KR20200014260A - Polyolefin Adhesive Composition - Google Patents

Abstract

[PROBLEMS] To provide an adhesive composition containing an acid-modified polyolefin and a polyfunctional polyisocyanate curing agent having good port life and good adhesiveness, chemical resistance and moldability of a metal substrate and a polyolefin resin substrate.
[Solution] An adhesive composition containing an acid-modified polyolefin (A), a polyfunctional polyisocyanate curing agent (B) and an organic solvent (C), wherein the acid value of the acid-modified polyolefin (A) is from 2 to 50 mgKOH / g-resin. Adhesive composition whose acetone extraction component ratio is 0.01-2 mass%.

Description

Polyolefin Adhesive Composition

This invention relates to the adhesive composition which shows the favorable adhesiveness, chemical-resistance, and moldability of a polyolefin resin base material and a metal base material. More specifically, it relates to an adhesive composition containing an acid-modified polyolefin, a polyfunctional polyisocyanate curing agent, and an organic solvent. In particular, it is related with the adhesive composition for lithium ion batteries (it abbreviates LiB hereafter), and the packaging material which is a laminated body containing the same.

In recent years, as a battery used in portable terminal devices such as personal computers and mobile phones, video cameras, satellites, and the like, LiB capable of ultra-thin and miniaturization has been developed in full swing. The packaging material of this LiB has a advantage that, unlike the metal tube used in the prior art, a laminate having a structure such as a base material layer / barrier layer / sealant layer can be used in the advantage that the shape of the battery can be freely selected.

LiB is an electrolyte solution in which lithium salt is dissolved in an aprotic solvent such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, etc. together with the positive electrode material and the negative electrode material as battery contents, or a polymer gel impregnated with the electrolyte solution. An electrolyte layer is formed. When such a strongly penetrating solvent passes through the sealant layer, the lamination strength between the barrier layer and the sealant layer is lowered, resulting in delamination, and finally, the electrolyte solution leaks. As lithium salts, which are electrolytes for batteries, materials such as LiPF 6 and LiBF 4 are used, but these salts generate hydrofluoric acid by hydrolysis reaction with water, and the hydrofluoric acid corrodes the barrier layer, thereby decreasing laminate strength. The battery packaging material needs to have resistance to electrolytes in this way.

In addition, assuming that LiB is used under various environments, it is necessary to have more severe resistance. For example, when used in a mobile device, the leakage resistance in the high temperature environment of 60-70 degreeC, such as an inside of a vehicle, is calculated | required. Furthermore, assuming that it is used in a mobile phone and dropped in the water by mistake, water resistance is also required so that moisture does not invade.

Under such a situation, various packaging materials for lithium batteries with improved electrolytic solution resistance have been proposed (see Patent Documents 1 to 3, for example).

In the battery packaging material, when the battery element is encapsulated, it is molded into a mold to form a space for accommodating the battery element. At the time of this shaping | molding, when a battery packaging material increases, there exists a problem that a crack and pinholes generate | occur | produce easily in a barrier layer in the flange part of a metal mold | die. In particular, with the recent demand for miniaturization and thinning of batteries, a thinner battery packaging material is required, and this problem is more likely to occur more remarkably.

Under these circumstances, battery packaging materials having improved moldability have been proposed (see, for example, Patent Documents 4 to 5).

Patent Document 1: Japanese Patent Application Laid-Open No. 2001-243928 Patent Document 2: Japanese Patent Application Laid-Open No. 2004-42477 Patent Document 3: Japanese Unexamined Patent Publication No. 2009-238475 Patent Document 4: Japanese Patent Application Laid-Open No. 2002-216714 Patent Document 5: Japanese Unexamined Patent Publication No. 2003-31188

However, the proposed packaging material for lithium batteries is still insufficient in terms of electrolyte resistance and moldability. Moreover, even if the improvement of electrolyte resistance and moldability was large, a problem was seen.

Specifically, it is difficult to secure both the port life property of the adhesive after the curing agent formulation and the electrolyte resistance (Patent Document 1), and the lamination expectations are restricted or the bonding at a high temperature by performing the adhesion by extrusion lamination. By this, a polyolefin base material is influenced by heat shrink (patent document 2), and drying time is long because a polyolefin main body is water-based, and production conditions are limited (patent document 3). Moreover, the process which coats an amide type slip agent with the outer layer film surface must be provided, productivity falls, and the laminated strength of an outer layer film and aluminum foil is not fully obtained by the coated amide type slip agent (patent Document 4) is a structure in which only an unstretched polypropylene resin film is arranged on the inner layer side than aluminum foil, or a structure in which only a film of a blend resin of polypropylene and polyethylene is arranged on the inner layer side than aluminum foil, so that When molding, pinholes were generated in the aluminum foil, or fractures (breaks) were likely to occur in the aluminum foil, and problems such as insufficient moldability were obtained (Patent Document 5).

The subject of this invention is providing the adhesive composition excellent in adhesiveness, chemical-resistance (electrolyte solution), and moldability, without the problem of port life property and a limitation of a production condition. Moreover, it is providing the battery packaging material containing the adhesive bond layer which consists of this adhesive composition, and the battery using the said packaging material.

MEANS TO SOLVE THE PROBLEM In order to achieve the said subject, the present inventors earnestly examined and discovered that it is effective to arrange | position the layer which can fully follow the elongation at the time of shaping | molding not only in the outer layer side but also inner layer side of aluminum foil, and propose the following invention. Reached.

An adhesive composition containing an acid-modified polyolefin (A), a polyfunctional polyisocyanate curing agent (B), and an organic solvent (C), wherein the acid value of the acid-modified polyolefin (A) is 2 to 50 mgKOH / g-resin, acetone extraction component. Adhesive composition whose ratio is 0.01-2 mass%.

It is preferable to contain 0.5-40 mass parts of polyfunctional polyisocyanate hardeners (B), and 80-2000 mass parts of organic solvents (C) with respect to 100 mass parts of said acid-modified polyolefins (A). In addition, the organic solvent (C) is a mixed liquid of the solvent (C1) and the solvent (C2), the solvent (C1) is one or more solvents selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons, Solvent (C2) is at least one solvent selected from the group consisting of alcohol solvents, ketone solvents, ester solvents and glycol ether solvents, solvent (C1) / solvent (C2) = 50 to 97/50 to 3 ( Mass ratio).

It is preferable that the said adhesive composition is used for adhesion | attachment of a polyolefin resin base material and a metal base material.

A packaging material for a lithium ion battery comprising a laminate of a polyolefin resin substrate and a metal substrate bonded with the adhesive composition and the laminate as a constituent member.

