CN110234721A - Polyolefin adhesive composition - Google Patents

Polyolefin adhesive composition Download PDF

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Publication number
CN110234721A
CN110234721A CN201880008954.3A CN201880008954A CN110234721A CN 110234721 A CN110234721 A CN 110234721A CN 201880008954 A CN201880008954 A CN 201880008954A CN 110234721 A CN110234721 A CN 110234721A
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CN
China
Prior art keywords
solvent
acid
mass parts
adhesive composition
modified polyolefin
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CN201880008954.3A
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Chinese (zh)
Inventor
坂田秀行
中岛桃子
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Dongyang Textile Mc Co ltd
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Toyobo Co Ltd
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Classifications

    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
    • 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
    • H01M50/121—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
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • 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
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

Project of the invention is to provide a kind of adhesive composition containing acid modified polyolefin and multifunctional polyisocyanate curing agent, and working life property is good, and the adhesiveness, chemical-resistant and formability between metal base and polyolefin resin substrate are good.A kind of adhesive composition, contain acid modified polyolefin (A), multifunctional polyisocyanate curing agent (B) and organic solvent (C), the acid value of acid modified polyolefin (A) is 2~50mgKOH/g resin, and acetone extract component ratio is 0.01~2 mass %.

Description

Polyolefin adhesive composition
Technical field
The present invention relates to the good adhesiveness, the chemicals-resistants that show between polyolefin resin substrate and metal base The adhesive composition of property, formability.In more detail, it is related to containing acid modified polyolefin, multifunctional polyisocyanate curing agent And the adhesive composition of organic solvent.More particularly to lithium ion battery (hereinafter referred to as LiB) with adhesive composition and Packaging material as the laminated body containing the adhesive composition.
Background technique
In recent years, as the battery for the mobile communication terminals such as personal computer, mobile phone, video camera, satellite etc., can surpass Slimming, the LiB minimized are just actively developed.The packaging material of the LiB is different from the made of metal tank used in the past, due to light The advantages of measuring and can freely selecting the shape of battery, is just beginning to use gradually such as substrate layer/barrier layer/sealant layer composition Laminated body.
LiB contains positive electrode and negative electrode material, while also containing lithium salts being dissolved in propylene carbonate, carbonic acid Asia second Electrolyte obtained by the non-protonic solvents such as ester, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate is soaked with the electricity by containing The electrolyte layer of polymer gel composition of liquid is solved as cell contents.If such strong penetrating solvents pass through sealant Layer, then can be such that the stacking strength between barrier layer and sealant layer reduces, be layered, and eventually generate such as electrolyte leakage Such problems.In addition, electrolyte, that is, lithium salts as battery, uses LiPF6、LiBF4Equal substances, but these salt can because with water Point hydrolysis and generate hydrofluoric acid, hydrofluoric acid can corrosion barrier layer, so that stacking strength be made to reduce.So, battery is used Packaging material need to have the tolerance to electrolyte.
Moreover, it is assumed that the case where using LiB under circumstances, need to have more harsh tolerance.Such as moving When dynamic equipment, it is desirable that the leakproof under 60~70 DEG C of the hot environment waited in the car.Furthermore, it is assumed that for mobile phone and Accidentally fall into the situation in water, it is also desirable to the water resistance that moisture will not immerse.
Based on such situation, it is thus proposed that the various packaging material for lithium battery for improving electrolyte resistances (such as are joined According to Patent Documents 1 to 3).
In addition, in battery use packing material, the die forming in enclosed cell device forms the sky for accommodating cell device Between.Since battery use packing material is stretched when the forming, have crack on the flange part barrier layer of mold, pin hole is asked Topic.Especially with the requirement of miniaturization, the slimming of battery in recent years, just seeking thinner battery use packing material, in this way The problem of be easy occur more significantly.
Based on this situation, it is thus proposed that the battery use packing material that formability is improved is (referring for example to patent document 4 ~5).
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2001-243928 bulletin
Patent document 2: Japanese Patent Laid-Open 2004-42477 bulletin
Patent document 3: Japanese Patent Laid-Open 2009-238475 bulletin
Patent document 4: Japanese Patent Laid-Open 2002-216714 bulletin
Patent document 5: Japanese Patent Laid-Open 2003-31188 bulletin
Summary of the invention
Problems to be solved by the invention
But the packaging material for lithium battery of aforementioned proposition is not yet satisfactory in terms of electrolyte resistance and formability. In addition, there are still problems even if the improvement of electrolyte resistance and formability is big.
Specifically, can observe following problem: be difficult to take into account the working life property of the adhesive after ensuring mixed curing agent with Electrolyte resistance (patent document 1)；Due to implement using squeeze stacking carry out bonding, therefore stacking board be restricted or because It is bonded in high temperature and causes polyolefin base material by the influence (patent document 2) being heat-shrinked；Since polyolefin host agent is water system, Therefore drying time is longer, working condition is limited (patent document 3).In addition, being not only necessarily placed at outer layer film surface coating amide It is the process of slip agent, productivity reduces, and leads to not due to the amide system slip agent of coating sufficiently to obtain outer layer thin The stacking strength (patent document 4) of film and aluminium foil；Due to being only to be configured with un-stretched polypropylene resin film from the internal layer side of aluminium foil Composition or the film in the hybrid resin for being only configured with polypropylene and polyethylene from the internal layer side of aluminium foil composition, therefore shape Whens for rectangular shape etc., aluminium foil can generate pin hole or aluminium foil is easy to produce fracture (crackle), can not obtain sufficient forming Property (patent document 5) etc..
Project of the invention be provide do not have working life property, working condition limitation the problems such as, and adhesiveness, chemicals-resistant Property (electrolyte resistance) and the adhesive composition having excellent formability.Further, project is to provide comprising by the adhesive group Close the battery use packing material for the adhesive phase that object is constituted and the battery using the packaging material.
To the means to solve the problem
In order to reach the above subject, inventor is attentively studied, and discovery is not only configured in the outer layer side of aluminium foil, and And the layer of the elongation when internal layer side, which also configures, sufficiently to follow forming is effective, so that propose invention below.
A kind of adhesive composition contains acid modified polyolefin (A), multifunctional polyisocyanate curing agent (B) and organic Solvent (C), the acid value of acid modified polyolefin (A) are 2~50mgKOH/g resin, the acetone extract ingredient of acid modified polyolefin (A) Ratio is 0.01~2 mass %.
Relative to 100 mass parts of aforementioned acid modified polyolefin (A), multifunctional polyisocyanate curing agent (B) is preferably comprised 0.5~40 mass parts, 80~2000 mass parts of organic solvent (C).In addition, organic solvent (C) is preferred: being solvent (C1) and solvent (C2) mixed liquor, solvent (C1) are in the group being made of aromatic hydrocarbon, aliphatic hydrocarbon, clicyclic hydrocarbon and halogenated hydrocarbons 1 kind or more of solvent, solvent (C2) alcohol series solvent, ketone series solvent, ester series solvent and glycol ether series solvent selected from being made of The solvent of one or more of group, and solvent (C1)/solvent (C2)=50~97/50~3 (mass ratio).
