KR20190038844A - Polyolefin-based adhesive composition - Google Patents

Abstract

An object of the present invention is to provide an adhesive composition containing a modified polyolefin and an epoxy resin, which has good portability and is excellent in adhesiveness between a metal substrate and a polyolefin resin substrate.
(A), a glycidylamine type epoxy resin (B1), a glycidyl ether type epoxy resin (B2) and an organic solvent (E) each having an acid value of 5 to 50 mgKOH / , And further contains either an acid anhydride monomer (C) or a heterocyclic compound (D) having two or more nitrogen atoms.

Description

Polyolefin-based adhesive composition

The present invention relates to an adhesive composition for bonding a polyolefin resin base material and a metal base material. More specifically, it relates to an adhesive composition containing a crystalline acid-modified polyolefin, an epoxy resin and an organic solvent, and further containing either an acid anhydride monomer or a heterocyclic compound having two or more nitrogen atoms.

BACKGROUND ART [0002] In recent years, a laminate obtained by applying a vinyl chloride resin (hereinafter, simply referred to as " vinyl chloride ") to a surface of a metal substrate such as an outer panel of a home electric appliance, a material for furniture, The problem has been solved up, and a polyolefin resin has been proposed as a substitute for vinyl chloride. The polyolefin resin has no toxicity and shows strong durability to acids, alkalis, and organic solvents, and has excellent mechanical strength and abrasion resistance, and is widely used in various fields because it is inexpensive.

However, since the polyolefin resin is non-polar, it has been difficult to bond with the metal base. Conventionally, various adhesives have been proposed for bonding the polyolefin resin and the metal substrate. Typically, a thermosetting resin such as a phenol resin, a melamine resin or an epoxy resin or a base adhesive obtained by dissolving a thermoplastic resin in an organic solvent is mixed with a solvent-dispersible modified polyolefin resin. However, it is difficult to say that these adhesives have sufficient adhesiveness. An adhesive composition (Patent Document 1) for blending a crystalline acid-modified polyolefin with an epoxy resin and catechol or the like or an adhesive composition for blending a maleic acid-modified chlorinated polypropylene with a chelate epoxy resin and a solvent has been proposed have.

Patent Document 1: Japanese Patent Application Laid-Open No. 2003-261847 Patent Document 2: JP-A-2009-292853

However, in the above method, the port life property after the acid-denatured polyolefin solution is poor, and the portability is not so serious, but the adhesion to the important metal substrate and the chemical resistance are insufficient. In other words, there was no satisfactory port lifetime, adhesiveness, and chemical resistance. Particularly, even when polypropylene (hereinafter also referred to as PP) base material is used, there is no adhesive capable of bonding and aging (curing) at a low temperature such as 80 DEG C or less, which is less affected by heat shrinkage or the like. The term "pot life" refers to the stability of the solution immediately after the compounding or after the lapse of a predetermined time by adding a crosslinking agent or a curing agent to the acid-modified polyolefin.

As a laminate of a polyolefin resin base material and a metal base material, a laminate obtained by bonding a polypropylene film and an aluminum foil to each other with an adhesive has been recently studied as an external body for a lithium ion battery. However, in an adhesive and a laminate, (Hereinafter also referred to as " electrolytic solution resistance ") is required.

The electrolytic solution of the lithium ion battery is obtained by dissolving a lithium salt such as LiPF ₆ and LiBF ₄ as an electrolyte in a nonaqueous solvent such as carbonic ester. The lithium salt used as an electrolyte hydrolyzes by moisture to generate hydrogen fluoride. For this reason, when hydrogen fluoride is generated, there arises a problem that the metallic member constituting the battery is corroded or the adhesiveness between the layers of the laminated film type packaging material used as the external body is lowered.

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems. As a result of intensive investigations, the inventors of the present invention have found that a crystalline acid-modified polyolefin (hereinafter simply referred to as an acid-modified polyolefin) And an organic solvent, and wherein the adhesive composition containing either an acid anhydride monomer or a heterocyclic compound having two or more nitrogen atoms has a pot life, a bondability at 80 DEG C or lower, an adhesion property at aging and a chemical resistance , In particular, the electrolytic solution obtained by mixing water into the electrolytic solution, thereby completing the present invention.

That is, the present invention relates to a polyolefin resin composition which is excellent in pot life after blending a crystalline acid-modified polyolefin, a curing agent and a curing accelerator, exhibits good adhesion to both the polyolefin resin base material and the metal base material at bonding and aging at low temperatures, It is an object of the present invention to provide an adhesive composition having chemical resistance.

Means for Solving the Problem In order to achieve the above object, the present inventors have made extensive studies and have proposed the following inventions.

(A), a glycidylamine type epoxy resin (B1), a glycidyl ether type epoxy resin (B2) and an organic solvent (E) each having an acid value of 5 to 50 mgKOH / , And further contains either an acid anhydride monomer (C) or a heterocyclic compound (D) having two or more nitrogen atoms.

The glycidylamine type epoxy resin (B1) is preferably an epoxy resin having at least two glycidyl groups per molecule.

The glycidylamine type epoxy resin (B1) is preferably a compound represented by the general formula (1).

(In the general formula (1), R represents an aryl group which may have a substituent, X1 and X2 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, m is 1 or 2, n is 1 Or 2).

The glycidyl ether type epoxy resin (B2) is preferably an epoxy resin having two or more glycidyl groups in one molecule and containing no nitrogen atom.

The acid anhydride monomer (C) is preferably a compound having at least one acid anhydride ring in one molecule and an acid value of 100 mgKOH / g or more.

It is preferable that the heterocyclic compound (D) having two or more nitrogen atoms is a 5-membered ring aromatic heterocyclic compound having two or more nitrogen atoms.

, 0.01 to 20 parts by mass of a glycidylamine-type epoxy resin (B1), 1 to 50 parts by mass of a glycidyl ether-type epoxy resin (B2), 100 to 200 parts by mass of an acid anhydride It is preferable that the composition contains from 1 to 50 parts by mass of the monomer (C), from 0.01 to 5 parts by mass of the heterocyclic compound (D) having two or more nitrogen atoms, and from 80 to 1000 parts by mass of the organic solvent (E).

Wherein the organic solvent (E) is a mixture of the solvent (E1) and the solvent (E2), the solvent (E1) is at least one solvent selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons, ) Is at least one solvent selected from the group consisting of an alcohol solvent, a ketone solvent, an ester solvent and a glycol ether solvent, and the solvent (E1) / solvent (E2) = 50 to 97/50 to 3 .