The adhesive composition according to the present invention contains an acid-modified polyolefin, a polyfunctional polyisocyanate curing agent and an organic solvent, and can maintain good pot life without causing thickening or gelation even after long-term storage. In addition, even when the polyolefin substrate is bonded at a low temperature such as 120 ° C. or less and the aging at a low temperature such as 40 ° C. or less, the good adhesion, chemical resistance and moldability of the polyolefin resin substrate and the metal substrate are compatible. It is possible.

According to the present invention, it can be sufficiently cured by the aging step after bonding while maintaining good pot life, and excellent adhesiveness and chemical resistance can be expressed. In addition, it is possible to obtain an adhesive layer that satisfies the storage modulus and elongation at break necessary to express excellent moldability.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

<Acid Modified Polyolefin (A)>

Acid-modified polyolefin (A) used by this invention is an acid-modified polyolefin whose acid value is 2-50 mgKOH / g-resin, and the acetone extraction component ratio is 0.01-2 mass%.

The acid-modified polyolefin (A) used in the present invention is not limited, but by grafting at least one of α, β-unsaturated carboxylic acid and its acid anhydride to at least one of polyethylene, polypropylene and propylene-α-olefin copolymer It is preferable to obtain.

The propylene-α-olefin copolymer is obtained by copolymerizing an α-olefin mainly on propylene. As the? -olefin, for example, ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate and the like can be used. Among these α-olefins, ethylene and 1-butene are preferable. Although the ratio of the propylene component and the alpha-olefin component of a propylene-alpha-olefin copolymer is not limited, It is preferable that it is 50 mol% or more, and it is more preferable that it is 70 mol% or more.

As at least 1 sort (s) of (alpha), (beta)-unsaturated carboxylic acid and its acid anhydride, maleic acid, itaconic acid, a citraconic acid, and these acid anhydrides are mentioned, for example. Among these, an acid anhydride is 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. A modified polyolefin can be used 1 type or in combination of 2 or more types.

The acid value of the acid-modified polyolefin (A) needs to be in the range of 2 to 50 mgKOH / g-resin from the viewpoint of the adhesiveness between the polyolefin resin substrate and the metal substrate and the electrolyte resistance. Preferably it is 3-45 mgKOH / g-resin, More preferably, it is 5-40 mgKOH / g-resin, Especially preferably, it is the range of 7-35 mgKOH / g-resin. If it is less than the said value, compatibility with a hardening | curing agent may become inadequate. Therefore, crosslinking density is low and adhesive strength and chemical-resistance (electrolyte solution resistance) may fall. When it exceeds the said value, since molecular weight is low and cohesion force becomes weak, adhesive strength and chemical-resistance (electrolyte resistance) may fall. Moreover, since manufacturing efficiency also falls, it is unpreferable.

The acid value of an acid-modified polyolefin (A) can be adjusted with the usage-amount of the acid anhydride of a (alpha), (beta)-unsaturated carboxylic acid, the (alpha), (beta)-unsaturated carboxylic acid, and a radical generator.

The acetone extraction component ratio of the acid-modified polyolefin (A) needs to be in the range of 0.01% by mass to 2% by mass from the viewpoint of the adhesiveness between the polyolefin resin substrate and the metal substrate and the electrolyte resistance. Preferably it is 0.03 mass%-1.7 mass%, More preferably, it is 0.05 mass%-1.4 mass%, More preferably, it is 0.07 mass%-1.2 mass%, Especially preferably, it is 0.1 mass%-1 mass% of Range. If it is less than the said value, since manufacturing efficiency will fall, it is unpreferable. When it exceeds the said value, cohesion force may become weak and it may be inferior to adhesiveness, chemical-resistance, and moldability.

The storage modulus (E ′) at 25 ° C. of the acid-modified polyolefin (A) is preferably in the range of 10 to 2000 MPa from the viewpoint of adhesion and chemical resistance (electrolyte resistance) of the polyolefin resin substrate and the metal substrate. Do. More preferably, it is 15-1700 Mpa, More preferably, it is 20-1400 Mpa, Especially preferably, it is 25-1100 Mpa, The most preferable is 30-800 Mpa. If it is less than the said value, it may lead to lack of cohesion of the adhesive bond layer which consists of an adhesive composition, and adhesiveness and chemical-resistance (electrolyte solution resistance) may be inferior. When the said value is exceeded, the followability of the adhesive bond layer which consists of adhesive compositions may fall, and adhesiveness may be inferior. Moreover, since adhesiveness and base material followability improve when it exists in the said range, since the moldability of a laminated body becomes favorable, it is more preferable as a packaging material for lithium ion batteries.

It is preferable that the tensile elongation at break (Eb) at 25 ° C of the acid-modified polyolefin (A) is in a range of 50% to 1000%. More preferably, it is 80%-900%, More preferably, it is 120%-800%, Especially preferably, it is 160%-700%, Most preferably, it is 200%-600%. If it is less than the said value, the followability of the adhesive bond layer which consists of adhesive compositions may fall, it may lead to pinholes at the time of shaping | molding, and inferior moldability. In general, tensile fracture elongation (Eb) and storage modulus (E ') are opposite properties, and when it exceeds the above value, storage modulus (E') may be lowered, resulting in poor adhesion and electrolyte resistance. Moreover, since adhesiveness and base material followability improve when it exists in the said range, since the moldability of a laminated body becomes favorable, it is more preferable as a packaging material for lithium ion batteries.

It is preferable that the weight average molecular weight (Mw) of acid-modified polyolefin (A) is 10,000-200,000. More preferably, it is the range of 20,000-180,000, More preferably, it is the range of 30,000-160,000, Especially preferably, it is the range of 40,000-140,000, Most preferably, it is the range of 50,000-110,000. If it is less than the said value, cohesion force may become weak and adhesiveness may be inferior. On the other hand, when it exceeds the said value, fluidity | liquidity may be low and a problem may arise in operability at the time of adhesion | attachment. If it is in the said range, since hardening reaction with a hardening | curing agent is exhibited, it is preferable.

Crystallinity in an acid-modified polyolefin (A) means using a differential scanning calorimeter (DSC) to raise the temperature up to -100 ° C to 250 ° C at 20 ° C / min and show a clear melting peak in the temperature raising process. .

By making an acid-modified polyolefin crystalline, it is advantageous because cohesion force is strong compared with amorphous, and it is excellent in adhesiveness and chemical-resistance.

It is preferable that melting | fusing point (Tm) of acid-modified polyolefin (A) is 50 degreeC-120 degreeC. More preferably, it is the range of 60 to 100 degreeC, Most preferably, it is the range of 70 to 90 degreeC. If it is less than the said value, the cohesion force derived from a crystal | crystallization may become weak, and adhesiveness and chemical-resistance may be inferior. On the other hand, when the said value is exceeded, solution stability and fluidity | liquidity may be low, and a problem may arise in operability at the time of adhesion | attachment.

