WO2015033703A1 - Polyolefin-type adhesive agent composition - Google Patents

Polyolefin-type adhesive agent composition Download PDF

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Publication number
WO2015033703A1
WO2015033703A1 PCT/JP2014/069953 JP2014069953W WO2015033703A1 WO 2015033703 A1 WO2015033703 A1 WO 2015033703A1 JP 2014069953 W JP2014069953 W JP 2014069953W WO 2015033703 A1 WO2015033703 A1 WO 2015033703A1
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Prior art keywords
mass
polyolefin
resin
acid
parts
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PCT/JP2014/069953
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French (fr)
Japanese (ja)
Inventor
坂田　秀行
健二 柏原
Original Assignee
東洋紡株式会社
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Publication date
Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to JP2015535382A priority Critical patent/JPWO2015033703A1/en
Priority to KR1020157033371A priority patent/KR20160048719A/en
Priority to CN201480044053.1A priority patent/CN105452411A/en
Publication of WO2015033703A1 publication Critical patent/WO2015033703A1/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 of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/121—Organic material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
    • C08J5/125—Adhesives in organic diluents
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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 of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • 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 of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • 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 of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
    • H01M50/126—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers
    • H01M50/129—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
    • 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 of a single cell or a single battery
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/193—Organic material
    • 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 of a single cell or a single battery
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/198—Sealing members characterised by the material characterised by physical properties, e.g. adhesiveness or hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • 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
    • B32B2457/00—Electrical equipment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2423/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/163—Metal in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/006—Presence of polyolefin in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
    • 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 an adhesive composition for bonding a polyolefin resin substrate and a metal substrate. More specifically, the present invention relates to an adhesive composition containing a modified polyolefin, polycarbodiimide and an organic solvent.
  • PVC vinyl chloride resin
  • metal base materials such as home appliance outer panels, furniture materials, and building interior members.
  • PVC vinyl chloride resin
  • polyolefin resins have been proposed as an alternative to PVC.
  • Polyolefin resins are not toxic, have strong durability against acids, alkalis, organic solvents, etc., are excellent in mechanical strength and abrasion resistance, are inexpensive, and are widely used in various fields.
  • the pot life property refers to the stability of the solution immediately after the compounding, or after a certain period of time, by blending the modified polyolefin with a crosslinking agent or a curing agent.
  • the present invention has been made in view of the above-described conventional problems, and as a result of intensive studies on the adhesive between a polyolefin-based resin base material and a metal base material, the present inventors have found that modified polyolefin, polycarbodiimide, and organic The present inventors have found that an adhesive composition containing a solvent achieves both pot life and adhesiveness, and has completed the present invention.
  • the present invention provides an adhesive composition having good pot life after blending a modified polyolefin and a crosslinking agent and having good adhesion to both a polyolefin resin substrate and a metal substrate.
  • the purpose is to do.
  • A1 Crystalline acid-modified polyolefin having an acid value of 10 to 50 mgKOH / g-resin
  • A2 Acid-modified chlorine having an acid value of 10 to 50 mgKOH / g-resin and a chlorine content of 5 to 40% by mass Polyolefin
  • polycarbodiimide (B) It is preferable to contain 0.5 to 10 parts by mass of polycarbodiimide (B) and 80 to 1000 parts by mass of organic solvent (C) with respect to 100 parts by mass of the modified polyolefin (A).
  • the organic solvent (C) is a mixed liquid of the solvent (C1) and the solvent (C2), and the solvent (C1) is composed of an aromatic hydrocarbon, an aliphatic hydrocarbon, an alicyclic hydrocarbon, and a halogenated hydrocarbon.
  • a packaging material for a lithium battery containing the laminate is provided.
  • the adhesive composition according to the present invention contains a modified polyolefin, polycarbodiimide, and an organic solvent, maintains good pot life without thickening or gelation even when stored for a long period of time, and is a polyolefin resin. It is possible to achieve both good adhesion between the base material and the metal base material.
  • the modified polyolefin (A) used in the present invention is a crystalline acid-modified polyolefin (A1) having an acid value of 10 to 50 mgKOH / g-resin, or an acid value of 10 to 50 mgKOH / g-resin and a chlorine content of 5 to It is 40 mass% acid-modified chlorinated polyolefin (A2).
  • the crystalline acid-modified polyolefin (A1) used in the present invention is not limited, but at least one of polyethylene, polypropylene and propylene- ⁇ -olefin copolymer includes ⁇ , ⁇ -unsaturated carboxylic acid and acid anhydride thereof. Those obtained by grafting at least one of the above are preferred.
  • the propylene- ⁇ -olefin copolymer is a copolymer in which ⁇ -olefin is copolymerized mainly with propylene.
  • ⁇ -olefin for example, ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate or the like can be used. Of these ⁇ -olefins, ethylene and 1-butene are preferred.
  • the ratio of the propylene component to the ⁇ -olefin component of the propylene- ⁇ -olefin copolymer is not limited, but the propylene component is preferably 50 mol% or more, and more preferably 70 mol% or more.
  • Production of a polypropylene random copolymer can be carried out by a known method.
  • a known method for example, according to the production method described in JP-A-2001-206914, propylene and an olefin having 4 or more carbon atoms are charged into a reaction kettle and hydrogen is supplied. However, it can manufacture continuously.
  • the polymerization method can be carried out by continuous polymerization of a known bulk polymerization method or gas phase polymerization method, and is preferably carried out in one step or multiple steps by bulk polymerization.
  • Examples of at least one of ⁇ , ⁇ -unsaturated carboxylic acid and acid anhydrides thereof include maleic acid, itaconic acid, citraconic acid, and acid anhydrides thereof.
  • acid anhydrides are preferable, and maleic anhydride is more preferable.
  • Specific examples include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, maleic anhydride-modified propylene-ethylene-butene copolymer, and the like.
  • These acid-modified polyolefins can be used alone or in combination of two or more.
  • the acid value of the crystalline acid-modified polyolefin (A1) must be at least 10 mgKOH / g-resin, preferably from the viewpoint of pot life and adhesion between the polyolefin resin substrate and the metal substrate, preferably 12 mgKOH / g-resin or more, more preferably 14 mgKOH / g-resin or more, further preferably 16 mgKOH / g-resin or more, particularly preferably 18 mgKOH / g-resin or more, most preferably 20 mgKOH / More than g-resin. If it is less than the above value, the compatibility with polycarbodiimide is low, and the adhesive strength may not be exhibited.
  • the upper limit needs to be 50 mgKOH / g-resin or less, preferably 48 mgKOH / g-resin or less, more preferably 46 mgKOH / g-resin or less, still more preferably 44 mgKOH / g-resin or less.
  • it is 42 mgKOH / g-resin or less, Most preferably, it is 40 mgKOH / g-resin or less.
  • the weight average molecular weight (Mw) of the crystalline acid-modified polyolefin (A1) is preferably in the range of 40,000 to 170,000. More preferably, it is in the range of 50,000 to 160,000, more preferably in the range of 60,000 to 150,000, particularly preferably in the range of 70,000 to 140,000, and most preferably 80. , 13,000 to 130,000. If it is less than the above value, the cohesive force becomes weak and the adhesiveness may be inferior. On the other hand, when the above value is exceeded, there may be a problem in operability when bonding due to low fluidity. If it is in the said range, since interaction with polycarbodiimide is utilized, it is preferable.
  • the crystallinity in the crystalline acid-modified polyolefin (A1) means that the temperature is raised from ⁇ 100 ° C. to 250 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC), and the melting process is clearly melted. This refers to the peak.
  • DSC differential scanning calorimeter
  • the melting point (Tm) of the crystalline acid-modified polyolefin (A1) is preferably in the range of 50 ° C to 120 ° C. More preferably, it is in the range of 60 ° C to 100 ° C, and most preferably in the range of 70 ° C to 90 ° C. If it is less than the above value, the crystal-derived cohesive force becomes weak, and the adhesiveness, heat resistance, and chemical resistance may be inferior. On the other hand, when the above value is exceeded, the solution stability and fluidity are low, and there may be a problem in operability when bonding.
  • the heat of fusion ( ⁇ H) of the crystalline acid-modified polyolefin (A1) is preferably in the range of 5 J / g to 60 J / g.
  • a range of 10 J / g to 50 J / g is more preferable, and a range of 20 J / g to 40 J / g is most preferable. If it is less than the above value, the crystal-derived cohesive force becomes weak, and the adhesiveness, heat resistance, and chemical resistance may be inferior. On the other hand, when the above value is exceeded, the solution stability and fluidity are low, and there may be a problem in operability when bonding.
  • the production method of the crystalline acid-modified polyolefin (A1) is not particularly limited.
  • a radical graft reaction that is, a radical species is generated with respect to a polymer as a main chain, and the radical species is used as a polymerization initiation point to produce an unsaturated carboxylic acid. Reaction for graft polymerization of acid and acid anhydride), and the like.
  • organic peroxide is not particularly limited, but di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy- Peroxides such as 2-ethylhexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauroyl peroxide; azobisisobutyronitrile, azobisisopropionitrile, etc. Examples thereof include azonitriles.
  • the acid-modified chlorinated polyolefin (A2) used in the present invention is not limited, but is preferably obtained by chlorinating the crystalline acid-modified polyolefin (A1).
  • the acid value of the acid-modified chlorinated polyolefin (A2) is required to be 10 mg KOH / g-resin or more from the viewpoint of pot life and adhesion between the polyolefin resin substrate and the metal substrate, preferably 12 mgKOH / g-resin or more, more preferably 14 mgKOH / g-resin or more, further preferably 16 mgKOH / g-resin or more, particularly preferably 18 mgKOH / g-resin or more, most preferably 20 mgKOH / More than g-resin. If it is less than the above value, the compatibility with polycarbodiimide is low, and the adhesive strength may not be exhibited.
  • the upper limit needs to be 50 mgKOH / g-resin or less, preferably 48 mgKOH / g-resin or less, more preferably 46 mgKOH / g-resin or less, still more preferably 44 mgKOH / g-resin or less.
  • it is 42 mgKOH / g-resin or less, Most preferably, it is 40 mgKOH / g-resin or less.
  • the lower limit of the chlorine content of the acid-modified chlorinated polyolefin (A2) needs to be 5% by mass or more, preferably 8 from the viewpoint of solution stability and the adhesion between the polyolefin resin substrate and the metal substrate. It is at least 10% by mass, more preferably at least 10% by mass, even more preferably at least 12% by mass, particularly preferably at least 14% by mass. If it is less than the above value, the solution stability may be lowered and the pot life may be deteriorated. Furthermore, the compatibility with the polycarbodiimide (B) is low, and the adhesive strength may not be exhibited.
  • the upper limit needs to be 40% by mass or less, preferably 38% by mass or less, more preferably 35% by mass or less, still more preferably 32% by mass or less, and particularly preferably 30% by mass or less. . If the above value is exceeded, the crystallinity of the acid-modified chlorinated polyolefin (A2) may be lowered, and the adhesive strength may be lowered.
  • the weight average molecular weight (Mw) of the acid-modified chlorinated polyolefin (A2) is preferably in the range of 40,000 to 170,000. More preferably, it is in the range of 50,000 to 160,000, more preferably in the range of 60,000 to 150,000, particularly preferably in the range of 70,000 to 140,000, and most preferably 80. , 13,000 to 130,000. If it is less than the above value, the cohesive force becomes weak and the adhesiveness may be inferior. On the other hand, when the above value is exceeded, there may be a problem in operability when bonding due to low fluidity. If it is in the said range, since interaction with polycarbodiimide (B) is utilized, it is preferable.
  • the production method of the acid-modified chlorinated polyolefin (A2) is not particularly limited, and can be obtained, for example, by dissolving the acid-modified polyolefin in a halogenated hydrocarbon such as chloroform and introducing chlorine.
  • the polycarbodiimide (B) used in the present invention is not particularly limited as long as it has two or more carbodiimide groups in the molecule.
  • the interaction between the modified polyolefin (A) and the polycarbodiimide (B) is not a cross-linking reaction accompanied by an abrupt increase in viscosity, but an interaction such as hydrogen bonding. It is considered that the adhesiveness can be improved without impairing the resistance.
  • the polycarbodiimide (B) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and 1.5 parts by mass or more with respect to 100 parts by mass of the modified polyolefin (A). It is more preferable that it is 2 parts by mass or more. Further, it is preferably 10 parts by mass or less, more preferably 9 parts by mass or less, further preferably 8.5 parts by mass or less, and particularly preferably 8 parts by mass or less. If the amount is less than the above range, there is a case where the interaction with the oxide film layer on the surface of the metal substrate does not occur and the adhesiveness may not be expressed, and if the range is exceeded, the production cost and the adhesion to the polyolefin resin substrate may be lowered. is there.
  • Organic solvent (C) used in the present invention is not particularly limited as long as it dissolves the modified polyolefin (A) and the polycarbodiimide (B).
  • aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, and alicyclic carbons such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane
  • Halogenated hydrocarbons such as hydrogen, trichloroethylene, dichloroethylene, chlorobenzene, chloroform, alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol, acetone, methyl isobutyl ketone, Ketone solvents such
  • the organic solvent (C) is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and still more preferably 100 parts by mass or more with respect to 100 parts by mass of the modified polyolefin (A). 110 parts by mass or more is particularly preferable. Further, it is preferably 1000 parts by mass or less, more preferably 900 parts by mass or less, still more preferably 800 parts by mass or less, and particularly preferably 700 parts by mass or less. If it is less than the said range, liquid state and pot life property may fall, and when it exceeds the said range, it may become disadvantageous from the surface of manufacturing cost and transport cost.
  • the organic solvent (C) is one selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons from the viewpoint of the liquidity and pot life properties of the adhesive composition.
  • a mixed liquid of at least one solvent (C2) selected from the group consisting of the above solvent (C1), alcohol solvent, ketone solvent, ester solvent and glycol ether solvent is preferable.
  • the adhesive composition according to the present invention is a mixture of the modified polyolefin (A), polycarbodiimide (B), and organic solvent (C).
  • the modified polyolefin (A) the crystalline acid-modified polyolefin (A1) may be used alone, the acid-modified chlorinated polyolefin (A2) may be used alone, or these may be used in combination. good.
  • the modified polyolefin (A) and the polycarbodiimide (B) may be dissolved or dispersed in the organic solvent (C). It is preferably dissolved from the viewpoint of pot life.
  • the adhesive composition according to the present invention is used by blending various additives in addition to the modified polyolefin (A), polycarbodiimide (B) and organic solvent (C) as long as the performance of the present invention is not impaired. be able to. Although it does not specifically limit as an additive, It is preferable to use a flame retardant, a pigment, an antiblocking agent, etc.
  • the laminate of the present invention is obtained by laminating a polyolefin resin substrate and a metal substrate with the adhesive composition according to the present invention.
  • the adhesive composition is applied to the surface of the metal substrate using an appropriate application means such as a roll coater or a bar coater, and dried. After drying, while the adhesive layer formed on the surface of the metal substrate is in a molten state, a laminate structure can be obtained by laminating and bonding a polyolefin resin substrate to the coated surface.
  • the thickness of the adhesive layer formed by the adhesive composition is not particularly limited, but is preferably 0.5 to 10 ⁇ m, more preferably 0.8 to 9.5 ⁇ m, and 1 to 9 ⁇ m. More preferably.
  • the polyolefin resin substrate may be appropriately selected from conventionally known polyolefin resins.
  • polyethylene, polypropylene, ethylene-propylene copolymer, and the like can be used.
  • CPP unstretched polypropylene film
  • the thickness is not particularly limited, but is preferably 20 to 100 ⁇ m, more preferably 25 to 95 ⁇ m, and even more preferably 30 to 90 ⁇ m.
  • Metal base material Although it does not specifically limit as a metal base material, various metals, such as aluminum, copper, steel, zinc, duralumin, die-casting, and its alloy can be used. Moreover, as the shape, arbitrary shapes, such as metal foil, a rolled steel plate, a panel, a pipe, a can, and a cap, can be taken. In general, aluminum foil is preferable from the viewpoint of workability and the like. Although it varies depending on the purpose of use, it is generally used in the form of a sheet having a thickness of 0.01 to 10 mm, preferably 0.02 to 5 mm. Moreover, the surface of these metal base materials may be surface-treated in advance, or may be left untreated. In either case, the same effect can be exhibited.
  • a propylene-butene copolymer (“Tuffmer (registered trademark) XM7080” manufactured by Mitsui Chemicals)
  • the liquid containing the resin was centrifuged to separate and purify an acid-modified propylene-butene copolymer grafted with maleic anhydride, (poly) maleic anhydride and a low molecular weight product. Thereafter, by drying at 70 ° C. under reduced pressure for 5 hours, a maleic anhydride-modified propylene-butene copolymer (PO-1, acid value 48 mgKOH / g-resin, weight average molecular weight 50,000, Tm 75 ° C., ⁇ H25J / g) was obtained.
  • PO-1 acid value 48 mgKOH / g-resin, weight average molecular weight 50,000, Tm 75 ° C., ⁇ H25J / g
  • Production Example 2 A maleic anhydride-modified propylene-butene copolymer (PO-2, acid value 25 mgKOH / g-resin, weight average) was obtained in the same manner as in Production Example 1 except that the amount of maleic anhydride charged was changed to 20 parts by mass. Molecular weight 80,000, Tm 75 ° C., ⁇ H 30 J / g) was obtained.
  • Production Example 3 A maleic anhydride-modified propylene-butene copolymer (PO—) was prepared in the same manner as in Production Example 1 except that the amount of maleic anhydride charged was changed to 10 parts by mass and that of di-tert-butyl peroxide was changed to 2 parts by mass. 3, an acid value of 10 mg KOH / g-resin, a weight average molecular weight of 150,000, Tm of 80 ° C., ⁇ H25 J / g).
  • Production Example 4 A maleic anhydride-modified propylene-butene copolymer (PO-4, acid value 55 mgKOH / g-resin, weight average) was obtained in the same manner as in Production Example 1 except that the amount of maleic anhydride charged was changed to 30 parts by mass. Molecular weight 40,000, Tm 70 ° C., ⁇ H 25 J / g) was obtained.
  • Production Example 5 A maleic anhydride-modified propylene-butene copolymer (PO--) was prepared in the same manner as in Production Example 1 except that the amount of maleic anhydride charged was changed to 5 parts by mass and di-tert-butyl peroxide was changed to 2 parts by mass. 5, acid value 7 mg KOH / g-resin, weight average molecular weight 170,000, Tm 80 ° C., ⁇ H 25 J / g).
  • the liquid containing the resin was centrifuged to separate and purify the acid-modified propylene-ethylene copolymer grafted with maleic anhydride, (poly) maleic anhydride and low molecular weight substances. Thereafter, the resultant was dried at 70 ° C. under reduced pressure for 5 hours to obtain a maleic anhydride-modified propylene-ethylene copolymer (PO-6). Subsequently, 100 parts by mass of PO-6 and 1700 parts by mass of chloroform were put in a 2 L glass-lined reaction can and sealed. The solution in the reaction can was heated while being stirred and dispersed, and dissolved in the can at a temperature of 120 ° C. for 1 hour.
  • PO-6 maleic anhydride-modified propylene-ethylene copolymer
  • Production Example 7 By changing the amount of maleic anhydride charged to 9 parts by mass, the amount of di-tert-butyl peroxide charged to 3 parts by mass, and the amount of chlorine introduced to 160 parts by mass, A maleic acid-modified chlorinated propylene-ethylene copolymer (CPO-2, acid value 10 mg KOH / g-resin, chlorine content 40 mass%, weight average molecular weight 70,000) was obtained.
  • CPO-2 chlorinated propylene-ethylene copolymer
  • Production Example 8 By changing the amount of maleic anhydride charged to 9 parts by mass, the amount of di-tert-butyl peroxide charged to 3 parts by mass, and the amount of chlorine introduced to 20 parts by mass, A maleic acid-modified chlorinated propylene-ethylene copolymer (CPO-3, acid value 10 mg KOH / g-resin, chlorine content 5 mass%, weight average molecular weight 65,000) was obtained.
  • CPO-3 chlorinated propylene-ethylene copolymer
  • Production Example 9 By changing the amount of maleic anhydride charged to 35 parts by mass, the amount of di-tert-butyl peroxide charged to 6 parts by mass, and the amount of chlorine introduced to 10 parts by mass, A maleic acid-modified chlorinated propylene-ethylene copolymer (CPO-4, acid value 48 mgKOH / g-resin, chlorine content 5 mass%, weight average molecular weight 42,000) was obtained.
  • CPO-4 chlorinated propylene-ethylene copolymer
  • Production Example 11 Maleic anhydride-modified chlorinated propylene-ethylene copolymer was prepared in the same manner as in Production Example 6 except that the amount of maleic anhydride charged was changed to 40 parts by mass and that of di-tert-butyl peroxide was changed to 6 parts by mass. A polymer (CPO-6, acid value 55 mgKOH / g-resin, chlorine content 20 mass%, weight average molecular weight 30,000) was obtained.
  • Production Example 12 A maleic anhydride modified chlorinated propylene-ethylene copolymer was prepared in the same manner as in Production Example 6 except that the amount of maleic anhydride charged was changed to 5 parts by mass and that of di-tert-butyl peroxide was changed to 2 parts by mass.
  • CPO-7 acid value 7 mg KOH / g-resin, chlorine content 20 mass%, weight average molecular weight 180,000).
  • Production Example 13 A maleic anhydride-modified chlorinated propylene-ethylene copolymer (CPO-8, acid value of 25 mg KOH / g-resin, containing chlorine was used except that the amount of chlorine introduced was changed to 200 parts by mass. And a weight average molecular weight of 60,000).
  • CPO-8 chlorinated propylene-ethylene copolymer
  • Production Example 14 A maleic anhydride-modified chlorinated propylene-ethylene copolymer (CPO-9, acid value 25 mgKOH / g-resin, containing chlorine was used except that the amount of chlorine introduced was changed to 6 parts by mass. 3% by mass and a weight average molecular weight of 60,000).
  • Example 1 500 parts by mass of main agent 1 and 3 parts by mass of polycarbodiimide carbodilite V-03 as a crosslinking agent were blended to obtain an adhesive composition.
  • Table 3 shows the pot life and adhesiveness.
  • Examples 2 to 20, Comparative Examples 1 to 15 The main agents 2 to 22 and the crosslinking agent were changed as shown in Tables 3 to 6, and Examples 2 to 20 and Comparative Examples 1 to 15 were performed in the same manner as in Example 1.
  • the blending amounts, pot life properties, and adhesive properties are shown in Tables 3 to 6.
  • the cross-linking agents used in Tables 3 to 6 are as follows.
  • Polycarbodiimide Carbodilite (registered trademark) V-05 (Nisshinbo Co., Ltd., solid content concentration: 100% by mass)
  • Polycarbodiimide Carbodilite (registered trademark) V-03 (Nisshinbo Co., Ltd., solid content concentration 50 mass%)
  • Polyisocyanate Duranate (registered trademark) TPA-100 (manufactured by Asahi Kasei Corporation)
  • Silane coupling agent KBM-403 (manufactured by Shin-Etsu Silicone)
  • the acid value (mgKOH / g-resin) is determined by using FT-IR (manufactured by Shimadzu Corporation, FT-IR8200PC), a stretching peak (1780 cm) of a carbonyl (C ⁇ O) bond of maleic anhydride.
  • FT-IR manufactured by Shimadzu Corporation, FT-IR8200PC
  • a stretching peak (1780 cm) of a carbonyl (C ⁇ O) bond of maleic anhydride -1
  • absorbance (I) isotactic specific peak (840 cm -1 ) absorbance (II)
  • factor (f) obtained from a calibration curve prepared with a chloroform solution of maleic anhydride (manufactured by Tokyo Kasei). It is the value calculated by the following formula using.
  • Acid value [absorbance (I) / absorbance (II) ⁇ (f) / molecular weight of maleic anhydride ⁇ 2 ⁇ molecular weight of potassium hydroxide ⁇ 1000 (mg) / 100 (%)] Molecular weight of maleic anhydride: 98.06 Molecular weight of potassium hydroxide: 56.11
  • Chlorine content is a value determined by titration according to JIS K-7210.
  • Weight average molecular weight (Mw) The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (hereinafter, GPC, standard substance: polystyrene resin, mobile phase: tetrahydrofuran).
  • Melting point and heat of fusion in the present invention are heated and melted at a rate of 20 ° C./minute using a differential scanning calorimeter (hereinafter DSC, manufactured by TA Instruments Japan, Q-2000). It is a value measured from the top temperature and area of the melting peak when the resin is cooled and melted at elevated temperature.
  • DSC differential scanning calorimeter
  • Pot life property refers to the stability of the solution immediately after compounding or after a certain time has elapsed after compounding with a modified polyolefin. If the pot life is good, it means that the viscosity of the solution is small and can be stored for a long time. If the pot life is poor, the viscosity of the solution increases (thickens). It indicates that gelation occurs and cannot be stored for a long time. After the pot life properties of the adhesive compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 15 were stored at 25 ° C. and 40 ° C. for 24 hours, a solution at 25 ° C. using a Brookfield viscometer was used. Evaluation was made by measuring the viscosity.
  • Adhesiveness was evaluated by preparing a laminate of a metal substrate and a polyolefin resin substrate and performing an initial T-type peel test and a T-type peel test after an electrolyte test. The evaluation results are shown in Tables 3-6.
  • Aluminum foil manufactured by Sumi Light Aluminum Foil Co., Ltd., 8079-0, thickness 40 ⁇ m
  • a stretched polypropylene film Toyobo Pyrene (registered trademark) film CT, thickness 40 ⁇ m
  • the adhesive compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 15 were applied to metal substrates using a bar coater so that the thickness of the adhesive layer after drying was adjusted to 3 ⁇ m.
