TW201823406A - Polyolefin adhesive composition - Google Patents

Abstract

An adhesive composition is provided which has an excellent pot life, has excellent adhesiveness between a metal substrate and a polyolefin resin substrate, and which contains a modified polyolefin and an epoxy resin. This adhesive composition contains (A) a crystalline acid-modified polyolefin with an acid value of 5-50 mgKOH/g-resin, (B1) a glycidyl amine-type epoxy resin, (B2) a glycidyl ether-type epoxy resin, and (E) an organic solvent, and further contains either (C) an acid anhydride monomer or (D) a heterocyclic compound that includes two or more nitrogens.

Description

Polyolefin-based adhesive composition

The present invention relates to an adhesive composition for adhering a polyolefin resin substrate and a metal substrate. More specifically, the adhesive composition contains a crystalline acid-modified polyolefin, an epoxy resin, and an organic solvent, and further contains any one of an acid anhydride monomer and a heterocyclic compound having two or more nitrogens.

Laminates have conventionally been used for metal substrates such as outer panels of home appliances, furniture materials, and building interior components, and this laminate system is coated with a vinyl chloride resin (hereinafter also referred to as "polyvinyl chloride"). ) After lamination, but recently environmental issues have been magnified, and some people have proposed replacing polyolefin with polyolefin resin. Polyolefin resin is non-toxic, exhibits strong durability against acids, alkalis, organic solvents, etc., and is also excellent in mechanical strength, abrasion resistance, and low cost, and is therefore widely used in various fields.

However, since the polyolefin resin is non-polar, adhesion to a metal substrate is difficult. In the past, various adhesives have been proposed for the adhesion of the polyolefin resin to a metal substrate. Representative ones are those obtained by dissolving a thermosetting resin such as a phenol resin, a melamine resin, an epoxy resin, or a thermoplastic resin in an organic solvent as a base adhesive, and mixing a solvent-dispersed modified polyolefin resin. However, it is difficult to say that these adhesives have sufficient adhesiveness. Moreover, it has also been proposed that a crystalline acid-modified polyolefin and an epoxy resin are mixed with an adhesive composition such as catechol (Patent Document 1), or a maleic acid-modified chlorinated polypropylene and a chelate are mixed. Adhesive composition of epoxy resin and solvent (Patent Document 2). [Prior Art Literature] [Patent Literature]

[Patent Document 1] JP 2003-261847 [Patent Document 2] JP 2009-292853

[Problems to be Solved by the Invention] However, the above method may sometimes have poor pot life characteristics after blending an acid-modified polyolefin solution, and even if the pot life characteristics are not too large, the most important issue is metal. The adhesiveness and chemical resistance of the substrate are still insufficient. That is, the above method is not intended to satisfy the pot life characteristics, adhesion, and chemical resistance. In particular, when a polypropylene (hereinafter also referred to as PP) substrate is used, it is not an adhesive capable of bonding and aging at a low temperature such as 80 ° C. or less with a small influence on heat shrinkage and the like. Here, the pot life characteristic refers to the stability of the solution after the cross-linking agent or hardener is blended in the acid-modified polyolefin and immediately after the blending or after a certain period of time.

As for laminates of polyolefin resin substrates and metal substrates, in recent years, discussions on the use of laminates of polypropylene films and aluminum foils bonded with adhesives as exterior bodies for lithium-ion batteries are gaining momentum. In the case of an adhesive and a laminate, chemical resistance to an electrolyte solution, which is a content (hereinafter, also referred to as electrolyte resistance) is sought.

The electrolytic solution of a lithium ion battery can be obtained by dissolving lithium salts such as LiPF ₆ and LiBF ₄ as electrolytes in a non-aqueous solvent such as carbonates. The lithium salt used as an electrolyte is hydrolyzed by moisture and generates hydrogen fluoride. Therefore, when hydrogen fluoride is generated, problems such as corrosion of a metal member constituting a battery or reduction in adhesion between layers of a laminated film-type packaging material used as an exterior body may occur.

The present invention has been made in view of the above-mentioned conventional problems. After conducting in-depth discussions on the adhesives for polyolefin resin substrates and metal substrates, the present inventors have found that crystalline acid-modified polyolefins (hereinafter also referred to as acid modification) Polyolefin), epoxy resin and organic solvent, and an adhesive composition containing any one of an acid anhydride monomer and a heterocyclic compound having two or more nitrogens, and has a pot life characteristic of 80 ° C or lower The adhesion and chemical resistance at the time of bonding or aging, especially the electrolyte resistance after mixing with water, have even completed the present invention.

That is, the object of the present invention is to provide an adhesive composition having good pot life characteristics after blending a crystalline acid-modified polyolefin, a hardener, and a hardening accelerator, and having a low-temperature bonding and maturation properties for polymer Good adhesion and chemical resistance of both olefin resin substrate and metal substrate. [Means for solving problems]

In order to achieve the above-mentioned problems, the present inventors have thoroughly studied and even proposed the following inventions.

Adhesive composition containing crystalline acid-modified polyolefin (A), epoxypropylamine type epoxy resin (B1), epoxypropyl ether type epoxy resin having an acid value of 5 to 50 mgKOH / g-resin The resin (B2) and the organic solvent (E) further contain any one of an acid anhydride monomer (C) and a heterocyclic compound (D) having two or more nitrogens.

The aforementioned epoxypropylamine epoxy resin (B1) is preferably an epoxy resin having two or more epoxypropyl groups in one molecule.

The aforementioned epoxypropylamine type epoxy resin (B1) is preferably a compound represented by the general formula (1). [Chemized 1] In the general formula (1), in the general formula (1), R is an aryl group which may have a substituent, X1 and X2 are each independently an alkylene group having 1 to 5 carbon atoms which may also have a substituent, and m is 1 Or 2, and n is 1 or 2.

The epoxy-epoxy-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 one or more acid anhydride rings in one molecule and having an acid value of 100 mgKOH / g or more.

The heterocyclic compound (D) having two or more nitrogens is preferably a 5-membered ring aromatic heterocyclic compound having two or more nitrogens.

Relative to 100 parts by mass of the crystalline acid-modified polyolefin (A), it is preferable to contain 0.01 to 20 parts by mass of an epoxypropylamine type epoxy resin (B1), and 1 to 50 parts by mass of an epoxypropyl ether type. Epoxy resin (B2), 1 to 50 parts by mass of an anhydride monomer (C), 0.01 to 5 parts by mass of a heterocyclic compound (D) having two or more nitrogens, and 80 to 1,000 parts by mass of an organic solvent ( E).