The heat of fusion (ΔH) of the acid-modified polyolefin (A) is preferably in the range of 1 J / g to 60 J / g. More preferably, it is the range of 3 J / g-50 J / g, Most preferably, it is the range of 5 J / g-40 J / g. If it is less than the said value, the cohesion force derived from a crystal | crystallization may become weak, and adhesiveness and chemical-resistance may be inferior. On the other hand, when the said value is exceeded, solution stability and fluidity | liquidity may be low, and a problem may arise in operability at the time of adhesion | attachment.

It does not specifically limit as a manufacturing method of an acid-modified polyolefin (A), For example, radical grafting reaction (that is, generating radical species with respect to a polymer used as a main chain, and graft unsaturated carboxylic acid and an acid anhydride using the radical species as a polymerization start point) Reaction to polymerize).

Although it does not specifically limit as a radical generator, It is preferable to use an organic peroxide. Although it does not specifically limit as an organic peroxide, Di-tert- butyl peroxy phthalate, tert- butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert- butyl peroxy benzoate, tert- butyl peroxy-2-ethyl Peroxides such as hexanoate, tert-butylperoxy pivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide and lauroyl peroxide; Azonitriles, such as azobisisobutyronitrile and azobisisopropionitrile, etc. are mentioned.

<Multifunctional Polyisocyanate Curing Agent (B)>

The polyfunctional polyisocyanate curing agent (B) used in the present invention is not particularly limited as long as it is a polyisocyanate having two or more isocyanate groups in one molecule, and known diisocyanates and compounds derived from them can be preferably used.

For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, bis (4- And diisocyanates such as isocyanate cyclohexyl) methane or hydrogenated diphenylmethane diisocyanate. In addition, compounds derived from the above diisocyanate, i.e., isocyanurate, adduct, biuret, uretdione, allophanate, and prepolymers having isocyanate residues of the diisocyanate (obtained from diisocyanates and polyols) Oligomers), or composites thereof. These may be used independently and may be used in combination of 2 or more type arbitrarily.

Moreover, you may use the compound which made one isocyanate group of the said isocyanate compound react with the compound which has the reactivity with an isocyanate group as a polyfunctional isocyanate hardening | curing agent. As a compound which has reactivity with an isocyanate group, Compound containing amino groups, such as butylamine, hexylamine, octylamine, 2-ethylhexylamine, dibutylamine, ethylenediamine, benzylamine, and aniline; Compounds containing hydroxyl groups such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, octanol, 2-ethylhexyl alcohol, dodecyl alcohol, ethylene glycol, propylene glycol, benzyl alcohol and phenol; Allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexane dimethanol diglycidyl Compounds having an epoxy group such as ether; And compounds containing carboxylic acids such as acetic acid, butanoic acid, hexanoic acid, octanoic acid, succinic acid, adipic acid, sebacic acid, and phthalic acid.

As a polyfunctional polyisocyanate hardener (B) used by this invention, it is preferable to have the isocyanurate body of the said diisocyanate especially because it is excellent in electrolyte resistance.

As for the compounding quantity of the polyfunctional polyisocyanate hardener (B) used by this invention, the range of 0.5-40 mass parts is preferable with respect to 100 mass parts of acid-modified polyolefins (A), More preferably, it is 1-35 mass parts, More preferably, it is 2-30 mass parts, Especially preferably, it is the range of 3-25 mass parts. If it is less than the said value, sufficient hardening effect may not be obtained and adhesiveness and chemical-resistance may be low. When it exceeds the said range, port life property and adhesiveness may fall, and pinhole may arise at the time of shaping | molding by fall of a followable property. It is also not preferable in terms of cost.

<Organic Solvent (C)>

The organic solvent (C) used in the present invention is not particularly limited as long as the acid-modified polyolefin (A) and the polyfunctional polyisocyanate curing agent (B) are dissolved. Specifically, for example, aliphatic hydrocarbons such as benzene, toluene, xylene, aliphatic hydrocarbons such as hexane, heptane, octane, decane, cycloaliphatic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, ethylcyclorexane and trichloroethylene Halogenated hydrocarbons such as dichloroethylene, chlorobenzene and chloroform, alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol and phenol, acetone, methyl isobutyl ketone, methyl ethyl ketone, Ketone solvents such as pentanone, hexanon, cyclohexanone, isophorone, acetophenone, cellosolves such as methyl cellosolve, ethyl cellosolve, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate Ester solvents such as ethylene glycol mono-n-butyl ether, ethylene glycol mono-iso-butyl ether, ethylene glycol mono-tert-butyl ether, and di Glycol ether solvents such as ethylene glycol mono-n-butyl ether, diethylene glycol mono-iso-butyl ether, triethylene glycol mono-n-butyl ether and tetraethylene glycol mono-n-butyl ether; These 1 type, or 2 or more types can be used together.

It is preferable that the organic solvent (C) is 80-2000 mass parts with respect to 100 mass parts of acid-modified polyolefins (A). More preferably, it is 90-1600 mass parts, More preferably, it is 100-1200 mass parts, Especially preferably, it is the range of 110-800 mass parts. If it is less than the above range, the solution state and the port life property may decrease, and if it exceeds the said range, it may become disadvantageous in terms of productivity, manufacturing cost, and transportation cost of the packaging material for LiB containing a laminated body and a laminated body. .

The organic solvent (C) is at least one solvent (C1) selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, cycloaliphatic hydrocarbons and halogenated hydrocarbons in view of the solution state and port life of the adhesive composition, alcohol solvents, ketones, and the like. A mixed solution of at least one solvent (C2) selected from the group consisting of a solvent, an ester solvent and a glycol ether solvent is preferable. As a mixing ratio, it is preferable that it is a range of solvent (C1) / solvent (C2) = 50-97 / 50-3 (mass ratio), It is more preferable that it is 55-95 / 45-5 (mass ratio), 60-90 / It is more preferable that it is 40-10 (mass ratio), and it is especially preferable that it is 70-80 / 30-20 (mass ratio). When out of the said range, the solution state and port life property of an adhesive composition may fall. Moreover, it is especially preferable that solvent (C1) is an aromatic hydrocarbon or alicyclic hydrocarbon, and solvent (C2) is a ketone solvent.

<Adhesive composition>

The adhesive composition which concerns on this invention is a mixture of the said acid-modified polyolefin (A), a polyfunctional polyisocyanate hardener (B), and an organic solvent (C), An acid-modified polyolefin (A) and a hardening | curing agent (B) are organic solvents ( It may be dissolved in C) and may be dispersed. It is preferable to melt | dissolve from a viewpoint of port life property.

