more, A method of curing for a period of preferably 3 days or more, for example 7 days or less (low temperature curing method), a high temperature, for example 100 ° C. or more, preferably 120 ° C. or more, for example 200 ° C. or less, A method of curing for 1 second or longer, preferably 0.5 seconds or longer, or for 60 seconds or shorter (high temperature curing method) can be used. Among these, a low-temperature curing method is preferable from the viewpoint that a laminate can be obtained without impairing the properties of the substrate and adherend, and that the degree of freedom in selecting the substrate and adherend is increased.
　基材と被着体とを接着させる際には、基材と被着体との間に圧力をかけながら接着させてもよい。 When the substrate and the adherend are bonded, the substrate and the adherend may be bonded while applying pressure.
　該圧力としては、例えば０．１ＭＰａ以上、好ましくは０．２ＭＰａ以上であり、また、好ましくは２ＭＰａ以下である。 The pressure is, for example, 0.1 MPa or more, preferably 0.2 MPa or more, and preferably 2 MPa or less.
　前記接着剤層の厚みは、所望の用途等に応じて適宜選択すればよく、特に制限されないが、例えば０．２μｍ以上、好ましくは１μｍ以上であり、また、例えば１００μｍ以下、好ましくは２０μｍ以下である。 The thickness of the adhesive layer may be appropriately selected according to the desired application and is not particularly limited. For example, the thickness is 0.2 μm or more, preferably 1 μm or more, and for example, 100 μm or less, preferably 20 μm or less. is there.
　前記積層体は、例えば、自動車内外装用部材；ＡＶ機器などの各種フロントパネル；ボタン、エンブレムなどの表面化粧材；携帯電話、カメラなど情報家電の筐体；ハウジング、表示窓、ボタンなどの各種部品；家具用外装材；浴室面、壁面、天井、床などの建築用内装材；サイディングなどの外壁、塀、屋根、門扉、破風板などの建築用外装材；窓枠、扉、手すり、敷居、鴨居、家具類の表面化粧材などの内装材；各種ディスプレイ、レンズ、ミラー、ゴーグル、窓ガラスなどの光学部材；電車、航空機、船舶などの自動車以外の各種乗り物の内外装用部材；瓶、化粧品容器、小物入れなどの各種容器；包装材料；その他各種物品に使用することができる。 The laminate includes, for example, automobile interior and exterior members; various front panels such as AV equipment; surface decorative materials such as buttons and emblems; housings for information appliances such as mobile phones and cameras; various parts such as housings, display windows, and buttons. Furniture exterior materials; bathroom interior surfaces, wall surfaces, ceilings, floors and other architectural interior materials; siding exterior walls, fences, roofs, gates, windbreak boards, etc .; window frames, doors, handrails, sills, Interior materials such as surface decoration materials for duck and furniture; optical members such as various displays, lenses, mirrors, goggles and window glass; interior and exterior materials for various vehicles other than automobiles such as trains, aircraft and ships; bottles and cosmetic containers It can be used for various containers such as small items; packaging materials; and other various articles.
　＜包材＞
　本発明の一実施形態における包材は、内層と接着剤層と基材とがこの順で積層された積層体を含む。なお、該接着剤層は、前記本コーティング剤の硬化物からなる層である。 <Wrapping material>
The packaging material in one embodiment of the present invention includes a laminate in which an inner layer, an adhesive layer, and a base material are laminated in this order. The adhesive layer is a layer made of a cured product of the coating agent.
　該包材は、前記接着剤層を有するため、基材と内層との接着強度に優れ、また、耐薬品性、耐電解液性に優れる。このため、該包材を長期間にわたって使用しても、基材と内層との接着強度の低下を有効に防止することができ、長期信頼性に優れる包材を得ることができる。 Since the packaging material has the adhesive layer, it has excellent adhesive strength between the base material and the inner layer, and is excellent in chemical resistance and electrolytic solution resistance. For this reason, even if this packaging material is used over a long period of time, a decrease in the adhesive strength between the base material and the inner layer can be effectively prevented, and a packaging material having excellent long-term reliability can be obtained.
　前記包材は、内層と接着剤層と基材とがこの順で積層されていれば特に制限されず、従来公知の層をこれらの層間または積層体の表面に用いてもよい。 The packaging material is not particularly limited as long as the inner layer, the adhesive layer, and the base material are laminated in this order, and a conventionally known layer may be used on these layers or the surface of the laminate.
　このような包材は、接着強度および耐薬品性（電解液性）に優れる電池ケース用包材や、接着強度および耐アルカリ性に優れる高アルカリ溶液用包材、さらには、接着強度および耐アルコール性に優れるアルコール含有溶液用包材に好適に用いられる。 Such packaging materials include battery case packaging materials with excellent adhesive strength and chemical resistance (electrolytic solution properties), packaging materials for highly alkaline solutions with excellent adhesive strength and alkali resistance, and further adhesive strength and alcohol resistance. It is suitably used for a packaging material for alcohol-containing solutions that excels in the quality.
　前記内層は、前記積層体の欄に記載した被着体に相当し、該被着体と同様の層が挙げられ、特に限定されないが、前記包材を高アルカリ溶液用包材やアルコール含有溶液用包材として用いる場合、該包材に耐薬品性（電解液性）、ヒートシール性等を付与するため、好ましくは、未延伸ポリプロピレンフィルム、低密度リニアポリエチレンなどの熱可塑性のポリオレフィンフィルムなどが使用される。 The inner layer corresponds to the adherend described in the column of the laminate, and includes the same layer as the adherend, and is not particularly limited. However, the packaging material may be a highly alkaline solution packaging material or an alcohol-containing solution. When used as a packaging material, a thermoplastic polyolefin film such as an unstretched polypropylene film or a low-density linear polyethylene is preferably used to impart chemical resistance (electrolytic solution property), heat sealability, etc. to the packaging material. used.
　前記基材としては、前記積層体の欄に記載した基材と同様の基材が挙げられ、特に限定されない。 Examples of the substrate include the same substrates as those described in the column of the laminate, and are not particularly limited.
　前記包材の厚みは、所望の用途に応じ適宜選択すればよいが、例えば３０μｍ以上であり、また、例えば２００μｍ以下である。 The thickness of the packaging material may be appropriately selected according to a desired application, and is, for example, 30 μm or more, and for example, 200 μm or less.
　前記包材は、内層に収容物、例えば、高アルカリ溶液やアルコール含有溶液が接触するように、内層を内側にした袋状にして用いてもよい。 The packaging material may be used in the form of a bag with the inner layer inside so that the inner layer comes into contact with a contained material, for example, a highly alkaline solution or an alcohol-containing solution.
　なお、前記高アルカリ溶液としては、ｐＨが、例えば９以上、好ましくは１０以上である溶液が挙げられる。具体的には、例えば、アルカリ洗剤や毛髪処理剤などが挙げられる。 Note that examples of the highly alkaline solution include solutions having a pH of, for example, 9 or more, preferably 10 or more. Specific examples include alkaline detergents and hair treatment agents.
　また、前記アルコール含有溶液としては、メタノール、エタノール、プロパノール、エチレングリコールなどを含む溶液が挙げられる。該アルコール含有溶液中のアルコール濃度は、例えば３質量％以上、好ましくは５質量％以上であり、また、例えば９５質量％以下、好ましくは８０質量％以下である。 Also, examples of the alcohol-containing solution include solutions containing methanol, ethanol, propanol, ethylene glycol, and the like. The alcohol concentration in the alcohol-containing solution is, for example, 3% by mass or more, preferably 5% by mass or more, and for example, 95% by mass or less, preferably 80% by mass or less.
　＜電池ケース用包材＞
　本発明の一実施形態における電池ケース用包材は、内層と内側接着剤層と基材と外側接着剤層と外層とがこの順で積層された積層体を含む。なお、該内側接着剤層は、前記本コーティング剤の硬化物からなる層である。 <Packaging material for battery case>
The battery case packaging material in one embodiment of the present invention includes a laminate in which an inner layer, an inner adhesive layer, a base material, an outer adhesive layer, and an outer layer are laminated in this order. The inner adhesive layer is a layer made of a cured product of the present coating agent.
　該電池ケース用包材は、前記接着剤層を有するため、基材と内層との接着強度に優れ、また、耐電解液性に優れる。このため、電池ケース用包材を長期間にわたって使用しても、基材と内層との接着強度の低下を有効に防止することができ、長期信頼性に優れる電池ケース用包材を得ることができる。 Since the battery case packaging material has the adhesive layer, it has excellent adhesive strength between the base material and the inner layer, and also has excellent electrolyte resistance. For this reason, even when the battery case packaging material is used for a long period of time, it is possible to effectively prevent a decrease in the adhesive strength between the base material and the inner layer, and to obtain a battery case packaging material having excellent long-term reliability. it can.
　前記電池ケース用包材は、内層と内側接着剤層と基材と外側接着剤層と外層とがこの順で積層されていれば特に制限されず、従来公知の層をこれらの層間または積層体の表面に用いてもよい。 The battery case packaging material is not particularly limited as long as the inner layer, the inner adhesive layer, the base material, the outer adhesive layer, and the outer layer are laminated in this order. You may use for the surface of.
　前記内層は、前記積層体の欄に記載した被着体に相当し、該被着体と同様の層が挙げられ、特に限定されないが、電池ケース用包材に耐薬品性（電解液性）、ヒートシール性等を付与するために、未延伸ポリプロピレンフィルムなどの熱可塑性のポリオレフィンフィルムなどを使用することが好ましい。 The inner layer corresponds to the adherend described in the column of the laminate, and includes the same layer as the adherend. Although not particularly limited, the battery case packaging material has chemical resistance (electrolytic solution property). In order to impart heat sealability and the like, it is preferable to use a thermoplastic polyolefin film such as an unstretched polypropylene film.