An adhesive composition according to any one of the above, which is used for bonding a polyolefin resin base material and a metal base material.

A laminate of a polyolefin resin substrate and a metal substrate adhered by an adhesive composition according to any one of the above. And the laminate as a constituent member.

The adhesive composition according to the present invention contains a crystalline acid-modified polyolefin, two kinds of epoxy resins and an organic solvent, and contains either an acid anhydride monomer or a heterocyclic compound having two or more nitrogen atoms, Good port lifetime can be maintained without causing thickening or gelation. Further, even when bonding and aging are carried out at a low temperature such as 80 DEG C or less, where the influence of heat shrinkage of the polyolefin substrate is small, good adhesion and chemical resistance of the polyolefin resin substrate and the metal substrate can be achieved.

Hereinafter, embodiments of the present invention will be described in detail.

≪ Crystalline acid-modified polyolefin (A) >

The crystalline acid-modified polyolefin (A) to be used in the present invention is not limited, but it is preferable that at least one of the?,? -Unsaturated carboxylic acid and its acid anhydride is added to at least one of the polyethylene, polypropylene and propylene- It is preferable to obtain by grafting the species.

The propylene-? -Olefin copolymer is obtained by copolymerizing? -Olefin with propylene as a main component. As the? -olefin, one or more kinds of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene and vinyl acetate can be used. Of these? -Olefins, ethylene and 1-butene are preferable. The ratio of the propylene component to the -olefin component in the propylene-? -Olefin copolymer is not limited, but is preferably 50 mol% or more, more preferably 70 mol% or more.

Examples of the at least one of the?,? - unsaturated carboxylic acid and its acid anhydride include maleic acid, itaconic acid, citraconic acid and their acid anhydrides. Of these, acid anhydrides are preferable, and maleic anhydride is more preferable. Specific examples thereof include a maleic anhydride-modified polypropylene, a maleic anhydride-modified propylene-ethylene copolymer, a maleic anhydride-modified propylene-butene copolymer, and a maleic anhydride-modified propylene-ethylene-butene copolymer. One or two or more kinds of the acid-modified polyolefins may be used in combination. Among them, a maleic anhydride-modified propylene-butene copolymer is preferable. The propylene component / 1-butene component (molar ratio) of the maleic anhydride-modified propylene-butene copolymer is preferably 90 to 50/10 to 50, more preferably 85 to 60/15 to 40, / 20 to 45, more preferably 75 to 60/25 to 40. By setting the amount in the above range, particularly excellent port life, adhesion and chemical resistance can be exhibited.

The lower limit of the acid value of the crystalline acid-modified polyolefin (A) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or less, from the viewpoint of pot life and adhesion between the polyolefin resin base and the metal base -Resin, more preferably not less than 14 mgKOH / g-resin, more preferably not less than 16 mgKOH / g-resin, particularly preferably not less than 18 mgKOH / g- Is not less than 20 mgKOH / g-resin. If the amount is less than the above-mentioned range, compatibility with the epoxy resin is low, the adhesive strength may not be exhibited, the crosslinking density may be low, and the chemical resistance may be insufficient. The upper limit should be not more than 50 mg KOH / g resin, preferably not more than 48 mg KOH / g resin, more preferably not more than 46 mg KOH / g resin, more preferably not more than 44 mg KOH / g resin -Resin, particularly preferably not more than 42 mgKOH / g-resin, and most preferably not more than 40 mgKOH / g-resin. Above the above value, the viscosity and stability of the solution are lowered, and the pot life may be deteriorated. In addition, the production efficiency is lowered, which is not preferable. The acid value can be controlled by the graft amount (addition amount) of at least one of the?,? - unsaturated carboxylic acid and the acid anhydride.

The weight average molecular weight (Mw) of the crystalline acid-modified polyolefin (A) is preferably in the range of 40,000 to 180,000. More preferably in the range of 50,000 to 160,000, more preferably in the range of 60,000 to 150,000, particularly preferably in the range of 70,000 to 140,000, and most preferably in the range of 80,000 to 130,000. If it is less than the above-mentioned value, the cohesive force is weakened and the adhesive property may be poor. On the other hand, when it exceeds the above-mentioned value, the fluidity is low and there is a problem in operability when bonding. Within the above range, a curing reaction with the epoxy resin is preferably exhibited.

The crystallinity of the crystalline acid-modified polyolefin (A) is measured by a differential scanning calorimeter (DSC) in which the temperature is raised from -100 DEG C to 250 DEG C at 20 DEG C / min, and a clear melting peak .

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

The melting point (Tm) of the crystalline acid-modified polyolefin (A) is preferably in the range of 50 占 폚 to 120 占 폚. More preferably in the range of 60 占 폚 to 100 占 폚, and most preferably in the range of 70 占 폚 to 90 占 폚. If the amount is less than the above-mentioned value, the cohesive force derived from the crystal is weakened, and the adhesion and chemical resistance may be poor. On the other hand, when the amount exceeds the above-mentioned range, the solution stability and fluidity are low, which may cause problems in operability when bonding.

The heat of fusion (? H) of the crystalline acid-modified polyolefin (A) is preferably in the range of 5 J / g to 60 J / g. More preferably in the range of 10 J / g to 50 J / g, and most preferably in the range of 20 J / g to 40 J / g. If the amount is less than the above-mentioned value, the cohesive force derived from the crystal is weakened, and the adhesion and chemical resistance may be poor. On the other hand, when the amount exceeds the above-mentioned range, the solution stability and fluidity are low, which may cause problems in operability when bonding.

The production method of the crystalline acid-modified polyolefin (A) is not particularly limited and, for example, a radical graft reaction (that is, a method in which radical species are generated for a polymer as a main chain and unsaturated carboxylic acids And reaction in which an acid anhydride is graft-polymerized).

The radical generator is not particularly limited, but it is preferable to use an organic peroxide. Examples of the organic peroxide include, but are not limited to, di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, Peroxides such as hexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, and lauroyl peroxide; And azonitriles such as azobisisobutylonitrile, azobisisopropionitrile, and the like.

≪ Glycidylamine type epoxy resin (B1) >

The glycidylamine type epoxy resin (B1) used in the present invention is not particularly limited as long as it is an epoxy resin having at least one glycidyl group in one molecule. It is preferable to have at least two glycidyl groups in one molecule of the epoxy resin, more preferably at least three glycidyl groups in one molecule of the epoxy resin, and more preferably at least four glycidyl groups in one molecule of the epoxy resin desirable.