Adhesive composition according to the present invention, in the range that does not impair the performance of the present invention, in addition to the acid-modified polyolefin (A), polyfunctional polyisocyanate curing agent (B) and organic solvent (C), various tackifiers, thermoplastic elastomers, A plasticizer can be mix | blended and used. Although it does not specifically limit as a tackifier, Polyterpene-type resin, rosin-type resin, aliphatic petroleum resin, alicyclic petroleum resin, copolymer petroleum resin, hydrogenated petroleum resin, etc. are mentioned. As the thermoplastic elastomer, styrene-based elastomers such as styrene-ethylene-butylene-styrene copolymer resin and styrene-ethylene-propylene-styrene, ethylene-propylene copolymer resin, ethylene-butene copolymer resin, ethylene-vinyl acetate copolymer resin and ethylene Olefin-type elastomers, such as ethyl acrylate copolymer resin, etc. are mentioned. Moreover, as a plasticizer, Preferably, liquid rubber, such as polyisoprene and polybutene, process oil, etc. are mentioned. In addition, 1 type of these tackifiers, a thermoplastic elastomer, and a plasticizer may be used, and 2 or more types may be used together.

The adhesive composition which concerns on this invention can use together various hardening agents other than the said acid-modified polyolefin (A), a polyfunctional polyisocyanate hardening | curing agent (B), and an organic solvent (C) in the range which does not impair the performance of this invention. . Although it does not specifically limit as a hardening | curing agent, An epoxy resin, a carbodiimide compound, an oxazoline compound, coupling agents, etc. are mentioned. Examples of the epoxy resin include glycidyl ester types such as hexahydrophthalic acid glycidyl ester and dimer acid glycidyl ester, triglycidyl isocyanurate, 3,4-epoxycyclohexylmethyl carboxylate, and epoxidized polybutadiene. And alicyclic or aliphatic epoxides such as epoxidized soybean oil, glycidyl ether type epoxy resins, or glycidylamine type epoxy resins. Moreover, as a carbodiimide compound, dimethyl carbodiimide, diisopropyl carbodiimide, dicyclohexyl carbodiimide, t-butylisopropyl carbodiimide, diphenyl carbodiimide, di- (beta) -naphthyl carbodiimide Monocarbodiimide compounds, such as mead, or organic diisocyanate, such as aliphatic diisocyanate, aromatic diisocyanate, or alicyclic diisocyanate, is produced by performing decarbonation condensation reaction in the presence of a condensation catalyst in a solventless or inert solvent. Polycarbodiimide compounds which can be mentioned are mentioned. As the oxazoline compound, 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, or 2,4-diphenyl-2 Monooxazoline compounds such as oxazoline, 2,2 '-(1,3-phenylene) -bis (2-oxazoline), 2,2'-(1,2-ethylene) -bis (2-oxa Diols such as sleepy), 2,2 '-(1,4-butylene) -bis (2-oxazoline), or 2,2'-(1,4-phenylene) -bis (2-oxazoline) An oxazoline compound etc. are mentioned. Moreover, a silane coupling agent, a titanate coupling agent, etc. are mentioned as a coupling agent.

The adhesive composition which concerns on this invention can mix | blend and use a hardening accelerator other than the said acid-modified polyolefin (A), a polyfunctional polyisocyanate hardener (B), and the organic solvent (C) in the range which does not impair the performance of this invention. have. Although it does not specifically limit as a hardening accelerator, A carboxylic acid metal salt, tertiary amines, a quaternary ammonium salt, an organic peroxide, a hydrazine compound, a metal chelate compound, a phosphorus compound, basic vulcanizing agents, etc. are mentioned. As said carboxylic acid metal salt, the metal salt of C1-C30 carboxylic acid is mentioned. Examples of the carboxylic acid constituting the carboxylic acid metal salt include acetic acid, butyric acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, octenic acid, erucic acid and elide. Aliphatic carboxylic acids such as acid, adipic acid, malonic acid, succinic acid, glutaric acid, citric acid, tartaric acid, malic acid, and diglycolic acid; Aromatic carboxylic acids such as benzoic acid, chlorobenzoic acid, aniseic acid, amino benzoic acid, phthalic acid, terephthalic acid, naphthoic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid; Naphthenic acid; Acetic acid etc. are mentioned. Moreover, as metal which comprises the said carboxylic acid metal salt, Li, Na, K, Mg, Ca, Zn, Al, Cu, Pb, Co, Fe, Mn, Sn, Ti etc. are mentioned, for example. Specifically as said carboxylic acid metal salt, lithium acetate, sodium acetate, magnesium acetate, aluminum acetate, potassium butyrate, calcium butyrate, zinc butyrate, sodium octanoate, calcium octanate, potassium decanoate, magnesium decanoate, zinc decanoate, la Lithium urate, sodium laurate, calcium laurate, aluminum laurate, potassium myristic acid, sodium myristic acid, aluminum myristic acid, sodium palmitate, zinc palmitate, magnesium palmitate, stearic acid Sodium acid, potassium stearate, calcium stearate, zinc stearate, sodium oleate, sodium behenate, sodium benzoate, zinc benzoate, sodium phthalate, aluminum phthalate, magnesium terephthalate, calcium naphthalene dicarboxylate, lauric dilaurate Acid tributyl tin, dioctyl laurate, tributyl tin acetate, dibutyl tin diacetate, di Tyltin diacetate, dibutyltin 2-ethylhexate, tetrabutyl titanate, tetraisobutyl titanate, tetra2-ethylhexyl titanate, cobalt naphthenate, copper naphthenate, magnesium naphthenate, cobalt acetoacetate Can be mentioned. Among these, Preferably, lithium laurate, sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, palmitic acid Zinc, magnesium palmitate, sodium stearate, potassium stearate, calcium stearate, zinc stearate, and sodium oleate. Moreover, as a metal salt of carboxylic acid, the polymer which has a metal salt structure of carboxylic acid can also be used. As such a polymer, what has a structure which copolymerized the salt of the metals (for example, Li, Na, K, Mg, Ca, Zn, Al etc.) of group IA, group IIA, group IIB, group IIIB of ethylene and radically polymerizable carboxylic acid; The thing which has the structure which multi-copolymerized the metal salt of ethylene and radically polymerizable carboxylic acid, another radically polymerizable carboxylic acid, and / or its derivative (s) is mentioned. Examples of the tertiary amines include dimethylaniline, triethanolamine, dimethyl-p-toluidine and the like. Moreover, 1-acetyl-2-phenylhydrazine etc. are mentioned as said hydrazine compound, for example. Moreover, vanadium acetylacetonate etc. are mentioned as said metal chelate compound, for example. Moreover, as said phosphorus compound, dimethyl phosphine, a triphenyl phosphine, etc. are mentioned, for example. Examples of the basic vulcanizing agents include hexamethylenetetraamine, n-butylaldehyde-aniline condensate, and the like.