  • the coated surface was dried for 10 minutes at 80 ° C. using a warm air dryer to obtain an adhesive layer having a thickness of 3 ⁇ m.
  • a polyolefin-based resin substrate was superposed on the surface of the adhesive layer, and thermocompression bonded at 120 ° C. and 0.1 MPa for 2 minutes to obtain a laminate.
  • the adhesion test strength at the initial stage and after the electrolyte test of the laminate was measured by a T-type peel test.
  • peel strength at a tensile speed of 50 mm / min was measured in a 25 ° C. environment using Tensilon RTM-100 manufactured by Orientec Corporation.
  • the peel strength (N / cm) between the metal substrate / polyolefin-based resin substrate was the average of five test values.
  • the initial laminate was allowed to stand in an atmosphere of 25 ° C. for 12 hours, then cut to a size of 100 mm ⁇ 15 mm, and adhesion was evaluated by a T-type peel test.
  • an electrolytic solution test was conducted in order to examine the utility of the lithium battery as a packaging material.
  • the adhesive composition according to the present invention contains a modified polyolefin (A), polycarbodiimide (B), and an organic solvent (C), and has good pot life without causing thickening or gelation even after long-term storage. And good adhesion between the metal substrate and the polyolefin resin substrate can be achieved. Therefore, the laminated structure of the polyolefin-based resin base material and the metal base material formed from the adhesive composition of the present invention is not only used in the fields of home appliance outer panels, furniture materials, building interior members, etc. It can also be widely used as a packaging material (pouch form) for lithium batteries used in mobile phones, video cameras and the like.
  • A modified polyolefin
  • B polycarbodiimide
  • C organic solvent

Abstract

Provided is an adhesive agent composition which has good pot life properties and good adhesion to a metallic base material and a polyolefin-type resin base material, and comprises a modified polyolefin and a carbodiimide compound. An adhesive agent composition comprising a modified polyolefin (A) that is a modified polyolefin (A1) or (A2) as mentioned below, a polycarbodiimide (B) and an organic solvent (C): (A1) a crystalline acid-modified polyolefin having an acid value of 10 to 50 mgKOH/g-resin; and (A2) an acid-modified chlorinated polyolefin having an acid value of 10 to 50 mgKOH/g-resin and a chlorine content of 5 to 40% by mass.

Description

ポリオレフィン系接着剤組成物Polyolefin adhesive composition
　本発明は、ポリオレフィン系樹脂基材と金属基材とを接着するための接着剤組成物に関する。より詳しくは変性ポリオレフィン、ポリカルボジイミドおよび有機溶剤を含有する接着剤組成物に関する。 The present invention relates to an adhesive composition for bonding a polyolefin resin substrate and a metal substrate. More specifically, the present invention relates to an adhesive composition containing a modified polyolefin, polycarbodiimide and an organic solvent.
　従来から、家電外板、家具用素材、建築内装用部材などの金属基材には、その表面に塩化ビニル樹脂（以下、単に「塩ビ」ともいう。）を塗布乃至ラミネートしてなる積層体が使用されてきたが、昨今環境問題がクローズアップされ、塩ビの代替としてポリオレフィン系樹脂が提案されている。ポリオレフィン系樹脂は毒性がなく酸、アルカリ、有機溶剤等に強い耐久性を示し、機械的強度、耐磨耗性にも優れ、安価であることから各種分野に幅広く使用されている。 Conventionally, laminates formed by applying or laminating vinyl chloride resin (hereinafter, also simply referred to as “PVC”) on the surface of metal base materials such as home appliance outer panels, furniture materials, and building interior members. Although it has been used, environmental problems have been highlighted recently, and polyolefin resins have been proposed as an alternative to PVC. Polyolefin resins are not toxic, have strong durability against acids, alkalis, organic solvents, etc., are excellent in mechanical strength and abrasion resistance, are inexpensive, and are widely used in various fields.
　しかしながら、ポリオレフィン系樹脂は非極性であることから、金属基材との接着が困難であった。従来かかるポリオレフィン系樹脂と金属基材との接着のため、種々の接着架橋剤が提案されている。典型的なものとしては、エポキシ系架橋剤、シランカップリング剤、多官能イソシアネート系架橋剤などである（特許文献１、２）。 However, since the polyolefin-based resin is nonpolar, it is difficult to adhere to the metal substrate. Conventionally, various adhesive cross-linking agents have been proposed for adhesion between such polyolefin-based resins and metal substrates. Typical examples include epoxy crosslinking agents, silane coupling agents, polyfunctional isocyanate crosslinking agents (Patent Documents 1 and 2).
ＷＯ２００９／０８７７７６号公報WO2009 / 087776 特開２００９－２９２８５３号公報JP 2009-292853 A
　しかしながら、これらの架橋剤では変性ポリオレフィン溶液配合後のポットライフ性が不良となる場合があり、またポットライフ性がさほど問題なくとも肝心の金属基材との接着性が十分ではなかった。すなわち、ポットライフ性と金属基材との接着性を両立させるものはなかった。ここで、ポットライフ性とは、変性ポリオレフィンに架橋剤または硬化剤を配合し、その配合直後または一定時間経過後の該溶液の安定性を指す。 However, these cross-linking agents may have poor pot life after blending with the modified polyolefin solution, and the adhesion to the metal base material is not sufficient even if the pot life is not a problem. That is, there is no one that achieves both pot life and adhesiveness to the metal substrate. Here, the pot life property refers to the stability of the solution immediately after the compounding, or after a certain period of time, by blending the modified polyolefin with a crosslinking agent or a curing agent.
　本発明は、上記の従来の問題に鑑みてなされたものであり、ポリオレフィン系樹脂基材と金属基材との接着剤につき、本発明者らは鋭意検討した結果、変性ポリオレフィン、ポリカルボジイミドおよび有機溶剤を含有する接着剤組成物が、ポットライフ性と接着性とを両立させることを見出し、本発明を完成するに至ったものである。 The present invention has been made in view of the above-described conventional problems, and as a result of intensive studies on the adhesive between a polyolefin-based resin base material and a metal base material, the present inventors have found that modified polyolefin, polycarbodiimide, and organic The present inventors have found that an adhesive composition containing a solvent achieves both pot life and adhesiveness, and has completed the present invention.
　すなわち、本発明は、変性ポリオレフィンと架橋剤とを配合した後のポットライフ性が良好であり、かつポリオレフィン系樹脂基材と金属基材双方への良好な接着性を有する接着剤組成物を提供することを目的とする。 That is, the present invention provides an adhesive composition having good pot life after blending a modified polyolefin and a crosslinking agent and having good adhesion to both a polyolefin resin substrate and a metal substrate. The purpose is to do.
　上記課題を達成するため、本発明者らは鋭意検討し、以下の発明を提案するに至った。 In order to achieve the above-mentioned problems, the present inventors have intensively studied and have come up with the following inventions.
　（Ａ１）または（Ａ２）である変性ポリオレフィン（Ａ）、ポリカルボジイミド（Ｂ）および有機溶剤（Ｃ）を含有する接着剤組成物。
　（Ａ１）：酸価が１０～５０ｍｇＫＯＨ／ｇ-resinである結晶性酸変性ポリオレフィン
　（Ａ２）：酸価が１０～５０ｍｇＫＯＨ／ｇ-resin、塩素含有率が５～４０質量％である酸変性塩素化ポリオレフィン An adhesive composition containing the modified polyolefin (A), the polycarbodiimide (B) and the organic solvent (C) which are (A1) or (A2).
(A1): Crystalline acid-modified polyolefin having an acid value of 10 to 50 mgKOH / g-resin (A2): Acid-modified chlorine having an acid value of 10 to 50 mgKOH / g-resin and a chlorine content of 5 to 40% by mass Polyolefin
　変性ポリオレフィン（Ａ）１００質量部に対して、ポリカルボジイミド（Ｂ）を０．５～１０質量部、有機溶剤（Ｃ）を８０～１０００質量部含有することが好ましい。 It is preferable to contain 0.5 to 10 parts by mass of polycarbodiimide (B) and 80 to 1000 parts by mass of organic solvent (C) with respect to 100 parts by mass of the modified polyolefin (A).
　有機溶剤（Ｃ）が、溶剤（Ｃ１）と溶剤（Ｃ２）の混合液であって、溶剤（Ｃ１）が芳香族炭化水素、脂肪族炭化水素、脂環族炭化水素およびハロゲン化炭化水素からなる群より選択された１種以上の溶剤であり、溶剤（Ｃ２）がアルコール系溶剤、ケトン系溶剤、エステル系溶剤、グリコールエーテル系溶剤からなる群より選択された１種以上の溶剤であり、溶剤（Ｃ１）／溶剤（Ｃ２）＝５０～９０／５０～１０（質量比）であることが好ましい。 The organic solvent (C) is a mixed liquid of the solvent (C1) and the solvent (C2), and the solvent (C1) is composed of an aromatic hydrocarbon, an aliphatic hydrocarbon, an alicyclic hydrocarbon, and a halogenated hydrocarbon. One or more solvents selected from the group, wherein the solvent (C2) is one or more solvents selected from the group consisting of alcohol solvents, ketone solvents, ester solvents, glycol ether solvents, It is preferable that (C1) / solvent (C2) = 50 to 90/50 to 10 (mass ratio).
　ポリオレフィン系樹脂基材と金属基材との接着に用いられる前記いずれかに記載の接着剤組成物。 The adhesive composition according to any one of the above, which is used for bonding a polyolefin resin substrate and a metal substrate.
　前記いずれかに記載の接着剤組成物によって接着されたポリオレフィン系樹脂基材と金属基材の積層体。 A laminate of a polyolefin-based resin base material and a metal base material adhered by any one of the adhesive compositions described above.
　前記積層体を含有するリチウム電池用包装材。 A packaging material for a lithium battery containing the laminate.
　本発明にかかる接着剤組成物は、変性ポリオレフィン、ポリカルボジイミドおよび有機溶剤を含有し、長期間保存しても増粘やゲル化を生じることなく良好なポットライフ性を維持し、かつポリオレフィン系樹脂基材と金属基材との良好な接着性を両立させることができる。 The adhesive composition according to the present invention contains a modified polyolefin, polycarbodiimide, and an organic solvent, maintains good pot life without thickening or gelation even when stored for a long period of time, and is a polyolefin resin. It is possible to achieve both good adhesion between the base material and the metal base material.
　以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
＜変性ポリオレフィン（Ａ）＞
　本発明で用いる変性ポリオレフィン（Ａ）は、酸価が１０～５０ｍｇＫＯＨ／ｇ-resinである結晶性酸変性ポリオレフィン（Ａ１）、または酸価が１０～５０ｍｇＫＯＨ／ｇ-resin、塩素含有率が５～４０質量％である酸変性塩素化ポリオレフィン（Ａ２）である。 <Modified polyolefin (A)>
The modified polyolefin (A) used in the present invention is a crystalline acid-modified polyolefin (A1) having an acid value of 10 to 50 mgKOH / g-resin, or an acid value of 10 to 50 mgKOH / g-resin and a chlorine content of 5 to It is 40 mass% acid-modified chlorinated polyolefin (A2).
＜結晶性酸変性ポリオレフィン（Ａ１）＞
　本発明で用いる結晶性酸変性ポリオレフィン（Ａ１）は限定的ではないが、ポリエチレン、ポリプロピレン及びプロピレン－α－オレフィン共重合体の少なくとも１種に、α，β－不飽和カルボン酸及びその酸無水物の少なくとも１種をグラフトすることにより得られるものが好ましい。 <Crystalline acid-modified polyolefin (A1)>
The crystalline acid-modified polyolefin (A1) used in the present invention is not limited, but at least one of polyethylene, polypropylene and propylene-α-olefin copolymer includes α, β-unsaturated carboxylic acid and acid anhydride thereof. Those obtained by grafting at least one of the above are preferred.
　プロピレン－α－オレフィン共重合体は、プロピレンを主体としてこれにα－オレフィンを共重合したものである。α－オレフィンとしては、例えば、エチレン、１－ブテン、１－ヘプテン、１－オクテン、４－メチル－１－ペンテン、酢酸ビニルなどを１種又は数種用いるこができる。これらのα－オレフィンの中では、エチレン、１－ブテンが好ましい。プロピレン－α－オレフィン共重合体のプロピレン成分とα－オレフィン成分との比率は限定されないが、プロピレン成分が５０モル％以上であることが好ましく、７０モル％以上であることがより好ましい。 The propylene-α-olefin copolymer is a copolymer in which α-olefin is copolymerized mainly with propylene. As the α-olefin, for example, ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate or the like can be used. Of these α-olefins, ethylene and 1-butene are preferred. The ratio of the propylene component to the α-olefin component of the propylene-α-olefin copolymer is not limited, but the propylene component is preferably 50 mol% or more, and more preferably 70 mol% or more.