　前記基材としては、前記積層体の欄に記載した基材と同様の基材が挙げられ、特に限定されないが、好ましくは金属箔、さらに好ましくは、アルミニウム箔、ＳＵＳ箔が挙げられる。また、基材表面は耐食性等の観点から化成処理を施していてもよい。 Examples of the substrate include the same substrates as those described in the section of the laminate, and are not particularly limited, but preferably include metal foil, more preferably aluminum foil and SUS foil. Further, the base material surface may be subjected to chemical conversion treatment from the viewpoint of corrosion resistance and the like.
　前記外側接着剤層は、外層と基材とが接着するような層であればよく、前記本コーティング剤の硬化物からなる層であってもよく、ドライラミネート用接着剤、無溶剤型接着剤などの従来公知の接着剤を用いて得られる層であってもよい。 The outer adhesive layer may be a layer that allows the outer layer and the base material to adhere to each other, and may be a layer made of a cured product of the present coating agent. An adhesive for dry lamination, a solventless adhesive It may be a layer obtained using a conventionally known adhesive such as.
　前記外層としては、特に限定されないが、電池製造時のヒートシール工程における耐熱性や加工時の成形性、耐ピンホール性、流通時の絶縁性等を付与するために、好ましくは、ポリエステルフィルム、ポリアミドフィルム、ポリプロピレンフィルムなどの延伸もしくは未延伸フィルムを単層または２層以上積層した多層フィルムが使用される。 The outer layer is not particularly limited, but in order to impart heat resistance in the heat sealing process during battery production, moldability during processing, pinhole resistance, insulation during distribution, etc., preferably a polyester film, A multilayer film in which stretched or unstretched films such as polyamide film and polypropylene film are laminated in a single layer or two or more layers is used.
　前記電池ケース用包材の厚みは、例えば６０μｍ以上、また、例えば１６０μｍ以下である。 The thickness of the battery case packaging material is, for example, 60 μm or more, and for example, 160 μm or less.
　＜電池＞
　本発明の一実施形態における電池は、前記電池ケース用包材と、該電池ケース用包材に包装される電解液とを備え、前記電池ケース用包材の内層の少なくとも一部が前記電解液に接触している電池である。該電池としては、特に制限されないが、例えば、リチウムイオン２次電池が挙げられる。以下、前記電池を、その一実施形態を示す図１を参照して説明する。 <Battery>
A battery according to an embodiment of the present invention includes the battery case packaging material and an electrolyte solution packaged in the battery case packaging material, wherein at least a part of an inner layer of the battery case packaging material is the electrolyte solution. The battery is in contact with the battery. Although it does not restrict | limit especially as this battery, For example, a lithium ion secondary battery is mentioned. Hereinafter, the battery will be described with reference to FIG. 1 showing an embodiment thereof.
　図１に示すように、電池１０は、電池ケース用包材１と、電池ケース用包材１に包装される電解液１１とを備える。また、電池１０は、電池ケース用包材１内に収容される正極１７、負極１８およびセパレータ１９を備える。 As shown in FIG. 1, the battery 10 includes a battery case packaging material 1 and an electrolyte solution 11 packaged in the battery case packaging material 1. The battery 10 also includes a positive electrode 17, a negative electrode 18, and a separator 19 that are accommodated in the battery case packaging material 1.
　該電池では、電池ケース用包材１における内層３の内面に電解液１１が接触するように、電池ケース用包材１が袋状に構成されており、該電池ケース用包材１は、その内側から、内層３、内側接着剤層５、基材２、外側接着剤層６および外層４がこの順で積層された積層体である。 In the battery, the battery case packaging material 1 is formed in a bag shape so that the electrolyte solution 11 contacts the inner surface of the inner layer 3 of the battery case packaging material 1. The inner layer 3, the inner adhesive layer 5, the substrate 2, the outer adhesive layer 6 and the outer layer 4 are laminated in this order from the inside.
　前記電解液１１としては、特に限定されず、例えば、エチレンカーボネート、ジエチルカーボネート、ジメチルカーボネート、６フッ化リン酸リチウムなどのリチウム塩などを含有する電解液が挙げられる。 The electrolytic solution 11 is not particularly limited, and examples thereof include electrolytic solutions containing lithium salts such as ethylene carbonate, diethyl carbonate, dimethyl carbonate, and lithium hexafluorophosphate.
　正極１７および負極１８は、電解液１１に接触するように、かつ、セパレータ１９を介して互いに間隔を隔てて対向配置されている。 The positive electrode 17 and the negative electrode 18 are disposed so as to be in contact with the electrolyte solution 11 and spaced from each other with a separator 19 therebetween.
　以下、実施例に基づいて本発明をより具体的に説明するが、本発明はこれら実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
　＜プロピレン含量、エチレン含量の測定＞
　13Ｃ－ＮＭＲを利用して求めた。 <Measurement of propylene content and ethylene content>
It was determined using 13 C-NMR.
　＜融点、融解熱量の測定＞
　示差走査熱量計（ＴＡ　Ｉｎｓｔｒｕｍｅｎｔｓ製；ＤＳＣ－Ｑ１０００）を用いて、融点および融解熱量を求めた。１０℃／ｍｉｎで３０℃から１８０℃まで昇温後、１８０℃で３分間保持し、１０℃／ｍｉｎで０℃まで降温し、再度１０℃／ｍｉｎで１５０℃まで昇温する過程において、２度目の昇温時のサーモグラムより、ＪＩＳ　Ｋ　７１２２に准じて融点と融解熱量を求めた。 <Measurement of melting point and heat of fusion>
The melting point and heat of fusion were determined using a differential scanning calorimeter (TA Instruments; DSC-Q1000). In the process of raising the temperature from 30 ° C. to 180 ° C. at 10 ° C./min, holding at 180 ° C. for 3 minutes, lowering the temperature to 0 ° C. at 10 ° C./min, and again raising the temperature to 150 ° C. at 10 ° C./min. From the thermogram at the time of the second temperature increase, the melting point and heat of fusion were determined according to JIS K7122.
　＜２００℃動粘度の測定＞
　ＪＩＳ Ｋ ２２８３に基づいて２００℃動粘度を求めた。 <Measurement of 200 ° C kinematic viscosity>
The kinematic viscosity at 200 ° C. was determined based on JIS K 2283.
　＜重量平均分子量（Ｍｗ）の測定＞
　ゲルパーミエーションクロマトグラフィー（島津製作所社製；ＬＣ－１０ ｓｅｒｉｅｓ）を用いて、以下の条件で、成分（Ａ）に相当する低結晶性オレフィン樹脂及び成分（Ｂ）に相当または類似する炭化水素系重合体の重量平均分子量（Ｍｗ）を測定した。 <Measurement of weight average molecular weight (Mw)>
Using a gel permeation chromatography (manufactured by Shimadzu Corporation; LC-10 series), a low crystalline olefin resin corresponding to component (A) and a hydrocarbon system corresponding to or similar to component (B) under the following conditions The weight average molecular weight (Mw) of the polymer was measured.
　・検出器：島津製作所社製；Ｃ－Ｒ４Ａ
　・カラム：ＴＳＫＧ　６０００Ｈ－ＴＳＫＧ　４０００Ｈ－ＴＳＫＧ　３０００Ｈ－ＴＳＫＧ　２０００Ｈ（東ソー社製）
　・移動相：テトラヒドロフラン
　・温度：４０℃
　・流量：０．８ｍｌ／ｍｉｎ
　単分散標準ポリスチレンより作成した検量線を用いて、Ｍｗを算出した。 Detector: Shimadzu Corporation; C-R4A
Column: TSKG 6000H-TSKG 4000H-TSKG 3000H-TSKG 2000H (manufactured by Tosoh Corporation)
-Mobile phase: Tetrahydrofuran-Temperature: 40 ° C
・ Flow rate: 0.8ml / min
Mw was calculated using a calibration curve prepared from monodisperse standard polystyrene.
　＜極性基含有単量体のグラフト量の測定＞
　1Ｈ－ＮＭＲによる測定から求めた。 <Measurement of graft amount of polar group-containing monomer>
It was determined from measurement by 1 H-NMR.
　＜塩素含有量＞
　ＪＩＳ Ｋ ７２２９に準じ、次式により塩素含有量を求めた。 <Chlorine content>
According to JIS K 7229, the chlorine content was determined by the following formula.
　　塩素含有量（質量％）＝｛（Ａ－Ｂ）×Ｆ｝／Ｓ×１００
　Ａ：試料の滴定に要した０．０２８２Ｎ硝酸銀水溶液の量（ｍＬ）
　Ｂ：空試料の滴定に要した０．０２８２Ｎ硝酸銀水溶液の量（ｍＬ）
　Ｆ：０．０２８２Ｎ硝酸銀水溶液の力価
　Ｓ：試料の質量（ｍｇ）
　［低結晶性オレフィン樹脂］
　＜製造例１－１：熱可塑性樹脂（Ａ－１）の合成 ＞
　充分に窒素置換した２リットルのオートクレーブに、ヘキサンを９００ｍＬ、1-ブテンを９０ｇ仕込み、トリイソブチルアルミニウムを１ミリモル加え、７０℃に昇温した後、プロピレンを供給して全圧７ｋｇ／ｃｍ2Ｇにし、メチルアルミノキサン０. ３０ミリモル、rac-ジメチルシリレン－ビス｛1-（2-メチル-4- フェニルインデニル）｝ジルコニウムジクロライドをＺｒ原子に換算して０. ００１ミリモル加え、プロピレンを連続的に供給して全圧を７ｋｇ／ｃｍ2Ｇに保ちながら３０分間重合を行った。重合後、脱気して大量のメタノール中でポリマーを回収し、１１０℃で１２時間減圧乾燥した。得られたプロピレン／１-ブテン共重合体（以下「熱可塑性樹脂（Ａ－１）」ともいう。）の融点は７８．３℃、融解熱量は２９．２Ｊ／ｇ、Ｍｗは３３０，０００、プロピレン含有量は６７．２モル％であった。 Chlorine content (% by mass) = {(AB) × F} / S × 100
A: Amount of 0.0282N silver nitrate aqueous solution required for titration of sample (mL)
B: Amount of 0.0282N silver nitrate aqueous solution required for titration of empty sample (mL)
F: Titer of 0.0282N silver nitrate aqueous solution S: Mass of sample (mg)
[Low crystalline olefin resin]
<Production Example 1-1: Synthesis of thermoplastic resin (A-1)>
A 2 liter autoclave thoroughly purged with nitrogen was charged with 900 mL of hexane and 90 g of 1-butene, 1 mmol of triisobutylaluminum was added, the temperature was raised to 70 ° C., and propylene was supplied to give a total pressure of 7 kg / cm 2 G Next, 0.30 mmol of methylaluminoxane and 0.001 mmol of rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride in terms of Zr atoms were added, and propylene was continuously added. Polymerization was carried out for 30 minutes while feeding and maintaining the total pressure at 7 kg / cm 2 G. After the polymerization, the polymer was degassed and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours. The resulting propylene / 1-butene copolymer (hereinafter also referred to as “thermoplastic resin (A-1)”) has a melting point of 78.3 ° C., a heat of fusion of 29.2 J / g, Mw of 330,000, The propylene content was 67.2 mol%.