In the present invention, such an adhesive composition can be used in combination with various additives in addition to the acid-modified polyolefin (A), polyfunctional polyisocyanate curing agent (B), and organic solvent (C) within a range that does not impair the performance of the present invention. Although it does not specifically limit as an additive, It is preferable to use a flame retardant, a pigment, an antiblocking agent, etc.

<Laminated body>

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.

As a method of laminating, a conventionally well-known lamination manufacturing technique can be used. For example, although it does not specifically limit, an adhesive composition is apply | coated to the surface of a metal base material using appropriate application | coating means, such as a roll coater and a bar coater, and is dried. After drying, while the layer (adhesive layer) of the adhesive composition formed on the surface of the metal substrate is in a molten state, the polyolefin resin substrate is laminated on the coated surface (lamination bonding) to obtain a laminate.

Although the thickness of the adhesive bond layer formed with the said adhesive composition is not specifically limited, It is preferable to set it as 0.5-10 micrometers, It is more preferable to set it as 0.8-9.5 micrometers, It is further more preferable to set it as 1-9 micrometers.

<Polyolefin resin base material>

What is necessary is just to select suitably from conventionally well-known polyolefin resin as a polyolefin resin base material. For example, although it does not specifically limit, polyethylene, a polypropylene, an ethylene propylene copolymer, etc. can be used. Especially, use of the non-stretched film of polypropylene (henceforth CPP) is preferable. Although the thickness is not specifically limited, It is preferable that it is 20-100 micrometers, It is more preferable that it is 25-95 micrometers, It is further more preferable that it is 30-90 micrometers. Moreover, a pigment and various additives may be mix | blended with the polyolefin resin base material as needed, and surface treatment may be given.

<Metal base material>

Although it does not specifically limit as a metal base material, For example, various metals, such as aluminum, copper, steel, chromium, zinc, duralumin, diecast, and its alloy can be used. Moreover, as the shape, arbitrary shapes, such as a metal foil, a rolled steel plate, a panel, a pipe, a can, a cap, can be taken. Generally, aluminum foil is preferable from a viewpoint of workability. Moreover, although it changes also according to a use purpose, it is generally used in the form of the sheet of thickness of 0.01-10 mm, Preferably it is 0.02-5 mm.

In addition, the surface of these metal base materials may be surface-treated beforehand, and may be left untreated. In either case, the equivalent effect can be obtained.

Hereinafter, an Example is given and this invention is demonstrated in detail. However, this invention is not limited to an Example. In the examples and the comparative examples, simply described as "parts" means parts by mass.

<Production example of acid-modified polyolefin (A)>

Production Example  One

In a 1 L autoclave, 100 parts by mass of propylene-ethylene copolymer (storage modulus of 320 MPa at 25 ° C., 760% of tensile fracture elongation at 25 ° C.), 233 parts by mass of toluene, 1 part by mass of maleic anhydride, di 0.5 mass part of -tert- butyl peroxides were added, and it heated up to 140 degreeC, and stirred further for 1 hour (herein, "reacted" for 1 hour). Then, after cooling the obtained reaction liquid to 100 degreeC, it poured into stirring the container which contained 717 mass parts of toluene and 950 mass parts of methyl ethyl ketone heated previously to 40 degreeC, cooled to 40 degreeC, stirred for 30 more minutes, and further added The resin was precipitated by cooling to 25 ° C. (here, the operation of pouring the reaction solution into a solvent such as methyl ethyl ketone while stirring and cooling to precipitate the resin by cooling is referred to as “reprecipitation”). Thereafter, the slurry liquid containing the resin was centrifuged to separate an acid-modified propylene-ethylene copolymer obtained by graft polymerization of maleic anhydride, (poly) maleic anhydride, and a low molecular weight product.

In addition, the acid-modified propylene-ethylene copolymer taken out by centrifugation was thrown into the container containing 2000 mass parts of methyl ethyl ketone which was previously warmed at 25 degreeC, stirring, and stirring was continued for 1 hour. Thereafter, the slurry liquid was centrifuged to separate an acid-modified propylene-ethylene copolymer, (poly) maleic anhydride, and a low molecular weight product. The above operation was repeated twice to purify (here, an acid-modified propylene-ethylene copolymer taken out by centrifugation was added to methyl ethyl ketone with stirring, followed by centrifugation again to reinforce the purification. Is called).

After purification, the mixture was dried at 70 ° C. under reduced pressure for 5 hours to give an acid-modified polyolefin maleic anhydride-modified propylene-ethylene copolymer (PO-1, acid value 2 mgKOH / g-resin, acetone extraction component ratio 0.1 mass%, 25 ° C). The storage modulus at 300 MPa, 600% of tensile elongation at break at 25 ° C, weight average molecular weight 190,000, Tm 88 ° C, and ΔH 37 J / g) were obtained.

Production Example  2

The acid-modified polyolefin was obtained in the same manner as in Production Example 1 except that the amount of maleic anhydride was changed to 3 parts by mass, the number of times of the slurry was changed, and the amount of methyl ethyl ketone to be introduced at the time of the slurry was changed to 1000 parts by mass. Maleic anhydride modified propylene-ethylene copolymer (PO-2, acid value 5 mgKOH / g-resin, acetone extraction component ratio 1.8 mass%, storage elastic modulus at 25 degreeC 280 Mpa, tensile elongation at break at 650 degreeC 650 %, Weight average molecular weight 180,000, Tm 88 degreeC, (DELTA) H 36 J / g) were obtained.

Production Example  3

150 parts by mass of toluene, 40 parts by mass of maleic anhydride, 8 parts by mass of di-tert-butyl peroxide, 3 hours of reaction time, 700 parts by mass of methyl ethyl ketone, A maleic anhydride modified propylene-ethylene copolymer (PO-3, acid value of 48 mgKOH / g-resin, acetone extraction component ratio 0.1) was prepared in the same manner as in Production Example 1 except that the number of Riesler was changed to five times. Mass%, storage elastic modulus in 25 degreeC, 180 Mpa, tensile breaking elongation 350% in 25 degreeC, weight average molecular weight 31,000, Tm 85 degreeC, (DELTA) H31J / g) were obtained.

