KR102340015B1 - Polyolefin-based adhesive composition - Google Patents

Abstract

To provide an adhesive composition containing a modified polyolefin and an epoxy resin having good pot life and good adhesion between a metal substrate and a polyolefin resin substrate.
An adhesive composition comprising a crystalline acid-modified polyolefin (A) having an acid value of 5 to 50 mgKOH/g-resin, a glycidylamine-type epoxy resin (B1), a chelate-modified epoxy resin (B2), and an organic solvent (C) .

Description

Polyolefin-based adhesive composition

The present invention relates to an adhesive composition for adhering a polyolefin resin substrate and a metal substrate. More particularly, it relates to an adhesive composition containing a crystalline acid-modified polyolefin, an epoxy resin, and an organic solvent.

Conventionally, a laminate formed by coating and laminating a vinyl chloride resin (hereinafter simply referred to as “vinyl chloride”) on the surface of a metal substrate such as an exterior plate for home appliances, a material for furniture, and a member for building interior has been used. The problem is close-up, and polyolefin resin is proposed as a substitute for vinyl chloride. Polyolefin resins are non-toxic, exhibit strong durability against acids, alkalis, and organic solvents, and have excellent mechanical strength and abrasion resistance, and are widely used in various fields because they are inexpensive.

However, since polyolefin resin is nonpolar, adhesion with a metal substrate was difficult. Conventionally, various adhesives have been proposed for bonding the polyolefin resin and the metal substrate. Typical examples are those obtained by mixing a solvent-dispersible modified polyolefin resin with a base adhesive obtained by dissolving a thermosetting resin or thermoplastic resin such as a phenol resin, a melamine resin, and an epoxy resin in an organic solvent. However, it is difficult to say that these adhesives have sufficient adhesiveness. In addition, an adhesive composition containing catechol or the like with crystalline acid-modified polyolefin and an epoxy resin (Patent Document 1), or an adhesive composition containing maleic acid-modified chlorinated polypropylene, a chelate epoxy resin, and a solvent (Patent Document 2) are also proposed. have.

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

However, in the above method, the pot life after blending with the acid-modified polyolefin solution is sometimes poor, and even if the pot life is not so problematic, the adhesion to important metal substrates and chemical resistance are not sufficient. That is, there was no thing which satisfies pot life property, adhesiveness, and chemical-resistance. In particular, even in the case of using a polypropylene (hereinafter also referred to as PP) substrate, there was no adhesive capable of bonding and aging (curing) at a low temperature such as 80° C. or less with little effect of heat shrinkage. Here, pot life property mix|blends a crosslinking agent or a hardening|curing agent with modified polyolefin, and refers to the stability of the solution immediately after the mix|blending or after a fixed period of time has elapsed.

The present invention has been made in view of the above conventional problems, and as a result of earnest examination by the present inventors for an adhesive for a polyolefin resin substrate and a metal substrate, an adhesive composition containing a crystalline acid-modified polyolefin, an epoxy resin, and an organic solvent, It has discovered that pot life property, bonding in 80 degrees C or less, the adhesiveness in aging, and chemical-resistance are compatible, and has come to complete this invention.

That is, the present invention has good pot life after blending the crystalline acid-modified polyolefin and the curing agent, and has good adhesion and chemical resistance to both the polyolefin resin substrate and the metal substrate in bonding and aging at low temperatures. An object of the present invention is to provide an adhesive composition.

In order to achieve the said subject, the present inventors earnestly examined and came to propose the following invention.

An adhesive composition comprising a crystalline acid-modified polyolefin (A) having an acid value of 5 to 50 mgKOH/g-resin, a glycidylamine-type epoxy resin (B1), a chelate-modified epoxy resin (B2), and an organic solvent (C) .

It is preferable that the said glycidylamine type epoxy resin (B1) is an epoxy resin which has two or more glycidyl groups in 1 molecule.

It is preferable that the said glycidylamine type epoxy resin (B1) is a compound represented by 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 have a substituent, m is 1 or 2, n is 1 or 2.)

It is preferable that the chelate-modified epoxy resin (B2) is an epoxy resin having two or more glycidyl groups in one molecule and at least one functional group having a chelating effect without containing a nitrogen atom.

With respect to 100 parts by mass of the crystalline acid-modified polyolefin (A), 0.01 to 20 parts by mass of the glycidylamine-type epoxy resin (B1), 1 to 20 parts by mass of the chelate-modified epoxy resin (B2), and the organic solvent (C) It is preferable to contain 80-1000 mass parts.