Further, the glycidylamine-type epoxy resin (B1) is preferable because the chemical resistance is further improved by using a compound represented by the following general formula (1).

In the general formula (1), R is an aryl group which may have a substituent, and is preferably a phenyl group which may have a substituent. The substituent of the aryl group is not particularly limited and includes an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, an amino group, a glycidyl group, a glycidyl amino group, have. X1 and X2 each independently represent a straight chain alkylene group having 1 to 5 carbon atoms and may have a substituent, and the number of carbon atoms is preferably 4 or less, more preferably 3 or less, still more preferably 2 or less. The substituent of the alkylene group is not particularly limited, and examples thereof include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an amino group. m is 1 or 2, and n is 1 or 2. Preferably, either m or n is 2, more preferably both m and n are 2.

Specific examples of the glycidylamine type epoxy resin (B1) include, but are not limited to, tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, N, N , N ', N'-tetraglycidyl-m-xylenediamine, and the like. Among them, N, N, N ', N'-tetraglycidyl-m-xylenediamine is preferable. These glycidylamine type epoxy resins (B1) may be used alone or in combination of two or more.

The blending amount of the glycidylamine type epoxy resin (B1) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more based on 100 parts by mass of the crystalline acid-modified polyolefin (A) More preferably 1 part by mass or more, and most preferably 2 parts by mass or more. If the amount is less than the above range, the catalytic action is not exhibited, and adhesion and aging resistance at 80 DEG C or lower may be low. It is more preferably 20 parts by mass or less, more preferably 18 parts by mass or less, even more preferably 16 parts by mass or less, particularly preferably 14 parts by mass or less, most preferably 12 parts by mass or less. Above the above range, excessive crosslinking reaction proceeds to increase the rigidity and tend to lower the adhesiveness. Further, the crosslinking reaction tends to proceed during the preservation of the solution of the adhesive composition, and the pot life tends to decrease.

≪ Glycidyl ether type epoxy resin (B2) >

The glycidyl ether type epoxy resin (B2) used in the present invention is not particularly limited as long as it is an epoxy resin having a glycidyl ether group in the molecule. The epoxy resin is preferably an epoxy resin having at least two glycidyl groups in one molecule of the epoxy resin, and more preferably an epoxy resin having at least two glycidyl groups in one molecule of the epoxy resin and no nitrogen atom.

The blending amount of the glycidyl ether type epoxy resin (B2) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and more preferably 3 parts by mass or more based on 100 parts by mass of the crystalline acid-modified polyolefin (A) More preferably at least 4 parts by mass, and most preferably at least 5 parts by mass. It is more preferably 50 parts by mass or less, more preferably 40 parts by mass or less, further preferably 30 parts by mass or less, particularly preferably 25 parts by mass or less, most preferably 20 parts by mass or less. By setting the content in the above range, excellent adhesion and chemical resistance can be exhibited.

Specific examples of the glycidyl ether type epoxy resin (B2) include, but are not limited to, phenol novolac type epoxy resin and cresol novolak type epoxy resin. From the standpoint of adhesion with a metal base material and chemical resistance desirable. These glycidyl ether type epoxy resins (B2) may be used alone or in combination of two or more.

In the present invention, two types of epoxy resins, the glycidylamine type epoxy resin (B1) and the glycidyl ether type epoxy resin (B2), are used in combination as essential components. By using the glycidylamine type epoxy resin (B1) and the glycidyl ether type epoxy resin (B2) in combination, excellent adhesiveness and chemical resistance can be exhibited. That is, the glycidylamine type epoxy resin (B1) has a reaction and curing action between the crystalline acid-modified polyolefin (A) and the glycidyl ether type epoxy resin (B2). Further, the glycidylamine type epoxy resin (B1) can be obtained by reacting the crystalline acid-modified polyolefin (A) with the glycidylamine type epoxy resin (B1), the glycidylamine type epoxy resin (B1) (B1) and the glycidyl ether type epoxy resin (B2) among the epoxy resins (B2) and the glycidyl ether type epoxy resin (B2), so that they can be used for bonding and aging at 80 DEG C or lower It is possible to improve the adhesion to the metal base material and the chemical resistance of the metal base.

The total amount of the glycidylamine-type epoxy resin (B1) and the glycidyl ether-type epoxy resin (B2) is preferably 2 to 70 parts by mass based on 100 parts by mass of the crystalline acid-modified polyolefin (A) More preferably 5 to 50 parts by mass, and most preferably 10 to 30 parts by mass. If the amount is less than the above range, a sufficient curing effect can not be obtained and adhesiveness and chemical resistance may be low. Above the above range, it is not preferable from the viewpoint of pot life, adhesiveness of the olefin substrate, and cost.

The blending amount of the glycidylamine type epoxy resin (B1) is preferably 1 to 50 mass%, more preferably 2 to 30 mass%, and most preferably 3 to 10 mass% of the total epoxy resin. If the blending amount is less than the above range, the catalytic action is not expressed, and the adhesion and chemical resistance in low temperature bonding and aging may be low. When the blending amount is less than the above range, excessive crosslinking reaction proceeds to increase the rigidity, . Further, the crosslinking reaction tends to proceed during the preservation of the solution of the adhesive composition, and the pot life tends to decrease.

As the epoxy resin used in the present invention, other epoxy resins can also be used in combination. Examples thereof include glycidyl ester types such as hexahydrophthalic acid glycidyl ester and dimeric acid glycidyl ester, triglycidyl isocyanurate or 3,4-epoxycyclohexylmethyl carboxylate, epoxidized polybutadiene, Aliphatic epoxides such as epoxidized soybean oil, and the like, and they may be used singly or in combination of two or more.

≪ Acid anhydride monomer (C) >

The acid anhydride monomer (C) used in the present invention is not particularly limited as long as it is a compound having at least one acid anhydride ring in one molecule, and examples thereof include phthalic anhydride, trimellitic acid anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, An alicyclic structure such as pentahydrophthalic anhydride, methyltrihydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, anhydrous hic acid and tetrabromophthalic anhydride, or an aromatic ring structure or an anhydride There may be mentioned succinic acid, maleic anhydride, anhydrous glutaric acid, butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecyl succinic anhydride, dodecenyl succinic anhydride, tetrapropenyl succinic anhydride, butyl maleic anhydride, pentyl maleic anhydride, Maleic anhydride, octyl maleic anhydride, decyl maleic anhydride, dodecyl maleic anhydride, butyl glutamic acid There may be mentioned those having an alkyl chain and an acid anhydride such as water, hexyl glutamic acid anhydride, heptyl glutamic acid anhydride, octyl glutamic acid anhydride, decyl glutamic acid anhydride, and dodecyl glutamic acid anhydride and may be used singly or in combination It is also good. Specifically, Ricard (registered trademark) manufactured by Shin-Nihon Rika Co., Ltd. is available and can be used.