Aforementioned adhesion agent composition is preferred for the bonding between polyolefin resin substrate and metal base.
A kind of laminated body of polyolefin resin substrate and metal base is bonded by aforementioned adhesion agent composition；And it is a kind of Lithium ion battery packaging material, using the laminated body as member of formation.
The effect of invention
Adhesive composition according to the present invention contains acid modified polyolefin, multifunctional polyisocyanate curing agent and has Solvent will not occur thickening, gelation, can maintain good working life property even if saving during long.Further, even if It is bonded in a low temperature of the thermal contraction of such as polyolefin base material influences small 120 DEG C or less, low as 40 DEG C or less It is cured under temperature, can still take into account good adhesiveness, the chemical-resistant between polyolefin resin substrate and metal base, Formability can more be taken into account.
According to the present invention, good working life property can be maintained, while it can be kept sufficiently solid by the curing step after fitting Change, excellent adhesiveness and chemical-resistant can be shown.Further, available satisfaction shows storage necessary to excellent formability The adhesive phase of energy modulus and elongation at break.
Specific embodiment
Hereinafter, being explained in detail to embodiments of the present invention.
<acid modified polyolefin (A)>
Acid modified polyolefin used in the present invention (A) is that acid value is 2~50mgKOH/g-resin, acetone extract ingredient Ratio is the acid modified polyolefin of 0.01~2 mass %.
Acid modified polyolefin used in the present invention (A) though do not limit, preferably by by α, beta-unsaturated carboxylic acid and At least one kind of in its acid anhydrides is grafted to substance obtained by least one kind of in polyethylene, polypropylene and propylene-alpha-olefin copolymers.
Propylene-alpha-olefin copolymers are to be total to copolymer obtained by Poly alpha Olefins (PAO) based on propylene and on it.As α- Alkene, for example, can be used a kind in ethylene, 1- butylene, 1- heptene, 1- octene, 4-methyl-1-pentene, vinyl acetate etc. or It is a variety of.Among these alpha-olefins, optimal ethylene, 1- butylene.The propylene ingredients of propylene-alpha-olefin copolymers and α-olefin content Though ratio is not defined, preferred propylene ingredient is 50 moles of % or more, more preferably 70 moles of % or more.
It is at least one kind of in beta-unsaturated carboxylic acid and its acid anhydrides as α, such as maleic acid, itaconic acid, citraconic acid can be enumerated And their acid anhydrides.Among these, preferred anhydrides, more preferable maleic anhydride.Can specifically enumerate maleic anhydride modified polypropylene, Maleic anhydride modified propylene-ethylene copolymers, maleic anhydride modified propene-1-butene copolymer, maleic anhydride modified propylene-second Alkene-butylene copolymer etc., these acid modified polyolefins can be used a kind, or two or more can be applied in combination.
Based on the viewpoint of adhesiveness and electrolyte resistance between polyolefin resin substrate and metal base, sour modified polyolefin The acid value of hydrocarbon (A) need to be the range of 2~50mgKOH/g resin.Preferably 3~45mgKOH/g resin, more preferably 5~ 40mgKOH/g resin, the range of particularly preferably 7~35mgKOH/g resin.When less than aforementioned value, have sometimes and curing agent The case where compatibility is short of.Therefore, crosslinking density is low sometimes, adhesive strength, chemical-resistant (electrolyte resistance) reduce The case where.When more than aforementioned value, since molecular weight is low, cohesive force dies down, so having adhesive strength, chemical-resistant sometimes The case where (electrolyte resistance) reduces.Further manufacture efficiency can also reduce, therefore not preferably.
The acid value of acid modified polyolefin (A), using α, beta-unsaturated carboxylic acid, α, the acid anhydrides and freedom of beta-unsaturated carboxylic acid The usage amount of base producing agent adjusts.
Based on the viewpoint of adhesiveness and electrolyte resistance between polyolefin resin substrate and metal base, sour modified polyolefin The acetone extract component ratio of hydrocarbon (A) is necessarily the range of 0.01 mass of mass %~2 %.Preferably 0.03 mass %~1.7 Quality %, the more preferably 0.05 mass % of mass %~1.4, further preferably 0.07 mass of mass %~1.2 %, it is especially excellent It is selected as the range of 0.1 mass of mass %~1 %.When less than aforementioned value, manufacture efficiency is reduced, thus not preferred.More than aforementioned value When, there is cohesive force to die down, the situation of adhesiveness, chemical-resistant and formability difference.
Sight based on adhesiveness and chemical-resistant (electrolyte resistance) between polyolefin resin substrate and metal base Point, storage modulus (E ') of the acid modified polyolefin (A) at 25 DEG C are preferably the range of 10~2000MPa.More preferably 15~ 1700MPa, further preferably 20~1400MPa, particularly preferably 25~1100MPa, the most preferably model of 30~800MPa It encloses.When less than aforementioned value, having causes the cohesive force for the adhesive phase being made of adhesive composition insufficient, adhesiveness and resistance toization Learn the situation of moral character (electrolyte resistance) difference.When more than aforementioned value, there is following for the adhesive phase being made of adhesive composition Property reduce, the case where poor adhesion.In addition, if in aforementioned range, since adhesiveness, substrate tracing ability are improved, because The formability of this laminated body also becomes well, therefore more preferable as lithium ion battery packaging material.
Tension fracture elongation rate (Eb) of the acid modified polyolefin (A) at 25 DEG C is preferably 50%~1000% range. More preferably 80%~900%, further preferably 120%~800%, particularly preferably 160%~700%, most preferably 200%~600%.When less than aforementioned value, the tracing ability that there is the adhesive phase being made of adhesive composition is reduced, and is caused into Pin hole etc. when shape, the situation of formability difference.In addition, general, tension fracture elongation rate (Eb) is opposite with storage modulus (E ') Property, be more than aforementioned value when, there is storage modulus (E ') to be lower, the situation of adhesiveness and electrolyte resistance difference.In addition, if preceding It states in range, then since adhesiveness, substrate tracing ability are improved, so the formability of laminated body also becomes well, therefore makees It is more preferable for lithium ion battery packaging material.
The weight average molecular weight (Mw) of acid modified polyolefin (A) is preferably 10,000~200,000 range.More preferably 20,000~180,000 range, further preferably 30,000~160,000 range, particularly preferably 40,000~ 140,000 range, most preferably 50,000~110,000 range.When less than aforementioned value, there is cohesive force to die down, adhesiveness The situation of difference.On the other hand, when being more than aforementioned value, operability the case where going wrong when having low mobility, bonding.If before again It states in range, is then used effectively with the curing reaction of curing agent, it is advantageous to.
The crystallinity of so-called acid modified polyolefin (A), refers to using differential scanning type calorimeter (DSC) with 20 DEG C/min It is warming up to 250 DEG C from -100 DEG C, specific melting peak person is shown in the temperature-rise period.
By making acid modified polyolefin crystallinity, compared to amorphism, cohesive force is stronger, adhesiveness, chemical-resistant It is excellent, so favorably.