　＜製造例１－２：熱可塑性樹脂（Ａ－２）の合成 ＞
　充分に窒素置換した２リットルのオートクレーブに、ヘキサンを９００ｍＬ、1-ブテンを８０ｇ仕込み、トリイソブチルアルミニウムを１ミリモル加え、７０℃に昇温した後、プロピレンを供給して全圧７ｋｇ／ｃｍ2Ｇにし、メチルアルミノキサン０. ３０ミリモル、rac-ジメチルシリレン－ビス｛1-（2-メチル-4- フェニルインデニル）｝ジルコニウムジクロライドをＺｒ原子に換算して０. ００１ミリモル加え、プロピレンを連続的に供給して全圧を７ｋｇ／ｃｍ2Ｇに保ちながら３０分間重合を行った。重合後、脱気して大量のメタノール中でポリマーを回収し、１１０℃で１２時間減圧乾燥した。得られたプロピレン／１-ブテン共重合体（以下「熱可塑性樹脂（Ａ－２）」ともいう。）の融点は８９．２℃、融解熱量は３１．５Ｊ／ｇ、Ｍｗは３３０，０００、プロピレン含有量は７３．５モル％であった。 <Production Example 1-2: Synthesis of thermoplastic resin (A-2)>
A 2 liter autoclave thoroughly purged with nitrogen was charged with 900 mL of hexane and 80 g of 1-butene, 1 mmol of triisobutylaluminum was added, the temperature was raised to 70 ° C., and propylene was supplied to give a total pressure of 7 kg / cm 2 G Next, 0.30 mmol of methylaluminoxane and 0.001 mmol of rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride in terms of Zr atoms were added, and propylene was continuously added. Polymerization was carried out for 30 minutes while feeding and maintaining the total pressure at 7 kg / cm 2 G. After the polymerization, the polymer was degassed and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours. The resulting propylene / 1-butene copolymer (hereinafter also referred to as “thermoplastic resin (A-2)”) has a melting point of 89.2 ° C., a heat of fusion of 31.5 J / g, Mw of 330,000, The propylene content was 73.5 mol%.
　＜製造例１－３：熱可塑性樹脂（Ａ－３）の合成 ＞
　製造例１－１で得られた熱可塑性樹脂（Ａ－１）３ｋｇを１０Ｌのトルエンに加え、窒素雰囲気下で１４５℃に昇温し、該共重合体をトルエンに溶解させた。さらに、攪拌下で無水マレイン酸３８２ｇ、ジ－ｔｅｒｔ－ブチルパーオキシド１７５ｇを４時間かけて系に供給し、続けて１４５℃で２時間攪拌を行った。冷却後、多量のアセトンを投入して変性された共重合体を沈殿させた。これをろ過し、アセトンで洗浄した後、真空乾燥した。得られた無水マレイン酸変性プロピレン／１-ブテン共重合体（以下「熱可塑性樹脂（Ａ－３）」ともいう。）の融点は７５．８℃、融解熱量は２８．６Ｊ／ｇ、Ｍｗは１１０，０００、無水マレイン酸のグラフト量は変性共重合体１００重量％に対して１重量％であった。 <Production Example 1-3: Synthesis of thermoplastic resin (A-3)>
3 kg of the thermoplastic resin (A-1) obtained in Production Example 1-1 was added to 10 L of toluene, and the temperature was raised to 145 ° C. in a nitrogen atmosphere to dissolve the copolymer in toluene. Further, 382 g of maleic anhydride and 175 g of di-tert-butyl peroxide were supplied to the system over 4 hours under stirring, and then stirred at 145 ° C. for 2 hours. After cooling, a large amount of acetone was added to precipitate the modified copolymer. This was filtered, washed with acetone, and then vacuum dried. The resulting maleic anhydride-modified propylene / 1-butene copolymer (hereinafter also referred to as “thermoplastic resin (A-3)”) has a melting point of 75.8 ° C., a heat of fusion of 28.6 J / g, and Mw is The graft amount of 110,000 maleic anhydride was 1% by weight with respect to 100% by weight of the modified copolymer.
　＜製造例１－４：熱可塑性樹脂（Ａ－４）の合成 ＞
　製造例１－２で得られた熱可塑性樹脂（Ａ－２）３ｋｇを１０Ｌのトルエンに加え、窒素雰囲気下で１４５℃に昇温し、該共重合体をトルエンに溶解させた。さらに、攪拌下で無水マレイン酸３８２ｇ、ジ－ｔｅｒｔ－ブチルパーオキシド１７５ｇを４時間かけて系に供給し、続けて１４５℃で２時間攪拌を行った。冷却後、多量のアセトンを投入して変性された共重合体を沈殿させた。これをろ過し、アセトンで洗浄した後、真空乾燥した。得られた無水マレイン酸変性プロピレン／１-ブテン共重合体（以下「熱可塑性樹脂（Ａ－４）」ともいう。）の融点は８５．９℃、融解熱量は２９．９Ｊ／ｇ、Ｍｗは１１０，０００、無水マレイン酸のグラフト量は変性共重合体１００重量％に対して１重量％であった。 <Production Example 1-4: Synthesis of thermoplastic resin (A-4)>
3 kg of the thermoplastic resin (A-2) obtained in Production Example 1-2 was added to 10 L of toluene, the temperature was raised to 145 ° C. in a nitrogen atmosphere, and the copolymer was dissolved in toluene. Further, 382 g of maleic anhydride and 175 g of di-tert-butyl peroxide were supplied to the system over 4 hours under stirring, and then stirred at 145 ° C. for 2 hours. After cooling, a large amount of acetone was added to precipitate the modified copolymer. This was filtered, washed with acetone, and then vacuum dried. The resulting maleic anhydride-modified propylene / 1-butene copolymer (hereinafter also referred to as “thermoplastic resin (A-4)”) has a melting point of 85.9 ° C., a heat of fusion of 29.9 J / g, and Mw of The graft amount of 110,000 maleic anhydride was 1% by weight with respect to 100% by weight of the modified copolymer.
　＜使用した低結晶性オレフィン樹脂の詳細＞
　後述する実施例および比較例で用いた成分（Ａ）に相当する低結晶性オレフィン樹脂の物性を下記表１に示す。 <Details of low crystalline olefin resin used>
Table 1 shows the physical properties of the low crystalline olefin resin corresponding to the component (A) used in Examples and Comparative Examples described later.
Figure JPOXMLDOC01-appb-T000001
 　表１中の記号の内容は以下のとおりである。
*1：A-1、A-2については、プロピレン含量（モル％）
　　A-3、A-4については、無水マレイン酸グラフト量（ｗｔ％）
　　A-5 については、塩素含有量（ｗｔ％）
*2：東洋紡（株）製「ハードレンＣＹ－９１２４Ｐ」
　［炭化水素系重合体］
　＜製造例２－１：炭化水素系重合体（Ｂ－１）の合成＞
　充分窒素置換した攪拌翼付連続重合反応器に、脱水精製したヘキサン１Ｌを加え、９６ｍｍｏｌ／Ｌに調整したエチルアルミニウムセスキクロリド（Ａｌ（Ｃ2Ｈ5）1.5・Ｃｌ1.5）のヘキサン溶液を５００ｍＬ／ｈの量で連続的に１時間供給した後、更に触媒として１６ｍｍｏｌ／Ｌに調整したＶＯ（ＯＣ2Ｈ5）Ｃｌ2のヘキサン溶液を５００ｍＬ／ｈ、ヘキサンを５００ｍＬ／ｈの量で連続的に供給した。一方、重合器上部から、重合液器内の重合液が常に１Ｌになるように重合液を連続的に抜き出した。次にバブリング管を用いてエチレンガスを４７Ｌ／ｈ、プロピレンガスを４７Ｌ／ｈ、水素ガスを２０Ｌ／ｈの量で供給した。共重合反応は、重合器外部に取り付けられたジャケットに冷媒を循環させることにより３５℃で行った。得られた重合溶液は、塩酸で脱灰した後に、大量のメタノールに投入して析出させた後、１３０℃で２４時間減圧乾燥を行った。得られたエチレン／プロピレン共重合体（以下「炭化水素系重合体（Ｂ－１）」ともいう。）のエチレン含量は５５．９モル％、重量平均分子量は１４，０００、４０℃動粘度は３７，５００ｍｍ2/ｓ、２００℃動粘度は１３２ｍｍ2/ｓであった。
Figure JPOXMLDOC01-appb-T000001
 The contents of the symbols in Table 1 are as follows.