By using the acid anhydride monomer (C) having reactivity with the glycidyl amine type epoxy resin (B1) and / or the glycidyl ether type epoxy resin (B2) in combination with the crystalline acid modified polyolefin (A), the crosslinking density is increased , For example, even when water is mixed in the electrolyte solution, the chemical resistance (electrolyte resistance) of the adhesive composition does not decrease and a favorable state can be maintained.

The acid value of the acid anhydride monomer is preferably 100 mgKOH / g or more, more preferably 150 mgKOH / g or more, and still more preferably 200 mgKOH / g or more. When the amount is less than the above-mentioned value, hardening promoting action is not exhibited, and the chemical resistance of the adhesive composition may be lowered. The acid value is preferably 1000 mgKOH / g or less, more preferably 900 mgKOH / g or less, and even more preferably 800 mgKOH / g or less. If the value is exceeded, the port lifetime may deteriorate.

The amount of the acid anhydride monomer (C) to be used in the present invention is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and more preferably 3 parts by mass or more based on 100 parts by mass of the crystalline acid-modified polyolefin (A) More preferably at least 4 parts by mass, and most preferably at least 5 parts by mass. It is more preferably 50 parts by mass or less, more preferably 48 parts by mass or less, even more preferably 45 parts by mass or less, particularly preferably 40 parts by mass or less, most preferably 35 parts by mass or less. By setting the content in the above range, excellent adhesion and chemical resistance can be exhibited.

<The heterocyclic compound (D) having two or more nitrogen atoms>

The heterocyclic compound (D) having two or more nitrogen atoms used in the present invention is preferably a heterocyclic compound having two or more nitrogen atoms in one molecule and preferably has two or more nitrogen atoms as a ring component of the heterocyclic ring. The heterocyclic compound (D) having two or more nitrogen atoms is a compound having an excellent hardening accelerating effect (B) of the crystalline polyolefin (A) and the glycidylamine type epoxy resin (B1) and / or the glycidyl ether type epoxy resin (Catalytic). Therefore, by containing the heterocyclic compound (D) having two or more nitrogen atoms, even when water is mixed in the electrolytic solution, the chemical resistance (electrolyte resistance) of the adhesive composition is not lowered, . In addition, when used in combination with the acid anhydride monomer (C), the crosslinking density can be increased efficiently, and excellent adhesion and chemical resistance can be exhibited. For example, even when water is mixed in the electrolyte solution, the chemical resistance (electrolyte resistance) of the adhesive composition does not decrease and an excellent state can be maintained.

The heterocyclic compound (D) having two or more nitrogen atoms is not particularly limited, and examples thereof include aliphatic heterocyclic compounds such as piperazine compounds, 5-membered aromatic heterocyclic compounds such as imidazole compounds and pyrazole compounds, pyrimidine compounds, A polycyclic aromatic heterocyclic compound such as a 6-membered ring aromatic heterocyclic compound such as a compound, a pyrazine compound and a triazine compound, a quinazoline compound, a phthalazine compound, a pteridine compound, a benzimidazole compound and a purine compound, An imidazole compound is particularly preferable from the viewpoints of catalytic effect and chemical resistance. Specific examples thereof include aliphatic dicarboxylic acids such as 1,2-dimethylimidazole, 1-methyl-2-ethylimidazole, 2-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl- Benzyl-2-ethylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-phenyl-4- Benzylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl- 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazolium trimellitate, 1-cyanoethyl-2- Phenylimidazolium trimellitate, 1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole, 2,4-diamino-6- [ - (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- - triazine, 2-methylimidazolium isocyanuric acid adduct, 2-phenylimidazolium isocyanuric acid adduct, 2,4-diamino-6- [2'-methylimidazolyl- (1 -] - ethyl-s-triazine-isocyanuric acid adduct, 2-phenyl-4,5-dihydroxylmethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole 2-methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride (hereinafter referred to as &quot; Methylimidazole benzotriazole adduct, 1-aminoethyl-2-ethylimidazole, 1- (cyanoethylaminoethyl) -2-methylimidazole, N, N '- [2 Methylimidazolyl- (1) -ethyl] urea, N- [2-methylimidazolyl (2-methylimidazolyl) Ethyl] dodecanedioleamide, N, N '- [2-methylimidazolyl- (1) '- [2-methylimidazolyl- (1) -ethyl] eicosanoyl diol diamide, 1-benzyl-2-phenylimidazole hydrochloride and the like.

The amount of the heterocyclic compound (D) having two or more nitrogen atoms is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and 0.05 parts by mass or less, relative to 100 parts by mass of the crystalline acid-modified polyolefin (A) More preferably 0.1 part by mass or more, and most preferably 0.2 part by mass or more. If the amount is less than the above range, the curing accelerating (catalytic) action may not be exhibited, and bonding at 80 ° C or lower may be difficult. For example, when the PP substrate is subjected to aging at about 40 DEG C at which the PP substrate is not affected by shrinkage or the like, the adhesion and chemical resistance may decrease, or the aging time may need to be prolonged. It is more preferably 5 parts by mass or less, more preferably 4 parts by mass or less, further preferably 3 parts by mass or less, particularly preferably 2 parts by mass or less, most preferably 1 part by mass or less. Above the above range, excessive crosslinking reaction proceeds to increase the rigidity and tend to lower the adhesiveness. Further, the crosslinking reaction tends to proceed during the preservation of the solution of the adhesive composition, and the pot life tends to decrease. Also, it is not preferable from the viewpoint of manufacturing cost.