The fusing point (Tm) of acid modified polyolefin (A) is preferably 50 DEG C~120 DEG C of range.More preferably 60 DEG C~100 DEG C Range, most preferably 70 DEG C~90 DEG C of range.When less than aforementioned value, there is the cohesive force from crystallization to die down, is adhesiveness, resistance to The situation of chemicals difference.When on the other hand, more than aforementioned value, operability occurs when having low stability of solution, mobility, bonding The case where problem.
The fusing of acid modified polyolefin (A) hot (Δ H) is preferably the range of 1J/g~60J/g.More preferably 3J/g~ The range of 50J/g, the most preferably range of 5J/g~40J/g.When less than aforementioned value, there is the cohesive force from crystallization to die down, glue Conjunction property, the situation of chemical-resistant difference.When on the other hand, more than aforementioned value, behaviour when having low stability of solution, mobility, bonding The case where going wrong as property.
The manufacturing method of acid modified polyolefin (A) is not particularly limited, such as can enumerate free radical grafting reaction (that is, right Polymer as main chain generates free radical kind, using the free radical kind as polymerization initiation point, and makes unsaturated carboxylic acid and acid anhydrides The reaction being graft-polymerized) etc..
There is no particular limitation for free-radical generating agent, it is preferable to use organic peroxide.Organic peroxide has no especially Limit, can enumerate di tert butyl peroxyphthalate, tert-butyl hydroperoxide, cumyl peroxide, benzoyl peroxide, Peroxidized t-butyl perbenzoate, peroxide -2-ethyl hexanoic acid tert-butyl, the peroxidating trimethylace tonitric tert-butyl ester, peroxidating first and second The peroxide such as ketone, di-tert-butyl peroxide, lauroyl peroxide；The azonitriles such as the double isopropyl nitriles of azobis isobutyronitrile, azo Class etc..
<multifunctional polyisocyanate curing agent (B)>
Multifunctional polyisocyanate curing agent (B) used in the present invention, as long as different with 2 or more in 1 molecule The polyisocyanates of cyanic acid ester group, is not particularly limited, it may be desirable to spread out using well known diisocyanate and by these The compound born.
Such as can enumerate 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI), benzene dimethylene diisocyanate, Methyl diphenylene diisocyanate, isophorone diisocyanate, 1,5- naphthalene diisocyanate, hexamethylene diisocyanate, Bis- (4- isocyanates cyclohexyl) diisocyanate such as methane or hydrogenated diphenyl methane diisocyanate.Further, it can enumerate The compound derived by aforementioned diisocyanates, that is, isocyanuric acid ester body, the addition body, biuret of aforementioned diisocyanates Type, two ketoboidies of urea, allophanate body, the prepolymer with isocyanate residue (are obtained by diisocyanate and polyalcohol Oligomer) or their complex etc..These can be used alone, and can also be used in any combination two or more.
Furthermore, it is possible to use make a part of isocyanate group of above-mentioned isocyanate compound and have with isocyanate group Compound obtained by reactive compound reaction is as polyfunctional isocyanate's curing agent.There is reactivity with isocyanate group Compound can enumerate the change containing amino such as butylamine, hexylamine, octylame, 2 ethyl hexylamine, dibutyl amine, ethylenediamine, benzylamine, aniline Close species；Methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, hexanol, octanol, 2-Ethylhexyl Alcohol, dodecyl alcohol, ethylene glycol, the third two The compounds containing hydroxyl such as alcohol, benzyl alcohol, phenol；Allyl glycidyl ether, 2- ethylhexyl glycidyl ether, phenyl epoxy Propyl ether, neopentyl glycol Diglycidyl, 1,6- hexane diol Diglycidyl, cyclohexanedimethanol Diglycidyl etc. contain ring The compounds of oxygroup；Acetic acid, butyric acid, caproic acid, octanoic acid, succinic acid, adipic acid, decanedioic acid, phthalic acid etc. contain carboxylic acid Compound etc..
Multifunctional polyisocyanate curing agent (B) used in the present invention, it is excellent to be particularly based on electrolyte resistance Reason, it is however preferred to have the isocyanuric acid ester body person of aforementioned diisocyanates.
The combined amount of multifunctional polyisocyanate curing agent (B) used in the present invention, relative to acid modified polyolefin (A) 100 mass parts, the preferably range of 0.5~40 mass parts, more preferably 1~35 mass parts, further preferably 2~30 mass Part, the particularly preferably range of 3~25 mass parts.When less than aforementioned value, have can not obtain sufficient solidification effect, adhesiveness and The low situation of chemical-resistant.More than aforementioned range, there is the case where working life property, adhesiveness reduce, in addition, having because tracing ability drops It is low and cause forming when generate pin hole the case where.It is based further on the viewpoint in terms of cost, not preferably.
<organic solvent (C)>
Organic solvent used in the present invention (C), as long as acid modified polyolefin (A), multifunctional polyisocyanic acid can be dissolved The substance of ester curing agent (B), that is, be not particularly limited.Specifically, the aromatic hydrocarbons such as benzene,toluene,xylene be can be used such as；Oneself The aliphatic hydrocarbons such as alkane, heptane, octane, decane；The clicyclic hydrocarbons such as hexamethylene, cyclohexene, hexahydrotoluene, ethyl cyclohexane；Three The halogenated hydrocarbons such as vinyl chloride, dichloroethylene, chlorobenzene, chloroform；Methanol, ethyl alcohol, isopropanol, butanol, amylalcohol, hexanol, propylene glycol, phenol Etc. alcohol series solvents；The ketone series solvents such as acetone, methylisobutylketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, different Buddhist ketone, acetophenone；First The cellulose families such as base cellulose, ethyl cellulose；Methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate etc. Ester series solvent；Ethylene glycol mono-n-butyl ether, ethylene glycol list isobutyl ether, the tertiary butyl ether of ethylene glycol list, diethylene glycol mono-n-butyl ether, diethyl two Glycol ether series solvents such as alcohol list isobutyl ether, triethylene glycol mono-n-butyl ether, tetraethylene glycol mono-n-butyl ether etc., these can be used a kind, Two or more may be used.
Relative to 100 mass parts of acid modified polyolefin (A), organic solvent (C) is preferably the range of 80~2000 mass parts. More preferably 90~1600 mass parts, further preferably 100~1200 mass parts, particularly preferably 110~800 mass parts Range.When less than aforementioned range, there is the case where solution state and working life property reduce, when being more than aforementioned range, have laminated body and Productivity, manufacturing cost, the shipment and delivery cost aspect of LiB packaging material comprising laminated body become adverse conditions.
The viewpoint of solution state and working life property based on adhesive composition, organic solvent (C) are preferably selected from by fragrance The solvent (C1) of one or more of the group that race's hydrocarbon, aliphatic hydrocarbon, clicyclic hydrocarbon and halogenated hydrocarbons are constituted and selected from molten by alcohol system The mixed liquor of the solvent (C2) of one or more of the group that agent, ketone series solvent, ester series solvent and glycol ether series solvent are constituted.It is mixed Composition and division in a proportion is preferably solvent (C1)/solvent (C2)=50~97/50~3 (mass ratio) range, more preferable 55~95/45~5 (matter Measure ratio), further preferred 60~90/40~10 (mass ratioes), particularly preferred 70~80/30~20 (mass ratioes).It is detached from above-mentioned When range, there is the case where solution state of adhesive composition and working life property reduce.In addition, particularly preferably: solvent (C1) is Aromatic hydrocarbon or clicyclic hydrocarbon, solvent (C2) are ketone series solvent.