* 1: Propylene content (mol%) for A-1 and A-2
For A-3 and A-4, maleic anhydride graft amount (wt%)
For A-5, chlorine content (wt%)
* 2: “Hardlen CY-9124P” manufactured by Toyobo Co., Ltd.
[Hydrocarbon polymer]
<Production Example 2-1: Synthesis of hydrocarbon polymer (B-1)>
To a continuous polymerization reactor equipped with stirring blades sufficiently purged with nitrogen, 1 L of dehydrated hexane was added, and a hexane solution of ethylaluminum sesquichloride (Al (C 2 H 5 ) 1.5 · Cl 1.5 ) adjusted to 96 mmol / L was added to 500 mL / L. After continuously supplying for 1 hour in an amount of h, a hexane solution of VO (OC 2 H 5 ) Cl 2 adjusted to 16 mmol / L as a catalyst was continuously added in an amount of 500 mL / h, and hexane was continuously supplied in an amount of 500 mL / h. Supplied. On the other hand, from the upper part of the polymerization vessel, the polymerization solution was continuously extracted so that the polymerization solution in the polymerization vessel was always 1 L. Next, ethylene gas was supplied at a rate of 47 L / h, propylene gas at 47 L / h, and hydrogen gas at 20 L / h using a bubbling tube. The copolymerization reaction was carried out at 35 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel. The obtained polymerization solution was deashed with hydrochloric acid, poured into a large amount of methanol and precipitated, and then dried under reduced pressure at 130 ° C. for 24 hours. The ethylene / propylene copolymer obtained (hereinafter also referred to as “hydrocarbon polymer (B-1)”) had an ethylene content of 55.9 mol%, a weight average molecular weight of 14,000, and a 40 ° C. kinematic viscosity. The kinematic viscosity at 37,500 mm 2 / s and 200 ° C. was 132 mm 2 / s.
　＜製造例２－２：炭化水素系重合体（Ｂ－５）の合成 ＞
　ＪＸエネルギー社製ポリイソブチレン「テトラックス４Ｔ」（以下「炭化水素系重合体（Ｂ－２）」ともいう。）１０ｋｇを１０Ｌのトルエンに加え、窒素雰囲気下で１４５℃に昇温し、該共重合体をトルエンに溶解させた。さらに、攪拌下で無水マレイン酸１００ｇ、ジ－ｔｅｒｔ－ブチルパーオキシド６０ｇを４時間かけて系に供給し、続けて１４５℃で２時間攪拌を行った。冷却後、多量のアセトンを投入し変性された共重合体を沈殿させ、ろ過し、アセトンで洗浄した後、真空乾燥した。得られた無水マレイン酸変性ポリイソブチレン（以下「炭化水素系重合体（Ｂ－５）」ともいう。）の重量平均分子量は４１，０００、２００℃動粘度は１，４００ｍｍ2/ｓ、無水マレイン酸のグラフト量は変性共重合体１００重量％に対して０．５重量％であった。 <Production Example 2-2: Synthesis of hydrocarbon polymer (B-5)>
10 kg of polyisobutylene “Tetrax 4T” (hereinafter also referred to as “hydrocarbon polymer (B-2)”) manufactured by JX Nippon Oil & Energy is added to 10 L of toluene, and the temperature is raised to 145 ° C. in a nitrogen atmosphere. The polymer was dissolved in toluene. Further, 100 g of maleic anhydride and 60 g of di-tert-butyl peroxide were supplied to the system over 4 hours with stirring, and the mixture was continuously stirred at 145 ° C. for 2 hours. After cooling, a large amount of acetone was added to precipitate the modified copolymer, filtered, washed with acetone, and then vacuum dried. The resulting maleic anhydride-modified polyisobutylene (hereinafter also referred to as “hydrocarbon polymer (B-5)”) has a weight average molecular weight of 41,000, 200 ° C. kinematic viscosity of 1,400 mm 2 / s, maleic anhydride The amount of acid grafted was 0.5% by weight based on 100% by weight of the modified copolymer.
　＜製造例２－３：炭化水素系重合体（Ｂ－６）の合成＞
　炭化水素系重合体（Ｂ－２）をＪＸエネルギー社製ポリイソブチレン「テトラックス５Ｔ」（以下「炭化水素系重合体（Ｂ－３）」ともいう。）に変更したこと以外は製造例２－２と同様にして、無水マレイン酸変性ポリイソブチレン（以下「炭化水素系重合体（Ｂ－６）ともいう。」を得た。得られた炭化水素系重合体（Ｂ－６）の重量平均分子量は４８，０００、２００℃動粘度は５，８００ｍｍ2/ｓ、無水マレイン酸のグラフト量は変性共重合体１００重量％に対して０．５重量％であった。 <Production Example 2-3: Synthesis of hydrocarbon polymer (B-6)>
Production Example 2- except that the hydrocarbon polymer (B-2) was changed to polyisobutylene “Tetrax 5T” (hereinafter also referred to as “hydrocarbon polymer (B-3)”) manufactured by JX Nippon Oil & Energy. The maleic anhydride-modified polyisobutylene (hereinafter also referred to as “hydrocarbon polymer (B-6)”) was obtained in the same manner as in 2. The weight average molecular weight of the obtained hydrocarbon polymer (B-6) Was 48,000, the kinematic viscosity at 200 ° C. was 5,800 mm 2 / s, and the graft amount of maleic anhydride was 0.5% by weight based on 100% by weight of the modified copolymer.
　＜製造例２－４：炭化水素系重合体（Ｂ－７）の合成 ＞
　炭化水素系重合体（Ｂ－２）をＪＸエネルギー社製ポリイソブチレン「テトラックス６Ｔ」（以下「炭化水素系重合体（Ｂ－４）ともいう。」に変更したこと以外は製造例２－２と同様にして、無水マレイン酸変性ポリイソブチレン（以下「炭化水素系重合体（Ｂ－７）ともいう。」を得た。得られた炭化水素系重合体（Ｂ－７）の重量平均分子量は５５，０００、２００℃動粘度は１２，０００ｍｍ2/ｓ、無水マレイン酸のグラフト量は変性共重合体１００重量％に対して０．５重量％であった。 <Production Example 2-4: Synthesis of hydrocarbon polymer (B-7)>
Production Example 2-2 except that the hydrocarbon polymer (B-2) was changed to a polyisobutylene “Tetrax 6T” (hereinafter also referred to as “hydrocarbon polymer (B-4)”) manufactured by JX Energy. In the same manner, maleic anhydride-modified polyisobutylene (hereinafter also referred to as “hydrocarbon polymer (B-7)”) was obtained. The weight average molecular weight of the obtained hydrocarbon polymer (B-7) was The kinematic viscosity at 55,000, 200 ° C. was 12,000 mm 2 / s, and the graft amount of maleic anhydride was 0.5% by weight based on 100% by weight of the modified copolymer.
　後述する実施例および比較例で用いた成分（Ｂ）に相当または類似する炭化水素系重合体の物性を下記表２に示す。 The physical properties of hydrocarbon polymers corresponding to or similar to the component (B) used in Examples and Comparative Examples described below are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000002
 　表２中の記号の内容は以下のとおりである。
*3：製造例２－１で得られたエチレン/プロピレン共重合体
*4：ＪＸ日鉱日石エネルギー（株）製「テトラックス４Ｔ」
*5：ＪＸ日鉱日石エネルギー（株）製「テトラックス５Ｔ」
*6：ＪＸ日鉱日石エネルギー（株）製「テトラックス６Ｔ」
*7：製造例２－２で得られた無水マレイン酸変性物（半固体状）
*8：製造例２－３で得られた無水マレイン酸変性物（半固体状）
*9：製造例２－４で得られた無水マレイン酸変性物（半固体状）
　［粘着付与剤］
　後述する実施例または比較例で用いた成分（Ｃ）に相当する粘着付与剤は以下のとおりである。
Figure JPOXMLDOC01-appb-T000002
 The contents of the symbols in Table 2 are as follows.
* 3: Ethylene / propylene copolymer obtained in Production Example 2-1.
* 4: “Tetrax 4T” manufactured by JX Nippon Oil & Energy
* 5: “Tetrax 5T” manufactured by JX Nippon Oil & Energy
* 6: “Tetrax 6T” manufactured by JX Nippon Oil & Energy Corporation
* 7: Maleic anhydride-modified product (semi-solid form) obtained in Production Example 2-2
* 8: Maleic anhydride modified product obtained in Production Example 2-3 (semi-solid)
* 9: Maleic anhydride modified product obtained in Production Example 2-4 (semi-solid)
[Tackifier]
The tackifiers corresponding to the component (C) used in Examples and Comparative Examples described below are as follows.
　（Ｃ－１）荒川化学工業（株）製「スーパーエステルＷ－１２５」（ロジンエステル、Ｍｗ：2,500、酸価（mgKOH/g）：14.3）
　［硬化剤］
　後述する実施例または比較例で用いた成分（Ｄ）に相当する硬化剤は以下のとおりである。 (C-1) “Super Ester W-125” manufactured by Arakawa Chemical Industries, Ltd. (rosin ester, Mw: 2,500, acid value (mgKOH / g): 14.3)
[Curing agent]
Curing agents corresponding to the component (D) used in Examples and Comparative Examples described below are as follows.
　（Ｄ－１）Ｃｏｖｅｓｔｒｏ社製「Desmodur N 3300」（ＨＤＩトリマー、ＮＣＯ含量（％）：21.8）
　（Ｄ－２）ダイセル化学工業社製「ＥＨＰＥ３１５０」（脂環式エポキシ樹脂、エポキシ当量（g/eq）：180）
　［触媒］
　後述する実施例または比較例で用いた成分（Ｅ）に相当する触媒は以下のとおりである。 (D-1) “Desmodur N 3300” manufactured by Covestro (HDI trimer, NCO content (%): 21.8)
(D-2) “EHPE3150” manufactured by Daicel Chemical Industries, Ltd. (alicyclic epoxy resin, epoxy equivalent (g / eq): 180)
[catalyst]
The catalyst corresponding to the component (E) used in Examples and Comparative Examples described below is as follows.