The organic solvent (C) is a mixture of the solvent (C1) and the solvent (C2), wherein the solvent (C1) is at least one solvent selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons, and the solvent (C2) ) is at least one solvent selected from the group consisting of alcohol solvents, ketone solvents, ester solvents and glycol ether solvents, and solvent (C1)/solvent (C2) = 50 to 97/50 to 3 (mass ratio) it is preferable

The adhesive composition in any one of the above used for adhesion|attachment of a polyolefin resin base material and a metal base material.

A laminate of a polyolefin resin substrate and a metal substrate adhered with the adhesive composition according to any one of the above.

The adhesive composition according to the present invention contains a crystalline acid-modified polyolefin, two types of epoxy resins and an organic solvent, and can maintain good pot life without causing thickening or gelation even after long-term storage. In addition, even when bonding and aging are performed at a low temperature such as 80° C. or lower, where the effect of heat shrinkage of the polyolefin substrate is small, it is possible to achieve both good adhesion and chemical resistance between the polyolefin resin substrate and the metal substrate.

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

<Crystalline acid-modified polyolefin (A)>

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

The propylene-α-olefin copolymer is obtained by copolymerizing α-olefin with propylene as a main component. As the α-olefin, for example, one or several types of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate and the like can be used. Among these ?-olefins, ethylene and 1-butene are preferable. The ratio of the propylene component to the α-olefin component of 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 α,β-unsaturated carboxylic acids and their acid anhydrides include maleic acid, itaconic acid, citraconic acid, and acid anhydrides thereof. Among these, an acid anhydride is preferable and maleic anhydride is more preferable. Specific examples thereof include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, maleic anhydride-modified propylene-ethylene-butene copolymer, and the like, and these crystals One type or a combination of two or more types of acid-modified polyolefins can be used. Among them, a maleic anhydride-modified propylene-butene copolymer is preferable. As a propylene component/1-butene component (molar ratio) of maleic anhydride-modified propylene-butene copolymer, it is preferable that it is 90-50/10-50, It is more preferable that it is 85-60/15-40, It is 80-55 It is more preferable that it is /20-45, and it is especially preferable that it is 75-60/25-40. By setting it as the said range, especially excellent pot life property, adhesiveness, and chemical-resistance can be expressed.

The lower limit of the acid value of the crystalline acid-modified polyolefin (A) needs to be 5 mgKOH/g-resin or more, preferably 10 mgKOH/g, from the viewpoint of pot life properties and adhesion between the polyolefin resin substrate and the metal substrate. -resin or more, more preferably 14 mgKOH/g-resin or more, still more preferably 16 mgKOH/g-resin or more, particularly preferably 18 mgKOH/g-resin or more, most preferably is greater than or equal to 20 mgKOH/g-resin. If it is less than the said value, compatibility with an epoxy resin may be low, adhesive strength may not be expressed, and a crosslinking density may be low and chemical-resistance may be insufficient. The upper limit needs to be 50 mgKOH/g-resin or less, preferably 48 mgKOH/g-resin or less, more preferably 46 mgKOH/g-resin or less, still more preferably 44 mgKOH/g -resin or less, particularly preferably 42 mgKOH/g-resin or less, and most preferably 40 mgKOH/g-resin or less. When the said value is exceeded, the viscosity and stability of a solution may fall, and pot life property may fall. Moreover, since manufacturing efficiency also falls, it is unpreferable. The acid value can be controlled by the graft amount (addition amount) of at least one of the α,β-unsaturated carboxylic acid and the acid anhydride thereof.

It is preferable that the range of the weight average molecular weight (Mw) of crystalline acid-modified polyolefin (A) is 40,000-180,000. More preferably, it is the range of 50,000-160,000, More preferably, it is the range of 60,000-150,000, Especially preferably, it is the range of 70,000-140,000, Most preferably, it is the range of 80,000-130,000. If it is less than the said value, cohesive force may become weak and adhesiveness may be inferior. On the other hand, when it exceeds the said value, fluidity|liquidity is low and a problem may arise in the operability at the time of bonding. If it exists in the said range, since hardening reaction with an epoxy resin is exhibited, it is preferable.

The crystallinity in the crystalline acid-modified polyolefin (A) is, using a differential scanning calorimeter (DSC), the temperature is raised from -100°C to 250°C at 20°C/min, and a clear melting peak is shown in the temperature increase process. refers to

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

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

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. More preferably, it is the range of 10 J/g - 50 J/g, Most preferably, it is the range of 20 J/g - 40 J/g. When it is less than the said value, the cohesive force derived from a crystal|crystallization may become weak and it may be inferior to adhesiveness and chemical-resistance. On the other hand, when it exceeds the said value, solution stability and fluidity|liquidity are low, and a problem may arise in the operability at the time of adhesion|attachment.