The organic solvent (E) is preferably a mixed solution of the solvent (E1) and the solvent (E2). The solvent (E1) is preferably selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons. More than one solvent, the solvent (E2) is preferably one or more solvents selected from the group consisting of alcohol solvents, ketone solvents, ester solvents, and glycol ether solvents, and the solvent (E1) / solvent (E2) = 50 ~ 97/50 ~ 3 (mass ratio) is ideal.

The adhesive composition according to any one of the foregoing, is used for adhesion between a polyolefin resin substrate and a metal substrate.

A laminated body of a polyolefin resin substrate and a metal substrate is adhered using the adhesive composition described in any one of the foregoing. A packaging material for a lithium-ion battery, comprising the laminate as a constituent member. [Effect of Invention]

The adhesive composition according to the present invention contains any one of a crystalline acid-modified polyolefin, two epoxy resins, and an organic solvent, and further contains an acid anhydride monomer and a heterocyclic compound having two or more nitrogens. No thickening or gelation occurs even after long-term storage, and good shelf life characteristics can be maintained. In addition, even if the polyolefin substrate has a low thermal shrinkage effect, such as bonding at a low temperature of 80 ° C or lower, it can still have good adhesion and chemical resistance with polyolefin resin substrates and metal substrates.

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

<Crystalline acid-modified polyolefin (A)> The crystalline acid-modified polyolefin (A) used in the present invention is not particularly limited, but is preferably obtained by mixing α, β-unsaturated carboxylic acid and its anhydride It is obtained by grafting at least one of polyethylene, polypropylene and propylene-α-olefin copolymer.

The propylene-α-olefin copolymer is composed of propylene as a main component, and an α-olefin is copolymerized thereon. Examples of the α-olefin include one or more of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, and vinyl acetate. Among these α-olefins, ethylene and 1-butene are preferred. The ratio of the propylene component to the α-olefin component in the propylene-α-olefin copolymer is not limited, but the propylene component is preferably 50 mol% or more, and more preferably 70 mol% or more.

Examples of at least one of the α, β-unsaturated carboxylic acids and their anhydrides include maleic acid, itaconic acid, citraconic acid, and their anhydrides. Among these, anhydrides are preferred, and maleic anhydride is more preferred. Specific examples include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, and maleic anhydride-modified propylene-ethylene-butene copolymer. These crystalline acid-modified polyolefins may be used singly or in combination of two or more kinds. Among them, maleic anhydride modified propylene-butene copolymer is preferred. As for the propylene component / 1-butene component (molar ratio) in the maleic anhydride-modified propylene-butene copolymer, it is preferably 90-50 / 50-50, and more preferably 85-60 / 15-40. , 80 ~ 55/20 ~ 45 is even better, and 75 ~ 60/25 ~ 40 is particularly good. By setting it within the above range, it is possible to particularly exhibit excellent pot life characteristics, adhesiveness, and chemical resistance.

Considering the pot life characteristics and the viewpoint of adhesion to polyolefin resin substrates and metal substrates, the lower limit of the acid value of the crystalline acid-modified polyolefin (A) must be 5 mgKOH / g-resin or more, preferably 10 mgKOH / g -resin or more, more preferably 14 mgKOH / g-resin or more, more preferably 16 mgKOH / g-resin or more, particularly preferably 18 mgKOH / g-resin or more, and most preferably 20 mgKOH / g-resin or more. If it does not reach the aforementioned value, the compatibility with the epoxy resin may be low and the adhesive strength may not be exhibited. In addition, the crosslink density may be low and the chemical resistance may be insufficient. The upper limit must be 50 mgKOH / g-resin or less, preferably 48 mgKOH / g-resin or less, more preferably 46 mgKOH / g-resin or less, more preferably 44 mgKOH / g-resin or less, and even more preferably 42 mgKOH / g-resin or less. It is preferably below 40 mgKOH / g-resin. If it exceeds the aforementioned value, the viscosity and stability of the solution may be reduced, and the shelf life characteristics may be reduced. In addition, manufacturing efficiency is also reduced, which is less desirable. The acid value can be controlled by the graft amount (addition amount) of at least one of α, β-unsaturated carboxylic acid and its 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. A range of 50,000 to 160,000 is more preferred, a range of 60,000 to 150,000 is even more preferred, a range of 70,000 to 140,000 is particularly preferred, and a range of 80,000 to 130,000 is most preferred. If it does not reach the above-mentioned value, cohesion may become weak and adhesiveness may be poor. On the other hand, if it exceeds the above-mentioned value, there may be a case where the fluidity is low and there is a problem in operability during adhesion. If it is in the said range, hardening reaction with an epoxy resin will be accelerated and it is preferable.

The crystallinity in the crystalline acid-modified polyolefin (A) means that a differential scanning calorimeter (DSC) is used to increase the temperature from -100 ° C to 250 ° C at 20 ° C / minute, and the temperature is displayed during the temperature rise. Clear melting peaks.

By setting the acid-modified polyolefin to be crystalline, it is advantageous because the former has stronger cohesion than the amorphous, and has excellent adhesion and chemical resistance.

The melting point (Tm) of the crystalline acid-modified polyolefin (A) is preferably in the range of 50 ° C to 120 ° C. A range of 60 ° C to 100 ° C is more preferable, and a range of 70 ° C to 90 ° C is most preferable. If it does not reach the above-mentioned value, the cohesive force derived from crystals may become weak and the adhesiveness and chemical resistance may be poor. On the other hand, if it exceeds the above-mentioned value, solution stability, low fluidity, and problems in operability during adhesion may occur.

The heat of fusion (ΔH) of the crystalline acid-modified polyolefin (A) is preferably in the range of 5 J / g to 60 J / g. A range of 10 J / g to 50 J / g is more preferable, and a range of 20 J / g to 40 J / g is most preferable. If it does not reach the above-mentioned value, the cohesive force derived from crystals may become weak and the adhesiveness and chemical resistance may be poor. On the other hand, if it exceeds the above-mentioned value, solution stability, low fluidity, and a problem in operability during adhesion may occur.

The manufacturing method of the crystalline acid-modified polyolefin (A) is not particularly limited. For example, a radical graft reaction (that is, generating a radical species to a polymer that becomes a main chain), and The radical species is used as a polymerization starting point, and the reaction of graft polymerization of unsaturated carboxylic acid and acid anhydride) is performed.

The radical generator is not particularly limited, and an organic peroxide is preferably used. The organic peroxide is not particularly limited, and examples thereof include di (tertiary butyl) peroxyphthalate, tertiary butyl hydroperoxide, dicumyl peroxide, benzamidine peroxide, and peroxide. Tert-butyl benzoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxytrimethylacetate, methyl ethyl ketone peroxide, di (tertiary butyl) peroxide, Peroxides such as laurel tin oxide; azobisisobutyronitrile, azobisisopropionitrile, etc.