　（Ｅ－１）サンアプロ（株）製「ＤＢＵ」（１，８－ジアザビシクロ［５．４．０］ウンデセン－７、ｐＫａ：12.5）
　［実施例１］
　熱可塑性樹脂（Ａ－３）８０ｇおよび炭化水素系重合体（Ｂ－２）２０ｇを４００ｇのトルエンに溶解させて、変性オレフィン重合体ワニス（１）を調製した。得られた変性オレフィン重合体ワニス（１）５００ｇに、硬化剤（Ｄ－１）５ｇを混合し、ラミネート用接着剤組成物を調製した。次いで、ラミネート用接着剤組成物をトルエンで希釈し、バーコーターを用いて、得られる塗膜付箔の坪量が３．３ｇ／ｍ2になるように、厚さ４０μｍのアルミニウム箔（Ａｌ箔、表面未処理）のツヤ面上に常温下において塗布し、溶媒を揮散させることで、塗膜付箔を得た。その後、得られた塗膜付箔の塗膜面と、厚さ６０μｍの未延伸ポリプロピレンフィルム（ＣＰＰ、片面コロナ処理品）におけるコロナ処理面とを４０℃のホットステージ上で貼り合わせ、６０℃で３日間養生することにより、前記塗膜を硬化させ、Ａｌ箔およびＣＰＰ間を接着させることで、Ａｌ箔、接着剤層およびＣＰＰがこの順で積層した積層体（複合フィルム）を得た。 (E-1) “DBU” (1,8-diazabicyclo [5.4.0] undecene-7, pKa: 12.5) manufactured by San Apro Co., Ltd.
[Example 1]
A modified olefin polymer varnish (1) was prepared by dissolving 80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-2) in 400 g of toluene. 500 g of the resulting modified olefin polymer varnish (1) was mixed with 5 g of a curing agent (D-1) to prepare an adhesive composition for laminating. Next, the laminate adhesive composition was diluted with toluene, and using a bar coater, a 40 μm thick aluminum foil (Al foil) was prepared so that the basis weight of the obtained coated foil was 3.3 g / m 2. The foil with a coating film was obtained by coating at room temperature on the glossy surface of the surface untreated) and volatilizing the solvent. Thereafter, the coated film surface of the obtained foil with coated film and the corona-treated surface of an unstretched polypropylene film (CPP, single-sided corona-treated product) having a thickness of 60 μm were bonded on a hot stage at 40 ° C., and at 60 ° C. By curing for 3 days, the coating film was cured and the Al foil and the CPP were adhered to each other, thereby obtaining a laminate (composite film) in which the Al foil, the adhesive layer, and the CPP were laminated in this order.
　［実施例２］
　硬化剤（Ｄ－１）を硬化剤（Ｄ－２）に変更し、更に触媒（Ｅ－１）５００ｐｐｍを添加したこと以外は実施例１と同様にして複合フィルムを得た。 [Example 2]
A composite film was obtained in the same manner as in Example 1 except that the curing agent (D-1) was changed to the curing agent (D-2) and 500 ppm of the catalyst (E-1) was further added.
　［実施例３］
　熱可塑性樹脂（Ａ－３）８０ｇおよび炭化水素系重合体（Ｂ－２）２０ｇを、熱可塑性樹脂（Ａ－３）７０ｇおよび炭化水素系重合体（Ｂ－５）３０ｇに変更したこと以外は実施例１と同様にして複合フィルムを得た。 [Example 3]
Except for changing 80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-2) to 70 g of the thermoplastic resin (A-3) and 30 g of the hydrocarbon polymer (B-5). A composite film was obtained in the same manner as in Example 1.
　［実施例４］
　熱可塑性樹脂（Ａ－３）８０ｇおよび炭化水素系重合体（Ｂ－２）２０ｇを、熱可塑性樹脂（Ａ－３）５０ｇおよび炭化水素系重合体（Ｂ－６）５０ｇに変更したこと以外は実施例１と同様にして複合フィルムを得た。 [Example 4]
Except for changing 80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-2) to 50 g of the thermoplastic resin (A-3) and 50 g of the hydrocarbon polymer (B-6). A composite film was obtained in the same manner as in Example 1.
　［実施例５］
　熱可塑性樹脂（Ａ－３）８０ｇおよび炭化水素系重合体（Ｂ－２）２０ｇを、熱可塑性樹脂（Ａ－３）５０ｇおよび炭化水素系重合体（Ｂ－７）５０ｇに変更したこと以外は実施例１と同様にして複合フィルムを得た。 [Example 5]
Except for changing 80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-2) to 50 g of the thermoplastic resin (A-3) and 50 g of the hydrocarbon polymer (B-7). A composite film was obtained in the same manner as in Example 1.
　［実施例６］
　熱可塑性樹脂（Ａ－３）を熱可塑性樹脂（Ａ－４）に変更し、４０℃の貼り合せ温度を７０℃に変更したこと以外は実施例１と同様にして複合フィルムを得た。 [Example 6]
A composite film was obtained in the same manner as in Example 1 except that the thermoplastic resin (A-3) was changed to the thermoplastic resin (A-4) and the bonding temperature at 40 ° C. was changed to 70 ° C.
　［実施例７］
　熱可塑性樹脂（Ａ－３）を熱可塑性樹脂（Ａ－４）に変更し、４０℃の貼り合せ温度を７０℃に変更したこと以外は実施例２と同様にして複合フィルムを得た。 [Example 7]
A composite film was obtained in the same manner as in Example 2 except that the thermoplastic resin (A-3) was changed to the thermoplastic resin (A-4) and the bonding temperature at 40 ° C. was changed to 70 ° C.
　［実施例８］
　熱可塑性樹脂（Ａ－３）を熱可塑性樹脂（Ａ－５）に変更したこと以外は実施例１と同様にして複合フィルムを得た。 [Example 8]
A composite film was obtained in the same manner as in Example 1 except that the thermoplastic resin (A-3) was changed to the thermoplastic resin (A-5).
　［比較例１］
　炭化水素系重合体（Ｂ－２）を炭化水素系重合体（Ｂ－１）に変更したこと以外は実施例１と同様にして複合フィルムを得た。 [Comparative Example 1]
A composite film was obtained in the same manner as in Example 1 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).
　［比較例２］
　炭化水素系重合体（Ｂ－２）を炭化水素系重合体（Ｂ－１）に変更したこと以外は実施例６と同様にして複合フィルムを得た。 [Comparative Example 2]
A composite film was obtained in the same manner as in Example 6 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).
　［比較例３］
　炭化水素系重合体（Ｂ－２）を炭化水素系重合体（Ｂ－１）に変更したこと以外は実施例２と同様にして複合フィルムを得た。 [Comparative Example 3]
A composite film was obtained in the same manner as in Example 2 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).
　［比較例４］
　炭化水素系重合体（Ｂ－２）を炭化水素系重合体（Ｂ－１）に変更したこと以外は実施例７と同様にして複合フィルムを得た。 [Comparative Example 4]
A composite film was obtained in the same manner as in Example 7 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).
　［比較例５］
　炭化水素系重合体（Ｂ－２）を炭化水素系重合体（Ｂ－１）に変更したこと以外は実施例８と同様にして複合フィルムを得た。 [Comparative Example 5]
A composite film was obtained in the same manner as in Example 8 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).
　［複合フィルムの評価 ］
　＜ＡＬ/ＣＰＰ接着強度 ＞
　実施例１～８および比較例１～５の複合フィルムを、長さ６０ｍｍ、幅１５ｍｍの大きさに切り出して試験片を作製した。この試験片について、万能引張測定装置を用いて、クロスヘッド速度５０ｍｍ／分にて、１８０°剥離試験を実施して、複合フィルムの初期接着強度を測定した。測定した初期接着強度に応じて、以下の基準にて評価を行った。結果を表３に示す。 [Evaluation of composite film]
<AL / CPP adhesive strength>
The composite films of Examples 1 to 8 and Comparative Examples 1 to 5 were cut into a size of 60 mm in length and 15 mm in width to prepare test pieces. About this test piece, the 180 degree peeling test was implemented at the crosshead speed of 50 mm / min using the universal tension measuring device, and the initial bond strength of the composite film was measured. Evaluation was performed according to the following criteria according to the measured initial adhesive strength. The results are shown in Table 3.