The method for producing the crystalline acid-modified polyolefin (A) is not particularly limited, and for example, a radical graft reaction (that is, a radical species is generated with respect to a polymer serving as a main chain, and the radical species is used as a polymerization initiation point for an unsaturated carboxylic acid and a reaction in which an acid anhydride is graft-polymerized).

Although it does not specifically limit as a radical generator, It is preferable to use an organic peroxide. The organic peroxide is not particularly limited, but di-tert-butylperoxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy-2-ethyl peroxides such as hexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, and lauroyl peroxide; Azonitriles, such as azobisisobutyronitrile and azobisisopropionitrile, etc. are mentioned.

<Glycidylamine type epoxy resin (B1)>

The glycidylamine type epoxy resin (B1) used for this invention will not be specifically limited if it is an epoxy resin which has one or more glycidyl groups in 1 molecule. It is preferable to have two or more glycidyl groups in one molecule of the epoxy resin, more preferably to have three or more glycidyl groups in one molecule of the epoxy resin, and more preferably to have four or more glycidyl groups in one molecule of the epoxy resin desirable.

Moreover, chemical-resistance improves further and the glycidylamine type epoxy resin (B1) is preferable by using the compound represented by following General formula (1).

In general formula (1), R is an aryl group which may have a substituent, Preferably it is a phenyl group which may have a substituent. Although it does not specifically limit as a substituent of the said aryl group, C1-C5 alkyl group, C1-C5 alkoxy group, hydroxyl group, amino group, glycidyl group, glycidylamino group, or a glycidyl ether group can be mentioned. have. X1 and X2 are each independently a linear alkylene group which may have a substituent having 1 to 5 carbon atoms, and preferably has 4 or less carbon atoms, more preferably 3 or less, and still more preferably 2 or less. Although it does not specifically limit as a substituent of the said alkylene group, A C1-C5 alkyl group, a C1-C5 alkoxy group, or an amino group is mentioned. 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.

Although it does not specifically limit as a specific example of a glycidylamine type epoxy resin (B1), Tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, N,N and glycidylamines such as ,N',N'-tetraglycidyl-m-xylenediamine. Among them, N,N,N',N'-tetraglycidyl-m-xylenediamine is preferable. These glycidylamine type epoxy resins (B1) can be used individually or 2 or more types can be used together.

It is preferable that the compounding quantity of a glycidylamine type epoxy resin (B1) is 0.01 mass part or more with respect to 100 mass parts of crystalline acid-modified polyolefin (A), It is more preferable that it is 0.05 mass part or more, It is 0.1 mass part or more More preferably, it is especially preferable that it is 1 mass part or more, and it is most preferable that it is 2 mass parts or more. If it is less than the said range, a catalytic action may not be expressed but adhesiveness and chemical-resistance in bonding in 80 degreeC or less and aging and chemical-resistance may be low. Moreover, it is preferable that it is 20 mass parts or less, It is more preferable that it is 18 mass parts or less, It is still more preferable that it is 16 mass parts or less, It is especially preferable that it is 14 mass parts or less, It is most preferable that it is 12 mass parts or less. If it exceeds the said range, a crosslinking reaction advances excessively, rigidity becomes high, and there exists a tendency for adhesiveness to fall. Moreover, a crosslinking reaction tends to advance during solution storage of an adhesive composition, and there exists a tendency for a pot life to fall.

<Chelate-modified epoxy resin (B2)>

The chelate-modified epoxy resin (B2) used for this invention will not be specifically limited if it is an epoxy resin which has a functional group which has a chelate effect in a molecule|numerator. Preferably, an epoxy resin having two or more glycidyl groups and one or more functional groups having a chelating effect in one molecule of the epoxy resin, and which does not contain a nitrogen atom, is preferable from the viewpoint of improving reactivity, adhesion and chemical resistance. do. That is, by mix|blending a chelate-modified epoxy resin (B2), the rust prevention property of metallic substrates, such as aluminum, improves, and chemical-resistance improves with it. Thereby, even if it does not perform surface treatment (eg, chromate treatment) of a metal substrate, the outstanding adhesiveness of an adhesive composition and the chemical-resistance of a metal substrate can be expressed.