<Glycidylamine-type epoxy resin (B1)> The epoxy-propylamine-type epoxy resin (B1) used in the present invention is an epoxy resin having one or more epoxy-propyl groups in one molecule. No special restrictions. It is preferable to have more than two epoxy groups in one molecule of epoxy resin, it is more preferable to have three or more epoxy groups in one molecule of epoxy resin, and it is preferable to have more than four epoxy groups in one molecule of epoxy resin. Even better.

In addition, the use of a compound represented by the following general formula (1) as the epoxypropylamine-type epoxy resin (B1) is more preferable because it improves chemical resistance. [Chemized 1] In the general formula (1), R is an aryl group which may have a substituent, and preferably a phenyl group which may also have a substituent. The substituent of the aryl 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, a hydroxyl group, an amino group, an epoxy group, and an epoxy group. Propylamino or epoxypropyl ether. X1 and X2 are each independently a linear alkylene group having a carbon number of 1 to 5 and optionally having a substituent. The ideal carbon number is 4 or less, more preferably 3 or less, and even 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, or an amine group. m is 1 or 2, and n is 1 or 2. Ideally, either m or n is 2, and more preferably, m and n are both 2.

Specific examples of the epoxypropylamine type epoxy resin (B1) are not particularly limited, and examples thereof include tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, and tetracyclic Oxypropyldiamine methylcyclohexanone, N, N, N ', N'-tetraepoxypropyl-m-xylylenediamine and other epoxypropylamines. Among them, N, N, N ', N'-tetraepoxypropyl-m-xylylenediamine is preferred. These epoxypropylamine-type epoxy resins (B1) can be used individually or in combination of 2 or more types.

The blending amount of the epoxypropylamine type epoxy resin (B1) is preferably 0.01 parts by mass or more, and more preferably 0.05 parts by mass or more, based on 100 parts by mass of the crystalline acid-modified polyolefin (A). It is more preferably 0.1 parts by mass or more, particularly preferably 1 part by mass or more, and most preferably 2 parts by mass or more. If it does not fall within the aforementioned range, the catalyst effect may not be exhibited, and the adhesion at 80 ° C or lower, the adhesion during ripening, and the chemical resistance may be low. In addition, it is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, still more preferably 16 parts by mass or less, particularly preferably 14 parts by mass or less, and most preferably 12 parts by mass or less. If it exceeds the said range, a crosslinking reaction will advance too much, rigidity will become high, and adhesiveness will fall. Furthermore, when the solution of the adhesive composition is stored, the crosslinking reaction tends to proceed and the pot life tends to decrease.

<Glycidyl ether epoxy resin (B2)> The glycidyl ether 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. . It is preferably an epoxy resin having more than two epoxy groups in one molecule of epoxy resin, an epoxy resin having more than two epoxy groups in one molecule of epoxy resin, and containing no nitrogen atom. good.

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

The specific examples of the epoxy propyl ether type epoxy resin (B2) are not particularly limited, and examples thereof include phenol novolac resin epoxy resin, cresol novolac resin epoxy resin, and metal substrates. From the viewpoint of adhesion and chemical resistance, they are preferable. These glycidyl ether epoxy resins (B2) can be used alone or in combination of two or more.

In the present invention, two types of epoxy resins of the aforementioned epoxypropylamine type epoxy resin (B1) and the aforementioned epoxypropyl ether type epoxy resin (B2) are used as essential components. By using a glycidylamine epoxy resin (B1) and a glycidyl ether epoxy resin (B2) together, excellent adhesion and chemical resistance can be exhibited. That is, the glycidylamine-type epoxy resin (B1) has a catalyst function when the crystalline acid-modified polyolefin (A) reacts with the glycidyl ether-type epoxy resin (B2). In addition, the epoxy-propylamine-type epoxy resin (B1) is a crystalline acid-modified polyolefin (A), the epoxy-propylamine-type epoxy resin (B1), and the epoxy-propylamine-type epoxy resin (B1). ) Each other, and the epoxy propylene ether type epoxy resin (B2), the epoxy propylamine type epoxy resin (B1) and the epoxy propyl ether type epoxy resin (B2) have a hardening catalyst function when they react with each other. Therefore, by admixing, the adhesion and chemical resistance to metal substrates during bonding and maturation below 80 ° C can be improved.

The total blending amount of the epoxypropylamine epoxy resin (B1) and the epoxypropyl ether epoxy resin (B2) is preferably 100 parts by mass with respect to 100 parts by mass of the crystalline acid-modified polyolefin (A). 2 to 70 parts by mass, more preferably 5 to 50 parts by mass, and most preferably 10 to 30 parts by mass. If it does not reach the above range, a sufficient hardening effect may not be obtained, and the adhesiveness and chemical resistance may be low. If it exceeds the above range, the pot life characteristics and the adhesion to the olefin substrate may be reduced. Considering the viewpoint of cost Less desirable.

The blending amount of the epoxypropylamine type epoxy resin (B1) is preferably 1 to 50% by mass of the whole epoxy resin, more preferably 2 to 30% by mass, and most preferably 3 to 10% by mass. If the blending amount is less than the above range, the catalyst effect may not be exhibited, and the adhesion and chemical resistance during low temperature bonding and maturation may be low. If the blending amount exceeds the foregoing range, the crosslinking reaction may proceed excessively. The rigidity tends to increase and the adhesiveness tends to decrease. In addition, during the storage of the adhesive composition, the crosslinking reaction tends to proceed easily and the pot life tends to decrease.

Other epoxy resins may be used in combination as the epoxy resin used in the present invention. Examples include propylene oxide type such as propylene glycol hexahydrophthalate, propylene glycol dimer acid, etc .; triglycidyl isocyanurate, or 3,4-epoxycyclohexyl formate. (3,4-epoxycyclohexyl methyl carboxylate), alicyclic or aliphatic epoxides such as epoxidized polybutadiene, epoxidized soybean oil, etc., may be used singly, or two or more kinds may be used in combination.

<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 one or more acid anhydride rings in one molecule. Examples include phthalic anhydride and trimellitic acid. Acid anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylpentahydrophthalic anhydride, methyltrihydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexyl Those having alicyclic structure or aromatic ring structure, such as dicarboxylic anhydride, chlorobridged anhydride, tetrabromophthalic anhydride, or succinic anhydride, maleic anhydride, glutaric anhydride, butylsuccinic anhydride, hexylsuccinic anhydride, octyl Succinic anhydride, dodecyl succinic anhydride, dodecenyl succinic anhydride, tetrapropenyl succinic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl maleic anhydride, octyl maleic anhydride, decyl maleic anhydride Maleic anhydride, dodecylmaleic anhydride, butylglutamic anhydride, hexylglutamic anhydride, heptylglutamic anhydride, octylglutamic anhydride, decylglutamic anhydride, dodecylglutamic anhydride, etc. The alkyl chain and the acid anhydride may be used singly or in combination. Specifically, RIKACID (registered trademark) and the like of the New Japan Physicochemical Co., Ltd. have been listed and can be used.