　（評価基準）
◎：１１Ｎ／１５ｍｍ以上
〇：７Ｎ／１５ｍｍ以上、１１Ｎ／１５ｍｍ未満
△：５Ｎ／１５ｍｍ以上、７Ｎ／１５ｍｍ未満
×：５Ｎ／１５ｍｍ未満 (Evaluation criteria)
◎: 11N / 15mm or more ○: 7N / 15mm or more, less than 11N / 15mm Δ: 5N / 15mm or more, less than 7N / 15mm ×: Less than 5N / 15mm
Figure JPOXMLDOC01-appb-T000003
 　［実施例９］
　熱可塑性樹脂（Ａ－３）４５ｇ、炭化水素系重合体（Ｂ－２）４５ｇおよび粘着付与剤（Ｃ－１）１０ｇを４００ｇのトルエンに溶解させて、変性オレフィン重合体ワニス（２）を調製した。得られた変性オレフィン重合体ワニス（２）４０ｇをキシレン６０ｇで希釈し、スプレー塗装用プライマー組成物を調製した。次いで、スプレー塗装用プライマー組成物を、硬質ＰＰの板（厚さ２ｍｍ）に対してスプレーで塗装し、室温で５分間乾燥することで、硬質ＰＰ上に１０μｍのプライマー層を得た。更に２液のホワイトベースウレタン塗料（日本ペイント・オートモーティブコーティングス社製Ｆ２８７／Ｆ２７１＝４／１）をプライマー層の上にスプレーで塗装し、８０℃で３０分間処理することで１０μｍの上塗り層を設け、プライマー／塗料積層膜を得た。
Figure JPOXMLDOC01-appb-T000003
 [Example 9]
A modified olefin polymer varnish (2) is prepared by dissolving 45 g of a thermoplastic resin (A-3), 45 g of a hydrocarbon polymer (B-2) and 10 g of a tackifier (C-1) in 400 g of toluene. did. 40 g of the obtained modified olefin polymer varnish (2) was diluted with 60 g of xylene to prepare a primer composition for spray coating. Next, the primer composition for spray coating was applied to a hard PP plate (thickness 2 mm) by spraying and dried at room temperature for 5 minutes to obtain a 10 μm primer layer on the hard PP. Furthermore, two-component white base urethane paint (F287 / F271 = 4/1 manufactured by Nippon Paint Automotive Coatings Co., Ltd.) is applied onto the primer layer by spraying, and treated at 80 ° C. for 30 minutes to form a 10 μm overcoat layer. And a primer / paint laminate film was obtained.
　［実施例１０］
　熱可塑性樹脂（Ａ－３） を熱可塑性樹脂（Ａ－１）に変更したこと以外は実施例９と同様にしてプライマー／塗料積層膜を得た。 [Example 10]
A primer / paint laminate film was obtained in the same manner as in Example 9 except that the thermoplastic resin (A-3) was changed to the thermoplastic resin (A-1).
　［比較例６］
　熱可塑性樹脂（Ａ－３）４５ｇおよび炭化水素系重合体（Ｂ－２）４５ｇを、熱可塑性樹脂（Ａ－３）７２ｇおよび炭化水素系重合体（Ｂ－１）１８ｇに変更したこと以外は実施例９と同様にしてプライマー／塗料積層膜を得た。 [Comparative Example 6]
Except for changing 45 g of the thermoplastic resin (A-3) and 45 g of the hydrocarbon polymer (B-2) to 72 g of the thermoplastic resin (A-3) and 18 g of the hydrocarbon polymer (B-1). A primer / paint laminate film was obtained in the same manner as in Example 9.
　［比較例７］
　炭化水素系重合体（Ｂ－２）を炭化水素系重合体（Ｂ－１） に変更したこと以外は実施例９と同様にしてプライマー／塗料積層膜を得た。 [Comparative Example 7]
A primer / paint laminate film was obtained in the same manner as in Example 9 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).
　［比較例８］
　炭化水素系重合体（Ｂ－２）を炭化水素系重合体（Ｂ－１） に変更したこと以外は実施例１０と同様にしてプライマー／塗料積層膜を得た。 [Comparative Example 8]
A primer / paint laminate film was obtained in the same manner as in Example 10 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).
　［プライマー／塗料積層膜の評価］
　＜スプレー適性＞
　実施例９～１０および比較例６～８のプライマー／塗料積層膜を作成する際に使用したスプレー塗装用プライマー組成物について、スプレー塗装を行った際の糸引き（プライマー組成物がＰＰ基材に塗着する前に空気中で糸状に析出する現象）の状態を以下の基準で評価した。結果を表４に示す。 [Evaluation of primer / paint laminate film]
<Sprayability>
For the primer composition for spray coating used in preparing the primer / paint laminated films of Examples 9 to 10 and Comparative Examples 6 to 8, stringing during spray coating (the primer composition was applied to the PP base material) The state of the phenomenon of precipitation in the form of yarn in the air before application) was evaluated according to the following criteria. The results are shown in Table 4.
　（評価基準）
〇：糸引きが全く発生せず、平滑なプライマー層が得られる。
△：糸引きの発生は顕著に見られないが、プライマー層に僅かな糸状異物が認められる。
×：糸引きが発生し、平滑なプライマー層が得られない。 (Evaluation criteria)
◯: No stringing occurs and a smooth primer layer is obtained.
Δ: The occurrence of stringing is not noticeable, but a slight amount of thread-like foreign matter is observed in the primer layer.
X: Stringing occurs and a smooth primer layer cannot be obtained.
　＜上塗りのハジキ＞
　実施例９～１０および比較例６～８のプライマー／塗料積層膜の作成において、２液のホワイトベースウレタン塗料を各々のプライマー層上にスプレー塗装した際の外観状態を以下の基準で評価した。結果を表４に示す。 <Overcoat repellent>
In the preparation of the primer / coating laminate films of Examples 9 to 10 and Comparative Examples 6 to 8, the appearance of the two-component white base urethane coatings when spray-coated on each primer layer was evaluated according to the following criteria. The results are shown in Table 4.
　（評価基準）
〇：塗装が均一に行われ、平滑な上塗り層が全面に塗着できる。
△：塗装は均一に行われたが、微小なクラックやボイドが上塗り層に認められる。
×：ハジキが発生し（２液のホワイトベースウレタン塗料がプライマー層上ではじかれて均一な塗装ができない）、平滑で均一な上塗り層が得られない。 (Evaluation criteria)
A: Coating is performed uniformly and a smooth topcoat layer can be applied to the entire surface.
(Triangle | delta): Although coating was performed uniformly, a micro crack and a void are recognized by the topcoat layer.
X: Repelling occurs (a two-part white base urethane coating is repelled on the primer layer and cannot be applied uniformly), and a smooth and uniform overcoat layer cannot be obtained.
　＜接着性＞
　実施例９～１０および比較例６～８で作成したプライマー／塗料積層膜に対して、ＪＩＳ Ｋ５６００－５－６に準じて碁盤目テープ剥離試験を行い、剥離数を記録し、密着性を以下の基準で評価した。結果を表４に示す。 <Adhesiveness>
The primer / paint laminate films prepared in Examples 9 to 10 and Comparative Examples 6 to 8 were subjected to a cross-cut tape peeling test according to JIS K5600-5-6, and the number of peelings was recorded. Evaluation based on the criteria. The results are shown in Table 4.
　（評価基準）
○：剥離なし
×：1個以上の剥離あり (Evaluation criteria)
○: No peeling ×: One or more peelings
Figure JPOXMLDOC01-appb-T000004
 　［実施例１１］
　熱可塑性樹脂（Ａ－３）２０ｇおよび炭化水素系重合体（Ｂ－２）８０ｇを４００ｇのトルエンに溶解させて、変性オレフィン重合体ワニス（１）を調製した。得られた変性オレフィン重合体ワニス（１）を、バーコーターを用いて、得られる塗膜付箔の坪量が８ｇ／ｍ２になるように、厚さ４０μｍのアルミニウム箔（Ａｌ箔、表面未処理）のツヤ面上に常温下において塗布し、１００℃で１分間の乾燥により溶媒を揮散させることで、塗膜付箔を得た。その後、得られた塗膜付箔の塗膜面を、厚さ２ｍｍのガラス板に２３℃、０．１ＭＰａで１０秒間圧着させ、ガラス、粘着剤層およびＡｌ箔がこの順で積層した積層体（粘着フィルム積層体）を得た。
Figure JPOXMLDOC01-appb-T000004
 [Example 11]
A modified olefin polymer varnish (1) was prepared by dissolving 20 g of the thermoplastic resin (A-3) and 80 g of the hydrocarbon-based polymer (B-2) in 400 g of toluene. Using the obtained modified olefin polymer varnish (1), using a bar coater, an aluminum foil (Al foil, surface untreated) with a thickness of 40 μm so that the basis weight of the resulting coated foil is 8 g / m 2. ) Was applied at room temperature, and the solvent was evaporated by drying at 100 ° C. for 1 minute to obtain a coated foil. Thereafter, the coated surface of the obtained coated foil was pressure-bonded to a 2 mm thick glass plate at 23 ° C. and 0.1 MPa for 10 seconds, and a laminate in which glass, an adhesive layer and an Al foil were laminated in this order. (Adhesive film laminate) was obtained.
　［実施例１２］
　炭化水素系重合体（Ｂ－２）を炭化水素系重合体（Ｂ－３）に変更したこと以外は実施例１１と同様にして粘着フィルム積層体を得た。 [Example 12]
A pressure-sensitive adhesive film laminate was obtained in the same manner as in Example 11, except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-3).
　［実施例１３］
　炭化水素系重合体（Ｂ－２）を炭化水素系重合体（Ｂ－４）に変更したこと以外は実施例１１と同様にして粘着フィルム積層体を得た。 [Example 13]
A pressure-sensitive adhesive film laminate was obtained in the same manner as in Example 11 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-4).
　［実施例１４］
　熱可塑性樹脂（Ａ－３）２０ｇおよび炭化水素系重合体（Ｂ－２）８０ｇを、熱可塑性樹脂（Ａ－３）３０ｇおよび炭化水素系重合体（Ｂ－４）７０ｇに変更したこと以外は実施例１１と同様にして粘着フィルム積層体を得た。 [Example 14]
Except for changing 20 g of the thermoplastic resin (A-3) and 80 g of the hydrocarbon polymer (B-2) to 30 g of the thermoplastic resin (A-3) and 70 g of the hydrocarbon polymer (B-4). In the same manner as in Example 11, an adhesive film laminate was obtained.
　［比較例９］
　熱可塑性樹脂（Ａ－３）２０ｇおよび炭化水素系重合体（Ｂ－２）８０ｇを、熱可塑性樹脂（Ａ－３）８０ｇおよび炭化水素系重合体（Ｂ－１）２０ｇに変更したこと以外は実施例１１と同様にして粘着フィルム積層体を得た。 [Comparative Example 9]
Except for changing 20 g of the thermoplastic resin (A-3) and 80 g of the hydrocarbon polymer (B-2) to 80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-1). In the same manner as in Example 11, an adhesive film laminate was obtained.