<adhesive composition>
Adhesive composition of the invention be aforementioned acid modified polyolefin (A), multifunctional polyisocyanate curing agent (B) and The mixture of organic solvent (C), acid modified polyolefin (A), curing agent (B) are dissolvable in water in organic solvent (C), are also dispersible in In organic solvent (C).Viewpoint based on working life property is preferably dissolved in organic solvent (C).
Adhesive composition of the invention, in the range of not undermining performance of the invention, except modified poly- using aforementioned acid Alkene (A), multifunctional polyisocyanate curing agent (B) and organic solvent (C) outside, can also mix and use various tackifier, heat Thermoplastic elastic, plasticizer.Tackifier are not particularly limited, and can enumerate polyterpene system resin, rosin series resin, aliphatic through-stone Oleoresin, alicyclic ring family Petropols, copolymerization through-stone oleoresin and hydrogenated petroleum resin etc..In addition, thermoplastic elastomer (TPE) can arrange Lift the styrene series elastomers such as styrene-ethylene-butylene-styrene copolymer resins, styrene ethylene-propylene-styrene；Second Alkene-propylene copolymer resin, Ethylene/Butylene copolymer resins, ethylene-vinyl acetate c resin, ethylene-ethylacrylate copolymerization Olefin-based elastomers such as resin etc..Further, plasticizer can preferably enumerate the liquids such as polyisoprene, polybutene rubber, processing Oil etc..In addition, these tackifier, thermoplastic elastomer (TPE), plasticizer can be used only a kind, also two or more may be used.
Adhesive composition of the invention, in the range of not undermining performance of the invention, except modified poly- using aforementioned acid Alkene (A), multifunctional polyisocyanate curing agent (B) and organic solvent (C) outside, can also and with various curing agent.Curing agent is simultaneously It is not particularly limited, epoxy resin, carbodiimide compound, oxazoline compound, coupling agent class etc. can be enumerated.Epoxy resin can arrange Lift the polyglycidyls types such as hexahydro phthalic acid polyglycidyl, dimeric dibasic acid polyglycidyl；Three polyglycidyl of isocyanuric acid, formic acid- 3,4- epoxycyclohexanecarboxylate, epoxidized polybutadiene, epoxidised soybean oil etc. be alicyclic or aliphatic epoxide；Epoxy third Ether type epoxy or epoxy propylamine type epoxy resin etc..In addition, carbodiimide compound can enumerate dimethyl carbodiimide, Diisopropylcarbodiimide, dicyclohexylcarbodiimide, ter /-butylisopropyl carbodiimide, diphenyl carbodiimide, two-β-naphthalene The single carbons diimine compounds class such as base carbodiimide；Or can by by aliphatic diisocyanate, aromatic diisocyanate or The organic diisocyanates such as alicyclic diisocyanate carry out in solvent-free or non-active solvent in the presence of condensation catalyst The reaction of decarboxylative condensation and the polycarbonimide compounds class etc. manufactured.In addition, oxazoline compound can enumerate 2- oxazoline, 2- first The monosubstituted oxazolyls such as base -2- oxazoline, 2- phenyl -2- oxazoline, 2,5- dimethyl -2- oxazoline or 2,4- diphenyl -2- oxazoline Quinoline compound；2,2 '-(1,3- phenylenes)-bis- (2- oxazolines), 2,2 '-(1,2- ethylidene)-bis- (2- oxazolines), 2,2 '- Bisoxazolines compound such as (1,4- butylidene)-bis- (2- oxazolines) or 2,2 '-(1,4- phenylenes)-bis- (2- oxazolines) etc.. In addition, coupling agent can enumerate silane coupling agent, titanate coupling agent etc..
Adhesive composition of the invention, in the range of not undermining performance of the invention, except modified poly- using aforementioned acid Alkene (A), multifunctional polyisocyanate curing agent (B) and organic solvent (C) outside, can also mix and use curing accelerator.Gu Change promotor to be not particularly limited, carboxylic metallic salt, tertiary amines, quaternary ammonium salt, organic peroxide, hydrazine compound, gold can be enumerated Belong to chelate compound, phosphorus-containing compound, alkaline vulcanizing agent class etc..Aforementioned carboxylic acid's metal salt can enumerate the carboxylic of carbon atom number 1~30 The metal salt of acid.As the carboxylic acid of the composition carboxylic metallic salt, such as acetic acid, butyric acid, octanoic acid, capric acid, lauric acid, meat can be enumerated Myristic acid, palmitinic acid, stearic acid, oleic acid, behenic acid, octenoic acid, erucic acid, elaidic acid, adipic acid, malonic acid, succinic acid, The aliphatic carboxylic acids such as glutaric acid, citric acid, tartaric acid, malic acid, diglycolic acid；Benzoic acid, chlorobenzoic acid, anisic acid, amino The aromatic carboxylic acids such as benzoic acid, phthalic acid, terephthalic acid (TPA), naphthoic acid, naphthalene dicarboxylic acids, benzene tricarbonic acid；Aphthenic acids；Acetone Acid etc..In addition, as constitute the carboxylic metallic salt metal, such as can enumerate Li, Na, K, Mg, Ca, Zn, Al, Cu, Pb, Co, Fe, Mn, Sn, Ti etc..As the carboxylic metallic salt, specific enumerable lithium acetate, sodium acetate, magnesium acetate, aluminium acetate, potassium butyrate, Calcium butyrate, zinc butyrate, Sodium Caprylate, calcium octoate, Capric acid potassium salt, capric acid magnesium, capric acid zinc, lithium laurate, sodium laurate, calcium laurate, Aluminum trilaurate, potassium myristate, Sodium myristate, aluminium myristate, sodium palmitate, zinc palmitate, magnesium palmitate, stearic acid Sodium, potassium stearate, calcium stearate, zinc stearate, enuatrol, Sodium docosanoate, sodium benzoate, zinc benzoate, O-phthalic Sour sodium, phthalic acid aluminium, terephthalic acid (TPA) magnesium, naphthalene dicarboxylic acids calcium, dibutyl tin laurate, tributyl tin laurate, laurel Sour dioctyl tin, tributyltin acetate, dibutyltin diacetate, dioctyl tin diacetate, 2 ethyl hexanoic acid dibutyl tin, metatitanic acid Four butyl esters, tetrabutyl titanate, four 2- ethylhexyl of metatitanic acid, cobalt naphthenate, copper naphthenate, magnesium naphthenate, acetoacetate cobalt etc.. Among these, can preferably enumerate lithium laurate, sodium laurate, calcium laurate, Aluminum trilaurate, potassium myristate, Sodium myristate, Aluminium myristate, sodium palmitate, zinc palmitate, magnesium palmitate, odium stearate, potassium stearate, calcium stearate, zinc stearate, oil Sour sodium.In addition, the metal salt as carboxylic acid, it is possible to use the polymer with carboxylic metallic salt structure.Polymer so can Enumerate with by the IA race of ethylene and free-radical polymerised carboxylic acid, Group IIA, Group IIB, IIIB race metal (such as Li, Na, K, Mg, Ca, Zn, A1 etc.) salt copolymerization obtained by structure person；With by the metal salt of ethylene, free-radical polymerised carboxylic acid, other free radicals Polymerism carboxylic acid and/or its derivative carry out structure person obtained by multi-component copolymer etc..In addition, as aforementioned tertiary amines, such as can Enumerate dimethylaniline, triethanolamine, dimethyl-p-toluidine etc..In addition, as aforementioned hydrazine compound, such as 1- second can be enumerated Acyl group -2- phenyl hydrazine etc..In addition, as aforementioned metal chelate compound, such as vanadium acetylacetonate can be enumerated etc..In addition, conduct Aforementioned phosphorus-containing compound, such as dimethyl phosphine, triphenylphosphine can be enumerated etc..In addition, as aforementioned base vulcanizing agent class, such as can Enumerate hexa, n-butanal-aniline condensation object etc..