Production Example  4

150 parts by mass of toluene, 40 parts by mass of maleic anhydride, 8 parts by mass of di-tert-butyl peroxide, 3 hours of reaction time, 700 parts by mass of methyl ethyl ketone, Maleic anhydride-modified propylene-ethylene copolymer (PO-4, acid value), which is an acid-modified polyolefin, in the same manner as in Production Example 1, except that 1000 parts by mass of methyl ethyl ketone and the number of times of the lithries were changed to three times. 48 mgKOH / g-resin, acetone extraction component ratio 1.8 mass%, storage modulus 150 MPa at 25 degreeC, tensile elongation at break in 300 degreeC 300%, weight average molecular weight 27,000, Tm 85 degreeC, (triangle | delta) H 30 J / g).

Production Example  5

150 parts by mass of toluene, 20 parts by mass of maleic anhydride, 6 parts by mass of di-tert-butyl peroxide, 3 hours of reaction time, 700 parts by mass of methyl ethyl ketone, Maleic anhydride-modified propylene-ethylene copolymer (PO-5, acid value), which is an acid-modified polyolefin, by making the solvent used in the slurry to be used in the same manner as in Production Example 1, except that 1000 parts by mass of methyl ethyl ketone and the number of times of the slurry were changed. 25 mgKOH / g-resin, acetone extraction component ratio 0.9 mass%, storage modulus 400 MPa at 25 ° C, tensile elongation at break at 500C 500%, weight average molecular weight 60,000, Tm 87 ° C, ΔH 35 J / g).

Production Example  6

100 parts by mass of the propylene-ethylene copolymer (storage modulus of 52 MPa at 25 ° C., 1050% of tensile elongation at 25 ° C.), 150 parts by mass of toluene, 30 parts by mass of injection of maleic anhydride, 6 parts by mass of the di-tert-butyl peroxide, reaction time of 3 hours, 700 parts by mass of methyl ethyl ketone for the reprecipitation, 1000 parts by mass of methyl ethyl ketone for the resludge, A maleic anhydride modified propylene-ethylene copolymer (PO-6, acid value 25 mgKOH / g-resin, acetone extraction component ratio 1.0 mass%, 25 degreeC) which is an acid-modified polyolefin except having changed by the circuit The tensile modulus of elongation at break in the storage modulus of 12 MPa and 25 ° C. at 900 ° C., weight average molecular weight 60,000, Tm 58 ° C., and ΔH 7 J / g) were obtained.

Production Example  7

100 parts by mass of a propylene homopolymer (storage modulus of 2100 MPa at 25 ° C., 900% of tensile fracture elongation at 25 ° C.), 150 parts by mass of toluene, and 30 parts by mass of di-maleic anhydride 6 parts by mass of the tert-butyl peroxide, 3 hours of reaction time, 700 parts by mass of methyl ethyl ketone for the solvent used for reprecipitation, 1000 parts by mass of methyl ethyl ketone for the slurry used, and 2 times the number of lithries In the same manner as in Production Example 1 except for the above, maleic anhydride-modified propylene homopolymer (PO-7, acid value 25 mgKOH / g-resin, acetone extraction component ratio 0.9 mass%, storage at 25 ° C) was obtained. 60% of tensile elongation at break in elasticity modulus 1800 Mpa, 25 degreeC, the weight average molecular weight 60,000, Tm 85 degreeC, (DELTA) H5J / g) were obtained.

Production Example  8

100 parts by mass of the propylene-ethylene copolymer (storage modulus of 2720 MPa at 25 ° C., 400% of tensile elongation at 25 ° C.), 186 parts by mass of toluene, 20 parts by mass of injectable maleic anhydride, 6 parts by mass of the di-tert-butyl peroxide, reaction time of 3 hours, 700 parts by mass of methyl ethyl ketone for the reprecipitation, 1000 parts by mass of methyl ethyl ketone for the resludge, A maleic anhydride modified propylene-ethylene copolymer (PO-8, acid value 25 mgKOH / g-resin, acetone extraction component ratio 1.0 mass%, 25 degreeC) which is an acid-modified polyolefin except having changed in circuit. The storage elastic modulus in 2350 Mpa, 38% of tensile elongation at break in 25 degreeC, the weight average molecular weight 60,000, Tm 125 degreeC, (DELTA) H63J / g) were obtained.

Production Example  9

186 parts by mass of toluene, 20 parts by mass of maleic anhydride, 6 parts by mass of di-tert-butyl peroxide, 3 hours of reaction time, 1200 parts by mass of methyl ethyl ketone, Maleic anhydride-modified propylene-ethylene copolymer (PO-9, acid value), which is an acid-modified polyolefin, in the same manner as in Production Example 1, except that 1200 parts by mass of methyl ethyl ketone and the number of times of lithries were changed to two solvents. 25 mgKOH / g-resin, acetone extraction component ratio 1.2 mass%, storage modulus at 25 ° C 7 MPa, tensile elongation at break at 1200C, 1200%, weight average molecular weight 60,000, no Tm peak, ΔH 0 J / g).

Production Example  10

100 parts by mass of the propylene-ethylene copolymer (storage modulus of 500 MPa at 25 ° C, 680% of tensile fracture elongation at 25 ° C), 150 parts by mass of toluene injection, 0.5 parts by mass of injection of maleic anhydride, 0.2 parts by mass of di-tert-butyl peroxide, reaction time of 1 hour, 1000 parts by mass of methyl ethyl ketone for solvents used for re-precipitation, 1000 parts by mass of methyl ethyl ketone for solvents, and 2 times of reslurry A maleic anhydride modified propylene-ethylene copolymer (PO-10, an acid value of 1 mgKOH / g-resin, acetone extraction component ratio of 0.1 mass%, 25 ° C) was prepared in the same manner as in Production Example 1 except that the circuit was changed. The storage modulus at 400 MPa, 600% of tensile fracture elongation at 25 ° C, weight average molecular weight 65,000, Tm 71 ° C, and ΔH 35 J / g) were obtained.

Production Example  11

150 parts by mass of toluene, 50 parts by mass of maleic anhydride, 10 parts by mass of di-tert-butyl peroxide, 3 hours of reaction time, 700 parts by mass of methyl ethyl ketone, Maleic anhydride-modified propylene-ethylene copolymer (PO-11, acid value), which was an acid-modified polyolefin, was made in the same manner as in Production Example 1 except that the solvent used for the slurry was changed to 1000 parts by mass of methyl ethyl ketone and the number of times of the slurry was changed to three times. 55 mgKOH / g-resin, 1.0% by weight of acetone extraction component, 150 MPa of storage modulus at 25 ° C, elongation at break at 320 ° C 320%, weight average molecular weight 30,000, Tm 83 ° C, ΔH 25 J / g).