　ポリプロピレン系ランダム共重合体の製造は、公知の方法で実施することができ、例えば特開２００１－２０６９１４に記載の製造方法に従って、反応釜にプロピレンおよび炭素数４以上のオレフィンを仕込み、水素を供給しながら連続的に製造を行うことができる。重合方法は、公知の塊状重合法、気相重合法の連続重合によって実施することができ、好ましくは、塊状重合で１段階もしくは多段階で実施される。 Production of a polypropylene random copolymer can be carried out by a known method. For example, according to the production method described in JP-A-2001-206914, propylene and an olefin having 4 or more carbon atoms are charged into a reaction kettle and hydrogen is supplied. However, it can manufacture continuously. The polymerization method can be carried out by continuous polymerization of a known bulk polymerization method or gas phase polymerization method, and is preferably carried out in one step or multiple steps by bulk polymerization.
　α，β－不飽和カルボン酸及びその酸無水物の少なくとも１種としては、例えば、マレイン酸、イタコン酸、シトラコン酸及びこれらの酸無水物が挙げられる。これらの中でも酸無水物が好ましく、無水マレイン酸がより好ましい。具体的には、無水マレイン酸変性ポリプロピレン、無水マレイン酸変性プロピレン－エチレン共重合体、無水マレイン酸変性プロピレン－ブテン共重合体、無水マレイン酸変性プロピレン－エチレン－ブテン共重合体等が挙げられ、これら酸変性ポリオレフィンを１種類又は２種類以上を組み合わせて使用することができる。 Examples of at least one of α, β-unsaturated carboxylic acid and acid anhydrides thereof include maleic acid, itaconic acid, citraconic acid, and acid anhydrides thereof. Among these, acid anhydrides are preferable, and maleic anhydride is more preferable. Specific examples include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, maleic anhydride-modified propylene-ethylene-butene copolymer, and the like. These acid-modified polyolefins can be used alone or in combination of two or more.
　結晶性酸変性ポリオレフィン（Ａ１）の酸価は、ポットライフ性およびポリオレフィン系樹脂基材と金属基材との接着性の観点から、下限は１０ｍｇＫＯＨ／ｇ-resin以上である必要があり、好ましくは１２ｍｇＫＯＨ／ｇ-resin以上であり、より好ましくは１４ｍｇＫＯＨ／ｇ-resin以上であり、さらに好ましくは１６ｍｇＫＯＨ／ｇ-resin以上であり、特に好ましくは１８ｍｇＫＯＨ／ｇ-resin以上であり、最も好ましくは２０ｍｇＫＯＨ／ｇ-resin以上である。前記の値未満であると、ポリカルボジイミドとの相溶性が低く、接着強度が発現しない場合がある。上限は５０ｍｇＫＯＨ／ｇ-resin以下である必要があり、好ましくは４８ｍｇＫＯＨ／ｇ-resin以下であり、より好ましくは４６ｍｇＫＯＨ／ｇ-resin以下であり、さらに好ましくは４４ｍｇＫＯＨ／ｇ-resin以下であり、特に好ましくは４２ｍｇＫＯＨ／ｇ-resin以下であり、最も好ましくは４０ｍｇＫＯＨ／ｇ-resin以下である。前記の値を超えると、溶液の粘度や安定性が低下し、ポットライフ性が低下することがある。さらに製造効率も低下するため好ましくない。 The acid value of the crystalline acid-modified polyolefin (A1) must be at least 10 mgKOH / g-resin, preferably from the viewpoint of pot life and adhesion between the polyolefin resin substrate and the metal substrate, preferably 12 mgKOH / g-resin or more, more preferably 14 mgKOH / g-resin or more, further preferably 16 mgKOH / g-resin or more, particularly preferably 18 mgKOH / g-resin or more, most preferably 20 mgKOH / More than g-resin. If it is less than the above value, the compatibility with polycarbodiimide is low, and the adhesive strength may not be exhibited. The upper limit needs to be 50 mgKOH / g-resin or less, preferably 48 mgKOH / g-resin or less, more preferably 46 mgKOH / g-resin or less, still more preferably 44 mgKOH / g-resin or less. Preferably it is 42 mgKOH / g-resin or less, Most preferably, it is 40 mgKOH / g-resin or less. When the above value is exceeded, the viscosity and stability of the solution may decrease, and the pot life may decrease. Furthermore, it is not preferable because the production efficiency is also lowered.
　結晶性酸変性ポリオレフィン（Ａ１）の重量平均分子量（Ｍｗ）は、４０，０００～１７０，０００の範囲であることが好ましい。より好ましくは５０，０００～１６０，０００の範囲であり、さらに好ましくは６０，０００～１５０，０００の範囲であり、特に好ましくは７０，０００～１４０，０００の範囲であり、最も好ましくは、８０，０００～１３０，０００の範囲である。前記の値未満であると、凝集力が弱くなり接着性が劣る場合がある。一方、前記の値を超えると、流動性が低く接着する際の操作性に問題が生じる場合がある。前記範囲内であれば、ポリカルボジイミドとの相互作用が活かされるため好ましい。 The weight average molecular weight (Mw) of the crystalline acid-modified polyolefin (A1) is preferably in the range of 40,000 to 170,000. More preferably, it is in the range of 50,000 to 160,000, more preferably in the range of 60,000 to 150,000, particularly preferably in the range of 70,000 to 140,000, and most preferably 80. , 13,000 to 130,000. If it is less than the above value, the cohesive force becomes weak and the adhesiveness may be inferior. On the other hand, when the above value is exceeded, there may be a problem in operability when bonding due to low fluidity. If it is in the said range, since interaction with polycarbodiimide is utilized, it is preferable.
　結晶性酸変性ポリオレフィン（Ａ１）における結晶性とは、示差走査型熱量計（ＤＳＣ）を用いて、－１００℃～２５０℃ まで２０℃／分で昇温し、該昇温過程に明確な融解ピークを示すものを指す。 The crystallinity in the crystalline acid-modified polyolefin (A1) means that the temperature is raised from −100 ° C. to 250 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC), and the melting process is clearly melted. This refers to the peak.
　酸変性ポリオレフィンを結晶性とすることで、非晶性に比べ、凝集力が強く、接着性や耐熱性、耐薬品性に優れるため有利である。 It is advantageous to make the acid-modified polyolefin crystalline, because it has higher cohesion than amorphous and has excellent adhesion, heat resistance, and chemical resistance.
　結晶性酸変性ポリオレフィン（Ａ１）の融点（Ｔｍ）は、５０℃～１２０℃の範囲であることが好ましい。より好ましくは６０℃～１００℃の範囲であり、最も好ましくは７０℃～９０℃の範囲である。前記の値未満であると、結晶由来の凝集力が弱くなり、接着性や耐熱性、耐薬品性が劣る場合がある。一方、前記の値を超えると、溶液安定性、流動性が低く接着する際の操作性に問題が生じる場合がある。 The melting point (Tm) of the crystalline acid-modified polyolefin (A1) is preferably in the range of 50 ° C to 120 ° C. More preferably, it is in the range of 60 ° C to 100 ° C, and most preferably in the range of 70 ° C to 90 ° C. If it is less than the above value, the crystal-derived cohesive force becomes weak, and the adhesiveness, heat resistance, and chemical resistance may be inferior. On the other hand, when the above value is exceeded, the solution stability and fluidity are low, and there may be a problem in operability when bonding.
　結晶性酸変性ポリオレフィン（Ａ１）の融解熱（ΔＨ）は、５Ｊ／ｇ～６０Ｊ／ｇの範囲であることが好ましい。より好ましくは１０Ｊ／ｇ～５０Ｊ／ｇの範囲であり、最も好ましくは２０Ｊ／ｇ～４０Ｊ／ｇの範囲である。前記の値未満であると、結晶由来の凝集力が弱くなり、接着性や耐熱性、耐薬品性が劣る場合がある。一方、前記の値を超えると、溶液安定性、流動性が低く接着する際の操作性に問題が生じる場合がある。 The heat of fusion (ΔH) of the crystalline acid-modified polyolefin (A1) is preferably in the range of 5 J / g to 60 J / g. A range of 10 J / g to 50 J / g is more preferable, and a range of 20 J / g to 40 J / g is most preferable. If it is less than the above value, the crystal-derived cohesive force becomes weak, and the adhesiveness, heat resistance, and chemical resistance may be inferior. On the other hand, when the above value is exceeded, the solution stability and fluidity are low, and there may be a problem in operability when bonding.
　結晶性酸変性ポリオレフィン（Ａ１）の製造方法としては、特に限定されず、例えばラジカルグラフト反応（すなわち主鎖となるポリマーに対してラジカル種を生成し、そのラジカル種を重合開始点として不飽和カルボン酸および酸無水物をグラフト重合させる反応）、などが挙げられる。 The production method of the crystalline acid-modified polyolefin (A1) is not particularly limited. For example, a radical graft reaction (that is, a radical species is generated with respect to a polymer as a main chain, and the radical species is used as a polymerization initiation point to produce an unsaturated carboxylic acid. Reaction for graft polymerization of acid and acid anhydride), and the like.
　ラジカル発生剤としては、特に限定されないが、有機過酸化物を使用することが好ましい。有機過酸化物としては、特に限定されないが、ジ－ｔｅｒｔ－ブチルパーオキシフタレート、ｔｅｒｔ－ブチルヒドロパーオキサイド、ジクミルパーオキサイド、ベンゾイルパーオキサイド、ｔｅｒｔ－ブチルパーオキシベンゾエート、ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔｅｒｔ－ブチルパーオキシピバレート、メチルエチルケトンパーオキサイド、ジ－ｔｅｒｔ－ブチルパーオキサイド、ラウロイルパーオキサイド等の過酸化物；アゾビスイソブチロニトリル、アゾビスイソプロピオニトリル等のアゾニトリル類等が挙げられる。 Although it does not specifically limit as a radical generator, It is preferable to use an organic peroxide. The organic peroxide is not particularly limited, but di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy- Peroxides such as 2-ethylhexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauroyl peroxide; azobisisobutyronitrile, azobisisopropionitrile, etc. Examples thereof include azonitriles.
＜酸変性塩素化ポリオレフィン（Ａ２）＞
　本発明で用いる酸変性塩素化ポリオレフィン（Ａ２）は限定的ではないが、前記結晶性酸変性ポリオレフィン（Ａ１）を塩素化することにより得られるものが好ましい。 <Acid-modified chlorinated polyolefin (A2)>
The acid-modified chlorinated polyolefin (A2) used in the present invention is not limited, but is preferably obtained by chlorinating the crystalline acid-modified polyolefin (A1).
　酸変性塩素化ポリオレフィン（Ａ２）の酸価は、ポットライフ性およびポリオレフィン系樹脂基材と金属基材との接着性の観点から、下限は１０ｍｇＫＯＨ／ｇ-resin以上である必要があり、好ましくは１２ｍｇＫＯＨ／ｇ-resin以上であり、より好ましくは１４ｍｇＫＯＨ／ｇ-resin以上であり、さらに好ましくは１６ｍｇＫＯＨ／ｇ-resin以上であり、特に好ましくは１８ｍｇＫＯＨ／ｇ-resin以上であり、最も好ましくは２０ｍｇＫＯＨ／ｇ-resin以上である。前記の値未満であると、ポリカルボジイミドとの相溶性が低く、接着強度が発現しない場合がある。上限は５０ｍｇＫＯＨ／ｇ-resin以下である必要があり、好ましくは４８ｍｇＫＯＨ／ｇ-resin以下であり、より好ましくは４６ｍｇＫＯＨ／ｇ-resin以下であり、さらに好ましくは４４ｍｇＫＯＨ／ｇ-resin以下であり、特に好ましくは４２ｍｇＫＯＨ／ｇ-resin以下であり、最も好ましくは４０ｍｇＫＯＨ／ｇ-resin以下である。前記の値を超えると、溶液の粘度や安定性が低下し、ポットライフ性が低下することがある。さらに製造効率も低下するため好ましくない。 The acid value of the acid-modified chlorinated polyolefin (A2) is required to be 10 mg KOH / g-resin or more from the viewpoint of pot life and adhesion between the polyolefin resin substrate and the metal substrate, preferably 12 mgKOH / g-resin or more, more preferably 14 mgKOH / g-resin or more, further preferably 16 mgKOH / g-resin or more, particularly preferably 18 mgKOH / g-resin or more, most preferably 20 mgKOH / More than g-resin. If it is less than the above value, the compatibility with polycarbodiimide is low, and the adhesive strength may not be exhibited. The upper limit needs to be 50 mgKOH / g-resin or less, preferably 48 mgKOH / g-resin or less, more preferably 46 mgKOH / g-resin or less, still more preferably 44 mgKOH / g-resin or less. Preferably it is 42 mgKOH / g-resin or less, Most preferably, it is 40 mgKOH / g-resin or less. When the above value is exceeded, the viscosity and stability of the solution may decrease, and the pot life may decrease. Furthermore, it is not preferable because the production efficiency is also lowered.