An acid anhydride monomer (C) having reactivity with a glycidylamine epoxy resin (B1) and / or a glycidyl ether epoxy resin (B2) and a crystalline acid-modified polyolefin ( A) When used in combination, the crosslinking density becomes high. For example, even when water is mixed in the electrolytic solution, the chemical resistance (electrolytic solution resistance) of the adhesive composition is not reduced, and a good 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 more preferably 200 mgKOH / g or more. If the value is not reached, the hardening-promoting effect may not be exhibited, and the chemical resistance of the adhesive composition may be reduced. 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 more than the above value, the pot life characteristics may be reduced.

The blending amount of the acid anhydride monomer (C) used in the present invention is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and 3 parts by mass relative to 100 parts by mass of the crystalline acid-modified polyolefin (A). More preferably, it is more preferably 4 parts by mass or more, and most preferably 5 parts by mass or more. It is 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, and most preferably 35 parts by mass or less. By setting in the aforementioned range, excellent adhesion and chemical resistance can be exhibited.

<Heterocyclic compound (D) having two or more nitrogens> The heterocyclic compound (D) having two or more nitrogens used in the present invention is a heterocyclic ring having two or more nitrogen atoms in one molecule The compound of the formula preferably has two or more nitrogen atoms in terms of the ring structure component of the heterocyclic ring. Heterocyclic compound (D) having two or more nitrogens, and having crystalline polyolefin (A), and epoxypropylamine type epoxy resin (B1) and / or epoxypropyl ether type epoxy resin (B2) Excellent hardening promoting effect (catalyst effect). Therefore, by containing a heterocyclic compound (D) having two or more nitrogens, for example, even when water is mixed in the electrolytic solution, the chemical resistance (electrolytic solution resistance) of the adhesive composition does not decrease, Can maintain good condition. In addition, by using it in combination with the acid anhydride monomer (C), the crosslinking density can be effectively increased, and excellent adhesion and chemical resistance can be exhibited. For example, even when water is mixed into the electrolytic solution, the chemical resistance (electrolytic resistance) of the adhesive composition is not reduced, and an excellent state can be maintained.

The heterocyclic compound (D) having two or more nitrogens is not particularly limited, and examples thereof include piperidine Aliphatic heterocyclic compounds such as compounds; 5-membered ring aromatic heterocyclic compounds such as imidazole compounds and pyrazole compounds; pyrimidine compounds, da Compounds, pyridine Compound, three 6-membered ring aromatic heterocyclic compounds such as compounds; quinazoline compounds, fluorene Polycyclic aromatic heterocyclic compounds such as compounds, pyrimidine compounds, benzimidazole compounds, and purine compounds are particularly preferred from the viewpoints of catalyst effect and chemical resistance. Specific examples include 1,2-dimethylimidazole, 1-methyl-2-ethylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-undecyl Imidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-phenylimidazole Triformate, 1-benzyl-2-ethylimidazole, 1-benzyl-2-ethyl-5-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-phenyl-4 -Benzylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1- Cyanoethyl-2-isopropylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-phenyl Imidazole trimellitate, 1-cyanoethyl-2-phenyl-4,5-bis (cyanoethoxymethyl) imidazole, 2,4-diamino-6- [2'-methylimidazole -(1 ')]-ethyl-s-tri , 2,4-diamino-6- [2'-ethyl-4-methylimidazolyl- (1 ')]-ethyl-s-tri , 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-tri , 2-methylimidazole isotricyanic acid adduct, 2-phenylimidazole isotricyanic acid adduct, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-Ethyl-s-tri -Isotricyanic acid adduct, 2-phenyl-4,5-dimethylol imidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 4,4'-methylene -Bis (2-ethyl-5-methylimidazole), 1-aminoethyl-2-methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazole chloride, 2- Methylimidazolium benzotriazole adduct, 1-aminoethyl-2-ethylimidazole, 1- (cyanoethylaminoethyl) -2-methylimidazole, N, N '-[2 -Methylimidazolyl- (1) -ethyl] -hexamethylenediamidamine, N, N'-bis- [2-methylimidazolyl- (1) -ethyl] urea, N- [2 -Methylimidazolyl-1-ethyl] urea, N, N '-[2-methylimidazolyl- (1) -ethyl] dodecanedifluorenyldiamine, N, N'-[2 -Methylimidazolyl- (1) -ethyl] eicosanedifluorenyldiamidine, 1-benzyl-2-phenylimidazolium hydrochloride, and the like.

The blending amount of the heterocyclic compound (D) having 2 or more nitrogen is preferably 0.01 parts by mass or more, and more preferably 0.02 parts by mass or more, based on 100 parts by mass of the crystalline acid-modified polyolefin (A). It is more preferably 0.05 parts by mass or more, particularly preferably 0.1 parts by mass or more, and most preferably 0.2 parts by mass or more. If it is not within the above range, the hardening-promoting (catalytic) effect may not be exhibited, and bonding at 80 ° C or lower may be difficult. For example, when ripening is performed at about 40 ° C., where the PP substrate is not affected by shrinkage or the like, adhesion, chemical resistance may be reduced, or the ripening time may need to be set longer. It is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, even more preferably 3 parts by mass or less, particularly preferably 2 parts by mass or less, and most preferably 1 part by mass or less. If it exceeds the said range, a crosslinking reaction will advance excessively, rigidity will become high, and adhesiveness will fall. In addition, the adhesive composition tends to undergo a cross-linking reaction easily during storage of the solution, thereby reducing the pot life. Furthermore, the viewpoint of considering manufacturing costs is also less desirable.

The blending amount of the heterocyclic compound (D) having two or more nitrogens is blended with respect to the total amount of the epoxypropylamine epoxy resin (B1) and the epoxypropyl ether epoxy resin (B2). The amount is preferably 1 to 100% by mass, more preferably 2 to 70% by mass, and most preferably 3 to 50% by mass. If the blending amount is less than the aforementioned range, the catalyst effect may not be exhibited, and the adhesion and chemical resistance during maturation at low temperatures may be low. If it exceeds the above range, the crosslinking reaction tends to proceed excessively, resulting in higher rigidity and lowered tackiness, or the adhesive composition tends to undergo a crosslinking reaction during solution storage, and tends to decrease the pot life. Furthermore, the viewpoint of considering manufacturing costs is also less desirable.