Production Example  12

Production Example except 150 parts by mass of toluene, 40 parts by mass of maleic anhydride, 8 parts by mass of di-tert-butyl peroxide, 3 hours of reaction time, and 3 times of reslurry. Maleic anhydride modified propylene-ethylene copolymer (PO-12, acid value 46 mgKOH / g-resin, acetone extraction component ratio 4.5 mass%, storage elastic modulus in 25 degreeC) 110 MPa which is an acid-modified polyolefin by carrying out similarly to 1 , Elongation at break at 90 ° C, elongation at break of 90%, weight average molecular weight of 35,000, Tm of 86 ° C, and ΔH 30 J / g) were obtained.

(Production of the topic 1)

In a 500 ml four-necked flask equipped with a water-cooled reflux condenser and a stirrer, 100 parts by mass of maleic anhydride-modified propylene-ethylene copolymer (PO-1) obtained in Production Example 1, 280 parts by mass of methylcyclohexane, and methyl ethyl ketone 120 mass parts of components were put, the temperature was raised to 80 degreeC, stirring, and after stirring continued for 1 hour, the main | base 1 was obtained by cooling. The solution state is shown in Table 1.

(Production of topics 2 to 19)

The acid-modified polyolefin and the organic solvent were changed as shown in Table 1, and subjects 2 to 19 were produced in the same manner as in subject 1. The compounding quantity and the solution state are shown in Table 1.

Example  One

500 mass parts of main materials 1 and 1 mass part of smitules (registered trademark) N-3300 were mix | blended as a polyfunctional polyisocyanate hardener (B), and the adhesive composition was obtained. Table 2 shows the evaluation results of the port life, adhesion, chemical resistance and moldability.

Example  2 to 21, Comparative example  1 to 3

Subjects 1-19 and each hardening | curing agent were changed as shown in Tables 2 and 3, and Examples 2-21 and Comparative Examples 1-3 were performed by the method similar to Example 1. Table 2 and 3 show the results of the blended amount, port life, adhesiveness, chemical resistance and moldability.

The hardening | curing agent used in Table 2, 3 is the following.

<Multifunctional Polyisocyanate Curing Agent (B)>

Isocyanurate body of hexamethylene diisocyanate: smitule (registered trademark) N-3300 (manufactured by Bayer Corporation)

Burette body of hexamethylene diisocyanate: Duranate (registered trademark) 24A-100 (manufactured by Asahi Kasei Chemical Co., Ltd.)

Each acid-modified polyolefin, the main ingredient, and the adhesive composition obtained as described above were subjected to analytical measurement and evaluation based on the following method.

Acid  Measure

Acid value (mgKOH / g-resin) in this invention refers to the amount of KOH required in order to neutralize 1 g of acid-modified polyolefin (A), and it measured according to the test method of JISK0070 (1992). . Specifically, after dissolving 1 g of an acid-modified polyolefin in 100 g of xylene temperature-controlled at 100 ° C., a phenolphthalein is used as an indicator at a same temperature, and a 0.1 mol / L potassium hydroxide ethanol solution [brand name “0.1 mol / L ethanol Titrated potassium hydroxide solution, manufactured by Wako Pure Chemical Industries, Ltd.]. At this time, the acid value (mgKOH / g) was calculated by converting the amount of potassium hydroxide required for titration into mg.

Measurement of Acetone Extraction Component Ratio

The acetone extraction component ratio in this invention was measured by refluxing with acetone for 2 hours using the soxhlet extractor. Specifically, 50 g of the acid-modified polyolefin (A) was weighed into a cylindrical filter paper, placed in a soxhlet extraction tube, and then assembled and assembled with a flat bottom flask containing 1100 mL of acetone and a cooling tube, and refluxed in a water bath for 2 hours. Acetone extraction. Thereafter, the cylindrical filter paper was taken out, the acetone extract in the flat bottom flask was filtered off, and the weight of the residue after further drying under reduced pressure at 100 ° C for 1 hour was weighed and calculated according to the following formula.

Acetone extraction component ratio (mass%) = (extraction residue weight / sample collection amount) * 100

At 25 ° C  Measurement of storage modulus (E ')

The storage elastic modulus (E ') in this invention was measured based on the test method of JISK7244-4 (1999). Specifically, it is the value measured, heating up at the speed of -50 degreeC from 5 degree-C / min at the frequency of 10 Hz using the Haiti Keisoku Seikagyo make, dynamic viscoelasticity measuring apparatus DVA-200.

At 25 ° C  Tensile breaking elongation ( Eb ) Measurement

Tensile breaking elongation (Eb) in this invention was measured based on the test method of JISK7161 (2014). Specifically, it is the value which measured elongation (%) at the time of fracture | rupture in the tension in 50 mm / min in 25 degreeC environment using Tensilon RTM-100 by Orient Tech Corporation.

Measurement of the weight average molecular weight (Mw)

The weight average molecular weight in this invention is the gel permeation chromatograph Alliance e2695 by Nihon Waters Co., Ltd. [hereafter, GPC, a standard substance: polystyrene resin, a mobile phase: tetrahydrofuran, a column: Shodex KF-806 + KF-803, a column temperature] : 40 ° C., flow rate: 1.0 ml / min, detector: photodiode array detector (wavelength 254 nm = ultraviolet ray)].

Melting point, measurement of melting calories

Melting | fusing point and melting calories in this invention are melt | dissolved by temperature rising and cooling resin at a speed | rate of 20 degree-C / min using a differential scanning calorimeter (hereinafter, DSC, T-A Instruments Japan, Q-2000), It is the value measured from the top temperature and area of the melting peak at the time of temperature rising and melting.

Evaluation of the Subject Solution Condition

About the solution state of the subject 1-19, it evaluated by measuring the solution viscosity of 25 degreeC using the Brookfield-type viscometer TVB-10M (henceforth a type-B viscometer) by Toki Sangyo.

<Evaluation Criteria>

◎ (excellent in practical use): less than 500mPas

○ (available): 500 mPa · s or more and less than 1000 mPa · s

× (not practical): Viscosity cannot be measured by 1000 mPa · s or more or by gelation

Port-life  evaluation

A port life property mix | blends a crosslinking agent or a hardening | curing agent with an acid-modified polyolefin, and refers to the stability of the solution immediately after the mixing | blending or after a fixed time after mixing | blending. If the port life property is good, the viscosity of the solution is low, and it can be stored for a long time. If the port life property is poor, the viscosity of the solution is increased (thickened), and in severe cases, gelation phenomenon occurs. It becomes difficult to apply and indicates that long term storage is impossible.

After storing potlife property of the adhesive composition obtained in Examples 1-21 and Comparative Examples 1-3 for 24 hours in 25 degreeC and 40 degreeC atmosphere, it evaluates by measuring the solution viscosity in 25 degreeC using a Brookfield viscometer. It was. The evaluation results are shown in Tables 2 and 3.

