Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/116—Primary casings; Jackets or wrappings 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
  • H01M50/116—Primary casings; Jackets or wrappings 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
  • H01M50/116—Primary casings; Jackets or wrappings 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
  • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
  • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
  • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
  • H01M50/129—Primary casings; Jackets or wrappings 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
  • 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
  • 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

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• 2014
  • 2014-07-29 JP JP2015535382A patent/JPWO2015033703A1/ja active Pending
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