The heterocyclic compound (D) having two or more nitrogens may be blended alone, a plurality of compounds may be used in combination, or other hardening accelerators may be used in combination. Examples of other hardening accelerators include metal carboxylic acid salts, tertiary amines, tertiary ammonium salts, organic peroxides, hydrazine compounds, metal chelate compounds, carbamides, phosphorus compounds, and alkaline vulcanizing agents Class, etc. Examples of the metal salt of a carboxylic acid include a metal salt of a carboxylic acid having 1 to 30 carbon atoms. Examples of the carboxylic acid constituting the metal carboxylic acid salt include acetic acid, butyric acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, octanoic acid, Aliphatic carboxylic acids such as erucic acid, oleic acid, adipic acid, malonic acid, succinic acid, glutaric acid, citric acid, tartaric acid, malic acid, diglycolic acid, etc. , Aminobenzoic acid, phthalic acid, terephthalic acid, naphthoic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid and other aromatic carboxylic acids; naphthenic acid; pyruvate and so on. 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 metal carboxylic acid salt include lithium acetate, sodium acetate, magnesium acetate, aluminum acetate, potassium butyrate, calcium butyrate, zinc butyrate, sodium caprylate, calcium caprylate, potassium caprate, and magnesium caprate. , Zinc caprate, lithium laurate, sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate, stearin Sodium, potassium stearate, calcium stearate, zinc stearate, sodium oleate, sodium behenate, sodium benzoate, zinc benzoate, sodium phthalate, aluminum phthalate, magnesium terephthalate, Calcium naphthalate, dibutyltin laurate, tributyltin laurate, dioctyltin laurate, tributyltin acetate, dibutyltin diacetate, dioctyltin diacetate, dibutyltin 2-ethylhexanoate, titanate Tetrabutyl ester, tetraisobutyl titanate, tetra-2-ethylhexyl titanate, cobalt naphthenate, copper naphthenate, magnesium naphthenate, cobalt acetate and the like. Among them, lithium laurate, sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate, hard Sodium stearate, potassium stearate, calcium stearate, zinc stearate, sodium oleate. A polymer having a metal salt structure of a carboxylic acid may be used as the metal salt of the carboxylic acid. Examples of such polymers include salts of metals (e.g., Li, Na, K, Mg, Ca, Zn, Al, etc.) having Group IA, Group IIA, Group IIB, and Group IIIB having ethylene and a radically polymerizable carboxylic acid. Those having a copolymerized structure; those having a structure in which a metal salt of ethylene and a radically polymerizable carboxylic acid are copolymerized with another radically polymerizable carboxylic acid and / or a derivative thereof, and the like. Examples of the tertiary amines include dimethylphenylamine, triethanolamine, and dimethyl-p-methylphenylamine. Examples of the hydrazine compound include 1-ethylfluorenyl-2-phenylhydrazine. Examples of the metal chelate compound include acetoacetone vanadium and the like. Examples of the phosphorus-containing compound include dimethylphosphine and triphenylphosphine. Examples of the basic vulcanizing agent include hexamethylenetetramine, n-butylaldehyde-aniline condensate, and the like.

<Organic solvent (E)> If the organic solvent (E) used in the present invention is a crystalline acid-modified polyolefin (A), an epoxypropylamine type epoxy resin (B1), or an epoxypropyl ether type The epoxy resin (B2), the acid anhydride monomer (C), and the heterocyclic compound (D) having two or more nitrogens are not particularly limited as long as they are dissolved. Specifically, for example, aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; cyclohexane, cyclohexene, and methylcyclohexane can be used. , Cycloaliphatic hydrocarbons such as ethyl cyclohexane; halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene, chloroform; methanol, ethanol, isopropanol, butanol, pentanol, hexanol, propylene glycol, phenol Alcohol solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone and other ketone solvents; methylcellulose, ethylcellulose Cellulose of Su et al; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate, etc .; ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, Glycol ethers such as ethylene glycol mono-tertiary butyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl ether, triethylene glycol mono-n-butyl ether, and tetraethylene glycol mono-n-butyl ether As the solvent, one kind of them may be used or two or more kinds may be used in combination.

The organic solvent (E) is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and more preferably 100 parts by mass or more, and 110 parts by mass based on 100 parts by mass of the crystalline acid-modified polyolefin (A). The above is particularly good. If it is not within the above range, the solution state and pot life characteristics may decrease. In addition, it is preferably 1,000 parts by mass or less, more preferably 900 parts by mass or less, even more preferably 800 parts by mass or less, and particularly preferably 700 parts by mass or less. If it exceeds the aforementioned range, it may be disadvantageous in terms of manufacturing cost and transportation cost.

Considering the solution state and pot life characteristics of the adhesive composition, the organic solvent (E) is preferably one or more selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and halogenated hydrocarbons. A solvent (E1) and a mixed solution of one or more solvents (E2) selected from the group consisting of an alcohol solvent, a ketone solvent, an ester solvent, and a glycol ether solvent are preferable. In terms of mixing ratio, it is preferable that the solvent (E1) / solvent (E2) = 50 ~ 97/50 ~ 3 (mass ratio), more preferably 55 ~ 95/45 ~ 5 (mass ratio), which is 60 ~ 90 / 40 ~ 10 (mass ratio) is even better, 70 ~ 80/30 ~ 20 (mass ratio) is particularly good. Outside the above range, the solution state and pot life characteristics of the adhesive composition may be reduced. The solvent (E1) is an aromatic hydrocarbon or an alicyclic hydrocarbon, and the solvent (E2) is particularly preferably a ketone-based solvent.

<Adhesive composition> The adhesive composition according to the present invention contains the crystalline acid-modified polyolefin (A), epoxypropylamine type epoxy resin (B1), and epoxypropyl ether type epoxy resin. (B2) and an organic solvent (E), and a composition containing any one of an acid anhydride monomer (C) and a heterocyclic compound (D) having two or more nitrogens. It preferably contains a crystalline acid-modified polyolefin (A), an epoxypropylamine type epoxy resin (B1), an epoxypropyl ether type epoxy resin (B2), an organic solvent (E), and an acid anhydride monomer. The composition of the compound (C) and the heterocyclic compound (D) having two or more nitrogens. Crystalline acid-modified polyolefin (A), epoxypropylamine type epoxy resin (B1), epoxypropyl ether type epoxy resin (B2), acid anhydride monomer (C), and two or more The nitrogen heterocyclic compound (D) may be dissolved in the organic solvent (E), or may be dispersed in the organic solvent (E). From the viewpoint of pot life characteristics, it is preferable to dissolve it in an organic solvent (E).

The adhesive composition related to the present invention may be blended with the aforementioned modified polyolefin (A), epoxypropylamine type epoxy resin (B1), and epoxypropyl ether within a range that does not impair the performance of the present invention. Epoxy resin (B2), acid anhydride monomer (C), heterocyclic compound (D) having two or more nitrogen, and various additives other than organic solvent (E) are used. There are no particular restrictions on additives, and flame retardants, pigments, anti-blocking agents, etc. are preferably used.