The amount of the heterocyclic compound (D) having two or more nitrogen atoms is preferably from 1 to 100% by weight, based on the total amount of the glycidylamine type epoxy resin (B1) and the glycidyl ether type epoxy resin (B2) , More preferably from 2 to 70 mass%, and most preferably from 3 to 50 mass%. If the blending amount is less than the above range, the catalytic action is not exhibited, and adhesion and chemical resistance at low temperatures may be low in bonding and aging. If the amount exceeds the above range, the crosslinking reaction proceeds excessively to increase the rigidity and tends to lower the adhesiveness, and the crosslinking reaction tends to proceed during the preservation of the solution of the adhesive composition, and the pot life tends to decrease. Also, it is not preferable from the viewpoint of manufacturing cost.

The heterocyclic compound (D) having two or more nitrogen atoms may be used alone, or a plurality of compounds may be used in combination with other curing accelerators. Examples of other curing accelerators include carboxylic acid metal salts, tertiary amines, quaternary ammonium salts, organic peroxides, hydrazine compounds, metal chelate compounds, thioureas, phosphorus compounds and basic vulcanizing agents. Examples of the carboxylic acid metal salt include metal salts of carboxylic acids having 1 to 30 carbon atoms. 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, Aliphatic carboxylic acids such as lidic 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, anisic acid, aminobenzoic acid, phthalic acid, terephthalic acid, naphthoic acid, naphthalene dicarboxylic acid and benzenetricarboxylic acid; Naphthenic acid; And acetone acid. Examples of the metal constituting the carboxylic acid metal salt include Li, Na, K, Mg, Ca, Zn, Al, Cu, Pb, Co, Fe, Mn, Sn and Ti. Specific examples of the carboxylic acid metal salt include lithium acetate, sodium acetate, magnesium acetate, aluminum acetate, potassium butyrate, calcium butyrate, zinc butyrate, sodium octanoate, calcium octanoate, potassium decanoate, magnesium decanoate, zinc decanoate , Sodium laurate, sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate, sodium stearate, potassium stearate , Calcium stearate, zinc stearate, sodium oleate, sodium benzoate, sodium benzoate, zinc benzoate, sodium phthalate, aluminum phthalate, magnesium terephthalate, calcium naphthalenedicarboxylate, dibutyltin laurate, tributyl tin laurate We can choose from the group consisting of acid-octyltin, tributyltin acetate, dibutyltin diacetate, dioctyltin diacetate Tetrabutyl titanate, tetra-2-ethylhexyl titanate, cobalt naphthenate, copper naphthenate, magnesium naphthenate, cobalt acetoate, and the like can be given . Among these, preferred are lithium laurate, sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate , Sodium stearate, potassium stearate, calcium stearate, zinc stearate, and sodium oleate. As the metal salt of the carboxylic acid, a polymer having a metal salt structure of a carboxylic acid may also be used. Examples of such a polymer include a copolymer of ethylene and a metal (for example, Li, Na, K, Mg, Ca, Zn, Al or the like) salt of a group IA, IIA, IIB or IIIB of a radically polymerizable carboxylic acid that; And those having a structure in which ethylene and a metal salt of a radically polymerizable carboxylic acid are polycondensated with other radically polymerizable carboxylic acid and / or derivative thereof. Examples of the tertiary amines include dimethylaniline, triethanolamine, and dimethyl-p-toluidine. Examples of the hydrazine compound include 1-acetyl-2-phenylhydrazine and the like. Examples of the metal chelate compound include vanadium acetylacetonate and the like. Examples of the thiourea species include dimethylphosphine and triphenylphosphine. Examples of the above compound include dimethylphosphine and triphenylphosphine. Examples of the basic vulcanizing agent include hexamethylenetetramine, n-butylaldehyde-aniline condensate, and the like.

&Lt; Organic solvent (E) >

The organic solvent (E) used in the present invention is a mixture of a crystalline acid-modified polyolefin (A), a glycidylamine type epoxy resin (B1), a glycidyl ether type epoxy resin (B2), an acid anhydride monomer (C) Is not particularly limited as far as it dissolves the heterocyclic compound (D) having at least two cyclic compounds (D). Specific examples include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane, Halogenated hydrocarbons such as ethylene, dichloroethylene, chlorobenzene and chloroform, alcoholic solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol and phenol, acetone, methyl isobutyl ketone, methyl ethyl ketone Ketone solvents such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, cyclohexanone, pentane, hexanone, cyclohexanone, isophorone and acetophenone, cellosolve such as methyl cellosolve and ethyl cellosolve, , Ethylene glycol mono-n-butyl ether, ethylene glycol mono-iso-butyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol Glycol ether solvents such as mono-n-butyl ether, diethylene glycol mono-iso-butyl ether, triethylene glycol mono-n-butyl ether and tetraethylene glycol mono-n-butyl ether. Or two or more species may be used in combination.

The amount of the organic solvent (E) is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, further preferably 100 parts by mass or more, and more preferably 110 parts by mass or more, per 100 parts by mass of the crystalline acid-modified polyolefin (A) Or more. Below the above range, the solution state and the pot life may deteriorate. It is more preferably 1000 parts by mass or less, more preferably 900 parts by mass or less, even more preferably 800 parts by mass or less, particularly preferably 700 parts by mass or less. Exceeding the above range may be disadvantageous in terms of manufacturing cost and transportation cost.

The organic solvent (E) is preferably at least one solvent (E1) selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons, alcohol solvents, ketone solvents (E2) selected from the group consisting of a solvent, an ester solvent and a glycol ether solvent is preferable. The mixing ratio of the solvent (E1) / the solvent (E2) is preferably 50 to 97/50 to 3 (mass ratio), more preferably 55 to 95/45 to 5 (mass ratio) 10 (mass ratio), and particularly preferably 70 to 80/30 to 20 (mass ratio). Outside of the above range, the solution state and pot life of the adhesive composition may be deteriorated. It is particularly preferable that the solvent (E1) is an aromatic hydrocarbon or an alicyclic hydrocarbon and the solvent (E2) is a ketone solvent.

&Lt; Adhesive composition >

The adhesive composition according to the present invention contains the crystalline acid-modified polyolefin (A), the glycidylamine type epoxy resin (B1), the glycidyl ether type epoxy resin (B2) and the organic solvent (E) (C) an acid anhydride monomer and (D) a heterocyclic compound having two or more nitrogen atoms. (A), a glycidylamine type epoxy resin (B1), a glycidyl ether type epoxy resin (B2) and an organic solvent (E), an acid anhydride monomer (C) (D) having at least one heterocyclic compound. (A), glycidylamine type epoxy resin (B1), glycidyl ether type epoxy resin (B2), acid anhydride monomer (C), and heterocyclic compound (D) having two or more nitrogen atoms. May be dissolved or dispersed in the organic solvent (E). It is preferable that it is dissolved in terms of pot life.