Chelate refers to the binding (coordination) to a metal ion by a ligand (polydentate ligand) having a plurality of coordination sites, and the functional group having a chelate effect is not particularly limited, carboxyl group, phosphonic acid group, sulfonic acid group, phosphate group, Acid groups, such as a sulfuric acid group, a nitric acid group, and a boric acid group, things other than acidic radicals, such as an alcoholic hydroxyl group, phenolic hydroxyl group, a nitrile group, a thiol group, and an amino group, are mentioned. Preferably, it is a phosphoric acid group.

The blending amount of the chelate-modified epoxy resin (B2) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, with respect to 100 parts by mass of the crystalline acid-modified polyolefin (A) , It is particularly preferably 4 parts by mass or more, and most preferably 5 parts by mass or more. Moreover, it is preferable that it is 20 mass parts or less, It is more preferable that it is 18 mass parts or less, It is still more preferable that it is 16 mass parts or less, It is especially preferable that it is 14 mass parts or less, It is most preferable that it is 12 mass parts or less. By setting it as the said range, the outstanding adhesiveness and chemical-resistance can be expressed.

The chelate-modified epoxy resin (B2) used for this invention may be used individually by 1 type, and may use two or more together. Specifically, the EP-49-10 series manufactured by ADEKA Co., Ltd. has been released and can be used.

In this invention, it is characterized by using together two types of epoxy resins, the said glycidylamine type epoxy resin (B1) and the said chelate-modified epoxy resin (B2) as essential components. By using together a glycidylamine type epoxy resin (B1) and a chelate-modified epoxy resin (B2), the outstanding adhesiveness and chemical-resistance can be expressed. That is, the glycidylamine-type epoxy resin (B1) has a reaction and curing action between the crystalline acid-modified polyolefin (A) and the chelate-modified epoxy resin (B2). In addition, the glycidylamine type epoxy resin (B1) includes a crystalline acid-modified polyolefin (A), a glycidylamine type epoxy resin (B1), a glycidylamine type epoxy resin (B1), and a chelate-modified epoxy resin ( Since B2) has a reaction of a glycidylamine-type epoxy resin (B1) and a chelate-modified epoxy resin (B2) and a curing catalytic action, by blending, bonding at 80° C. or less, and the metal substrate in aging Adhesiveness and chemical resistance can be improved.

It is preferable that the compounding quantity of the total of a glycidylamine type epoxy resin (B1) and a chelate-modified epoxy resin (B2) is 2-40 mass parts with respect to 100 mass parts of crystalline acid-modified polyolefin (A), 5-20 It is more preferable that it is a mass part, and it is most preferable that it is 10-16 mass parts. If it is less than the said range, sufficient hardening effect cannot be acquired, but adhesiveness and chemical-resistance may be low, and if it exceeds the said range, it is unpreferable from a viewpoint of pot life property, adhesiveness fall with an olefin base material, and a viewpoint of cost.

It is preferable that it is 1-50 mass % of the whole epoxy resin, as for the compounding quantity of a glycidylamine type epoxy resin (B1), It is more preferable that it is 2-30 mass %, It is most preferable that it is 3-10 mass %. If the blending amount is less than the above, the catalytic action is not expressed, and adhesion and chemical resistance in low-temperature bonding and aging may be low. tends to do Moreover, a crosslinking reaction tends to advance during solution storage of an adhesive composition, and there exists a tendency for a pot life to fall.

As an epoxy resin used for this invention, another epoxy resin can also be used together. For example, a glycidyl ether type epoxy resin, a glycidyl ester type such as glycidyl hexahydrophthalate, dimer acid glycidyl ester, triglycidyl isocyanurate, or 3,4-epoxycyclohexylmethyl and alicyclic or aliphatic epoxides such as carboxylate, epoxidized polybutadiene, and epoxidized soybean oil. Specific examples of the glycidyl ether type epoxy resin include, but are not particularly limited to, phenol novolac type epoxy resins; Cresol novolak-type epoxy resins are mentioned, These may be used individually by 1 type, or may use 2 or more types together.

<Organic solvent (C)>

The organic solvent (C) used in the present invention is not particularly limited as long as it dissolves the crystalline acid-modified polyolefin (A), the glycidylamine-type epoxy resin (B1), and the chelate-modified epoxy resin (B2). Specifically, for example, aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; cycloaliphatic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane; trichloro Halogenated hydrocarbons such as ethylene, dichloroethylene, chlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; acetone, methyl isobutyl ketone, methyl ethyl ketone Ketone solvents such as pentanone, hexanone, cyclohexanone, isophorone and acetophenone, cellosolves such as methyl cellosolve and ethyl cellosolve, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate Ester solvents such as ethylene glycol mono-n-butyl ether, ethylene glycol mono-iso-butyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-iso- Glycol ether solvents, such as butyl ether, triethylene glycol mono-n-butyl ether, and tetraethylene glycol mono-n-butyl ether, etc. can be used, These 1 type, or 2 or more types can be used together.