<Laminated body> The laminated body 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.

For the lamination method, a conventional lamination manufacturing technique can be used. It is not particularly limited, but for example, an adhesive composition can be applied to the surface of a metal substrate using an appropriate coating method such as a roll coater or a coating bar, and dried. After drying, when the adhesive layer already formed on the surface of the metal substrate is still in a molten state, the polyolefin resin substrate is laminated and adhered to the coating surface to obtain a laminated structure. The thickness of the aforementioned adhesive layer formed by using the adhesive composition is not particularly limited, and is preferably set to 0.5 to 10 μm, more preferably 0.8 to 9.5 μm, and more preferably 1 to 9 μm.

<Polyolefin resin substrate> The polyolefin resin substrate may be appropriately selected from conventionally known polyolefin resins. It is not particularly limited, but, for example, polyethylene, polypropylene, ethylene-propylene copolymer, and the like can be used. Among them, polypropylene-free stretch film (hereinafter also referred to as CPP) is suitable. Its thickness is not particularly limited, but is preferably 20 to 100 μm, more preferably 25 to 95 μm, and more preferably 30 to 90 μm. In addition, the polyolefin resin substrate may be blended with pigments and various additives as required.

<Metal substrate> There is no particular limitation on the metal substrate. For example, various metals such as aluminum, copper, steel, zinc, durumumin, die cast, and alloys thereof can be used. Moreover, as for the shape, arbitrary shapes, such as a metal foil, a rolled steel plate, a flat plate, a pipe, a can, and a lid, can be acquired. In general, aluminum foil is preferred from the viewpoint of processability and the like. In addition, although it varies depending on the purpose of use, it is generally used in the form of a sheet having a thickness of 0.01 to 10 mm, and it is preferably used in the form of a sheet having a thickness of 0.02 to 5 mm. In addition, from the viewpoint of corrosion resistance and adhesion to these metal substrates, it is preferable to apply a surface treatment to the surface in advance, and specific examples thereof include chromate treatment.

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the examples. In the examples and comparative examples, the abbreviated part represents mass parts.

<Production example of crystalline acid-modified polyolefin (A)> [Production example 1] 100 parts by mass of a propylene-butene copolymer ("TAFMER (registered trademark) XM7080" manufactured by Mitsui Chemicals), 150 parts by mass of toluene, and 25 parts by mass of maleic anhydride and 6 parts by mass of di (tertiary butyl) peroxide were added to a 1 L autoclave, and the temperature was raised to 140 ° C., followed by stirring for 3 hours. Then, the obtained reaction liquid was cooled, and then it was poured into a container into which a large amount of methyl ethyl ketone had been placed to precipitate a resin. Thereafter, the liquid containing the resin was centrifuged, and the acid-modified propylene-butene copolymer obtained by graft polymerization of maleic anhydride was separated from (poly) maleic anhydride and low-molecular-weight substances and purified. . Thereafter, by drying at 70 ° C. for 5 hours under reduced pressure, a maleic anhydride-modified propylene-butene copolymer (PO-1, an acid value of 48 mgKOH / g-resin, a weight average molecular weight of 50,000, and a Tm of 75 ° C., △ H25J / g).

[Production Example 2] A maleic anhydride-modified propylene-butene copolymer (PO-2) was obtained in the same manner as in Production Example 1 except that the amount of maleic anhydride was changed to 20 parts by mass. , Acid value 25mgKOH / g-resin, weight average molecular weight 80,000, Tm75 ° C, △ H30J / g).

[Production Example 3] The same procedure as in Production Example 1 was performed except that the feed amount of maleic anhydride was changed to 3 parts by mass and the di (tri-butyl) peroxide was changed to 0.5 parts by mass. This was performed to obtain a maleic anhydride-modified propylene-butene copolymer (PO-3, acid value: 5 mgKOH / g-resin, weight average molecular weight: 180,000, Tm80 ° C, ΔH25J / g).

[Production Example 4] A maleic anhydride-modified propylene-butene copolymer (PO-4) was obtained in the same manner as in Production Example 1 except that the amount of maleic anhydride was changed to 30 parts by mass. , Acid value 55mgKOH / g-resin, weight average molecular weight 40,000, Tm70 ° C, ΔH25J / g).

[Production Example 5] The same procedure as in Production Example 1 was performed except that the amount of maleic anhydride was changed to 2 parts by mass and the di (tributyl) peroxide was changed to 0.5 parts by mass. This was performed to obtain a maleic anhydride-modified propylene-butene copolymer (PO-5, acid value: 3 mgKOH / g-resin, weight average molecular weight: 200,000, Tm80 ° C, ΔH25J / g).

(Production of Base 1) 100 parts by mass of maleic anhydride-modified propylene-butene copolymer (PO-1) obtained in Production Example 1, 280 parts by mass of methylcyclohexane, and 120 parts by mass of methyl ethyl ketone were charged. The material was placed in a 500-ml four-necked flask equipped with a water-cooled reflux condenser and a stirrer, and the temperature was raised to 80 ° C while stirring, and the stirring was continued for 1 hour to obtain the main agent 1. The state of the solution is shown in Table 1.

(Production of Base Agents 2 to 12) The crystalline acid-modified polyolefin and the organic solvent were changed as shown in Table 1, and base agents 2 to 12 were obtained in the same manner as the base agent 1. The blending amount and solution state are shown in Table 1.

[Table 1] [Example 1] Blended with 500 parts by mass of the main agent 1, 20 parts by mass of jER (registered trademark) of the epoxy-propyl ether type epoxy resin (B2) as a hardener, 152.2 parts by mass of the ring TETRAD (registered trademark) -X of the oxypropylamine type epoxy resin (B1) and 20 parts by mass of RIKACID (registered trademark) DDSA of the acid anhydride monomer (C) as an additive, to obtain an adhesive composition. Table 2 shows the evaluation results of its pot life characteristics, adhesion, and chemical resistance.

[Examples 2 to 69, Comparative Examples 1 to 7] The main agents 1 to 12 and each hardener were changed as shown in Tables 2 to 5, and Examples 2 to 69 were compared in the same manner as in Example 1. Examples 1 ~ 7. The blending amount, pot life characteristics, adhesion and chemical resistance are shown in Tables 2 to 5.