The adhesive composition according to the present invention may contain the modified polyolefin (A), the glycidylamine type epoxy resin (B1), the glycidyl ether type epoxy resin (B2), the acid anhydride monomer (C), a heterocyclic compound (D) having two or more nitrogen atoms, and an organic solvent (E), as well as various additives. The additive is not particularly limited, but it is preferable to use a flame retardant, a pigment, an antiblocking agent, or the like.

<Laminate>

The laminate of the present invention is obtained by laminating a polyolefin resin base material and a metal base material with an adhesive composition according to the present invention.

As a lamination method, conventionally known laminate manufacturing techniques can be used. For example, although not particularly limited, the adhesive composition is applied to the surface of the metal base material by using a suitable coating means such as a roll coater or a bar coater, and dried. After drying, while the adhesive layer formed on the surface of the metal substrate is in a molten state, a polyolefin resin substrate is laminated and adhered to the coated surface to obtain a laminated structure.

The thickness of the adhesive layer formed by the adhesive composition is not particularly limited, but is preferably 0.5 to 10 占 퐉, more preferably 0.8 to 9.5 占 퐉, and further preferably 1 to 9 占 퐉.

&Lt; Polyolefin resin substrate &

As the polyolefin resin substrate, conventionally known polyolefin resins may be appropriately selected. For example, although not particularly limited, polyethylene, polypropylene, ethylene-propylene copolymer and the like can be used. Among them, it is preferable to use a polypropylene unstretched film (hereinafter also referred to as CPP). The thickness is not particularly limited, but it is preferably 20 to 100 占 퐉, more preferably 25 to 95 占 퐉, and further preferably 30 to 90 占 퐉. Further, pigments and various additives may be added to the polyolefin resin base material, if necessary.

&Lt; Metal substrate &

The metal base material is not particularly limited, but various metals such as aluminum, copper, steel, zinc, duralumin, die cast, and alloys thereof can be used. As the shape, any shape such as a metal foil, a rolled steel plate, a panel, a pipe, a can, a cap, and the like can be adopted. Generally, aluminum foil is preferable from the viewpoint of workability and the like. It is generally used in the form of a sheet having a thickness of 0.01 to 10 mm, preferably 0.02 to 5 mm, depending on the purpose of use.

In addition, from the viewpoints of corrosion resistance and adhesiveness, it is preferable to use those metal substrates that have been subjected to surface treatment in advance in view of the corrosion resistance and adhesiveness. Specific examples thereof include chromate treatment and the like.

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the embodiments. In the examples and comparative examples, simply referred to are parts by mass.

&Lt; Production example of crystalline acid-modified polyolefin (A) >

Manufacturing example  One

A 1 L autoclave was charged with 100 parts by mass of a propylene-butene copolymer ("TFMER (registered trademark) XM7080" manufactured by Mitsui Chemicals, Inc.), 150 parts by mass of toluene, 25 parts by mass of maleic anhydride, And the temperature was raised to 140 캜, followed by further stirring for 3 hours. Thereafter, the obtained reaction solution was cooled and then poured into a container containing a large amount of methyl ethyl ketone to precipitate a resin. Thereafter, the solution containing the resin was centrifuged to separate and purify an acid-modified propylene-butene copolymer obtained by graft-polymerizing maleic anhydride, (poly) maleic anhydride and a low molecular weight product. (PO-1, acid value of 48 mgKOH / g resin, weight average molecular weight of 50,000, Tm of 75 DEG C, DELTA H of 25 J / g) by drying under reduced pressure at 70 DEG C for 5 hours to obtain a maleic anhydride-modified propylene- g).

Manufacturing example  2

Maleic anhydride-modified propylene-butene copolymer (PO-2, acid value of 25 mgKOH / g resin, weight average molecular weight of 80,000, Tm (weight average molecular weight of 80,000) and maleic anhydride 75 占 폚,? H30 J / g) was obtained.

Manufacturing example  3

Butene copolymer (PO-3, acid value: 5 mg) was obtained in the same manner as in Preparation Example 1 except that the content of maleic anhydride was changed to 3 parts by mass and the amount of di-tert-butyl peroxide was changed to 0.5 parts by mass, KOH / g-resin, weight average molecular weight 180,000, Tm 80 ° C,? H 25 J / g).

Manufacturing example  4

Maleic anhydride-modified propylene-butene copolymer (PO-4, acid value of 55 mgKOH / g resin, weight average molecular weight of 40,000, Tm (weight average molecular weight of 40,000) was obtained in the same manner as in Production Example 1 except that the content of maleic anhydride was changed to 30 parts by mass. 70 캜,? H 25 J / g).

Manufacturing example  5

Maleic anhydride-modified propylene-butene copolymer (PO-5, acid value: 3 mg) was obtained in the same manner as in Production Example 1, except that the content of maleic anhydride was changed to 2 parts by mass and the amount of di-tert-butyl peroxide was changed to 0.5 parts by mass. KOH / g-resin, weight average molecular weight of 200,000, Tm of 80 占 폚,? H of 25 J / g).

(Production of topic 1)

100 parts by mass of the maleic anhydride-modified propylene-butene copolymer (PO-1) obtained in Production Example 1, 280 parts by mass of methylcyclohexane, and 100 parts by mass of methylethyl (meth) acrylate were added to a 500 ml four-necked flask equipped with a stirrer, Ketone was added in an amount of 120 parts by mass, the temperature was raised to 80 캜 while stirring, and stirring was continued for 1 hour to obtain subject 1. Table 1 shows the solution state.

(Production of topics 2-12)

Modified acid-modified polyolefin and organic solvent were changed as shown in Table 1, and Sections 2 to 12 were produced in the same manner as in the item 1. The compounding amount and the solution state are shown in Table 1.

Example  One

, 20 parts by mass of jER (registered trademark) 152 as a glycidyl ether type epoxy resin (B2) as a curing agent, TETRAD (registered trademark) -X as a glycidylamine type epoxy resin (B1) And 20 parts by mass of RICASIDE (registered trademark) DDSA as an acid anhydride monomer (C) as an additive were blended to obtain an adhesive composition. Table 2 shows the evaluation results of the pot life, adhesion and chemical resistance.

Example  2 to 69, Comparative Example  1 to 7

Examples 1 to 12 and each of the curing agents were changed as shown in Tables 2 to 5, and Examples 2 to 69 and Comparative Examples 1 to 7 were carried out in the same manner as in Example 1. The compounding amount, pot life, adhesion and chemical resistance are shown in Tables 2 to 5.