　［比較例１０］
　炭化水素系重合体（Ｂ－２）を炭化水素系重合体（Ｂ－１）に変更したこと以外は実施例１１と同様にして粘着フィルム積層体を得た。 [Comparative Example 10]
An adhesive film laminate was obtained in the same manner as in Example 11 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).
　［ＡＬ/ガラス粘着強度］
　実施例１１～１４および比較例９，１０の粘着フィルム積層体を、長さ６０ｍｍ、幅１５ｍｍの大きさに切り出して試験片を作製した。この試験片について、万能引張測定装置を用いて、クロスヘッド速度１００ｍｍ／分にて、１８０°剥離試験を実施して、粘着フィルム積層体の粘着強度を測定した。測定した粘着強度に応じて、以下の基準にて評価を行った。結果を表５に示す。 [AL / Glass adhesive strength]
The adhesive film laminates of Examples 11 to 14 and Comparative Examples 9 and 10 were cut into a size of 60 mm in length and 15 mm in width to produce test pieces. About this test piece, the 180 degree peeling test was implemented at the crosshead speed of 100 mm / min using the universal tension measuring device, and the adhesive strength of the adhesive film laminated body was measured. Evaluation was performed according to the following criteria according to the measured adhesive strength. The results are shown in Table 5.
　（評価基準）
◎：７Ｎ／１５ｍｍ以上
〇：５Ｎ／１５ｍｍ以上、７Ｎ／１５ｍｍ未満
△：３Ｎ／１５ｍｍ以上、５Ｎ／１５ｍｍ未満
×：３Ｎ／１５ｍｍ未満 (Evaluation criteria)
◎: 7N / 15mm or more ○: 5N / 15mm or more, less than 7N / 15mm △: 3N / 15mm or more, less than 5N / 15mm ×: Less than 3N / 15mm
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

Claims (22)

  1. 　ＪＩＳ　Ｋ　７１２２に従って測定した融解熱量が０～５０Ｊ/ｇの範囲にあり、かつＧＰＣ法により測定した重量平均分子量（Ｍｗ）が１×１０4～１０００×１０4であるオレフィン重合体（Ａ）と、
    　２００℃動粘度が１，０００～１００，０００ｍｍ2/ｓの半固体状炭化水素（Ｂ）と
    を含有するコーティング剤。     An olefin polymer (A) having a heat of fusion measured in accordance with JIS K 7122 in the range of 0 to 50 J / g and a weight average molecular weight (Mw) measured by GPC method of 1 × 10 4 to 1000 × 10 4 ; ,
    A coating agent containing a semi-solid hydrocarbon (B) having a kinematic viscosity at 200 ° C. of 1,000 to 100,000 mm 2 / s.
  2. 　前記オレフィン重合体（Ａ）が、以下の（Ａ１）～（Ａ３）からなる群より選ばれる１種以上であることを特徴とする請求項１に記載のコーティング剤：
    　（Ａ１）炭素数２～２０のα－オレフィン由来の構成単位を含む重合体；
    　（Ａ２）炭素数２～２０のα－オレフィン由来の構成単位を含む重合体であって、その一部または全部が極性基含有単量体でグラフト変性されてなる変性オレフィン系重合体；
    　（Ａ３）炭素数２～２０のα－オレフィン由来の構成単位を含む重合体であって、その一部または全部がハロゲン化変性されてなるハロゲン化オレフィン系重合体。     The coating agent according to claim 1, wherein the olefin polymer (A) is at least one selected from the group consisting of the following (A1) to (A3):
    (A1) a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms;
    (A2) A modified olefin polymer comprising a structural unit derived from an α-olefin having 2 to 20 carbon atoms, part or all of which is graft-modified with a polar group-containing monomer;
    (A3) A halogenated olefin polymer comprising a structural unit derived from an α-olefin having 2 to 20 carbon atoms, part or all of which is halogenated.
  3. 　前記（Ａ２）が以下の（Ａ２'）であり、前記（Ａ３）が以下の（Ａ３'）であることを特徴とする請求項２に記載のコーティング剤：
    　（Ａ２'）炭素数２～２０のα－オレフィン由来の構成単位を含む重合体であって、その一部または全部が極性基含有単量体でグラフト変性されてなる変性オレフィン系重合体であり、当該変性オレフィン系重合体１００重量部に対して、極性基含有単量体由来の構成単位を０．１～１５重量部含む変性オレフィン系重合体；
    　（Ａ３'）炭素数２～２０のα－オレフィン由来の構成単位を含む重合体であって、その一部または全部がハロゲン化変性されてなるハロゲン化変性オレフィン重合体であり、当該ハロゲン化変性オレフィン重合体１００重量部に対してハロゲン含有量が２～４０重量部であるハロゲン化変性オレフィン系重合体。     The coating agent according to claim 2, wherein (A2) is the following (A2 ') and (A3) is the following (A3'):
    (A2 ′) a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, a part or all of which is a modified olefin polymer obtained by graft modification with a polar group-containing monomer. A modified olefin polymer containing 0.1 to 15 parts by weight of a structural unit derived from a polar group-containing monomer with respect to 100 parts by weight of the modified olefin polymer;
    (A3 ′) a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, a part or all of which is halogenated and modified. A halogenated modified olefin polymer having a halogen content of 2 to 40 parts by weight per 100 parts by weight of the olefin polymer.
  4. 　前記（Ａ１）が以下の（Ａ１''）であり、前記（Ａ２'）が以下の（Ａ２''）であり、前記（Ａ３'）が以下の（Ａ３''）であることを特徴とする請求項３に記載のコーティング剤：
    　（Ａ１''）プロピレン由来の構成単位を５０～１００モル％、炭素数２～２０のα－オレフィン（ただしプロピレンを除く）由来の構成単位を５０～０モル％（ここでプロピレンと炭素数２～２０のα－オレフィン由来の構成単位との合計を１００モル％とする）含有するプロピレン系重合体；
    　（Ａ２''）プロピレン由来の構成単位を５０～１００モル％、炭素数２～２０のα－オレフィン（ただしプロピレンを除く）由来の構成単位を５０～０モル％（ここでプロピレンと炭素数２～２０のα－オレフィン由来の構成単位との合計を１００モル％とする）含有するプロピレン系重合体であって、その一部または全部が極性基含有単量体でグラフト変性されてなる変性オレフィン系重合体であり、当該変性オレフィン系重合体１００重量部に対して、極性基含有単量体由来の構成単位を０．１～１５重量部含む変性オレフィン系重合体；
    　（Ａ３''）プロピレン由来の構成単位を５０～１００モル％、炭素数２～２０のα－オレフィン（ただしプロピレンを除く）由来の構成単位を５０～０モル％（ここでプロピレンと炭素数２～２０のα－オレフィン由来の構成単位との合計を１００モル％とする）含有するプロピレン系重合体であって、その一部または全部がハロゲン化変性されてなるハロゲン化変性オレフィン系重合体であり、当該ハロゲン化変性オレフィン系重合体１００重量部に対してハロゲン含有量が２～４０重量部であるハロゲン化オレフィン系重合体。     The (A1) is the following (A1 ″), the (A2 ′) is the following (A2 ″), and the (A3 ′) is the following (A3 ″), The coating agent according to claim 3:
    (A1 ″) 50 to 100 mol% of propylene-derived structural units and 50 to 0 mol% of structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) (where propylene and carbon number 2) A propylene-based polymer containing up to 20 mol% of α-olefin-derived structural units)
    (A2 ″) 50 to 100 mol% of propylene-derived structural units and 50 to 0 mol% of structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) (where propylene and carbon number 2) And a modified olefin obtained by graft-modifying a part or all of the propylene polymer with a polar group-containing monomer. A modified olefin polymer comprising 0.1 to 15 parts by weight of a structural unit derived from a polar group-containing monomer with respect to 100 parts by weight of the modified olefin polymer;
    (A3 ″) 50 to 100 mol% of structural units derived from propylene and 50 to 0 mol% of structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) (where propylene and carbon number 2) A propylene-based polymer containing a total of 100 to 20 mol% of α-olefin-derived structural units), a part or all of which is halogenated and modified. A halogenated olefin polymer having a halogen content of 2 to 40 parts by weight based on 100 parts by weight of the halogenated modified olefin polymer.
  5. 　前記極性基含有単量体が、不飽和カルボン酸及び不飽和カルボン酸無水物から選ばれる１種以上である請求項２～４のいずれか１項に記載のコーティング剤。 The coating agent according to any one of claims 2 to 4, wherein the polar group-containing monomer is at least one selected from an unsaturated carboxylic acid and an unsaturated carboxylic anhydride.
  6. 　前記半固体状炭化水素（Ｂ）が、炭素数２～２０のオレフィンの重合体である請求項１～５のいずれか１項に記載のコーティング剤。 The coating agent according to any one of claims 1 to 5, wherein the semi-solid hydrocarbon (B) is an olefin polymer having 2 to 20 carbon atoms.
  7. 　前記オレフィン重合体（Ａ）の含有量が１０～９９重量部であり、前記半固体状炭化水素（Ｂ）の含有量が１～９０重量部（ただし（Ａ）と（Ｂ）との合計を１００重量部とする）である請求項１～６のいずれか１項に記載のコーティング剤。 The content of the olefin polymer (A) is 10 to 99 parts by weight, and the content of the semisolid hydrocarbon (B) is 1 to 90 parts by weight (however, the total of (A) and (B) is The coating agent according to any one of claims 1 to 6, wherein the coating agent is 100 parts by weight.