[Table 2]

[table 3]

[Table 4]

[table 5]

The hardeners used in Tables 2 to 5 are shown below. <Glycidyl epoxy resin (B1)> N, N, N ', N'-tetraglycid m-xylylene diamine: TETRAD (registered trademark) -X (Mitsubishi Gas Chemical Co., Ltd.) ＜ Glycidyl ether epoxy resin (B2)> Phenolic novolac resin epoxy resin: jER (registered trademark) 152 (manufactured by Mitsubishi Chemical Corporation) o-cresol novolac resin epoxy resin: YDCN-700-3 (Manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) <Other hardeners> Polyisocyanate: DURANATE (registered trademark) TPA-100 (manufactured by Asahi Kasei Corporation) Silane coupling agent: KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd.) <Acid anhydride monomer (C) ＞ Tetrapropenyl succinic anhydride: RIKACID (registered trademark) DDSA Tetrahydrophthalic anhydride: RIKACID (registered trademark) TH ＜ Heterocyclic compound (D) having two or more nitrogens ＞ 1-Benzyl-2-formyl Chimidazole: CUREZOL (registered trademark) 1B2MZ (manufactured by Shikoku Kasei Corporation)

Analytical measurement and evaluation were performed on each of the modified polyolefin, the main agent, and the adhesive composition obtained as described above according to the following method. [Measurement of Acid Value] <Crystalline acid-modified polyolefin (A)> The acid value (mgKOH / g-resin) of the crystalline acid-modified polyolefin (A) in the present invention refers to an acid modification that neutralizes 1 g The amount of KOH required for the polyolefin (A) is measured in accordance with the test method of JIS K0070 (1992). Specifically, after dissolving 1 g of acid-modified polyolefin in 100 g of xylene whose temperature has been adjusted to 100 ° C., phenolphthalein is used as an indicator at the same temperature, and 0.1 mol / L potassium hydroxide ethanol solution [trade name] "0.1 mol / L ethanolic potassium hydroxide solution", manufactured by Wako Pure Chemical Industries, Ltd.] was titrated. At this time, the amount of potassium hydroxide required for the titration was converted into mg to calculate the acid value (mgKOH / g-resin).

<Acid anhydride monomer (C)> The acid value (mgKOH / g) of the acid anhydride monomer (C) in the present invention is based on the molecular weight (M) of the acid anhydride monomer and the number of succinic anhydride groups (n). Calculated value. Acid value (mgKOH / g-resin) = [Molecular weight of succinic anhydride (M) × (n) × 2 × Molecular weight of potassium hydroxide × 1000 (mg) / Molecular weight of succinic anhydride] Molecular weight of succinic anhydride: 100.07, hydroxide Molecular weight of potassium: 56.11

[Measurement of weight average molecular weight (Mw)] The weight average molecular weight in the present invention is a gel permeation chromatograph Alliance e2695 (hereinafter referred to as GPC, standard material: polystyrene resin, mobile phase: tetrahydrofuran, tube) Column: Shodex KF-806 + KF-803, column temperature: 40 ° C, flow rate: 1.0ml / min, detector: photodiode array detector (wavelength 254nm = ultraviolet light) measured value.

[Measurement of Melting Point and Melting Heat] The melting point and melting heat in the present invention is a differential scanning calorimeter (hereinafter referred to as DSC, manufactured by TA Instruments Japan, Q-2000), and is melted and cooled by heating at a rate of 20 ° C / minute. After the resinization, the temperature and area of the highest point of the melting peak at the time of melting and heating again were measured.

[Evaluation of the solution state of the main agent] For the solution state of the main agent 1 to 12, a Brookfield viscometer TVB-10M (hereinafter also referred to as a B-type viscometer) manufactured by Toki Sangyo Co., Ltd. was measured at 25 ° C. The solution viscosity was evaluated. <Evaluation Criteria> ○ (excellent in practical use): less than 500 mPa ･ s △ (practical): 500 mPa ･ s or more but less than 1000 mPa ･ s × (not practical): 1000 mPa ･ s or more or impossible due to gelation Measuring viscosity

[Evaluation of shelf life characteristics] The shelf life characteristics refer to the stability of the solution after a crosslinking agent or a hardener is added to the crystalline acid-modified polyolefin and a certain period of time has elapsed after the blending or blending. Cases with good pot life characteristics mean that the solution has a small increase in viscosity and can be stored for a long time. Cases with poor pot life characteristics mean that the solution has a rise in viscosity (thickening), which can cause gelation in severe cases and is difficult to apply to The substrate cannot be stored for a long time. The pot life characteristics of the adhesive composition obtained in Examples 1 to 69 and Comparative Examples 1 to 7 were measured after storing at 25 ° C and 40 ° C in ambient gas for 24 hours, and then measuring the viscosity of the solution at 25 ° C using a B-type viscometer Evaluation. The evaluation results are shown in Tables 2 to 5. <Evaluation Criteria> ○ (excellent in practical use): less than 500 mPa ･ s △ (available): 500 mPa ･ s or more but less than 1000 mPa ･ s × (not practical): 1000 mPa ･ s or more or impossible due to gelation Measuring viscosity

[Production of a laminated body of a metal substrate and a polyolefin resin substrate] A chromate-treated aluminum foil (Sumika Aluminum Foil Co., Ltd., 8079-0, thickness: 40 μm) was used for the metal substrate, and a polyolefin resin substrate was used. Stretched polypropylene film (PYLEN (registered trademark) FILM CT, manufactured by Toyobo Co., Ltd., thickness 40 μm) (hereinafter also referred to as CPP). The adhesive composition obtained in Examples 1 to 69 and Comparative Examples 1 to 7 was applied to a metal substrate using a coating rod, and the thickness of the dried adhesive layer was adjusted to 3 μm. The coated surface was dried with a warm air dryer at 100 ° C. for 1 minute to obtain an adhesive layer having a thickness of 3 μm. A polyolefin resin substrate was laminated on the surface of the aforementioned adhesive layer, and a small table test laminator (SA-1010-S) manufactured by TESTER SANGYO was used to apply the adhesive at 80 ° C, 0.3 MPa, and 1 m / min. Then, they were aged at 40 ° C. and 50% RH for 120 hours to obtain a laminate.

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

[Evaluation of Adhesiveness] The laminate was cut into a size of 100 mm × 15 mm, and the adhesiveness was evaluated by a T-peel test. The evaluation results are shown in Tables 2 and 3.

<T-Peel Test> According to the test method of ASTM-D1876-61, TENSILON RTM-100 manufactured by ORIENTEC Corporation was used, and the peel strength at a tensile speed of 50 mm / min was measured at 25 ° C. The peel strength (N / cm) between the metal base material / polyolefin resin base material is an average of five test values.