　酸変性塩素化ポリオレフィン（Ａ２）の塩素含有率は、溶液安定性およびポリオレフィン系樹脂基材と金属基材との接着性の観点から、下限は５質量％以上である必要があり、好ましくは８質量％以上であり、より好ましくは１０質量％以上であり、さらに好ましくは１２質量％以上であり、特に好ましくは１４質量％以上である。前記の値未満であると、溶液安定性が低下しポットライフ性が悪くなることがある。さらに、ポリカルボジイミド（Ｂ）との相溶性が低く、接着強度が発現しない場合がある。上限は４０質量％以下である必要があり、好ましくは３８質量％以下であり、より好ましくは３５質量％以下であり、さらに好ましくは３２質量％以下であり、特に好ましくは３０質量％以下である。前記の値を超えると、酸変性塩素化ポリオレフィン（Ａ２）の結晶性が低下し、接着強度が低下する場合がある。 The lower limit of the chlorine content of the acid-modified chlorinated polyolefin (A2) needs to be 5% by mass or more, preferably 8 from the viewpoint of solution stability and the adhesion between the polyolefin resin substrate and the metal substrate. It is at least 10% by mass, more preferably at least 10% by mass, even more preferably at least 12% by mass, particularly preferably at least 14% by mass. If it is less than the above value, the solution stability may be lowered and the pot life may be deteriorated. Furthermore, the compatibility with the polycarbodiimide (B) is low, and the adhesive strength may not be exhibited. The upper limit needs to be 40% by mass or less, preferably 38% by mass or less, more preferably 35% by mass or less, still more preferably 32% by mass or less, and particularly preferably 30% by mass or less. . If the above value is exceeded, the crystallinity of the acid-modified chlorinated polyolefin (A2) may be lowered, and the adhesive strength may be lowered.
　酸変性塩素化ポリオレフィン（Ａ２）の重量平均分子量（Ｍｗ）は、４０，０００～１７０，０００の範囲であることが好ましい。より好ましくは５０，０００～１６０，０００の範囲であり、さらに好ましくは６０，０００～１５０，０００の範囲であり、特に好ましくは７０，０００～１４０，０００の範囲であり、最も好ましくは、８０，０００～１３０，０００の範囲である。前記の値未満であると、凝集力が弱くなり接着性が劣る場合がある。一方、前記の値を超えると、流動性が低く接着する際の操作性に問題が生じる場合がある。前記範囲内であれば、ポリカルボジイミド（Ｂ）との相互作用が活かされるため好ましい。 The weight average molecular weight (Mw) of the acid-modified chlorinated polyolefin (A2) is preferably in the range of 40,000 to 170,000. More preferably, it is in the range of 50,000 to 160,000, more preferably in the range of 60,000 to 150,000, particularly preferably in the range of 70,000 to 140,000, and most preferably 80. , 13,000 to 130,000. If it is less than the above value, the cohesive force becomes weak and the adhesiveness may be inferior. On the other hand, when the above value is exceeded, there may be a problem in operability when bonding due to low fluidity. If it is in the said range, since interaction with polycarbodiimide (B) is utilized, it is preferable.
　酸変性塩素化ポリオレフィン（Ａ２）の製造方法としては、特に限定されず、例えば酸変性ポリオレフィンをクロロホルム等のハロゲン化炭化水素に溶解させ、塩素を導入することにより得ることができる。 The production method of the acid-modified chlorinated polyolefin (A2) is not particularly limited, and can be obtained, for example, by dissolving the acid-modified polyolefin in a halogenated hydrocarbon such as chloroform and introducing chlorine.
＜ポリカルボジイミド（Ｂ）＞
　本発明で用いるポリカルボジイミド（Ｂ）は、分子内に２以上のカルボジイミド基を有するものであれば、特に限定されない。ポリカルボジイミド（Ｂ）を使用することによって、変性ポリオレフィン（Ａ）とポリカルボジイミド（Ｂ）間に、急激な粘度上昇を伴う架橋反応ではなく、水素結合などの相互作用が生じることで、ポットライフ性を損なうことなく接着性を向上することが可能になると考えられる。 <Polycarbodiimide (B)>
The polycarbodiimide (B) used in the present invention is not particularly limited as long as it has two or more carbodiimide groups in the molecule. By using the polycarbodiimide (B), the interaction between the modified polyolefin (A) and the polycarbodiimide (B) is not a cross-linking reaction accompanied by an abrupt increase in viscosity, but an interaction such as hydrogen bonding. It is considered that the adhesiveness can be improved without impairing the resistance.
　ポリカルボジイミド（Ｂ）は、変性ポリオレフィン（Ａ）１００質量部に対して、０．５質量部以上であることが好ましく、１質量部以上であることがより好ましく、１．５質量部以上であることがさらに好ましく、２質量部以上であることが特に好ましい。また、１０質量部以下であることが好ましく、９質量部以下であることがより好ましく、８．５質量部以下であることがさらに好ましく、８質量部以下であることが特に好ましい。前記範囲未満では金属基材表面の酸化膜層との相互作用が生じず接着性が発現しない場合があり、前記範囲を超えると製造コスト、ポリオレフィン系樹脂基材との接着性が低下する場合がある。 The polycarbodiimide (B) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and 1.5 parts by mass or more with respect to 100 parts by mass of the modified polyolefin (A). It is more preferable that it is 2 parts by mass or more. Further, it is preferably 10 parts by mass or less, more preferably 9 parts by mass or less, further preferably 8.5 parts by mass or less, and particularly preferably 8 parts by mass or less. If the amount is less than the above range, there is a case where the interaction with the oxide film layer on the surface of the metal substrate does not occur and the adhesiveness may not be expressed, and if the range is exceeded, the production cost and the adhesion to the polyolefin resin substrate may be lowered. is there.
＜有機溶剤（Ｃ）＞
　本発明で用いる有機溶剤（Ｃ）は、変性ポリオレフィン（Ａ）およびポリカルボジイミド（Ｂ）を溶解させるものであれば、特に限定されない。具体的には、例えば、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、デカン等の脂肪族系炭化水素、シクロヘキサン、シクロヘキセン、メチルシクロヘキサン、エチルシクロへキサン等の脂環族炭化水素、トリクロルエチレン、ジクロルエチレン、クロルベンゼン、クロロホルム等のハロゲン化炭化水素、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系溶剤、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、シクロヘキサノン、イソホロン、アセトフェノン等のケトン系溶剤、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系溶剤、エチレングリコールモノn -ブチルエーテル、エチレングリコールモノi s o -ブチルエーテル、エチレングリコールモノt e r t - ブチルエーテル、ジエチレングリコールモノn -ブチルエーテル、ジエチレングリコールモノi s o -ブチルエーテル、トリエチレングリコールモノn -ブチルエーテル、テトラエチレングリコールモノn -ブチルエーテ等のグリコールエーテル系溶剤等を使用することができ、これら１種または２種以上を併用することができる。 <Organic solvent (C)>
The organic solvent (C) used in the present invention is not particularly limited as long as it dissolves the modified polyolefin (A) and the polycarbodiimide (B). Specifically, for example, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, and alicyclic carbons such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane Halogenated hydrocarbons such as hydrogen, trichloroethylene, dichloroethylene, chlorobenzene, chloroform, alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol, acetone, methyl isobutyl ketone, Ketone solvents such as methyl ethyl ketone pentanone, hexanone, cyclohexanone, isophorone, acetophenone, cellsolves such as methyl cellosolve, ethyl cellosolve, methyl acetate, ethyl acetate, acetic acid Ester solvents such as chill, methyl propionate, butyl formate, ethylene glycol mono n-butyl ether, ethylene glycol mono iso-butyl ether, ethylene glycol mono tert-butyl ether, diethylene glycol mono n-butyl ether, diethylene glycol mono iso-butyl ether, triethylene glycol Glycol ether solvents such as mono n-butyl ether and tetraethylene glycol mono n-butyl ether can be used, and one or more of these can be used in combination.
　有機溶剤（Ｃ）は、変性ポリオレフィン（Ａ）１００質量部に対して、８０質量部以上であることが好ましく、９０質量部以上であることがより好ましく、１００質量部以上であることがさらに好ましく、１１０質量部以上であることが特に好ましい。また、１０００質量部以下であることが好ましく、９００質量部以下であることがより好ましく、８００質量部以下であることがさらに好ましく、７００質量部以下であることが特に好ましい。前記範囲未満では、液状およびポットライフ性が低下することがあり、前記範囲を超えると製造コスト、輸送コストの面から不利となる場合がある。 The organic solvent (C) is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and still more preferably 100 parts by mass or more with respect to 100 parts by mass of the modified polyolefin (A). 110 parts by mass or more is particularly preferable. Further, it is preferably 1000 parts by mass or less, more preferably 900 parts by mass or less, still more preferably 800 parts by mass or less, and particularly preferably 700 parts by mass or less. If it is less than the said range, liquid state and pot life property may fall, and when it exceeds the said range, it may become disadvantageous from the surface of manufacturing cost and transport cost.
　有機溶剤（Ｃ）は、接着剤組成物の液状およびポットライフ性の観点から、芳香族炭化水素、脂肪族炭化水素、脂環族炭化水素およびハロゲン化炭化水素からなる群より選択された１種以上の溶剤（Ｃ１）、アルコール系溶剤、ケトン系溶剤、エステル系溶剤およびグリコールエーテル系溶剤からなる群より選択された１種以上の溶剤（Ｃ２）の混合液が好ましい。混合比としては、溶剤（Ｃ１）／溶剤（Ｃ２）＝５０～９０／５０～１０（質量比）であることが好ましく、５５～８５／４５～１５（質量比）であることがより好ましく、６０～８０／４０～２０（質量比）であることがさらに好ましい。上記範囲を外れると接着剤組成物の液状およびポットライフ性が低下することがある。また、溶剤（Ｃ１）が脂環族炭化水素、溶剤（Ｃ２）がケトン系溶剤であることが特に好ましい。 The organic solvent (C) is one selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons from the viewpoint of the liquidity and pot life properties of the adhesive composition. A mixed liquid of at least one solvent (C2) selected from the group consisting of the above solvent (C1), alcohol solvent, ketone solvent, ester solvent and glycol ether solvent is preferable. The mixing ratio is preferably solvent (C1) / solvent (C2) = 50 to 90/50 to 10 (mass ratio), more preferably 55 to 85/45 to 15 (mass ratio), More preferably, it is 60-80 / 40-20 (mass ratio). If it is out of the above range, the liquid state and pot life of the adhesive composition may be lowered. Further, it is particularly preferable that the solvent (C1) is an alicyclic hydrocarbon and the solvent (C2) is a ketone solvent.
＜接着剤組成物＞
　本発明にかかる接着剤組成物は、前記変性ポリオレフィン（Ａ）、ポリカルボジイミド（Ｂ）および有機溶剤（Ｃ）の混合物である。変性ポリオレフィン（Ａ）としては、結晶性酸変性ポリオレフィン（Ａ１）を単独で使用しても良いし、酸変性塩素化ポリオレフィン（Ａ２）を単独で使用しても良いし、これらを併用しても良い。変性ポリオレフィン（Ａ）およびポリカルボジイミド（Ｂ）は有機溶剤（Ｃ）に溶解しても良いし、分散しても良い。ポットライフ性の観点から溶解していることが好ましい。 <Adhesive composition>
The adhesive composition according to the present invention is a mixture of the modified polyolefin (A), polycarbodiimide (B), and organic solvent (C). As the modified polyolefin (A), the crystalline acid-modified polyolefin (A1) may be used alone, the acid-modified chlorinated polyolefin (A2) may be used alone, or these may be used in combination. good. The modified polyolefin (A) and the polycarbodiimide (B) may be dissolved or dispersed in the organic solvent (C). It is preferably dissolved from the viewpoint of pot life.
　本発明にかかる接着剤組成物は、本発明の性能を損なわない範囲で前記変性ポリオレフィン（Ａ）、ポリカルボジイミド（Ｂ）および有機溶剤（Ｃ）の他に各種の添加剤を配合して使用することができる。添加剤としては、特に限定されないが、難燃剤、顔料、ブロッキング防止剤等を使用することが好ましい。 The adhesive composition according to the present invention is used by blending various additives in addition to the modified polyolefin (A), polycarbodiimide (B) and organic solvent (C) as long as the performance of the present invention is not impaired. be able to. Although it does not specifically limit as an additive, It is preferable to use a flame retardant, a pigment, an antiblocking agent, etc.
＜積層体＞
　本発明の積層体は、ポリオレフィン系樹脂基材と金属基材を本発明にかかる接着剤組成物で積層したものである。 <Laminate>
The laminate of the present invention is obtained by laminating a polyolefin resin substrate and a metal substrate with the adhesive composition according to the present invention.