Adhesive composition of the invention, in the range of not undermining performance of the invention, except modified poly- using aforementioned acid Alkene (A), multifunctional polyisocyanate curing agent (B) and organic solvent (C) outside, can also mix and use various additives.Add Agent is added to be not particularly limited, it is preferable to use fire retardant, pigment, anti-blocking agent etc..
<laminated body>
Laminated body of the invention is that polyolefin resin substrate and metal base are laminated with adhesive composition of the invention And obtain person.
Laminating method can utilize known lamination manufacturing technology.Such as roller coating can be used on the surface of metal base The spreading implement coating adhesive composition appropriate such as machine, spreading rod simultaneously makes it dry, and is not particularly limited.After drying, in shape At during the adhesive composition layer of metallic substrate surface (adhesive phase) is in a molten state, in its coated face, will gather Olefin resin substrate laminate adhesive (laminate adhesive) and obtain laminated body.
The thickness of the adhesive phase formed by aforementioned adhesion agent composition is not particularly limited, and preferably 0.5~10 μm, More preferably 0.8~9.5 μm, further preferably 1~9 μm.
<polyolefin resin substrate>
As polyolefin resin substrate, as long as suitably being selected from known polyolefin resin.Such as it can make With polyethylene, polypropylene, ethylene-propylene copolymer etc., it is not particularly limited.Wherein, it is preferable to use polyacrylic unstretching film (being also known as CPP below).Its thickness is not particularly limited, preferably 20~100 μm, more preferably 25~95 μm, further excellent It is selected as 30~90 μm.In addition, in polyolefin resin substrate can hybrid pigment, various additives as needed, also implementable surface Processing.
<metal base>
Metal base is not particularly limited, such as the various metals such as aluminium, copper, steel, chromium, zinc, duralumin, die casting can be used And its alloy.In addition, its shape can adopt the arbitrary shapes such as metal foil, calendering steel plate, plate, pipe, tank, lid.In general, being based on The viewpoint of processability etc., preferably aluminium foil.In addition, depend on using purpose and it is different, generally with 0.01~10mm, preferably The sheet-form of the thickness of 0.02~5mm uses.
It can also be untreated state in addition, surface treatment can be imposed in advance to the surface of these metal bases.Any feelings Shape can play equivalent effect.
[embodiment]
The present invention is described in more detail by the following examples.Only the present invention is not limited to embodiments.In embodiment And part is simply recorded in comparative example, indicate mass parts.
<Production Example of acid modified polyolefin (A)>
Production Example 1
Propylene-ethylene copolymers are added in 1L autoclave, and (storage modulus 320MPa at 25 DEG C, the stretching at 25 DEG C are disconnected Split elongation 760%) 1 mass parts of 100 mass parts, 233 mass parts of toluene and maleic anhydride, 0.5 matter of di-tert-butyl peroxide Part is measured, after being warming up to 140 DEG C, is futher stirred 1 hour (herein, referred to as " reacting " 1 hour).Later, by the reaction solution of acquisition After being cooled to 100 DEG C, it is injected into while stirring equipped with 717 mass parts of toluene and 950 mass of methyl ethyl ketone for being heated up to 40 DEG C in advance In the container of part, 40 DEG C are cooled to, is stirred for 30 minutes, is cooled further to 25 DEG C, passes through resin precipitation (herein, Reaction solution is injected into methyl ethyl ketone equal solvent while stirring and carries out cooling so that the operation that resin is precipitated is known as " sinking again Form sediment ").Later, it is centrifuged by by the slurries containing the resin, and there is the acid of maleic anhydride to be modified third for being graft-polymerized Alkene-ethylene copolymer is separated with (poly-) maleic anhydride and low molecular weight object.
Further, the sour modified propylene-ethylene's copolymer for being centrifugated and having taken out puts into preparatory guarantor while stirring Temperature continues stirring 1 hour in 25 DEG C of the in addition container of the methyl ethyl ketone equipped with 2000 mass parts.Later, by by slurries into Row centrifuge separation, further separates sour modified propylene-ethylene's copolymer with (poly-) maleic anhydride and low molecular weight object.Repeating should Operation 2 times, being purified (herein, will be centrifugated and the sour modified propylene-ethylene's copolymer taken out puts into first while stirring It is centrifugated in ethyl ketone and again, " repulped " is thus known as with the operation for strengthening purification).
It after purification, is made it dry 5 hours by 70 DEG C under reduced pressure, obtains changing as the maleic anhydride of acid modified polyolefin Property propylene-ethylene copolymers (PO-1, acid value 2mgKOH/g resin, 0.1 mass % of acetone extract component ratio, the storage at 25 DEG C It can modulus 300MPa, the tension fracture elongation rate 600% at 25 DEG C, weight average molecular weight 190,000, Tm88 DEG C, Δ H37J/g).
Production Example 2
The additive amount of maleic anhydride is changed to 3 mass parts, repulped number be changed to 1 time, it is repulped when the first that puts into Other than the quantitative change of ethyl ketone more 1000 mass parts, it is carried out similarly with Production Example 1, thus obtains the horse as acid modified polyolefin Come anhydride-modified propylene-ethylene copolymer (PO-2, acid value 5mgKOH/g resin, 1.8 mass % of acetone extract component ratio, 25 Storage modulus 280MPa at DEG C, the tension fracture elongation rate 650% at 25 DEG C, weight average molecular weight 180,000, Tm88 DEG C, Δ H36J/g)。
Production Example 3
The additive amount of toluene is changed to 150 mass parts, the additive amount of maleic anhydride is changed to 40 mass parts, di-t-butyl The additive amount of peroxide is changed to 8 mass parts, the reaction time be changed to 3 hours, the solvent that uses of reprecipitation be changed to first and second 700 mass parts of ketone, repulped number are changed to other than 5 times, are carried out similarly with Production Example 1, are thus obtained modified poly- as acid Maleic anhydride modified propylene-ethylene copolymers (PO-3, acid value 48mgKOH/g resin, acetone extract component ratio 0.1 of alkene Quality %, the storage modulus 180MPa at 25 DEG C, the tension fracture elongation rate 350% at 25 DEG C, weight average molecular weight 31,000, Tm85℃、ΔH 31J/g)。
Production Example 4
The additive amount of toluene is changed to 150 mass parts, the additive amount of maleic anhydride is changed to 40 mass parts, di-t-butyl The additive amount of peroxide is changed to 8 mass parts, the reaction time be changed to 3 hours, the solvent that uses of reprecipitation be changed to first and second 700 mass parts of ketone, it is repulped used in solvent is changed to 1000 mass parts of methyl ethyl ketone, repulped number is changed to other than 3 times, It is carried out similarly with Production Example 1, thus obtains the maleic anhydride modified propylene-ethylene copolymers (PO- as acid modified polyolefin 4, acid value 48mgKOH/g resin, 1.8 mass % of acetone extract component ratio, the storage modulus 150MPa at 25 DEG C, at 25 DEG C Tension fracture elongation rate 300%, weight average molecular weight 27,000, Tm85 DEG C, Δ H30J/g).