The organic solvent (C) is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, still more preferably 100 parts by mass or more, and 110 parts by mass with respect to 100 parts by mass of the crystalline acid-modified polyolefin (A). The above is particularly preferable. If it is less than the said range, a solution state and pot life may fall. Moreover, it is preferable that it is 1000 mass parts or less, It is more preferable that it is 900 mass parts or less, It is still more preferable that it is 800 mass parts or less, It is especially preferable that it is 700 mass parts or less. When it exceeds the said range, it may become disadvantageous in terms of manufacturing cost and transport cost.

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

<Adhesive composition>

The adhesive composition according to the present invention is a mixture of the crystalline acid-modified polyolefin (A), a glycidylamine-type epoxy resin (B1), a chelate-modified epoxy resin (B2), and an organic solvent (C). The crystalline acid-modified polyolefin (A), the glycidylamine-type epoxy resin (B1), and the chelate-modified epoxy resin (B2) may be dissolved in the organic solvent (C) or may be dispersed. It is preferable to melt|dissolve from a viewpoint of pot life.

The adhesive composition according to the present invention comprises the crystalline acid-modified polyolefin (A), a glycidylamine-type epoxy resin (B1), a chelate-modified epoxy resin (B2) and an organic solvent ( In addition to C), various curing accelerators may be mixed and used. Although it does not specifically limit as a hardening accelerator, A carboxylate metal salt, tertiary amines, quaternary ammonium salt, an organic peroxide, a hydrazine compound, a metal chelate compound, thiourea, a phosphorus compound, basic vulcanizing agents, etc. are mentioned. As said carboxylate metal salt, the metal salt of C1-C30 carboxylic acid is mentioned. Examples of the carboxylic acid constituting the carboxylate metal salt include acetic acid, butyric acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, octhenic acid, erucic acid, L aliphatic carboxylic acids such as lydic 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, naphthalenedicarboxylic acid, and benzenetricarboxylic acid; naphthenic acid; acetonic acid etc. are mentioned. Moreover, as a metal which comprises the said carboxylate metal salt, Li, Na, K, Mg, Ca, Zn, Al, Cu, Pb, Co, Fe, Mn, Sn, Ti, etc. are mentioned, for example. Specific examples of the metal carboxylate 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. , 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, sodium oleate, sodium behenate, sodium benzoate, zinc benzoate, sodium phthalate, aluminum phthalate, magnesium terephthalate, naphthalenedicarboxylate, dibutyltin laurate, tributyltin laurate, la dioctyltin urate, tributyltin acetate, dibutyltin diacetate, dioctyltin diacetate, dibutyltin 2-ethylhexoate, tetrabutyl titanate, tetraisobutyl titanate, tetra2-ethylhexyl titanate, Cobalt naphthenate, copper naphthenate, magnesium naphthenate, cobalt acetoacetate, etc. are mentioned. Among these, lithium laurate, sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, and magnesium palmitate are preferable. , sodium stearate, potassium stearate, calcium stearate, zinc stearate, and sodium oleate. Moreover, as a metal salt of carboxylic acid, the polymer which has a metal salt structure of carboxylic acid can also be used. As such a polymer, it has a structure in which ethylene and a salt of a radically polymerizable carboxylic acid of Group IA, Group IIA, Group IIB, or Group IIIB (eg Li, Na, K, Mg, Ca, Zn, Al, etc.) are copolymerized. thing; The thing which has the structure which carried out the multicomponent copolymerization of ethylene, the metal salt of radically polymerizable carboxylic acid, another radically polymerizable carboxylic acid, and/or its derivative(s), etc. are mentioned. Moreover, as said tertiary amine, dimethylaniline, triethanolamine, dimethyl-p-toluidine etc. are mentioned, for example. Moreover, as said hydrazine compound, 1-acetyl-2-phenylhydrazine etc. are mentioned, for example. Moreover, as said metal chelate compound, vanadium acetylacetonate etc. are mentioned, for example. Moreover, as said thiourea, dimethylphosphine, triphenylphosphine, etc. are mentioned, for example. Moreover, as said phosphorus compound, dimethylphosphine, triphenylphosphine, etc. are mentioned, for example. Moreover, as said basic vulcanizing agent, hexamethylenetetraamine, n-butylaldehyde-aniline condensate, etc. are mentioned, for example.