　積層する方法としては、従来公知のラミネート製造技術を利用することができる。例えば、特に限定されないが、金属基材の表面に接着剤組成物をロールコータやバーコータ等の適当な塗布手段を用いて塗布し、乾燥させる。乾燥後、金属基材表面に形成された接着剤層が溶融状態にある間に、その塗布面にポリオレフィン系樹脂基材を積層接着してラミネート構造体を得ることができる。
　前記接着剤組成物により形成される接着剤層の厚みは、特に限定されないが、０．５～１０μｍにすることが好ましく、０．８～９．５μｍにすることがより好ましく、１～９μｍにすることがさらに好ましい。 As a lamination method, a conventionally known laminate manufacturing technique can be used. For example, although not particularly limited, the adhesive composition is applied to the surface of the metal substrate using an appropriate application means such as a roll coater or a bar coater, and dried. After drying, while the adhesive layer formed on the surface of the metal substrate is in a molten state, a laminate structure can be obtained by laminating and bonding a polyolefin resin substrate to the coated surface.
The thickness of the adhesive layer formed by the adhesive composition is not particularly limited, but is preferably 0.5 to 10 μm, more preferably 0.8 to 9.5 μm, and 1 to 9 μm. More preferably.
＜ポリオレフィン系樹脂基材＞
　ポリオレフィン系樹脂基材としては、従来から公知のポリオレフィン系樹脂の中から適宜選択すればよい。例えば、特に限定されないが、ポリエチレン、ポリプロピレン、エチレン－プロピレン共重合体などを用いることができる。中でも、ポリプロピレンの無延伸フィルム（以下、ＣＰＰともいう。）の使用が好ましい。その厚さは、特に限定されないが、２０～１００μｍであることが好ましく、２５～９５μｍであることがより好ましく、３０～９０μｍであることがさらに好ましい。なお、ポリオレフィン系樹脂基材には必要に応じて顔料や種々の添加物を配合してもよい。 <Polyolefin resin substrate>
The polyolefin resin substrate may be appropriately selected from conventionally known polyolefin resins. For example, although not particularly limited, polyethylene, polypropylene, ethylene-propylene copolymer, and the like can be used. Among these, the use of an unstretched polypropylene film (hereinafter also referred to as CPP) is preferable. The thickness is not particularly limited, but is preferably 20 to 100 μm, more preferably 25 to 95 μm, and even more preferably 30 to 90 μm. In addition, you may mix | blend a pigment and various additives with a polyolefin-type resin base material as needed.
＜金属基材＞
　金属基材としては、特に限定されないが、例えばアルミニウム、銅、鉄鋼、亜鉛、ジュラルミン、ダイカストなどの各種金属およびその合金を使用することができる。また、その形状としては、金属箔、圧延鋼板、パネル、パイプ、カン、キャップなど任意の形状を取り得ることができる。一般的には、加工性等の観点からアルミ二ウム箔が好ましい。また、使用目的によっても異なるが、一般的には０．０１～１０ｍｍ、好ましくは０．０２～５ｍｍの厚みのシートの形で使用される。
　また、これら金属基材の表面を予め表面処理を施しておいてもよいし、未処理のままでもよい。いずれも場合であっても同等の効果を発揮することができる。 <Metal base material>
Although it does not specifically limit as a metal base material, For example, various metals, such as aluminum, copper, steel, zinc, duralumin, die-casting, and its alloy can be used. Moreover, as the shape, arbitrary shapes, such as metal foil, a rolled steel plate, a panel, a pipe, a can, and a cap, can be taken. In general, aluminum foil is preferable from the viewpoint of workability and the like. Although it varies depending on the purpose of use, it is generally used in the form of a sheet having a thickness of 0.01 to 10 mm, preferably 0.02 to 5 mm.
Moreover, the surface of these metal base materials may be surface-treated in advance, or may be left untreated. In either case, the same effect can be exhibited.
　以下、実施例を挙げて本発明を更に詳細に説明する。但し、本発明は実施例に限定されない。実施例中および比較例中に単に部とあるのは質量部を示す。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples. In the examples and comparative examples, “parts” simply means “parts by mass”.
＜結晶性酸変性ポリオレフィン（Ａ１）の製造例＞
製造例１
　撹拌機を取り付けた１Ｌオートクレーブに、プロピレン－ブテン共重合体（三井化学社製「タフマー（登録商標）ＸＭ７０８０」）１００質量部、トルエン１５０質量部及び無水マレイン酸２５質量部、ジ－ｔｅｒｔ－ブチルパーオキサイド６質量部を加え、１４０℃まで昇温した後、更に３時間撹拌した。その後、得られた反応液を冷却後、多量のメチルエチルケトンが入った容器に注ぎ、樹脂を析出させた。その後、当該樹脂を含有する液を遠心分離することにより、無水マレイン酸がグラフト重合した酸変性プロピレン－ブテン共重合体と（ポリ）無水マレイン酸および低分子量物とを分離、精製した。その後、減圧下７０℃で５時間乾燥させることにより、無水マレイン酸変性プロピレン－ブテン共重合体（ＰＯ－１、酸価４８ｍｇＫＯＨ／ｇ-resin、重量平均分子量５０，０００、Ｔｍ７５℃、△Ｈ２５Ｊ／ｇ）を得た。 <Example of production of crystalline acid-modified polyolefin (A1)>
Production Example 1
In a 1 L autoclave equipped with a stirrer, 100 parts by mass of a propylene-butene copolymer (“Tuffmer (registered trademark) XM7080” manufactured by Mitsui Chemicals), 150 parts by mass of toluene and 25 parts by mass of maleic anhydride, di-tert-butyl After adding 6 parts by mass of peroxide and raising the temperature to 140 ° C., the mixture was further stirred for 3 hours. Then, after cooling the obtained reaction liquid, it poured into the container containing a lot of methyl ethyl ketone, and resin was deposited. Thereafter, the liquid containing the resin was centrifuged to separate and purify an acid-modified propylene-butene copolymer grafted with maleic anhydride, (poly) maleic anhydride and a low molecular weight product. Thereafter, by drying at 70 ° C. under reduced pressure for 5 hours, a maleic anhydride-modified propylene-butene copolymer (PO-1, acid value 48 mgKOH / g-resin, weight average molecular weight 50,000, Tm 75 ° C., ΔH25J / g) was obtained.
製造例２
　無水マレイン酸の仕込み量を２０質量部に変更した以外は製造例１と同様にすることにより、無水マレイン酸変性プロピレン－ブテン共重合体（ＰＯ－２、酸価２５ｍｇＫＯＨ／ｇ-resin、重量平均分子量８０，０００、Ｔｍ７５℃、△Ｈ３０Ｊ／ｇ）を得た。 Production Example 2
A maleic anhydride-modified propylene-butene copolymer (PO-2, acid value 25 mgKOH / g-resin, weight average) was obtained in the same manner as in Production Example 1 except that the amount of maleic anhydride charged was changed to 20 parts by mass. Molecular weight 80,000, Tm 75 ° C., ΔH 30 J / g) was obtained.
製造例３
　無水マレイン酸の仕込み量を１０質量部、ジ－ｔｅｒｔ－ブチルパーオキサイドを２質量部に変更した以外は製造例１と同様にすることにより、無水マレイン酸変性プロピレン－ブテン共重合体（ＰＯ－３、酸価１０ｍｇＫＯＨ／ｇ-resin、重量平均分子量１５０，０００、Ｔｍ８０℃、△Ｈ２５Ｊ／ｇ）を得た。 Production Example 3
A maleic anhydride-modified propylene-butene copolymer (PO—) was prepared in the same manner as in Production Example 1 except that the amount of maleic anhydride charged was changed to 10 parts by mass and that of di-tert-butyl peroxide was changed to 2 parts by mass. 3, an acid value of 10 mg KOH / g-resin, a weight average molecular weight of 150,000, Tm of 80 ° C., ΔH25 J / g).
製造例４
　無水マレイン酸の仕込み量を３０質量部に変更した以外は製造例１と同様にすることにより、無水マレイン酸変性プロピレン－ブテン共重合体（ＰＯ－４、酸価５５ｍｇＫＯＨ／ｇ-resin、重量平均分子量４０，０００、Ｔｍ７０℃、△Ｈ２５Ｊ／ｇ）を得た。 Production Example 4
A maleic anhydride-modified propylene-butene copolymer (PO-4, acid value 55 mgKOH / g-resin, weight average) was obtained in the same manner as in Production Example 1 except that the amount of maleic anhydride charged was changed to 30 parts by mass. Molecular weight 40,000, Tm 70 ° C., ΔH 25 J / g) was obtained.
製造例５
　無水マレイン酸の仕込み量を５質量部、ジ－ｔｅｒｔ－ブチルパーオキサイドを２質量部に変更した以外は製造例１と同様にすることにより、無水マレイン酸変性プロピレン－ブテン共重合体（ＰＯ－５、酸価７ｍｇＫＯＨ／ｇ-resin、重量平均分子量１７０，０００、Ｔｍ８０℃、△Ｈ２５Ｊ／ｇ）を得た。 Production Example 5
A maleic anhydride-modified propylene-butene copolymer (PO--) was prepared in the same manner as in Production Example 1 except that the amount of maleic anhydride charged was changed to 5 parts by mass and di-tert-butyl peroxide was changed to 2 parts by mass. 5, acid value 7 mg KOH / g-resin, weight average molecular weight 170,000, Tm 80 ° C., ΔH 25 J / g).
＜酸変性塩素化ポリオレフィン（Ａ２）の製造例＞
製造例６
　撹拌機を取り付けた１Ｌオートクレーブに、プロピレン-エチレン共重合体（230℃雰囲気下のMFR=5g/10分）１００質量部、トルエン１５０質量部及び無水マレイン酸２０質量部、ジ－ｔｅｒｔ－ブチルパーオキサイド５質量部を加え、１４０℃まで昇温した後、更に３時間撹拌した。その後、得られた反応液を冷却後、多量のメチルエチルケトンが入った容器に注ぎ、樹脂を析出させた。その後、当該樹脂を含有する液を遠心分離することにより、無水マレイン酸がグラフト重合した酸変性プロピレン－エチレン共重合体と（ポリ）無水マレイン酸および低分子量物とを分離、精製した。その後、減圧下７０℃で５時間乾燥させることにより、無水マレイン酸変性プロピレン－エチレン共重合体（ＰＯ－６）を得た。次いで、２Ｌのグラスライニング製反応缶にＰＯ－６を１００質量部、クロロホルムを１７００質量部入れ密閉にした。反応缶内の液を撹拌して分散しながら加温し、缶内温度１２０℃で１時間溶解した。缶内温度を１１０℃まで冷却した後に、ｔ－ブチルパーオキシ－２－エチルヘキサエノエートを０．５ｇ添加し、塩素を７０質量部導入した。缶内温度を６０℃まで冷却し、クロロホルム１４００質量部を留去した後に、安定剤としてｐ－ｔ－ブチルフェニルグリシジルエーテルを４質量部添加した。その後、乾燥することにより、無水マレイン酸変性塩素化プロピレン－エチレン共重合体（ＣＰＯ－１、酸価２５ｍｇＫＯＨ／ｇ-resin、塩素含有率２０質量％、重量平均分子量６０，０００）を得た。 <Production example of acid-modified chlorinated polyolefin (A2)>
Production Example 6
In a 1 L autoclave equipped with a stirrer, 100 parts by mass of propylene-ethylene copolymer (MFR = 5 g / 10 min at 230 ° C. atmosphere), 150 parts by mass of toluene and 20 parts by mass of maleic anhydride, di-tert-butyl par After 5 parts by mass of oxide was added and the temperature was raised to 140 ° C., the mixture was further stirred for 3 hours. Then, after cooling the obtained reaction liquid, it poured into the container containing a lot of methyl ethyl ketone, and resin was deposited. Thereafter, the liquid containing the resin was centrifuged to separate and purify the acid-modified propylene-ethylene copolymer grafted with maleic anhydride, (poly) maleic anhydride and low molecular weight substances. Thereafter, the resultant was dried at 70 ° C. under reduced pressure for 5 hours to obtain a maleic anhydride-modified propylene-ethylene copolymer (PO-6). Subsequently, 100 parts by mass of PO-6 and 1700 parts by mass of chloroform were put in a 2 L glass-lined reaction can and sealed. The solution in the reaction can was heated while being stirred and dispersed, and dissolved in the can at a temperature of 120 ° C. for 1 hour. After cooling the inside temperature to 110 ° C., 0.5 g of t-butylperoxy-2-ethylhexanoate was added, and 70 parts by mass of chlorine was introduced. The temperature inside the can was cooled to 60 ° C., 1400 parts by mass of chloroform was distilled off, and 4 parts by mass of pt-butylphenylglycidyl ether was added as a stabilizer. Thereafter, drying was performed to obtain a maleic anhydride-modified chlorinated propylene-ethylene copolymer (CPO-1, acid value 25 mg KOH / g-resin, chlorine content 20 mass%, weight average molecular weight 60,000).