Production Example 5
The additive amount of toluene is changed to 150 mass parts, the additive amount of maleic anhydride is changed to 20 mass parts, di-t-butyl The additive amount of peroxide is changed to 6 mass parts, the reaction time be changed to 3 hours, the solvent that uses of reprecipitation be changed to first and second 700 mass parts of ketone, it is repulped used in solvent is changed to 1000 mass parts of methyl ethyl ketone, repulped number is changed to other than 2 times, It is carried out similarly with Production Example 1, thus obtains the maleic anhydride modified propylene-ethylene copolymers (PO- as acid modified polyolefin 5, acid value 25mgKOH/g resin, 0.9 mass % of acetone extract component ratio, the storage modulus 400MPa at 25 DEG C, 25 DEG C of drawing Stretch elongation at break 500%, weight average molecular weight 60,000, Tm87 DEG C, Δ H 35J/g).
Production Example 6
It is changed to propylene-ethylene copolymers (storage modulus 52MPa at 25 DEG C, the tension fracture elongation rate at 25 DEG C 1050%) 100 mass parts, the additive amount of toluene is changed to 150 mass parts, the additive amount of maleic anhydride is changed to 30 mass Part, the additive amount of di-tert-butyl peroxide be changed to 6 mass parts, the reaction time be changed to 3 hours, it is molten used in reprecipitation Agent is changed to 700 mass parts of methyl ethyl ketone, repulped used solvent is changed to 1000 mass parts of methyl ethyl ketone, the change of repulped number It other than more 2 times, is carried out similarly with Production Example 1, thus obtains maleic anhydride modified propylene-second as acid modified polyolefin Alkene copolymer (PO-6, acid value 25mgKOH/g resin, 1.0 mass % of acetone extract component ratio, the storage modulus at 25 DEG C 12MPa, the tension fracture elongation rate 900% at 25 DEG C, weight average molecular weight 60,000, Tm58 DEG C, Δ H7J/g).
Production Example 7
It is changed to Noblen (storage modulus 2100MPa at 25 DEG C, the tension fracture elongation rate 900% at 25 DEG C) 100 mass parts, the additive amount of toluene is changed to 150 mass parts, the additive amount of maleic anhydride is changed to 30 mass parts, two tertiary fourths The additive amount of base peroxide is changed to 6 mass parts, the reaction time is changed to 3 hours, solvent is changed to used in reprecipitation 700 mass parts of methyl ethyl ketone, it is repulped used in solvent is changed to 1000 mass parts of methyl ethyl ketone, repulped number is changed to 2 times In addition, it is carried out similarly with Production Example 1, thus obtains the maleic anhydride modified Noblen (PO- as acid modified polyolefin 7, acid value 25mgKOH/g resin, 0.9 mass % of acetone extract component ratio, 25 DEG C of storage modulus 1800MPa, at 25 DEG C Tension fracture elongation rate 60%, weight average molecular weight 60,000, Tm85 DEG C, Δ H 5J/g).
Production Example 8
It is changed to propylene-ethylene copolymers (storage modulus 2720MPa at 25 DEG C, the tension fracture elongation rate at 25 DEG C 400%) 100 mass parts, the additive amount of toluene is changed to 186 mass parts, the additive amount of maleic anhydride is changed to 20 mass parts, The additive amount of di-tert-butyl peroxide is changed to 6 mass parts, the reaction time is changed to 3 hours, solvent used in reprecipitation It is changed to 700 mass parts of methyl ethyl ketone, repulped used solvent is changed to 1000 mass parts of methyl ethyl ketone, the change of repulped number It other than 2 times, is carried out similarly with Production Example 1, thus obtains the maleic anhydride modified propylene-ethylene as acid modified polyolefin Copolymer (PO-8, acid value 25mgKOH/g resin, 1.0 mass % of acetone extract component ratio, the storage modulus at 25 DEG C 2350MPa, the tension fracture elongation rate 38% at 25 DEG C, weight average molecular weight 60,000, Tm125 DEG C, Δ H63J/g).
Production Example 9
The additive amount of toluene is changed to 186 mass parts, the additive amount of maleic anhydride is changed to 20 mass parts, di-t-butyl The additive amount of peroxide is changed to 6 mass parts, the reaction time is changed to 3 hours, solvent is changed to first used in reprecipitation 1200 mass parts of ethyl ketone, it is repulped used in solvent be changed to 1200 mass parts of methyl ethyl ketone, repulped number be changed to 2 times with Outside, it is carried out similarly with Production Example 1, thus obtains the maleic anhydride modified propylene-ethylene copolymers as acid modified polyolefin (PO-9, acid value 25mgKOH/g resin, 1.2 mass % of acetone extract component ratio, the storage modulus 7MPa at 25 DEG C, at 25 DEG C Tension fracture elongation rate 1200%, weight average molecular weight 60,000, without the peak Tm, Δ H OJ/g).
Production Example 10
It is changed to propylene-ethylene copolymers (storage modulus 500MPa at 25 DEG C, the tension fracture elongation rate at 25 DEG C 680%) 100 mass parts, the additive amount of toluene is changed to 150 mass parts, the additive amount of maleic anhydride is changed to 0.5 mass Part, the additive amount of di-tert-butyl peroxide is changed to 0.2 mass parts, the reaction time is changed to 1 hour, used in reprecipitation Solvent is changed to 1000 mass parts of methyl ethyl ketone, repulped used solvent is changed to 1000 mass parts of methyl ethyl ketone, and repulped time Number is changed to other than 2 times, is carried out similarly with Production Example 1, is thus obtained maleic anhydride modified third as acid modified polyolefin Alkene-ethylene copolymer (PO-10, acid value 1mgKOH/g resin, 0.1 mass % of acetone extract component ratio, 25 DEG C of storage modulus 400MPa, the tension fracture elongation rate 600% at 25 DEG C, weight average molecular weight 65,000, Tm71 DEG C, Δ H35J/g).