The adhesive composition according to the present invention comprises the crystalline acid-modified polyolefin (A), a glycidylamine-type epoxy resin (B1), a chelate-modified epoxy resin (B2) and an organic solvent ( In addition to C), various additives may be mixed and used. Although it does not specifically limit as an additive, It is preferable to use a flame retardant, a pigment, an antiblocking agent, etc.

<Laminate>

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

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

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

<Polyolefin resin base material>

As a polyolefin resin base material, what is necessary is just to select suitably from conventionally well-known polyolefin resin. For example, although it does not specifically limit, Polyethylene, polypropylene, an ethylene-propylene copolymer, etc. can be used. Among them, use of a polypropylene unstretched film (hereinafter also referred to as CPP) is preferred. Although the thickness is not specifically limited, It is preferable that it is 20-100 micrometers, It is more preferable that it is 25-95 micrometers, It is more preferable that it is 30-90 micrometers. Moreover, you may mix|blend a pigment and various additives with a polyolefin resin base material as needed.

<Metal base>

Although it does not specifically limit as a metal base material, For example, various metals, such as aluminum, copper, steel, zinc, duralumin, die-cast, and its alloy can be used. In addition, as the shape, arbitrary shapes, such as metal foil, a rolled steel plate, a panel, a pipe, a can, a cap, can be taken. Generally, an aluminum foil is preferable from a viewpoint of workability etc. 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, preferably 0.02 to 5 mm.

In addition, the surface of these metal base materials may be surface-treated previously, and it may remain untreated. In any case, the same effect can be exerted.

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 Examples and Comparative Examples, simply referring to parts indicates parts by mass.

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

production example One

In a 1 L autoclave, 100 parts by mass of a propylene-butene copolymer (“Tapmer (registered trademark) XM7080” manufactured by Mitsui Chemicals Corporation), 150 parts by mass of toluene, and 25 parts by mass of maleic anhydride, di-tert-butyl peroxide 6 After adding a mass part and heating up to 140 degreeC, it stirred for further 3 hours. Then, after cooling the obtained reaction liquid, it poured into the container with a large amount of methyl ethyl ketone, and resin was deposited. Thereafter, the liquid containing the resin was centrifuged to separate and purify the acid-modified propylene-butene copolymer obtained by graft polymerization of maleic anhydride, (poly)maleic anhydride, and low molecular weight substances. Thereafter, by drying at 70° C. under reduced pressure for 5 hours, maleic anhydride-modified propylene-butene copolymer (PO-1, acid value 48 mgKOH/g-resin, weight average molecular weight 50,000, Tm 75° C., ΔH 25 J/ g) was obtained.

production example 2

Maleic anhydride-modified propylene-butene copolymer (PO-2, acid value 25 mgKOH/g-resin, weight average molecular weight 80,000, Tm) by carrying out the same procedure as in Production Example 1 except that the content of maleic anhydride was changed to 20 parts by mass 75° C., ΔH 30 J/g) was obtained.

production example 3

A maleic anhydride-modified propylene-butene copolymer (PO-3, acid value 5 mg) was carried out in the same manner as in Production Example 1 except that the content of maleic anhydride was changed to 3 parts by mass and di-tert-butyl peroxide was changed to 0.5 parts by mass. KOH/g-resin, weight average molecular weight 180,000, Tm 80° C., ΔH 25 J/g) was obtained.

production example 4

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

production example 5

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

(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 methylethyl 120 mass parts of ketones were put, it heated up to 80 degreeC, stirring, and the main body 1 was obtained by continuing stirring for 1 hour. The solution state is shown in Table 1.

(Production of topics 2 to 12)

The crystalline acid-modified polyolefin and the organic solvent were changed as shown in Table 1, and subjects 2 to 12 were produced in the same manner as in the subject 1. A compounding quantity and a solution state are shown in Table 1.

Example One

500 parts by mass of the main agent 1, 2 parts by mass of Adekaresin (registered trademark) EP-49-10P, which is a chelate-modified epoxy resin (B2) as a curing agent, and TETRAD (registered trademark) as a glycidylamine-type epoxy resin (B1) 0.2 mass parts of -X was mix|blended, and the adhesive composition was obtained. Table 2 shows the evaluation results of pot life, adhesiveness, and chemical resistance.