<Evaluation Criteria> ☆ (especially excellent in practical terms): 8.0 N / cm or more, or CPP material damage (hereinafter also referred to as "material damage") Material damage means that the interface of the metal substrate / CPP does not peel, but the metal When the substrate or CPP is damaged. ◎ (Excellent in practical use): 7.5N / cm or more but less than 8.0N / cm ○ (Practical): 7.0N / cm or more and less than 7.5N / cm × (Not practical): 7.0N / cm or less

[Evaluation of Chemical Resistance] In order to investigate the usability of the packaging material of lithium ion batteries, which is one of the use forms of the laminated body of aluminum foil and CPP, the chemical resistance (hereinafter also referred to as electrolytic resistance) using the electrolyte test was implemented. Liquidity). The aforementioned laminated body was cut into a size of 100 mm × 15 mm, and an electrolyte solution to which 300 ppm of water had been added [Hexafluorocarbonate was added to ethylene carbonate / diethyl carbonate / dimethyl carbonate = 1/1/1 (volume ratio) Produced by lithium phosphate (LiPF ₆ )], immersed at 85 ° C for 3 days, or immersed in an electrolytic solution to which 500 ppm of water has been added, immersed at 85 ° C for 5 days. Thereafter, the laminated body was taken out and washed with ion-exchanged water, and the water was wiped off with a paper wiper, the moisture was sufficiently dried, cut into a size of 100 mm × 15 mm, and chemical resistance was performed by a T-peel test. Evaluation.

<Evaluation Criteria> ☆ (especially excellent in practical use): 8.0 N / cm or more or broken material ◎ (excellent in practical use): 7.5 N / cm or more and less than 8.0 N / cm ○ (practical): 7.0 N / 7.5N / cm or more × cm (Not practical): 7.0N / cm or less [Industrial availability]

The adhesive composition related to the present invention contains any one of an acid-modified polyolefin, an epoxy resin, an organic solvent, an acid anhydride monomer, and a heterocyclic compound having two or more nitrogens, and will not occur even after long-term storage. Tackifying and gelling, can maintain good pot life characteristics, and can have good adhesion to metal substrates and polyolefin resin substrates. Therefore, the laminated structure of a polyolefin resin substrate and a metal substrate formed from the adhesive composition of the present invention can be used not only in the fields of home appliances, furniture materials, and building interior components, but also in a wide range of applications. It is used as a packaging material (bag form) for lithium batteries used in personal computers, mobile phones, and video cameras.

Claims (13)

Adhesive composition containing crystalline acid-modified polyolefin (A), epoxypropylamine type epoxy resin (B1), epoxypropyl ether type epoxy resin having an acid value of 5 to 50 mgKOH / g-resin The resin (B2) and the organic solvent (E) further contain any one of an acid anhydride monomer (C) and a heterocyclic compound (D) having two or more nitrogens. For example, the adhesive composition of the first patent application range, wherein the epoxypropylamine epoxy resin (B1) is an epoxy resin having two or more epoxypropyl groups in one molecule. For example, the adhesive composition according to item 1 or 2 of the patent application range, wherein the epoxypropylamine epoxy resin (B1) is a compound represented by the general formula (1); In the general formula (1), in the general formula (1), R is an aryl group which may have a substituent, X1 and X2 are each independently an alkylene group having 1 to 5 carbon atoms which may also have a substituent, and m is 1 Or 2, and n is 1 or 2. For example, the adhesive composition according to item 1 or 2 of the patent application range, wherein the epoxypropyl ether epoxy resin (B2) is a ring having 2 or more epoxypropyl groups and containing no nitrogen atom in one molecule. Oxygen resin. For example, the adhesive composition according to item 1 or 2 of the patent application range, wherein the acid anhydride monomer (C) is a compound having one or more acid anhydride rings in one molecule and having an acid value of 100 mgKOH / g or more. For example, the adhesive composition according to item 1 or 2 of the patent application range, wherein the heterocyclic compound (D) having two or more nitrogens is a 5-membered ring aromatic heterocyclic compound having two or more nitrogens. For example, the adhesive composition in the first or second patent application scope contains a crystalline acid-modified polyolefin (A), an epoxypropylamine type epoxy resin (B1), an epoxypropyl ether type epoxy resin ( B2), acid anhydride monomer (C) and organic solvent (E), and contains 0.01 to 20 parts by mass of epoxypropylamine-type epoxy resin relative to 100 parts by mass of crystalline acid-modified polyolefin (A) (B1), 1 to 50 parts by mass of an epoxy-propyl ether type epoxy resin (B2), 1 to 50 parts by mass of an anhydride monomer (C), and 80 to 1,000 parts by mass of an organic solvent (E). For example, the adhesive composition in the first or second patent application scope contains a crystalline acid-modified polyolefin (A), an epoxypropylamine type epoxy resin (B1), an epoxypropyl ether type epoxy resin ( B2) Heterocyclic compound (D) and organic solvent (E) having two or more nitrogens, and containing 0.01 to 20 parts by mass of the ring with respect to 100 parts by mass of the crystalline acid-modified polyolefin (A) Oxypropylamine type epoxy resin (B1), 1 to 50 parts by mass of epoxypropyl ether type epoxy resin (B2), 0.01 to 5 parts by mass of heterocyclic compound (D with 2 or more nitrogen) ), 80 to 1000 parts by mass of an organic solvent (E). For example, the adhesive composition in the first or second patent application scope contains a crystalline acid-modified polyolefin (A), an epoxypropylamine type epoxy resin (B1), an epoxypropyl ether type epoxy resin ( B2), an acid anhydride monomer (C), a heterocyclic compound (D) having two or more nitrogens, and an organic solvent (E), and containing 100 parts by mass of the crystalline acid-modified polyolefin (A), 0.01 to 20 parts by mass of epoxypropylamine epoxy resin (B1), 1 to 50 parts by mass of epoxypropyl ether epoxy resin (B2), 1 to 50 parts by mass of anhydride monomer (C) 0.01 to 5 parts by mass of a heterocyclic compound (D) having two or more nitrogens, and 80 to 1000 parts by mass of an organic solvent (E). For example, the adhesive composition according to item 1 or 2 of the patent application scope, wherein the organic solvent (E) is a mixed solution of the solvent (E1) and the solvent (E2), and the solvent (E1) is selected from the group consisting of aromatic hydrocarbons and fatty acids. One or more solvents in the group consisting of an aliphatic hydrocarbon, an alicyclic hydrocarbon and a halogenated hydrocarbon, and the solvent (E2) is selected from the group consisting of alcohol solvents, ketone solvents, ester solvents, and glycol ether solvents. One or more solvents in the group, and the solvent (E1) / solvent (E2) = 50 ~ 97/50 ~ 3 (mass ratio). For example, the adhesive composition in the scope of patent application No. 1 or 2 is used for the adhesion of polyolefin resin substrates and metal substrates. A laminated body of a polyolefin resin substrate and a metal substrate is adhered by using an adhesive composition according to any one of claims 1 to 11 of the scope of patent application. A packaging material for a lithium ion battery, comprising a laminated body of a polyolefin resin substrate and a metal substrate as described in claim 12 of the patent application as a constituent member.