製造例７
　無水マレイン酸の仕込み量を９質量部、ジ－ｔｅｒｔ－ブチルパーオキサイドの仕込み量を３質量部、塩素の導入量を１６０質量部に変更した以外は製造例６と同様にすることにより、無水マレイン酸変性塩素化プロピレン－エチレン共重合体（ＣＰＯ－２、酸価１０ｍｇＫＯＨ／ｇ-resin、塩素含有率４０質量％、重量平均分子量７０，０００）を得た。 Production Example 7
By changing the amount of maleic anhydride charged to 9 parts by mass, the amount of di-tert-butyl peroxide charged to 3 parts by mass, and the amount of chlorine introduced to 160 parts by mass, A maleic acid-modified chlorinated propylene-ethylene copolymer (CPO-2, acid value 10 mg KOH / g-resin, chlorine content 40 mass%, weight average molecular weight 70,000) was obtained.
製造例８
　無水マレイン酸の仕込み量を９質量部、ジ－ｔｅｒｔ－ブチルパーオキサイドの仕込み量を３質量部、塩素の導入量を２０質量部に変更した以外は製造例６と同様にすることにより、無水マレイン酸変性塩素化プロピレン－エチレン共重合体（ＣＰＯ－３、酸価１０ｍｇＫＯＨ／ｇ-resin、塩素含有率５質量％、重量平均分子量６５，０００）を得た。　 Production Example 8
By changing the amount of maleic anhydride charged to 9 parts by mass, the amount of di-tert-butyl peroxide charged to 3 parts by mass, and the amount of chlorine introduced to 20 parts by mass, A maleic acid-modified chlorinated propylene-ethylene copolymer (CPO-3, acid value 10 mg KOH / g-resin, chlorine content 5 mass%, weight average molecular weight 65,000) was obtained.
製造例９
　無水マレイン酸の仕込み量を３５質量部、ジ－ｔｅｒｔ－ブチルパーオキサイドの仕込み量を６質量部、塩素の導入量を１０質量部に変更した以外は製造例６と同様にすることにより、無水マレイン酸変性塩素化プロピレン－エチレン共重合体（ＣＰＯ－４、酸価４８ｍｇＫＯＨ／ｇ-resin、塩素含有率５質量％、重量平均分子量４２，０００）を得た。 Production Example 9
By changing the amount of maleic anhydride charged to 35 parts by mass, the amount of di-tert-butyl peroxide charged to 6 parts by mass, and the amount of chlorine introduced to 10 parts by mass, A maleic acid-modified chlorinated propylene-ethylene copolymer (CPO-4, acid value 48 mgKOH / g-resin, chlorine content 5 mass%, weight average molecular weight 42,000) was obtained.
製造例１０
　無水マレイン酸の仕込み量を３５質量部、ジ－ｔｅｒｔ－ブチルパーオキサイドの仕込み量を６質量部、塩素の導入量を１６０質量部に変更した以外は製造例６と同様にすることにより、無水マレイン酸変性塩素化プロピレン－エチレン共重合体（ＣＰＯ－５、酸価４８ｍｇＫＯＨ／ｇ-resin、塩素含有率４０質量％、重量平均分子量４８，０００）を得た。 Production Example 10
By changing the amount of maleic anhydride charged to 35 parts by mass, the amount of di-tert-butyl peroxide charged to 6 parts by mass, and the amount of chlorine introduced to 160 parts by mass, A maleic acid-modified chlorinated propylene-ethylene copolymer (CPO-5, acid value 48 mgKOH / g-resin, chlorine content 40 mass%, weight average molecular weight 48,000) was obtained.
製造例１１
　無水マレイン酸の仕込み量を４０質量部、ジ－ｔｅｒｔ－ブチルパーオキサイドの仕込み量を６質量部に変更した以外は製造例６と同様にすることにより、無水マレイン酸変性塩素化プロピレン－エチレン共重合体（ＣＰＯ－６、酸価５５ｍｇＫＯＨ／ｇ-resin、塩素含有率２０質量％、重量平均分子量３０，０００）を得た。 Production Example 11
Maleic anhydride-modified chlorinated propylene-ethylene copolymer was prepared in the same manner as in Production Example 6 except that the amount of maleic anhydride charged was changed to 40 parts by mass and that of di-tert-butyl peroxide was changed to 6 parts by mass. A polymer (CPO-6, acid value 55 mgKOH / g-resin, chlorine content 20 mass%, weight average molecular weight 30,000) was obtained.
製造例１２
　無水マレイン酸の仕込み量を５質量部、ジ－ｔｅｒｔ－ブチルパーオキサイドを２質量部に変更した以外は製造例６と同様にすることにより、無水マレイン酸変性塩素化プロピレン－エチレン共重合体（ＣＰＯ－７、酸価７ｍｇＫＯＨ／ｇ-resin、塩素含有率２０質量％、重量平均分子量１８０，０００）を得た。 Production Example 12
A maleic anhydride modified chlorinated propylene-ethylene copolymer was prepared in the same manner as in Production Example 6 except that the amount of maleic anhydride charged was changed to 5 parts by mass and that of di-tert-butyl peroxide was changed to 2 parts by mass. CPO-7, acid value 7 mg KOH / g-resin, chlorine content 20 mass%, weight average molecular weight 180,000).
製造例１３
　塩素の導入量を２００質量部に変更した以外は製造例６と同様にすることにより、無水マレイン酸変性塩素化プロピレン－エチレン共重合体（ＣＰＯ－８、酸価２５ｍｇＫＯＨ／ｇ-resin、塩素含有率４５質量％、重量平均分子量６０，０００）を得た。 Production Example 13
A maleic anhydride-modified chlorinated propylene-ethylene copolymer (CPO-8, acid value of 25 mg KOH / g-resin, containing chlorine was used except that the amount of chlorine introduced was changed to 200 parts by mass. And a weight average molecular weight of 60,000).
製造例１４
　塩素の導入量を６質量部に変更した以外は製造例６と同様にすることにより、無水マレイン酸変性塩素化プロピレン－エチレン共重合体（ＣＰＯ－９、酸価２５ｍｇＫＯＨ／ｇ-resin、塩素含有率３質量％、重量平均分子量６０，０００）を得た。 Production Example 14
A maleic anhydride-modified chlorinated propylene-ethylene copolymer (CPO-9, acid value 25 mgKOH / g-resin, containing chlorine was used except that the amount of chlorine introduced was changed to 6 parts by mass. 3% by mass and a weight average molecular weight of 60,000).
（主剤１の作製）
　水冷還流凝縮器と撹拌機を備えた５００ｍｌの四つ口フラスコに、製造例１で得られた無水マレイン酸変性プロピレン－ブテン共重合体（ＰＯ－１）を１００質量部、メチルシクロヘキサンを２８０質量部およびメチルエチルケトンを１２０質量部仕込み、撹拌しながら８０℃まで昇温し、撹拌を１時間続けることで主剤１を得た。溶液状態を表１に示す。 (Preparation of main agent 1)
In a 500 ml four-necked flask equipped with a water-cooled reflux condenser and a stirrer, 100 parts by mass of maleic anhydride-modified propylene-butene copolymer (PO-1) obtained in Production Example 1 and 280 parts by mass of methylcyclohexane 120 parts by mass and methyl ethyl ketone were charged, the temperature was raised to 80 ° C. while stirring, and stirring was continued for 1 hour to obtain main agent 1. The solution state is shown in Table 1.
（主剤２～２２の作製）
　結晶性酸変性ポリオレフィンまたは酸変性塩素化ポリオレフィン、および有機溶剤を表１～２に示すとおりに変更し、主剤１と同様な方法で主剤２～２２を作製した。配合量、溶液状態を表１～２に示す。ただし、主剤９、１９、２２は溶液状態が悪く、ゲル状になったため接着剤として評価することができなかった。 (Preparation of main agent 2-22)
Crystalline acid-modified polyolefin or acid-modified chlorinated polyolefin and organic solvent were changed as shown in Tables 1 and 2, and main agents 2 to 22 were produced in the same manner as main agent 1. The blending amounts and solution states are shown in Tables 1 and 2. However, since the main agents 9, 19, and 22 were in a poor solution state and became gelled, they could not be evaluated as adhesives.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
実施例１
　主剤１を５００質量部、架橋剤としてポリカルボジイミド　カルボジライトV-03を３質量部配合し、接着剤組成物を得た。ポットライフ性および接着性を表３に示す。 Example 1
500 parts by mass of main agent 1 and 3 parts by mass of polycarbodiimide carbodilite V-03 as a crosslinking agent were blended to obtain an adhesive composition. Table 3 shows the pot life and adhesiveness.
実施例２～２０、比較例１～１５
　主剤２～２２および架橋剤を表３～６に示すとおりに変更し、実施例１と同様な方法で実施例２～２０、比較例１～１５を行った。配合量、ポットライフ性および接着性を表３～６に示す。 Examples 2 to 20, Comparative Examples 1 to 15
The main agents 2 to 22 and the crosslinking agent were changed as shown in Tables 3 to 6, and Examples 2 to 20 and Comparative Examples 1 to 15 were performed in the same manner as in Example 1. The blending amounts, pot life properties, and adhesive properties are shown in Tables 3 to 6.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表３～６で用いた架橋剤は以下のものである。
　ポリカルボジイミド：カルボジライト（登録商標）Ｖ－０５（日清紡社製、固形分濃度１００質量％）
　ポリカルボジイミド：カルボジライト（登録商標）Ｖ－０３（日清紡社製、固形分濃度５０質量％）
　ポリイソシアネート：デュラネート（登録商標）ＴＰＡ－１００（旭化成社製）
　シランカップリング剤：ＫＢＭ－４０３（信越シリコーン社製） The cross-linking agents used in Tables 3 to 6 are as follows.
Polycarbodiimide: Carbodilite (registered trademark) V-05 (Nisshinbo Co., Ltd., solid content concentration: 100% by mass)
Polycarbodiimide: Carbodilite (registered trademark) V-03 (Nisshinbo Co., Ltd., solid content concentration 50 mass%)
Polyisocyanate: Duranate (registered trademark) TPA-100 (manufactured by Asahi Kasei Corporation)
Silane coupling agent: KBM-403 (manufactured by Shin-Etsu Silicone)
酸価
　本発明における酸価（ｍｇＫＯＨ／ｇ-resin）は、ＦＴ－ＩＲ（島津製作所社製、ＦＴ－ＩＲ８２００ＰＣ）を使用して、無水マレイン酸のカルボニル（C=O）結合の伸縮ピーク（1780cm-1）の吸光度（I）、アイソタクチック特有のピーク（840cm-1）の吸光度（II）および無水マレイン酸（東京化成製）のクロロホルム溶液によって作成した検量線から得られるファクター（ｆ）を用いて下記式により算出した値である。
酸価＝［吸光度（I）／吸光度（II）×（ｆ）／無水マレイン酸の分子量×２×水酸化カリウムの分子量×１０００（ｍｇ）／１００（％）］
無水マレイン酸の分子量：98.06　水酸化カリウムの分子量：56.11 Acid Value In the present invention, the acid value (mgKOH / g-resin) is determined by using FT-IR (manufactured by Shimadzu Corporation, FT-IR8200PC), a stretching peak (1780 cm) of a carbonyl (C═O) bond of maleic anhydride. -1 ) absorbance (I), isotactic specific peak (840 cm -1 ) absorbance (II), and factor (f) obtained from a calibration curve prepared with a chloroform solution of maleic anhydride (manufactured by Tokyo Kasei). It is the value calculated by the following formula using.
Acid value = [absorbance (I) / absorbance (II) × (f) / molecular weight of maleic anhydride × 2 × molecular weight of potassium hydroxide × 1000 (mg) / 100 (%)]
Molecular weight of maleic anhydride: 98.06 Molecular weight of potassium hydroxide: 56.11
塩素含有率
　本発明における塩素含有率はJIS K-7210に準じて滴定によって求められる値である。 Chlorine content The chlorine content in the present invention is a value determined by titration according to JIS K-7210.
重量平均分子量（Ｍｗ）
　本発明における重量平均分子量はゲルパーミエーションクロマトグラフィー（以下、ＧＰＣ、標準物質：ポリスチレン樹脂、移動相：テトラヒドロフラン）によって測定した値である。 Weight average molecular weight (Mw)
The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (hereinafter, GPC, standard substance: polystyrene resin, mobile phase: tetrahydrofuran).
融点、融解熱量
　本発明における融点、融解熱量は示差走査熱量計（以下、ＤＳＣ、ティー・エー・インスツルメント・ジャパン製、Ｑ－２０００）を用いて、２０℃／分の速度で昇温融解、冷却樹脂化して、再度昇温融解した際の融解ピークのトップ温度および面積から測定した値である。 Melting point and heat of fusion Melting point and heat of fusion in the present invention are heated and melted at a rate of 20 ° C./minute using a differential scanning calorimeter (hereinafter DSC, manufactured by TA Instruments Japan, Q-2000). It is a value measured from the top temperature and area of the melting peak when the resin is cooled and melted at elevated temperature.