Example 2-21, comparative example 1-7

Subjects 1 to 12 and each curing agent were changed as shown in Tables 2 and 3, and Examples 2 to 21 and Comparative Examples 1 to 7 were performed in the same manner as in Example 1. A compounding quantity, pot life property, adhesiveness, and chemical-resistance are shown in Tables 2 and 3.

The curing agents used in Tables 2 and 3 are as follows.

<Glycidylamine type epoxy resin (B1)>

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

<Chelate-modified epoxy resin (B2)>

Chelate-modified epoxy resin: Adeka Resin (registered trademark) EP-49-10P (manufactured by ADEKA)

Phosphoric acid-modified epoxy resin: Uradil DD-79 (manufactured by DSM Coating Resins)

<Glycidyl ether type epoxy resin>

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

<Other hardeners>

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

Silane coupling agent: KBM-403 (manufactured by Shin-Etsu Silicone)

Analysis, measurement and evaluation were performed based on the following method for each crystalline acid-modified polyolefin, the main agent, and the adhesive composition obtained as described above.

mountain measurement

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), JIS K0070 (1992) ) was measured according to the test method. Specifically, after dissolving 1 g of acid-modified polyolefin in 100 g of xylene temperature-controlled at 100°C, at the same temperature, using phenolphthalein as an indicator, a 0.1 mol/L potassium hydroxide ethanol solution [brand name "0.1 mol/L ethanol Potassium hydroxide solution", manufactured by Wako Pure Chemical Industries, Ltd.]. At this time, the amount of potassium hydroxide required for titration was converted into mg to calculate the acid value (mgKOH/g-resin).

Measurement of weight average molecular weight (Mw)

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

Measurement of melting point and heat of fusion

In the present invention, the melting point and heat of fusion are measured by using a differential scanning calorimeter (hereinafter, DSC, manufactured by TAA Instruments Japan, Q-2000) at a rate of 20 ° C./min. It is a value measured from the top temperature and area of the melting peak at the time of heating-melting again.

Assessment of subject solution status

The solution state of the main subjects 1-13 was evaluated by measuring the solution viscosity of 25 degreeC using the Brookfield type viscometer TVB-10M (henceforth a B type viscometer) by the Toki Sangyo company.

<Evaluation criteria>

○ (excellent in practice): less than 500 mPa·s

△ (practicable): 500 mPa·s or more and less than 1000 mPa·s

× (impossible to use): 1000 mPa·s or more, or viscosity measurement impossible due to gelation

port of life evaluation

Pot life property refers to the stability of the solution immediately after mixing or after mixing for a certain period of time after mixing the crosslinking agent or curing agent with the crystalline acid-modified polyolefin. When the pot life property is good, the viscosity of the solution is small and long-term storage is possible, and when the pot life property is poor, the viscosity of the solution rises (thickens), and in severe cases, it causes a gelation phenomenon, coating becomes difficult, indicating that long-term storage is impossible.

After storing for 24 hours in 25 degreeC and 40 degreeC atmosphere, the pot life of the adhesive composition obtained in Examples 1-18 and Comparative Examples 1-8 was evaluated by measuring the solution viscosity of 25 degreeC using the B-type viscometer. . The evaluation results are shown in Tables 2 and 3.

<Evaluation criteria>

○ (excellent in practice): less than 500 mPa·s

△ (practicable): 500 mPa·s or more and less than 1000 mPa·s

× (impossible to use): not less than 1000 mPa·s or impossible to measure viscosity due to gelation

of a metal substrate and a polyolefin resin substrate of laminate produce

Aluminum foil (manufactured by Sumike Aluminum Haku Co., Ltd., 8079-0, thickness 40 µm) was used for the metal substrate, and an unstretched polypropylene film [Pyrene (registered trademark) film CT manufactured by Toyobo Corporation, thickness 40 µm) was used for the polyolefin resin substrate. ] (hereinafter also referred to as CPP) was used.

The adhesive compositions obtained in Examples 1 to 32 and Comparative Examples 1 to 15 were applied to a metal substrate by using a bar coater to adjust the thickness of the adhesive layer after drying to 3 µm. The coated surface was dried for 1 minute in an atmosphere of 100°C using a warm air dryer to obtain an adhesive layer having a thickness of 3 µm. Polyolefin resin substrate is polymerized on the surface of the adhesive layer, and bonded at 80° C., 0.3 MPa, 1 m/min using a small tabletop test laminator (SA-1010-S) manufactured by Tester Sangyo Co., Ltd., 40° C., 50% A laminate was obtained by curing at RH for 120 hours.