The curing agents used in Tables 2 to 5 are as follows.

&Lt; Glycidylamine type epoxy resin (B1) >

N, N, N ', N'-tetraglycidyl-m-xylenediamine: TETRAD (registered trademark) -X (manufactured by Mitsubishi Gas Chemical Company)

&Lt; Glycidyl ether type epoxy resin (B2) >

Phenol novolak type epoxy resin: jER (registered trademark) 152 (manufactured by Mitsubishi Kagaku)

o-cresol novolak type epoxy resin: YDCN-700-3 (manufactured by Shinnitetsu Sumikinka Chemical Co., Ltd.)

&Lt; Other curing agent >

Polyisocyanate: Dyuranate (registered trademark) TPA-100 (manufactured by Asahi Kasei Corporation)

Silane coupling agent: KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd.)

&Lt; Acid anhydride monomer (C) >

Tetrapropenyl anhydrous succinic acid: Ricaside (R) DDSA

Tetrahydrophthalic anhydride: Ricaside (R) TH

<The heterocyclic compound (D) having two or more nitrogen atoms>

1-benzyl-2-methylimidazole: Curezol (registered trademark) 1B2MZ (manufactured by Shikoku Chemicals)

The modified polyolefin, the subject and the adhesive composition thus obtained were subjected to analytical measurement and evaluation based on the following methods.

Mountain  Measure

&Lt; Crystalline acid-modified polyolefin (A) >

The acid value (mgKOH / g-resin) of the crystalline acid-modified polyolefin (A) in the present invention refers to the amount of KOH required to neutralize 1 g of the acid-modified polyolefin (A) ). &Lt; / RTI &gt; Concretely, 1 g of the acid-modified polyolefin was dissolved in 100 g of xylene which had been adjusted to 100 DEG C, and 0.1 mol / L of potassium hydroxide ethanol solution (trade name &quot; 0.1 mol / L ethanol Potassium hydroxide solution &quot;, manufactured by Wako Pure Chemical Industries, Ltd.). At this time, the acid value (mgKOH / g-resin) was calculated by converting the amount of potassium hydroxide required for titration into mg.

&Lt; Acid anhydride monomer (C) >

The acid value (mgKOH / g) of the acid anhydride monomer (C) in the present invention is a value calculated by the following formula using the molecular weight (M) of the acid anhydride monomer and the number (n) Acid value (mgKOH / g-resin) = [molecular weight of anhydrous succinic acid (M) × (n) × 2 × molecular weight of potassium hydroxide × 1000 (mg)

Molecular weight of succinic anhydride: 100.07, Molecular weight of potassium hydroxide: 56.11

Measurement of weight average molecular weight (Mw)

The weight average molecular weight in the present invention was determined by gel permeation chromatography (trade name: Alliance e2695, hereinafter referred to as GPC, standard material: polystyrene resin, mobile phase: tetrahydrofuran, column: Shodex KF-806 + KF-803, manufactured by Nihon Waters Corporation) : 40 占 폚, flow rate: 1.0 ml / min, detector: photodiode array detector (wavelength: 254 nm = ultraviolet ray)].

Measurement of melting point, melting calorie

The melting point and the heat of fusion according to the present invention were obtained by melting and heating at a rate of 20 ° C / minute using a differential scanning calorimeter (hereinafter, DSC, manufactured by Tie-A-Instrument Co., Ltd., Japan) Is the value measured from the top temperature and area of the melting peak when the temperature is again increased by melting.

Evaluation of Topical Solution Condition

The solution states of the subjects 1 to 12 were evaluated by measuring the solution viscosity at 25 캜 using a Brookfield viscometer TVB-10M (hereinafter also referred to as a B-type viscometer) manufactured by Toray Industries.

<Evaluation Criteria>

○ (Practically excellent): less than 500 mPa · s

? (Practicable): 500 mPa 占 퐏 or more and less than 1000 mPa 占 퐏

× (practically impossible): Viscosity can not be measured by gelation or more than 1000 mPa · s

port Life Castle  evaluation

The term "pot life" refers to the stability of the solution immediately after or after a certain period of time after the compounding of the crystalline acid-modified polyolefin with a crosslinking agent or a curing agent. When the pot life is good, the viscosity of the solution is low, indicating that the viscosity can be maintained for a long period of time. When the pot life is poor, the viscosity of the solution is increased (thickening) And it is impossible to store them for a long period of time.

The pot life properties of the adhesive compositions obtained in Examples 1 to 69 and Comparative Examples 1 to 7 were evaluated by measuring the solution viscosity at 25 占 폚 using a B-type viscometer after storing in an atmosphere of 25 占 폚 and 40 占 폚 for 24 hours . The evaluation results are shown in Tables 2 to 5.

<Evaluation Criteria>

○ (Practically excellent): less than 500 mPa · s

? (Practicable): 500 mPa 占 퐏 or more and less than 1000 mPa 占 퐏

× (practically impossible): Viscosity can not be measured by gelation or more than 1000 mPa · s

The metal substrate and the polyolefin resin substrate Of the laminate  making

An aluminum foil (8079-0, thickness: 40 占 퐉) was subjected to a chromate treatment on an aluminum foil, and a polyolefin resin substrate was coated with an unleaded polypropylene film (Pylen (registered trademark) film CT manufactured by Toyobo Co., , Thickness: 40 [mu] m) (hereinafter also referred to as CPP) was used.

The adhesive compositions obtained in Examples 1 to 69 and Comparative Examples 1 to 7 were coated on a metal substrate using a bar coater so that the thickness of the dried adhesive layer became 3 占 퐉. The coated surface was dried in a 100 占 폚 atmosphere for 1 minute using a hot air dryer to obtain an adhesive layer having a thickness of 3 占 퐉. The polyolefin resin base material was polymerized on the surface of the adhesive layer and joined at 80 DEG C and 0.3 mPa at 1 m / min using a small table test laminator (SA-1010-S) RH for 120 hours to obtain a laminate.

The laminate thus obtained was evaluated by the following method.

Evaluation of adhesion

The laminate was cut into a size of 100 mm x 15 mm, and the adhesion was evaluated by a T-type peel test. The evaluation results are shown in Tables 2 and 3.