  8. 　ＪＩＳ　Ｋ　００７０に従って求まる酸価が１０以上であり、かつＧＰＣ法により測定した重量平均分子量（Ｍｗ）が１×１０3～３×１０3である粘着付与剤（Ｃ）をさらに含有するとともに、
    　前記オレフィン重合体（Ａ）の含有割合が１０～８８重量％であり、前記半固体状炭化水素（Ｂ）の含有割合が１～８５重量％であり、前記粘着付与剤（Ｃ）の含有割合が５～４０重量％（ただし（Ａ）と（Ｂ）と（Ｃ）との合計を１００重量％とする）である請求項１～６のいずれか１項に記載のコーティング剤。     And further containing a tackifier (C) having an acid value determined according to JIS K 0070 of 10 or more and a weight average molecular weight (Mw) measured by GPC method of 1 × 10 3 to 3 × 10 3 ,
    The content of the olefin polymer (A) is 10 to 88% by weight, the content of the semisolid hydrocarbon (B) is 1 to 85% by weight, and the content of the tackifier (C) The coating agent according to any one of claims 1 to 6, wherein the coating agent is 5 to 40% by weight (provided that the total of (A), (B) and (C) is 100% by weight).
  9. 　前記粘着付与剤（Ｃ）が、ロジンエステルおよびその誘導体である請求項８に記載のコーティング剤。 The coating agent according to claim 8, wherein the tackifier (C) is a rosin ester and a derivative thereof.
  10. 　硬化剤（Ｄ）をさらに含有する請求項１～９のいずれか１項に記載のコーティング剤。 The coating agent according to any one of claims 1 to 9, further comprising a curing agent (D).
  11. 　前記硬化剤（Ｄ）が、脂肪族ポリイソシアネートおよび脂肪族ポリイソシアネートの多量体から選ばれる１種以上である請求項１０に記載のコーティング剤。 The coating agent according to claim 10, wherein the curing agent (D) is one or more selected from aliphatic polyisocyanates and multimers of aliphatic polyisocyanates.
  12. 　前記硬化剤（Ｄ）が、エポキシ化合物およびオキサゾリン化合物から選ばれる１種以上である請求項１０に記載のコーティング剤。 The coating agent according to claim 10, wherein the curing agent (D) is at least one selected from an epoxy compound and an oxazoline compound.
  13. 　ｐＫａが１１以上である触媒（Ｅ）をさらに含有する請求項１０～１２のいずれか１項に記載のコーティング剤。 The coating agent according to any one of claims 10 to 12, further comprising a catalyst (E) having a pKa of 11 or more.
  14. 　プライマーである請求項１～１３のいずれか１項に記載のコーティング剤。 The coating agent according to any one of claims 1 to 13, which is a primer.
  15. 　塗料である請求項１～１３のいずれか１項に記載のコーティング剤。 The coating agent according to any one of claims 1 to 13, which is a paint.
  16. 　ホットメルト接着剤または感圧接着剤である請求項１～１３のいずれか１項に記載のコーティング剤。 The coating agent according to any one of claims 1 to 13, which is a hot-melt adhesive or a pressure-sensitive adhesive.
  17. 　請求項１～１３のいずれか１項に記載のコーティング剤から得られる層を少なくとも１層有する加飾フィルム。 A decorative film having at least one layer obtained from the coating agent according to any one of claims 1 to 13.
  18. 　請求項１７に記載の加飾フィルムによって加飾された成形体。 A molded body decorated with the decorative film according to claim 17.
  19. 　前記加飾が、真空圧空成形装置によって行われた請求項１８に記載の成形体。 The molded body according to claim 18, wherein the decoration is performed by a vacuum / pressure air forming apparatus.
  20. 　内層と接着剤層と基材とがこの順で積層された積層体を含み、該接着剤層が、請求項１～１３のいずれか１項に記載のコーティング剤の硬化物からなる層である包材。 A laminate comprising an inner layer, an adhesive layer, and a base material laminated in this order is included, and the adhesive layer is a layer made of a cured product of the coating agent according to any one of claims 1 to 13. Packaging material.
  21. 　内層と内側接着剤層と基材と外側接着剤層と外層とがこの順で積層された積層体を含み、該内側接着剤層が、請求項１～１３のいずれか１項に記載のコーティング剤の硬化物からなる層である電池ケース用包材。 The coating according to any one of claims 1 to 13, comprising a laminate in which an inner layer, an inner adhesive layer, a base material, an outer adhesive layer, and an outer layer are laminated in this order. A battery case packaging material, which is a layer made of a cured product of an agent.
  22. 　請求項２１に記載の電池ケース用包材と、前記電池ケース用包材に包装される電解液とを備え、前記電池ケース用包材の内層の少なくとも一部が前記電解液に接触している電池。 A battery case packaging material according to claim 21 and an electrolyte solution packaged in the battery case packaging material, wherein at least a part of an inner layer of the battery case packaging material is in contact with the electrolyte solution. battery.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019188284A1 (en) * 2018-03-30 2019-10-03 東洋紡株式会社 Polyolefin-based adhesive composition
JP2020164554A (en) * 2019-03-28 2020-10-08 Dic株式会社 Coating agent, and laminate, packaging material and processed product coated therewith
WO2021054068A1 (en) * 2019-09-19 2021-03-25 東洋紡株式会社 Polyolefin-based coating composition
JP2021102700A (en) * 2019-12-25 2021-07-15 Dic株式会社 Coating agent, laminate, molded body and packaging material
KR102313853B1 (en) * 2021-02-26 2021-10-15 동우 화인켐 주식회사 Adhesive composition and packaging material for battery
KR102336272B1 (en) * 2021-02-19 2021-12-06 동우 화인켐 주식회사 Adhesive composition and packaging material for battery
WO2023106345A1 (en) * 2021-12-07 2023-06-15 大日本印刷株式会社 Packaging film for power storage devices, and power storage device
JP7444319B1 (en) 2023-05-30 2024-03-06 東洋紡エムシー株式会社 Adhesive composition, adhesive sheet, laminate, and printed wiring board containing the same
JP7444318B1 (en) 2023-05-30 2024-03-06 東洋紡エムシー株式会社 Adhesive composition, adhesive sheet, laminate, and printed wiring board containing the same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114729246B (en) * 2019-12-23 2024-05-28 三井化学株式会社 Adhesive for electronic tag and electronic tag
CN113881367B (en) * 2021-09-29 2023-04-28 科建高分子材料（上海）股份有限公司 Waterproof butyl sealant for sealing automobile windows without wiredrawing

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0748553A (en) * 1993-08-06 1995-02-21 Toho Rika Kogyo Kk Pressure-sensitive adhesive composition for capturing living being
WO1999045064A1 (en) * 1998-03-02 1999-09-10 Kureha Chemical Industry Co., Ltd. Polypropylene resin compositions and packaging stretched film made thereof
JP2003019778A (en) * 2001-07-09 2003-01-21 Asahi Kasei Corp Polypropylene multilayer lap film
JP2009524705A (en) * 2006-01-24 2009-07-02 スリーエム イノベイティブ プロパティズ カンパニー Adhesive encapsulating composition film and organic electroluminescence device
JP2011524919A (en) * 2008-06-04 2011-09-08 テーザ・ソシエタス・ヨーロピア Pressure-sensitive adhesive material made of polypropylene resin
WO2013164976A1 (en) * 2012-05-01 2013-11-07 三井化学株式会社 Coating agent, decorative film and molded body
WO2014123183A1 (en) * 2013-02-07 2014-08-14 三井化学株式会社 Adhesive, layered body, cell case packaging, cell, high-alkali solution packaging, alcohol-containing solution packaging, and package
JP2015137333A (en) * 2014-01-23 2015-07-30 三井化学株式会社 Sheet like encapsulation material and sheet for encapsulation containing the same
JP2016020402A (en) * 2014-07-11 2016-02-04 綜研化学株式会社 Adhesive vapor barrier laminate and image display device
WO2016080297A1 (en) * 2014-11-17 2016-05-26 三井化学株式会社 Coating agent, decorative film, and molded body
JP2016132716A (en) * 2015-01-19 2016-07-25 三井化学株式会社 Composition, coating agent, adhesive, and laminate
WO2017126520A1 (en) * 2016-01-21 2017-07-27 三井化学株式会社 Composition, laminate, packaging material, packaging material for battery cases, and battery

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08157791A (en) * 1994-12-12 1996-06-18 Sekisui Chem Co Ltd Surface protective film
JP3893501B2 (en) * 1996-04-09 2007-03-14 株式会社ソフト９９コーポレーション Clay cleaner
JP3616312B2 (en) * 1999-07-22 2005-02-02 三洋化成工業株式会社 Hot melt adhesive
JP4456460B2 (en) * 2004-10-20 2010-04-28 電気化学工業株式会社 Sealing material using polyisobutylene
CN101248135B (en) * 2005-06-24 2013-03-27 埃克森美孚化学专利公司 Plasticized functionalized propylene copolymer adhesive composition
US8344086B2 (en) * 2008-04-22 2013-01-01 Basell Poliolefine Italia S.R.L. 1-butene terpolymers
JP2010180390A (en) * 2009-02-03 2010-08-19 Toyo Adl Corp Hot-melt type adhesion composition and laminate obtained by using the same
EP2927298A4 (en) * 2012-11-30 2016-05-25 Lintec Corp Adhesive agent composition, adhesive sheet, and electronic device
WO2015046251A1 (en) * 2013-09-25 2015-04-02 株式会社クラレ Thermoplastic polymer composition, layered body, and protective film
JP6326253B2 (en) * 2014-03-13 2018-05-16 三井化学株式会社 Hot melt adhesive composition

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0748553A (en) * 1993-08-06 1995-02-21 Toho Rika Kogyo Kk Pressure-sensitive adhesive composition for capturing living being
WO1999045064A1 (en) * 1998-03-02 1999-09-10 Kureha Chemical Industry Co., Ltd. Polypropylene resin compositions and packaging stretched film made thereof
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JPWO2018221331A1 (en) 2020-05-21

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