Production Example 11
The additive amount of toluene is changed to 150 mass parts, the additive amount of maleic anhydride is changed to 50 mass parts, di-t-butyl The additive amount of peroxide is changed to 10 mass parts, the reaction time is changed to 3 hours, solvent is changed to first used in reprecipitation 700 mass parts of ethyl ketone, it is repulped used in solvent be changed to 1000 mass parts of methyl ethyl ketone, repulped number be changed to 3 times with Outside, it is carried out similarly with Production Example 1, thus obtains the maleic anhydride modified propylene-ethylene copolymers as acid modified polyolefin (PO-11, acid value 55mgKOH/g resin, 1.0 mass % of acetone extract component ratio, the storage modulus 150MPa at 25 DEG C, 25 Tension fracture elongation rate 320%, weight average molecular weight 30,000, Tm83 DEG C, Δ H25J/g at DEG C).
Production Example 12
The additive amount of toluene is changed to 150 mass parts, the additive amount of maleic anhydride is changed to 40 mass parts, di-t-butyl The additive amount of peroxide is changed to 8 mass parts, the reaction time is changed to 3 hours, and repulped number is changed to other than 3 times, with Production Example 1 is carried out similarly, and thus obtains the maleic anhydride modified propylene-ethylene copolymers (PO- as acid modified polyolefin 12, acid value 46mgKOH/g resin, 4.5 mass % of acetone extract component ratio, the storage modulus 110MPa at 25 DEG C, at 25 DEG C Tension fracture elongation rate 90%, weight average molecular weight 35,000, Tm86 DEG C, Δ H30J/g).
(production of host agent 1)
The horse obtained in Production Example 1 is added in the 500ml four-hole boiling flask equipped with water-cooled reflux condenser and blender Come 100 mass parts of anhydride-modified propylene-ethylene copolymer (PO-l), 120 mass of 280 mass parts of hexahydrotoluene and methyl ethyl ketone Part, warming while stirring is cooling after continuing stirring 1 hour to 80 DEG C, thus obtains host agent 1.Solution state is shown in table 1.
(production of host agent 2~19)
Change acid modified polyolefin and organic solvent as shown in table 1, with method same as host agent 1 production host agent 2~ 19.Combined amount, solution state are shown in table 1.
[table 1]
Embodiment 1
By the SUMIDUR (note as multifunctional polyisocyanate curing agent (B) of the host agent 1 of 500 mass parts, 1 mass parts Volume trade mark) N-3300 mixing, obtain adhesive composition.Working life property, adhesiveness, chemical-resistant and formability evaluation knot Fruit is shown in table 2.
Embodiment 2~21, comparative example 1~3
Host agent 1~19 and each curing agent are changed as shown in Table 2,3, carry out embodiment 2 in method similarly to Example 1 ~21, comparative example 1~3.Combined amount, working life property, adhesiveness, chemical-resistant and formability as the result is shown in table 2,3.
[table 2]
[table 3]
Curing agent used in table 2,3 is as follows.
<multifunctional polyisocyanate curing agent (B)>
The isocyanuric acid ester body of hexamethylene diisocyanate: SUMIDUR (registered trademark) N-3300 (Beyer Co., Ltd's system)
The biuret body of hexamethylene diisocyanate: DURANATE (registered trademark) 24A-100 (chemical company, Asahi Chemical Industry System)
To each acid modified polyolefin, host agent and the adhesive composition obtained in the above described manner, implemented according to following method Analysis measurement and evaluation.
The measurement of acid value
KOH amount needed for acid value (mgKOH/g resin) in the present invention refers to the acid modified polyolefin (A) for neutralizing lg, according to The test method of JIS K0070 (1992) and measure.Specifically, acid modified polyolefin 1g is dissolved in temperature and is adjusted to 100 DEG C Dimethylbenzene 100g, then, at such a temperature using phenolphthalein as indicator, with 0.1mol/L potassium hydroxide-ethanol solution [commodity Name " the alcohol repellency potassium hydroxide solution of 0.1mol/L ", Wako Pure Chemicals Co., Ltd. system] it is titrated.At this point, by needed for titration Potassium hydroxide amount is converted into mg and calculates acid value (mgKOH/g).
The measurement of acetone extract component ratio
Acetone extract component ratio in the present invention is measured using soxhlet's extractor with acetone progress reflux in 2 hours. Specifically following value: weighing acid modified polyolefin (A) 50g to cylindrical filter paper, put it into soxhlet extraction Guan Zhonghou, group Boiling flask, the cooling tube of 1100mL acetone are contained, flows back 2 hours in a water bath and carries out acetone extract.Later, circle is taken out Cylinder filter paper, and the acetone extract liquid in boiling flask is evaporated, further weigh 100 DEG C × l hours the residual after being dried under reduced pressure The weight of object, is calculated by following formula.
Acetone extract component ratio (quality %)=(extraction leftover weight/sampling amount) × l00
[measurement of the storage modulus (E ') at 25 DEG C]
Storage modulus (E ') in the present invention according to (1999) JIS K7244-4 test method determination.Specifically using IT measures the measurement of dynamic viscoelasticity device DVA-200 of Zhi Yu company manufacture, in frequency 10Hz from -50 DEG C with 5 DEG C/min of speed Value obtained by degree heating side is measured.
[measurement of 25 DEG C of tension fracture elongation rate (Eb)]
Tension fracture elongation rate (Eb) in the present invention is the test method determination according to (2014) JIS K7161.Specifically, It is the TENSILON RTM-100 using Orientic Coporation corporation, with speed 50mm/ minutes under environment at 25 DEG C It is stretched, is worth obtained by the elongation (%) when measurement is broken.
[measurement of weight average molecular weight (Mw)]
Weight average molecular weight in the present invention utilizes the hydrogel permeation layer analyzer Alliance of Japanese Waters corporation E2695 (hereinafter referred to as GPC, standard substance: polystyrene resin, mobile phase: tetrahydrofuran, chromatographic column: Shodex KF-806+ KF-803, chromatogram column temperature: 40 DEG C, flow velocity: 1.0ml/ minutes, detector: photodiode array detector (wavelength 254nm= Ultraviolet light)) value that measures.
[measurement of fusing point, fusing heat]
Fusing point, fusing heat in the present invention, are by using differential scanning calorimeter (hereinafter referred to as DSC, TA Instrument Japan system, Q-2000), it is melted with 20 DEG C/min of speed heating, cooling resinification, heating melts again When melting peak head temperature and the value that measures of area.
[evaluation of host agent solution state]
To the solution state of host agent 1~19, using Dong Ji industry companies Bu Shi type viscosimeter TVB-10M (below again Referred to as Brookfield viscometer) 25 DEG C of solution viscosity is measured to be evaluated.
<evaluation criteria>
◎ (practical excellent): less than 500mPas
〇 (can be practical): 500mPas or more, it is less than 1000mPas
× (can not be practical): 1000mPas or more can not measure viscosity because of gelation
The evaluation of working life property
Working life property refers to mixed cross-linker or curing agent in acid modified polyolefin, just mixing when or mixing after through one timing Between after the solution stability.The good situation of working life property refer to solution viscosity rise less, can grow during save；Working life Property bad situation refer to that the viscosity of solution rises (thickening), can occur gel phenomenon when serious, it is difficult to be coated on substrate, can not It is saved during length.