<T-type peel test>

In accordance with the test method of ASTM-D1876-61, the peel strength at a tensile rate of 50 mm / min was measured at 25 占 폚 using Tensilon RTM-100 manufactured by Orientech Corporation. The peel strength (N / cm) between the metal substrate and the polyolefin resin substrate was an average value of five test values.

<Evaluation Criteria>

☆ (practically excellent): 8.0 N / cm or more, or CPP material is broken (hereinafter also referred to simply as &quot; material breakage &quot;). The material breakage means that the metal substrate or the CPP is broken without peeling at the interface between the metal substrate and the CPP.

◎ (practically excellent): 7.5 N / cm or more and 8.0 N / cm or less

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

× (practically impossible): less than 7.0 N / cm

Evaluation of Chemical Resistance

In order to examine the usability of a lithium ion battery as one of modes of use of a laminate of aluminum foil and CPP, evaluation of chemical resistance (hereinafter also referred to as electrolytic solution resistance) by electrolytic solution test was performed. The laminate was cut into a size of 100 mm x 15 mm and was prepared by adding lithium hexafluorophosphate to an electrolytic solution (ethylene carbonate / diethyl carbonate / dimethyl carbonate = 1/1/1 (volume ratio) ] Was added to 300 ppm of water, and the resultant was immersed at 85 캜 for 3 days or at a temperature of 85 캜 for 5 days in which 500 ppm of water was added to the electrolytic solution. Thereafter, the laminate was taken out, washed with ion-exchanged water, and wiped off with a paper wiper to sufficiently dry the water, cut into a size of 100 mm x 15 mm, and evaluated for chemical resistance by a T- .

<Evaluation Criteria>

☆ (Practically excellent): Above 8.0 N / cm or material destruction

◎ (practically excellent): 7.5 N / cm or more and 8.0 N / cm or less

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

× (practically impossible): less than 7.0 N / cm

The adhesive composition according to the present invention contains an acid-denatured polyolefin, an epoxy resin, an organic solvent, an acid anhydride monomer and a heterocyclic compound having two or more nitrogen atoms, and does not generate thickening or gelation Good port life can be maintained, and good adhesion between the metal substrate and the polyolefin resin substrate can be achieved. Therefore, the laminated structure of the polyolefin resin base material and the metal base material formed from the adhesive composition of the present invention can be used not only in the fields of home electric appliance, furniture materials, building interior fittings, etc., but also lithium ion batteries used in personal computers, mobile phones, And can be widely used as a packaging material (pouch type) of a battery.

Claims (13)

(A), a glycidylamine type epoxy resin (B1), a glycidyl ether type epoxy resin (B2) and an organic solvent (E) each having an acid value of 5 to 50 mgKOH / , And further contains either an acid anhydride monomer (C) or a heterocyclic compound (D) having two or more nitrogen atoms. The adhesive composition according to claim 1, wherein the glycidylamine type epoxy resin (B1) is an epoxy resin having at least two glycidyl groups in one molecule. The adhesive composition according to claim 1 or 2, wherein the glycidylamine type epoxy resin (B1) is a compound represented by the general formula (1).

(In the general formula (1), R represents an aryl group which may have a substituent, X1 and X2 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, m is 1 or 2, n is 1 Or 2). The adhesive composition according to any one of claims 1 to 3, wherein the glycidyl ether type epoxy resin (B2) is an epoxy resin having two or more glycidyl groups in one molecule and no nitrogen atom . The adhesive composition according to any one of claims 1 to 4, wherein the acid anhydride monomer (C) has at least one acid anhydride ring in one molecule and an acid value of 100 mgKOH / g or more. The adhesive composition according to any one of claims 1 to 5, wherein the heterocyclic compound (D) having at least two nitrogen atoms is a 5-membered ring aromatic heterocyclic compound having two or more nitrogen atoms. The epoxy resin composition according to any one of claims 1 to 6, wherein the crystalline acid-modified polyolefin (A), the glycidylamine type epoxy resin (B1), the glycidyl ether type epoxy resin (B2), the acid anhydride monomer ) And an organic solvent (E), wherein 0.01 to 20 parts by mass of a glycidylamine-type epoxy resin (B1), 100 parts by mass of a glycidyl ether-type epoxy resin ( B2) in an amount of 1 to 50 parts by mass, the acid anhydride monomer (C) in an amount of 1 to 50 parts by mass, and the organic solvent (E) in an amount of 80 to 1,000 parts by mass. The positive photosensitive resin composition according to any one of claims 1 to 6, wherein the crystalline acid-modified polyolefin (A), the glycidylamine type epoxy resin (B1), the glycidyl ether type epoxy resin (B2) 0.01 to 20 parts by mass of a glycidylamine-type epoxy resin (B1), 100 parts by mass of a glycidyl amine-modified polyolefin (A) 1 to 50 parts by mass of a diester type epoxy resin (B2), 0.01 to 5 parts by mass of a heterocyclic compound (D) having two or more nitrogen atoms, and 80 to 1,000 parts by mass of an organic solvent (E). The epoxy resin composition according to any one of claims 1 to 6, wherein the crystalline acid-modified polyolefin (A), the glycidylamine type epoxy resin (B1), the glycidyl ether type epoxy resin (B2), the acid anhydride monomer ), A heterocyclic compound (D) having at least two nitrogen atoms and an organic solvent (E), wherein the glycidylamine type epoxy resin (B1) is contained in an amount of 0.01 1 to 50 parts by mass of a glycidyl ether type epoxy resin (B2), 1 to 50 parts by mass of an acid anhydride monomer (C), 0.01 to 50 parts by mass of a heterocyclic compound (D) having two or more nitrogen atoms, , And 80 to 1000 parts by mass of an organic solvent (E). The organic EL device according to any one of claims 1 to 9, wherein the organic solvent (E) is a mixed liquid of a solvent (E1) and a solvent (E2), wherein the solvent (E1) is an aromatic hydrocarbon, an aliphatic hydrocarbon, (E2) is at least one solvent selected from the group consisting of an alcohol-based solvent, a ketone-based solvent, an ester-based solvent and a glycol ether-based solvent, and the solvent (E1) / solvent (E2) = 50 to 97/50 to 3 (mass ratio). 11. The adhesive composition according to any one of claims 1 to 10, which is used for bonding a polyolefin resin substrate and a metal substrate. A laminate of a polyolefin resin base material and a metal base material adhered by the adhesive composition according to any one of claims 1 to 11. A packaging material for a lithium ion battery comprising the laminate according to claim 12 as a constituent member.