<Evaluation Criteria>

◎ (excellent in practical use): less than 500mPas

○ (available): 500 mPa · s or more and less than 1000 mPa · s

× (not practical): Viscosity cannot be measured by 1000 mPa · s or more or by gelation

Of metal substrate and polyolefin resin substrate Laminate  making

Aluminum foil (8079-0, 40 micrometers in thickness) was used for a metal base material, and an unstretched polypropylene film [Pylen (Toyobo Co., Ltd.) film CT, 40 micrometers in thickness is used for the polyolefin resin base material ] (Hereinafter also referred to as CPP).

The adhesive composition obtained in Examples 1-19 and Comparative Examples 1-15 was apply | coated adjusting to the metal base material so that the film thickness of the adhesive bond layer after drying might be set to 3 micrometers using the bar coater. The coated surface was dried for 1 minute in 100 degreeC atmosphere using the warm air dryer, and the metal base material which laminated | stacked the adhesive bond layer of 3 micrometers in thickness was obtained. The polyolefin resin base material was polymerized on the surface of the adhesive layer, and bonded at 0.3 MPa and 1 m / min at a lamination temperature of 80 ° C or 120 ° C using a small tabletop test laminator (SA-1010-S) manufactured by Tester Sangyo Co., Ltd. Then, the laminate was obtained by curing at 25 ° C. and 50% RH for 36 hours.

The laminated body obtained as mentioned above was evaluated by the following method.

Evaluation of adhesion

The laminated body was cut into the size of 100 mm x 15 mm, and the adhesiveness was evaluated by the T-type peeling test according to the following criteria. The evaluation results are shown in Tables 2-3.

<T type peeling test>

Based on the test method of ASTM-D1876-61, peeling strength in the tension rate of 50 mm / min was measured in 25 degreeC environment using Tensil RTM-100 by Orient Tech Corporation. Peeling strength (N / cm) between a metal base material / polyolefin resin base material was made into the average value of five test values.

<Evaluation Criteria>

☆ (particularly excellent in practical use): 8.0 N / cm or more or CPP repulses (hereinafter also referred to simply as "repulse"). Reparing means that peeling does not generate | occur | produce in the interface of a metal base material / CPP, and a metal base material or CPP is destroyed.

(Excellent in practical use): 7.5 N / cm or more and less than 8.0 N / cm

○ (available): 7.0 N / cm or more and less than 7.5 N / cm

× (not practical): less than 7.0 N / cm

Evaluation of chemical resistance

In order to examine the usability as a packaging material of LiB, the chemical resistance (henceforth electrolyte resistance) was evaluated by the electrolyte solution test. The laminate was cut into a size of 100 mm x 15 mm, and added to lithium hexafluorophosphate in an electrolyte solution [ethylene carbonate / diethyl carbonate / dimethyl carbonate = 1/1/1 (volume ratio)] at 85 ° C. Immerse for days. Then, the laminated body was taken out, the water was wiped off with ion-exchange water washing | cleaning and a paper wiper, water was fully dried, and the chemical-resistance was evaluated by the T-type peeling test according to the following criteria. The evaluation results are shown in Tables 2-3.

<Evaluation Criteria>

☆ (especially for practical use): 8.0 N / cm or more or ash

(Excellent in practical use): 7.5 N / cm or more and less than 8.0 N / cm

○ (available): 7.0 N / cm or more and less than 7.5 N / cm

× (not practical): less than 7.0 N / cm

Evaluation of formability

Similarly, in order to examine the usability as a packaging material of LiB, the moldability was evaluated by the deep bridge tester.

The laminate was cut into an 80 × 120 mm size, and cold forming was performed. Specifically, a long-acting molding machine (article number: TP-25C-X2) manufactured by AMADA Co., Ltd., a forming mold (female) having a diameter of 55 mm x 35 mm, and a molding die (male) corresponding thereto were used. Then, the molding depth was changed in 0.5 mm units from 0.5 mm molding depth at 0.4 MPa in a 25 ° C atmosphere, and cold forming was performed on each of 10 samples (laminate). About the sample after cold forming, the deepest molding depth which pinholes and a crack does not generate | occur | produce in all 10 samples in a wrinkle and an aluminum foil was made into the limit molding depth of the sample. From this limit molding depth, the moldability of the battery packaging material was evaluated according to the following criteria. The evaluation results are shown in Tables 3 to 4.

<Judge criteria>

☆ (especially for practical use): 6.0 mm or more of the limit molding depth

(Excellent in practical use): limit molding depth 4.0 mm or more and less than 6.0 mm

○ (practical possibility): 2.0 mm or more of limit molding depth is less than 4.0 mm

×: limit molding depth less than 2.0 mm

The adhesive composition according to the present invention contains an acid-modified polyolefin, a polyfunctional polyisocyanate curing agent, and an organic solvent, and maintains good port life without causing thickening or gelation even after long-term storage, and also provides a metal base and a polyolefin resin. Good adhesion of the substrate, electrolyte resistance, and moldability can be achieved. Therefore, the laminated body of the polyolefin resin base material and the metal base material formed from the adhesive composition of this invention is used not only in the field of home appliances, furniture materials, building interior members, etc. but also lithium used for personal computers, mobile phones, a video camera, etc. It can be used widely as a battery packaging material (pouch form).

Claims (6)

An adhesive composition containing an acid-modified polyolefin (A), a polyfunctional polyisocyanate curing agent (B), and an organic solvent (C), wherein the acid value of the acid-modified polyolefin (A) is 2 to 50 mgKOH / g-resin, acetone extraction component. Adhesive composition whose ratio is 0.01-2 mass%. The adhesive composition of Claim 1 which contains 0.5-40 mass parts of polyfunctional polyisocyanate hardening | curing agents (B), and 80-2000 mass parts of organic solvents (C) with respect to 100 mass parts of said acid-modified polyolefins (A). The group according to claim 1 or 2, wherein the organic solvent (C) is a mixture of a solvent (C1) and a solvent (C2), wherein the solvent (C1) is composed of an aromatic hydrocarbon, an aliphatic hydrocarbon, an alicyclic hydrocarbon, and a halogenated hydrocarbon. At least one solvent selected from the group consisting of alcohol solvents, ketone solvents, ester solvents and glycol ether solvents, at least one solvent (C1) / solvent (C2) = Adhesive composition which is 50-97 / 50-3 (mass ratio). The adhesive composition in any one of Claims 1-3 used for adhesion | attachment of a polyolefin resin base material and a metal base material. The laminated body of the polyolefin resin base material and the metal base material adhere | attached by the adhesive composition in any one of Claims 1-4. The packaging material for lithium ion batteries which uses the laminated body of Claim 6 as a structural member.