The working life property of the adhesive composition obtained in Examples 1 to 21 and comparative example 1~3, by 25 DEG C and 40 After DEG C environment saves 24 hours, evaluated using Brookfield viscometer in 25 DEG C of measurement solution viscosities.Evaluation result is shown in table 2、3。
<evaluation criteria>
◎ (practical excellent): less than 500mPas
〇 (can be practical): 500mPas or more, it is less than 1000mPas
× (can not be practical): 1000mPas or more can not measure viscosity because of gelation
The production of the laminated body of metal base and polyolefin resin substrate
Metal base uses aluminium foil (firmly light aluminium foil corporation, 8079-0,40 μm of thickness), and polyolefin resin substrate is not using Stretched polypropylene films (Dongyang spinning company Pylen (registered trademark) film CT, 40 μm of thickness) (are also known as CPP) below.
The adhesive composition obtained in embodiment 1~19 and comparative example 1~15 is coated on Metal Substrate using spreading rod Material, be adjusted to make it is dry after the film thickness of adhesive phase become 3 μm.It will be applied in 100 DEG C of atmosphere using warm wind drying machine Cloth cover is 1 minute dry, and acquisition is laminated with the metal base of 3 μm of film thickness of adhesive phase.On aforementioned adhesion oxidant layer surface, overlapping is poly- Olefin resin substrate tests laminating machine (SA-1010-S) using on the small-sized table of TESTER SANGYO corporation, laminating temperature It 80 DEG C or 120 DEG C, is bonded with 0.3MPa, 1m/ minutes conditions, cures 36 hours in 25 DEG C, 50%RH to obtain laminated body.
For the laminated body obtained in the above described manner, evaluated using following method.
The evaluation of adhesiveness
Aforementioned laminated body is cut into 100mm × l5mm size, is bonded using T-type disbonded test according to following benchmark Property evaluation.Evaluation result is shown in table 2,3.
<T-type disbonded test>
According to the test method(s) of ASTM-D1876-61, the TENSILON of Orientic Coporation corporation is used RTM-100 measures peel strength when tensile speed is 50mm/ minutes under 25 DEG C of atmosphere.Metal base/polyolefin resin base Peel strength (N/cm) between material takes the average value of 5 test values.
☆ (practical upper especially excellent): 8.0N/cm or more or CPP generating material destroy (following again referred to as " material is broken "). The broken finger of material is not peeling-off at the interface metal base/CPP, but metal base or CPP are destroyed.
◎ (practical excellent): 7.5N/cm or more, it is less than 8.0N/cm
〇 (can be practical): 7.0N/cm or more, it is less than 7.5N/cm
× (can not be practical): less than 7.0N/cm
The evaluation of chemical-resistant
In order to study the usability of the packaging material as LiB, implement (following using the chemical-resistant of electrolyte test Also known as electrolyte resistance) evaluation.Aforementioned laminated body is cut into 100mm × l5mm size, in electrolyte [carbonic acid Asia second Addition lithium hexafluoro phosphate forms in ester/diethyl carbonate/dimethyl carbonate=1/1/1 (volumetric ratio)] in impregnated 1 day at 85 DEG C. Later, laminated body is taken out and is kept moisture sufficiently dry with cleansing tissue wiping water with ion exchange water washing, removed using T-type The following benchmark of experimental evidence carries out chemical-resistant evaluation.Evaluation result is shown in table 2~3.
<evaluation criteria>
☆ (practical upper especially excellent): 8.0N/cm or more or material it is broken
◎ (practical excellent): 7.5N/cm or more, it is less than 8.0N/cm
〇 (can be practical): 7.0N/cm or more, it is less than 7.5N/cm
× (can not be practical): less than 7.0N/cm
The evaluation of formability
For the purposes of studying the usability of the packaging material as LiB, implement the formability for utilizing deep drawn testing machine Evaluation.Aforementioned laminated body is cut into 80 × 120mm size, and carries out cold-press moulding.Specifically, using Co., Ltd. AMADA The stretch former (model: TP-25C-X2) of system, with 55mm × 35mm bore shaping dies (master mold) and with it is corresponding Shaping dies (male model), under 25 DEG C of atmosphere with bias pressure 0.4MPa from the Forming depth of 0.5mm with 0.5mm Unit alteration Forming depth carries out cold-press moulding to 10 samples (laminated body) respectively.It, will be equal in 10 samples to the sample after cold-press moulding Wrinkle, aluminium foil are not generated does not generate limit Forming depth of the most deep Forming depth of pin hole, crackle as the sample.By this Limit Forming depth carries out the formability evaluation of battery use packing material according to following benchmark.Evaluation result is shown in table 3~4.
<determinating reference>
☆ (practical upper especially excellent): limit Forming depth 6.0mm or more
◎ (practical excellent): limit Forming depth 4.0mm or more, it is less than 6.0mm
〇 (can be practical): limit Forming depth 2.0mm or more, it is less than 4.0mm
×: limit Forming depth is less than 2.0mm
Industrial availability
Adhesive composition according to the present invention contains acid modified polyolefin, multifunctional polyisocyanate curing agent and has Thickening, gelation will not occur long-term preservation, can maintain good working life property, and can take into account Metal Substrate for solvent Good adhesiveness between material and polyolefin resin substrate, electrolyte resistance, formability.Therefore, by adhesive of the invention Composition formed polyolefin resin substrate and metal base laminated body, not only using Outside panel for home electrical appliances, furniture material, The built-in fields such as component are built, the packaging of lithium battery used in personal computer, mobile phone, video camera etc. is also widely used as Material (pouch form).

Claims (6)

1. a kind of adhesive composition, containing acid modified polyolefin A, multifunctional polyisocyanate curing agent B and organic solvent C, The acid value of acid modified polyolefin A is 2~50mgKOH/g resin, the acetone extract component ratio of acid modified polyolefin A is 0.01~ 2 mass %.
2. adhesive composition according to claim 1, described viscous relative to acid modified polyolefin A described in 100 mass parts Mixture composite contains the organic solvent of the multifunctional polyisocyanate curing agent B of 0.5~40 mass parts, 80~2000 mass parts C。
3. adhesive composition described according to claim 1~any one of 2, organic solvent C is solvent C 1 and solvent C 2 Mixed liquor, solvent C 1 are selected from one or more of the group being made of aromatic hydrocarbon, aliphatic hydrocarbon, clicyclic hydrocarbon and halogenated hydrocarbons Solvent, solvent C 2 be in the group being made of alcohol series solvent, ketone series solvent, ester series solvent and glycol ether series solvent 1 Kind or more solvent, and by quality ratio, 1/ solvent C 2=50~97/50~3 of solvent C.
4. adhesive composition described in any one of claim 1 to 3, described adhesive composition is used for polyolefin tree Bonding between aliphatic radical material and metal base.
5. a kind of laminated body of polyolefin resin substrate and metal base, passes through bonding according to any one of claims 1 to 4 Agent composition and bond.
6. a kind of lithium ion battery packaging material, using laminated body as claimed in claim 6 as member of formation.
CN201880008954.3A 2017-05-29 2018-04-12 Polyolefin adhesive composition Pending CN110234721A (en)

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