About the laminated body obtained by making it above, the following method evaluated.

Adhesion evaluation

The laminate was cut to a size of 100 mm x 15 mm, and adhesion was evaluated by a T-type peel test. An evaluation result is shown to Tables 3-6.

<T-type peel test>

According to the test method of ASTM-D1876-61, the peel strength in a tensile rate of 50 mm/min was measured in 25 degreeC environment using the Tensilon RTM-100 by the Orientech Corporation. The peeling strength (N/cm) between a metal base material / polyolefin resin base material was made into the average value of five test values.

<Evaluation criteria>

☆ (very particularly good in practice): 8.0 N/cm or more or CPP material failure (hereinafter also simply referred to as "material destruction"). Material destruction means that the metal substrate or CPP is destroyed without peeling at the interface of the metal substrate/CPP.

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

○ (excellent in practice): 7.0 N/cm or more and less than 7.5 N/cm

△ (practicable): 6.0 N/cm or more and less than 7.0 N/cm

× (not practical): less than 6.0 N/cm

Evaluation of chemical resistance

In order to examine the usability as a packaging material for a lithium ion battery, which is one of the usage forms of the laminate of aluminum foil and CPP, chemical resistance (hereinafter also referred to as electrolyte resistance) was evaluated by an electrolyte test. The laminate was cut to a size of 100 mm x 15 mm, and lithium hexafluorophosphate was added to the electrolyte [ethylene carbonate/diethyl carbonate/dimethyl carbonate = 1/1/1 (volume ratio). ] was immersed at 85°C for 1 day. After that, the laminate was taken out, washed with ion-exchanged water, wiped off with a paper wiper, dried sufficiently, cut into a size of 100 mm x 15 mm, and chemical resistance was evaluated by a T-type peel test. did

<Evaluation criteria>

☆ (very particularly good in practice): more than 8.0 N/cm or material destruction

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

○ (excellent in practice): 7.0 N/cm or more and less than 7.5 N/cm

△ (practicable): 6.0 N/cm or more and less than 7.0 N/cm

× (not practical): less than 6.0 N/cm

The adhesive composition according to the present invention contains a crystalline acid-modified polyolefin, an epoxy resin and an organic solvent, and maintains good pot life without causing thickening or gelation even after long-term storage, and furthermore, a metal substrate and a polyolefin resin substrate good adhesiveness can be achieved. Therefore, the laminated structure of the polyolefin resin substrate and the metal substrate formed from the adhesive composition of the present invention is lithium used not only in fields such as exterior plates for home appliances, materials for furniture, and members for building interiors, but also personal computers, mobile phones, video cameras, and the like. It can be widely used also as a battery packaging material (pouch form).

Claims (8)

It contains a crystalline acid-modified polyolefin (A) having an acid value of 5 to 50 mgKOH/g-resin, a glycidylamine-type epoxy resin (B1), a chelate-modified epoxy resin (B2) and an organic solvent (C); The adhesive composition whose glycidylamine type epoxy resin (B1) is a compound represented by 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 have a substituent, m is 1 or 2, and n is 1 or 2.) The adhesive composition according to claim 1, wherein the glycidylamine-type epoxy resin (B1) is an epoxy resin having two or more glycidyl groups in one molecule. delete The epoxy resin according to claim 1 or 2, wherein the chelate-modified epoxy resin (B2) has two or more glycidyl groups in one molecule, and does not contain a nitrogen atom and has at least one functional group having a chelating effect. adhesive composition. The glycidylamine-type epoxy resin (B1) is contained in an amount of 0.01 to 20 parts by mass, and the chelate-modified epoxy resin (B2) is contained in an amount of 1 to 100 parts by mass of the crystalline acid-modified polyolefin (A). The adhesive composition containing - 20 mass parts and 80-1000 mass parts of organic solvents (C). The organic solvent (C) according to claim 1 or 2, wherein the organic solvent (C) is a mixture of the solvent (C1) and the solvent (C2), and the solvent (C1) is from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons. at least one selected solvent, the solvent (C2) is at least one solvent selected from the group consisting of alcohol solvents, ketone solvents, ester solvents and glycol ether solvents, and solvent (C1)/solvent (C2) = 50 -97/50-3 (mass ratio) adhesive composition. The adhesive composition according to claim 1 or 2, which is used for bonding the polyolefin resin substrate and the metal substrate. A laminate of a polyolefin resin substrate and a metal substrate adhered with the adhesive composition according to claim 1 or 2.