主剤溶液状態の評価
　主剤１～１８の溶液状態について、ブルックフィールド型粘度計を用いて２５℃の溶液粘度を測定することで評価した。
＜評価基準＞
　○（実用上優れる）：５００ｍＰａ・ｓ未満
　△（実用可能）：５００ｍＰａ・ｓ以上１０００ｍＰａ・ｓ未満
　×（実用不可能）：１０００ｍＰａ・ｓ以上またはゲル化により粘度測定不可 Evaluation of main agent solution state The solution states of main agents 1 to 18 were evaluated by measuring the solution viscosity at 25 ° C. using a Brookfield viscometer.
<Evaluation criteria>
○ (Excellent in practical use): Less than 500 mPa · s Δ (Practical use): 500 mPa · s or more and less than 1000 mPa · s × (Unusable): 1000 mPa · s or more or viscosity measurement is impossible due to gelation
ポットライフ性の評価
　ポットライフ性とは、変性ポリオレフィンに架橋剤または硬化剤を配合し、その配合直後または配合後一定時間経過後の該溶液の安定性を指す。ポットライフ性が良好な場合は、溶液の粘度上昇が少なく長期間保存が可能であることを指し、ポットライフ性が不良な場合は、溶液の粘度が上昇（増粘）し、ひどい場合にはゲル化現象を起こし、長期間保存が不可能であることを指す。
　実施例１～１９および比較例１～１５で得られた接着剤組成物のポットライフ性を、２５℃および４０℃雰囲気で２４時間貯蔵した後に、ブルックフィールド型粘度計を用いて２５℃の溶液粘度を測定することで評価した。評価結果を表３～６に示す。
＜評価基準＞
　○（実用上優れる）：５００ｍＰａ・ｓ未満
　△（実用可能）：５００ｍＰａ・ｓ以上１０００ｍＰａ・ｓ未満
　×（実用不可能）：１０００ｍＰａ・ｓ以上またはゲル化により粘度測定不可 Evaluation of pot life property Pot life property refers to the stability of the solution immediately after compounding or after a certain time has elapsed after compounding with a modified polyolefin. If the pot life is good, it means that the viscosity of the solution is small and can be stored for a long time. If the pot life is poor, the viscosity of the solution increases (thickens). It indicates that gelation occurs and cannot be stored for a long time.
After the pot life properties of the adhesive compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 15 were stored at 25 ° C. and 40 ° C. for 24 hours, a solution at 25 ° C. using a Brookfield viscometer was used. Evaluation was made by measuring the viscosity. The evaluation results are shown in Tables 3-6.
<Evaluation criteria>
○ (Excellent in practical use): Less than 500 mPa · s Δ (Practical use): 500 mPa · s or more and less than 1000 mPa · s × (Unusable): 1000 mPa · s or more or viscosity measurement is impossible due to gelation
接着性の評価
　接着性は、後記のとおり、金属基材とポリオレフィン系樹脂基材との積層体を作製し、初期のＴ型剥離試験および電解液試験後のＴ型剥離試験によって評価した。評価結果を表３～６に示す。 Evaluation of Adhesiveness As described later, the adhesiveness was evaluated by preparing a laminate of a metal substrate and a polyolefin resin substrate and performing an initial T-type peel test and a T-type peel test after an electrolyte test. The evaluation results are shown in Tables 3-6.
金属基材とポリオレフィン系樹脂基材との積層体の作製
　金属基材にはアルミニウム箔（住軽アルミ箔社製、８０７９－０、厚さ４０μｍ）を使用し、ポリオレフィン系樹脂基材には無延伸ポリプロピレンフィルム（東洋紡社製パイレン（登録商標）フィルムＣＴ、厚さ４０μｍ）を使用した。
　実施例１～１９および比較例１～１５で得られた接着剤組成物を金属基材にバーコータを用いて乾燥後の接着剤層の膜厚が３μｍになるように調整して塗布した。塗布面を温風乾燥機を用いて８０℃雰囲気で１０分間乾燥させ、膜厚３μｍの接着剤層を得た。前記接着剤層表面にポリオレフィン系樹脂基材を重ね合わせ、１２０℃、０．１ＭＰａで２分間熱圧着することで積層体を得た。 Fabrication of laminate of metal substrate and polyolefin resin substrate Aluminum foil (manufactured by Sumi Light Aluminum Foil Co., Ltd., 8079-0, thickness 40 μm) is used for the metal substrate, and none is used for the polyolefin resin substrate. A stretched polypropylene film (Toyobo Pyrene (registered trademark) film CT, thickness 40 μm) was used.
The adhesive compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 15 were applied to metal substrates using a bar coater so that the thickness of the adhesive layer after drying was adjusted to 3 μm. The coated surface was dried for 10 minutes at 80 ° C. using a warm air dryer to obtain an adhesive layer having a thickness of 3 μm. A polyolefin-based resin substrate was superposed on the surface of the adhesive layer, and thermocompression bonded at 120 ° C. and 0.1 MPa for 2 minutes to obtain a laminate.
　前記積層体の初期および電解液試験後の接着試強度をＴ型剥離試験により測定した。 The adhesion test strength at the initial stage and after the electrolyte test of the laminate was measured by a T-type peel test.
Ｔ型剥離試験
　ＡＳＴＭ－Ｄ１８７６－６１の試験法に準拠し、オリエンテックコーポレーション社製のテンシロンＲＴＭ－１００を用いて、２５℃環境下で、引張速度５０ｍｍ／分における剥離強度を測定した。金属基材／ポリオレフィン系樹脂基材間の剥離強度（Ｎ／ｃｍ）は５回の試験値の平均値とした。 In accordance with the test method of T-type peel test ASTM-D1876-61, peel strength at a tensile speed of 50 mm / min was measured in a 25 ° C. environment using Tensilon RTM-100 manufactured by Orientec Corporation. The peel strength (N / cm) between the metal substrate / polyolefin-based resin substrate was the average of five test values.
初期
　前記積層体を２５℃雰囲気で１２時間静置後、１００ｍｍ×１５ｍｍ大きさに切断し、Ｔ型剥離試験により接着性の評価を行った。
＜評価基準＞
　◎（実用上特に優れる）：８Ｎ／ｃｍ以上
　○（実用上優れる）：７Ｎ／ｃｍ以上８Ｎ／ｃｍ未満
　△（実用可能）：６Ｎ／ｃｍ以上７Ｎ／ｃｍ未満
　×（実用不可能）：６Ｎ／ｃｍ未満 The initial laminate was allowed to stand in an atmosphere of 25 ° C. for 12 hours, then cut to a size of 100 mm × 15 mm, and adhesion was evaluated by a T-type peel test.
<Evaluation criteria>
◎ (particularly excellent in practical use): 8 N / cm or more ○ (excellent in practical use): 7 N / cm or more and less than 8 N / cm Δ (practical): 6 N / cm or more and less than 7 N / cm × (impractical): 6 N / less than cm
電解液試験後
　リチウム電池の包装材としての利用性を検討するため電解液試験を実施した。前記積層体を２５℃雰囲気で１２時間静置した後、電解液［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＝１／１／１（容積比）に６フッ化リン酸リチウムを添加したもの］に８５℃で３日間浸漬させた。その後、積層体を取り出しイオン交換水で洗浄、ペーパーワイパーで水を拭き取り、十分に水分を乾燥させ、１００ｍｍ×１５ｍｍ大きさに切断し、Ｔ型剥離試験により接着性の評価を行った。
＜評価基準＞
　◎（実用上特に優れる）：８Ｎ／ｃｍ以上
　○（実用上優れる）：７Ｎ／ｃｍ以上８Ｎ／ｃｍ未満
　△（実用可能）：６Ｎ／ｃｍ以上７Ｎ／ｃｍ未満
　×（実用不可能）：６Ｎ／ｃｍ未満 After the electrolytic solution test, an electrolytic solution test was conducted in order to examine the utility of the lithium battery as a packaging material. The laminate was allowed to stand in an atmosphere of 25 ° C. for 12 hours, and then added to an electrolytic solution [ethylene carbonate / diethyl carbonate / dimethyl carbonate = 1/1/1 (volume ratio) to which lithium hexafluorophosphate was added]. It was immersed at 3 ° C. for 3 days. Thereafter, the laminate was taken out, washed with ion-exchanged water, wiped off with a paper wiper, sufficiently dried, cut into a size of 100 mm × 15 mm, and evaluated for adhesiveness by a T-type peel test.
<Evaluation criteria>
◎ (particularly excellent in practical use): 8 N / cm or more ○ (excellent in practical use): 7 N / cm or more and less than 8 N / cm Δ (practical): 6 N / cm or more and less than 7 N / cm × (impractical): 6 N / less than cm
　本発明にかかる接着剤組成物は、変性ポリオレフィン（Ａ）、ポリカルボジイミド（Ｂ）および有機溶剤（Ｃ）を含有し、長期保存しても増粘やゲル化を生じることなく良好なポットライフ性を維持し、かつ金属基材とポリオレフィン系樹脂基材との良好な接着性を両立させることができる。そのため、本発明の接着剤組成物から形成されるポリオレフィン系樹脂基材と金属基材との積層構造体は、家電外板、家具用素材、建築内装用部材などの分野のみならず、パソコン、携帯電話、ビデオカメラなどに用いられるリチウム電池の包装材（パウチ形態）としても幅広く利用し得るものである。 The adhesive composition according to the present invention contains a modified polyolefin (A), polycarbodiimide (B), and an organic solvent (C), and has good pot life without causing thickening or gelation even after long-term storage. And good adhesion between the metal substrate and the polyolefin resin substrate can be achieved. Therefore, the laminated structure of the polyolefin-based resin base material and the metal base material formed from the adhesive composition of the present invention is not only used in the fields of home appliance outer panels, furniture materials, building interior members, etc. It can also be widely used as a packaging material (pouch form) for lithium batteries used in mobile phones, video cameras and the like.

Claims (6)

  1. 　（Ａ１）または（Ａ２）である変性ポリオレフィン（Ａ）、ポリカルボジイミド（Ｂ）および有機溶剤（Ｃ）を含有する接着剤組成物。
    　（Ａ１）：酸価が１０～５０ｍｇＫＯＨ／ｇ-resinである結晶性酸変性ポリオレフィン
    　（Ａ２）：酸価が１０～５０ｍｇＫＯＨ／ｇ-resin、塩素含有率が５～４０質量％である酸変性塩素化ポリオレフィン     An adhesive composition containing the modified polyolefin (A), the polycarbodiimide (B) and the organic solvent (C) which are (A1) or (A2).
    (A1): Crystalline acid-modified polyolefin having an acid value of 10 to 50 mgKOH / g-resin (A2): Acid-modified chlorine having an acid value of 10 to 50 mgKOH / g-resin and a chlorine content of 5 to 40% by mass Polyolefin
  2. 　変性ポリオレフィン（Ａ）１００質量部に対して、ポリカルボジイミド（Ｂ）を０．５～１０質量部、有機溶剤（Ｃ）を８０～１０００質量部含有する請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, comprising 0.5 to 10 parts by mass of polycarbodiimide (B) and 80 to 1000 parts by mass of organic solvent (C) with respect to 100 parts by mass of the modified polyolefin (A).
  3. 　有機溶剤（Ｃ）が、溶剤（Ｃ１）と溶剤（Ｃ２）の混合液であって、溶剤（Ｃ１）が芳香族炭化水素、脂肪族炭化水素、脂環族炭化水素およびハロゲン化炭化水素からなる群より選択された１種以上の溶剤であり、溶剤（Ｃ２）がアルコール系溶剤、ケトン系溶剤、エステル系溶剤、グリコールエーテル系溶剤からなる群より選択された１種以上の溶剤であり、溶剤（Ｃ１）／溶剤（Ｃ２）＝５０～９０／５０～１０（質量比）である請求項１または２に記載の接着剤組成物。 The organic solvent (C) is a mixed liquid of the solvent (C1) and the solvent (C2), and the solvent (C1) is composed of an aromatic hydrocarbon, an aliphatic hydrocarbon, an alicyclic hydrocarbon, and a halogenated hydrocarbon. One or more solvents selected from the group, wherein the solvent (C2) is one or more solvents selected from the group consisting of alcohol solvents, ketone solvents, ester solvents, glycol ether solvents, 3. The adhesive composition according to claim 1, wherein (C1) / solvent (C2) = 50 to 90/50 to 10 (mass ratio).
  4. 　ポリオレフィン系樹脂基材と金属基材との接着に用いられる請求項１～３のいずれかに記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 3, which is used for adhesion between a polyolefin resin substrate and a metal substrate.
  5. 　請求項１～４のいずれかに記載の接着剤組成物によって接着されたポリオレフィン系樹脂基材と金属基材の積層体。 A laminate of a polyolefin resin substrate and a metal substrate bonded by the adhesive composition according to any one of claims 1 to 4.
  6. 　請求項５に記載の積層体を含有するリチウム電池用包装材。
     
          The packaging material for lithium batteries containing the laminated body of Claim 5.

PCT/JP2014/069953 2013-09-03 2014-07-29 Polyolefin-type adhesive agent composition WO2015033703A1 (en)

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